JP2016011381A - Resin for sugar solution purification, filter for sugar solution purification, and sugar solution purification method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin for sugar solution purification with a high treatment rate, provide a filter for sugar solution purification having excellent handleability and allowing for efficient purification, and provide a sugar solution purification method using the filter.SOLUTION: The present invention provides a resin for sugar solution purification which uses an ethylene-vinyl alcoholic copolymer as a base, and comprises an amino group introduced thereinto. The present invention also provides a filter for sugar solution purification comprising binder 2-100 pts. mass relative to the resin for sugar solution purification 100 pts. mass.

Description

  The present invention relates to a sugar liquid purification resin, and more specifically, an amino group is chemically bonded to an ethylene-vinyl alcohol copolymer which is a highly hydrophilic polymer or has an amino group. The present invention relates to a sugar liquid refining resin that has a high affinity with a processing solution and a high processing speed because the component is dispersed in the ethylene-vinyl alcohol copolymer without a chemical bond. The present invention also relates to a resin solution for sugar solution purification having excellent handling properties and a method for treating a sugar solution using the filter.

  In the purification of various sugar solutions such as sugarcane sugar and sugar beet sugar, ion exchange resins have been used for a long time for the purpose of removing hardness components and decolorizing. Decolorization with an ion exchange resin can be easily regenerated and repeated by passing a sodium chloride aqueous solution as an eluent after adsorbing the dye component.

  As the ion exchange resin used for the purification (decolorization) of the sugar solution, for example, a basic ion exchange resin having a primary to tertiary amine or a quaternary ammonium group is used (Patent Document 1). However, most conventional ion exchange resins are based on a hydrophobic structure such as styrene, and have a low affinity with sugar solution, so there is a limit to the processing speed in order to fully exhibit the decolorization performance. There is a problem that satisfactory processing efficiency cannot always be obtained.

  Japanese Patent Laid-Open No. 5-49951

  Accordingly, an object of the present invention is to provide a resin for purifying a sugar solution that has a high affinity with the sugar solution and is excellent in processing speed. Furthermore, it aims at providing the filter for sugar liquid refinement | purification which is excellent in the handleability using the said resin for sugar liquid refinement | purification, and the sugar liquid refinement | purification method using the said filter.

  As a result of intensive studies on materials containing amino groups in order to solve the above problems, the present inventors have reached the present invention. The present invention is as follows.

[1] A resin for purifying a sugar solution into which an amino group is introduced, which is based on an ethylene-vinyl alcohol copolymer.
[2] Resin for purifying a sugar solution, wherein the amino group introduction amount is 2.0 mmol / g to 15 mmol / g.
[3] Resin for purifying sugar solution having a particle shape and a particle diameter of 10 to 3000 μm.
[4] A resin for purifying a sugar solution which is porous and has an average pore diameter formed on the surface thereof in the range of 0.01 to 50 μm.
[5] A sugar solution purification filter containing 2 to 100 parts by mass of a binder with respect to 100 parts by mass of the resin for sugar solution purification.
[6] A housing in which the sugar liquid purification filter is loaded.
[7] A method for purifying a sugar solution using the housing.

  The resin for purifying a sugar solution of the present invention is excellent in the processing speed of sugar solution purification, particularly decolorization. Furthermore, a sugar liquid purification filter using the resin for purifying sugar liquid is excellent in handleability and can purify the sugar liquid with high efficiency and low cost by a simple operation.

  The present invention is described in detail below. The resin for purifying a sugar solution of the present invention uses an ethylene-vinyl alcohol copolymer as a base material, and an amino group is introduced as an adsorptive functional group of a substance to be removed (coloring component, etc.).

(Ethylene-vinyl alcohol copolymer)
The ethylene-vinyl alcohol copolymer contained in the sugar liquid purification resin of the present invention is not particularly limited as long as the desired performance is obtained. For example, the ethylene content is about 10 to 60 mol%. It is good and about 20-50 mol% is preferable. If the ethylene content is less than 10 mol%, the water resistance of the resulting sugar liquid purification resin may be reduced. On the other hand, when the ethylene content exceeds 60 mol%, it is difficult to produce and difficult to obtain.

  The saponification degree of the ethylene-vinyl alcohol copolymer is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 99 mol% or more. When the degree of saponification is less than 90 mol%, moldability may be deteriorated, and the water resistance of the resulting sugar liquid purification resin may be reduced.

  The melt flow rate (MFR) (210 ° C., load 2160 g) of the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 0.1 g / min or more, and more preferably 0.5 g / min or more. If it is less than 0.1 g / min, water resistance and strength may be reduced. In addition, the upper limit of a melt flow rate should just be the range normally used, for example, 25 g / min or less may be sufficient.

The said ethylene-vinyl alcohol-type copolymer may contain another unsaturated monomer unit in the range which does not impair the effect of this invention. The content of the unsaturated monomer unit is preferably 10 mol% or less, more preferably 5% mol or less.
Such ethylene-vinyl alcohol copolymers can be used alone or in combination of two or more.

(Amino group)
The amino group contained in the sugar liquid purification resin of the present invention may be in a state chemically bonded to the ethylene-vinyl alcohol copolymer, and the component having an amino group is an ethylene-vinyl alcohol copolymer. It may be in a state of being dispersed without intermingling chemical bonds in the coalescence. Hereinafter, preferred embodiments will be described for each.

  As a method for introducing an amino group in a state of being chemically bonded to an ethylene-vinyl alcohol copolymer, for example, by copolymerizing a monomer having an amino group at the time of forming an ethylene-vinyl alcohol copolymer. Examples thereof include a method of introducing, an ethylene-vinyl alcohol copolymer, and a method of chemically modifying the copolymer as a base material with a compound having an amino group. From the viewpoint of forming amino groups on the resin surface with high density, a method of chemically modifying with an amino group-containing compound using the copolymer as a base material after the formation of an ethylene-vinyl alcohol copolymer is preferred. From the same viewpoint, the amino group is preferably introduced into the graft chain (branched polymer) using an ethylene-vinyl alcohol copolymer as a backbone polymer.

  As a method for introducing a graft chain having an amino group into an ethylene-vinyl alcohol copolymer, (1) an unsaturated monomer having a halogenated alkyl group such as chloromethylstyrene or chloroethyl (meth) acrylate, or glycidyl A method in which an unsaturated monomer having an epoxy group such as methacrylate is previously graft-polymerized based on an ethylene-vinyl alcohol copolymer, and the graft chain is reacted with a compound having an amino group, (2) an amino group And a method of graft-polymerizing an unsaturated monomer having an ethylene-vinyl alcohol copolymer as a base point to produce a graft polymer. From the viewpoint of easy reaction, the method (1) is preferred. As the method, various known methods are possible. For example, a method of introducing a graft chain using radical polymerization using a polymerization initiator, a radical is generated using ionizing radiation, and a graft chain is introduced. The method of doing is mentioned. Among these, from the viewpoint of high graft chain introduction efficiency, a method of introducing a graft chain using ionizing radiation is preferably used.

  As a method of graft polymerization of an unsaturated monomer to an ethylene-vinyl alcohol copolymer using ionizing radiation, radiation is irradiated in the presence of the ethylene-vinyl alcohol copolymer and the unsaturated monomer. Both of the mixed irradiation method and the pre-irradiation method in which only the ethylene-vinyl alcohol copolymer is irradiated with radiation in advance and then the unsaturated monomer and the ethylene-vinyl alcohol copolymer are brought into contact with each other are possible. The pre-irradiation method, which is the latter method, has a feature that it is difficult to generate side reactions other than graft polymerization.

  Although it does not specifically limit as a dose irradiated with ionizing radiation, 5-230 kGy is preferable, 10-200 kGy is more preferable, 15-180 kGy is further more preferable. 20-160 kGy is most preferred. If it is less than 5 kGy, the dose is too small and the grafting rate is lowered, and the target aldehyde removal performance may not be obtained. When it exceeds 230 kGy, there is a concern that the treatment process is costly and the resin deteriorates during irradiation.

  When conducting graft polymerization to introduce a graft chain having an amino group, the unsaturated monomer is not limited to the unsaturated monomer having a functional group such as alkyl halide and epoxy as described above, and performance is impaired. Other unsaturated monomers may be used in combination as long as they are not present. For example, divinylbenzene, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, bismethylene acrylamide and the like can be used.

  Examples of the compound having an amino group to be reacted with the graft chain include ethylenediamine, trimethylenediamine, 2-methyl-1,3-propanediamine, propylenediamine, tetramethylenediamine, 3-methylaminopropylamine, 1, 3-diamino-2-propanol, 2-methyl-1,2-propanediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, 1,4-butanediamine, 1,3-pentanediamine, 1,4- Cyclohexanediamine, 1,3-cyclohexanediamine, trans-1,2-cyclohexanediamine, 2-methyl-1,5-pentanediamine, 1,5-pentanediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, deca Methylenedia , N- (2-aminoethyl) piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, hexamethyleneheptamine, polyvinylamine, polyallylamine, polyethyleneimine, 2-aminobenzylamine, 3-amino Benzylamine, 4-aminobenzylamine, benzylamine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 4- (methylamino) pyridine 4-amino (2-methyl) pyridine, 4-amino (3- Methyl) pyridine, 2-picolylamine, 3-picolylamine, 4-picolylamine, 4- (ethylaminomethyl) pyridine, 3- (2-aminomethyl) pyridine, 2- (2-aminoethyl) pyridine, bis ( 3-pyridylmethyl) amine Bis (2-pyridylmethyl) amine, 2-amino-4-methylpyridine, 3-amino-4-methylpyridine, imidazole compounds (2-aminoimidazole, 1- (3-aminopropyl) imidazole, 2-amino Benzimidazole, etc.), triazole compounds (4-amino-1,2,4-triazole, 3-amino-1H-1,2,4-triazole, etc.), benzotriazole compounds (1-hydroxybenzotriazole, 1- Aminobenzotriazole, etc.), 4-aminoindole, 5-aminoindole, 6-aminoindole, histamine, tryptamine, tryptophan, polyvinylamine, polyallylamine, polyethyleneimine and the like. Among these, a polyvalent amine is particularly preferable from the viewpoint of ease of production and sugar liquid decolorization performance.

  As a method for introducing an amino group in a state where the component having an amino group is dispersed in the ethylene-vinyl alcohol copolymer without a chemical bond, a compound having an amino group and an ethylene-vinyl alcohol copolymer are used. And a method of removing the solvent after molding, and a method of melt-kneading the compound having an amino group and the ethylene-vinyl alcohol copolymer. In the present invention, mixing by melt kneading, which does not require a solvent and can be easily molded, is preferred. In the case of mixing by melt kneading, as the compound having an amino group, an amine polymer having an amino group in a repeating unit is preferably used.

  The amino group of the amine polymer may be any one of a primary amino group, a secondary amino group, and a tertiary amino group, and is preferably a primary amino group or a secondary amino group. The repeating unit having an amino group may be one type or two or more types. Therefore, the amine-based polymer may be a polymer in which two or more kinds of repeating units having an amino group are random, block, alternating, or graft copolymerized. Moreover, the repeating unit which does not have an amino group may be included in the range which does not inhibit the effect of this invention.

  The amine-based polymer having an amino group in the repeating unit is not particularly limited, and examples thereof include polyvinylamine, polyvinylalkylamine, polyalkyleneimine, polyaniline, and salts thereof. At least one selected from this group is preferably used. More preferably, at least one selected from the group consisting of polyvinyl alkylamines, polyalkyleneimines, and salts thereof is used.

  The amount of amino groups introduced, that is, the number of moles of amino groups per unit mass of the sugar liquid purification resin of the present invention is not particularly limited, but from the viewpoint of sugar liquid decolorization performance, 2.0 mmol / g to 15 mmol / G, more preferably 3.0 mmol / g to 12 mmol / g, and still more preferably 4.0 mmol / g to 10 mmol / g. When the amount introduced is less than 2.0 mmol / g, the sugar solution decolorization performance may not be sufficiently obtained. On the other hand, when the number of moles of the functional group exceeds 15 mmol / g, the swelling / shrinkage of the resin is large, the sugar solution purification resin may be collapsed due to a volume change, and is often difficult to manufacture.

(shape)
There is no restriction | limiting in particular in the shape of resin for sugar liquid refinement | purification of this invention, A particulate form, a fiber form, etc. are mentioned, Preferably it is a particulate form. In the present invention, the term “particle” is a concept including powder. When the sugar liquid purification resin is in the form of particles, the particle diameter is not particularly limited, but is preferably 10 to 3000 μm, more preferably 30 to 2500 μm, and even more preferably 40 to 2000 μm. When the particle diameter is less than 10 μm, it is difficult to handle, for example, the fine powder easily floats. When the particle diameter exceeds 3000 μm, the sugar liquid decolorization performance may not be sufficiently obtained. In addition, a particle diameter shows the value classified by sieving.

  The resin for purifying a sugar solution of the present invention may be porous. In the present invention, the term “porous” means that a plurality of pores are present on at least the resin surface. The pores may have a continuous structure or an independent structure. The pores formed on the surface may have an average pore diameter of about 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm, more preferably about 0.2 μm to 10 μm. When the average pore diameter is less than 0.01 μm, the sugar liquid decolorization performance may be insufficient. When the average pore diameter is larger than 50 μm, the mechanical strength of the resin for refining a sugar solution is low, and there is a possibility that it will collapse in the use environment. The average pore diameter of these pores is a value measured by the method described in the examples described later.

  The resin for purifying a sugar solution of the present invention may contain additives such as a crosslinking agent, inorganic fine particles, a light stabilizer, and an antioxidant as long as the effects of the present invention are not impaired.

(filter)
The sugar liquid purification filter of the present invention can be molded by mixing a sugar liquid purification resin and a binder. There are no particular restrictions on the type and form of the binder contained in the filter as long as it retains the resin for purifying the sugar solution and can maintain the filter shape, and examples include fibrous binders, powdered binders, etc. A fibrous binder, more preferably a fibrillated (small fiber) fibrous binder. Fibrous binders can be widely used regardless of whether they are synthetic products or natural products. Examples include acrylic fibers, polyethylene fibers, polypropylene fibers, polyacrylonitrile fibers, cellulose fibers, nylon fibers, aramid fibers, and polyester fibers. Can be mentioned. These fibrous binders can be fibrillated by a known method such as beating, and the fibrillated fibrous binder is also available as a commercial product. The fiber length of the fibrous binder is preferably 4 mm or less.

  There is no particular limitation on the form in which the sugar liquid refining resin is held by the binder. For example, when the binder is a fibrillated fibrous binder, the sugar liquid refining resin is fibrillated. Desirably, the resin is captured and fixed on the network structure formed by the binder, and the sugar liquid refining resin is supported on the fibrous binder. When the binder is a heat-fusible fibrous binder (eg, polyethylene fiber, polypropylene fiber, polyester fiber, etc.), the sugar liquid refining resins are bonded together by a once melted fibrous binder, and the sugar liquid purification is performed. The resin is held by the binder. In addition, when the binder is a heat-fusion resin powder binder (eg, polyethylene powder, polypropylene powder, polystyrene powder, polyethylene terephthalate powder, etc.) as a powdery binder, a powder in which the resins for sugar solution purification are once melted together The sugar solution refining resin is held by the binder.

  The blending ratio of the sugar solution refining resin and the binder in the sugar solution refining filter of the present invention is such that the binder is contained in 100 parts by weight of the sugar solution refining resin from the viewpoint of decolorization effect, suppression of filter swelling and moldability. The amount is 2 to 100 parts by mass, preferably 3 to 50 parts by mass, and more preferably 5 to 20 parts by mass.

  The manufacturing method of the sugar liquid purification filter is not particularly limited, and a known molding method using a binder can be employed. A slurry suction method is preferable in terms of efficient production. In the slurry suction method, for example, a double tubular container including an inner tube and an outer tube each having a large number of suction holes is prepared, and a sugar liquid purification resin and a binder are included between the inner tube and the outer tube. A filter molded into a hollow cylindrical shape can be obtained by pouring the slurry and sucking the slurry from the center (inner tube side). Since the slurry can be efficiently produced, the slurry is preferably prepared by dispersing the sugar liquid refining resin and the fibrous binder in water so that the solid content concentration is 5 to 15% by mass.

  In the sugar solution purification method of the present invention, the method for contacting the sugar solution purification resin and the sugar solution is not particularly limited. For example, the continuous method of passing the sugar solution into the housing filled with the filter for sugar solution purification, The sugar solution can be purified (decolored) by any method, such as a method of adding a sugar solution refining resin into a container containing the sugar solution and stirring or standing. Furthermore, it can be carried out by loading a filter in which a resin for refining a sugar solution is formed into a hollow cylinder or the like and passing the sugar solution through the housing.

  The contact temperature between the sugar liquid refining resin of the present invention and the sugar liquid is not particularly limited, but is usually 40 ° C to 100 ° C. As the liquid passing temperature is higher, the viscosity of the sugar liquid can be suppressed, and the pressure loss during the liquid passing can be reduced. Since the resin for purifying a sugar solution of the present invention is also excellent in heat resistance, it can be used without problems even at high temperature treatment (for example, 80 ° C.). Further, the contact time is not particularly limited, and can be set by appropriately conducting preliminary experiments.

  Since the sugar liquid purification method of the present invention can efficiently decolorize the sugar liquid, it is very effective for shortening the processing time of the sugar making process, for example.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. In addition, each numerical value in an Example was measured with the following method.

[Calculation of average pore diameter]
The surface of the particles was observed using a scanning electron microscope. Arbitrary 50 pores were selected from the pores formed on the surface, and the major axis of each pore was measured. The 50 major diameters were averaged, and the average value was derived as the average pore diameter. However, in the case of 1 nm or less, since it cannot be distinguished from scratches, deposits, etc., it was excluded from the selection.

[Graft ratio]
Calculation was performed according to the following formula.
Graft rate [w / w (%)] = 100 × (weight of attached graft chain) / (weight of substrate)

[Amino group introduction amount]
(When an amino group is chemically introduced into an ethylene-vinyl alcohol copolymer)
Let W be the mass change before and after the reaction for introducing an amino group. Calculation was performed according to the following formula.
Amino group amount [mmol / g] = (number of nitrogen atoms per molecule of reaction substrate [pieces] × W [g] / reaction substrate molecular weight [g / mol]) / (resin mass after reaction) × 1000
(When an amino group is physically introduced into an ethylene-vinyl alcohol copolymer)
The composite ratio of the amine polymer is defined as W (mass%). Calculation was performed according to the following formula.
Amino group amount [mmol / g] = number of nitrogen atoms per amine polymer unit structure [pieces] × (W / 100 [g] / amine polymer unit molecular weight [g / mol]) × 1000

(Evaluation method for decolorization performance of sugar solution)
(Examples 1-7 and Comparative Examples 1-3)
The sugar liquid purification resin was packed in a chromatography column with a diameter of 30 mm to a height of 60 mm (42.4 mL), the entire column was immersed in a constant temperature water bath, and the inside of the column was kept at 50 ° C. Here, 0.13 L of Brix 20% raw material sugar solution was passed at various flow rates (SV0.05 = 2.1 mL / hr, SV0.2 = 8.5 mL / hr, SV0.5 = 21.2 mL / hr). To do. Thereafter, the effluent was mixed, and the absorbance at 420 nm was measured with an ultraviolet-visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation) and converted to ICUMSA color value. The decolorization rate was calculated according to the following formula.
Decolorization rate [%] = {(ICUMSA color value before passing through the column−ICUMSA color value after passing through the column) / ICUMSA color value before passing through the column} × 100
(Examples 8 and 9)
The sugar liquid purification filter is loaded in a 1.5 L capacity housing, and Brix 20% raw sugar solution 45 L is passed at the same flow rate as above. Thereafter, the effluent was mixed, and the decolorization rate was calculated in the same manner as described above.

[Example 1]
90 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd., F101) and 10 parts by mass of a vinyl alcohol polymer (Kuraray Co., Ltd., PVA403) were melt-kneaded in a lab plast mill. Thereafter, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle diameter of 212 μm to 425 μm were classified using a sieve. Further, the obtained particles were treated with hot water at 100 ° C. to extract a vinyl alcohol polymer to obtain porous ethylene-vinyl alcohol copolymer particles. The average pore long diameter of the porous particles was 0.23 μm. The porous particles were irradiated with 60 kGy of ionizing radiation, immersed in and stirred in a nitrogen-substituted glycidyl methacrylate solution at 80 ° C., and graft polymerization was performed. When the graft ratio was evaluated, it was 310%. Further, the particles were immersed in an isopropanol solution of ethylenediamine and allowed to react, and then crosslinked using ethylene glycol diglycidyl ether. The particles were washed with methanol, dried, and classified into particles having a particle diameter of 300 μm to 500 μm using a sieve to obtain the intended resin for purifying sugar solution. The evaluation results are shown in Table 1. The amino group introduction amount of the resin for purifying sugar solution was 6.0 mmol / g.

[Example 2]
After melt-kneading 90 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (F101, manufactured by Kuraray Co., Ltd.) and 10 parts by mass of a vinyl alcohol polymer (PVA205, manufactured by Kuraray Co., Ltd.) in a lab plast mill. The compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle diameter of 106 μm to 212 μm were classified using a sieve. Further, the obtained particles were treated in hot water to extract a vinyl alcohol polymer, and porous ethylene-vinyl alcohol copolymer particles were obtained. The average pore long diameter of the porous particles was 0.27 μm. The porous particles were irradiated with 100 kGy ionizing radiation, immersed in and stirred in a nitrogen-substituted glycidyl methacrylate solution at 80 ° C., and graft polymerization was performed. When the graft ratio was evaluated, it was 374%. Further, the particles were immersed and reacted in an isopropanol solution of diethylenetriamine, and then cross-linked using ethylene glycol diglycidyl ether. The particles were washed with methanol, dried, and classified into particles having a particle diameter of 212 μm to 425 μm using a sieve to obtain the desired resin for purifying sugar solution. The evaluation results are shown in Table 1. The amount of amino group introduced into the sugar liquid purification resin was 8.7 mmol / g.

[Example 3]
After pulverizing a commercially available ethylene-vinyl alcohol copolymer (F101, manufactured by Kuraray Co., Ltd.), particles having a particle diameter of 150 μm to 300 μm were prepared using a sieve. No pores were formed in the particles. The particles were irradiated with ionizing radiation of 150 kGy, immersed in a 60% by mass isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 90 minutes for graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and then the graft ratio was evaluated to be 210%. Further, the particles were immersed in an isopropanol solution of ethylenediamine and allowed to react, and then crosslinked using ethylene glycol diglycidyl ether. The particles were washed with methanol, dried, and classified into particles having a particle diameter of 212 μm to 425 μm using a sieve to obtain the desired resin for purifying sugar solution. The evaluation results are shown in Table 1. In addition, the amino group introduction amount of the resin for purification of sugar solution was 5.4 mmol / g.

[Example 4]
99 parts by mass of a commercially available ethylene-vinyl alcohol copolymer (C109, manufactured by Kuraray Co., Ltd.) and 1 part by mass of a vinyl alcohol polymer (PVA205, manufactured by Kuraray Co., Ltd.) at 210 ° C. After melt-kneading for 3 minutes at a temperature, the compound obtained by cooling and solidifying the melt was pulverized, and particles having a particle diameter of 300 μm to 500 μm were produced using a sieve. Further, the obtained particles were stirred in hot water at 100 ° C. for 2 hours to extract only the vinyl alcohol polymer, thereby obtaining porous ethylene-vinyl alcohol copolymer particles. The average pore diameter of the pores of the porous particles was 0.13 μm. The porous particles were irradiated with 100 kGy of ionizing radiation, immersed in a 40% by mass isopropanol solution of glycidyl methacrylate substituted with nitrogen at 80 ° C., and stirred for 90 minutes for graft polymerization. Thereafter, the obtained particles were washed with methanol and dried, and the graft ratio was evaluated to be 365%. Further, the particles were immersed and reacted in an isopropanol solution of diethylenetriamine, and then cross-linked using ethylene glycol diglycidyl ether. The particles were washed with methanol, dried, and classified into particles having a particle diameter of 500 μm to 710 μm using a sieve to obtain the intended resin for purifying sugar solution. The evaluation results are shown in Table 1. In addition, the amino group introduction amount of the resin for purification of sugar solution was 8.1 mmol / g.

[Example 5]
An ethylene-vinyl alcohol copolymer (E105, manufactured by Kuraray Co., Ltd.) and polyethyleneimine having a weight average molecular weight of 10,000 (Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd.) were used. An ethylene-vinyl alcohol copolymer is melt-kneaded at 210 ° C. by a lab plast mill, and polyethyleneimine is contained therein in an amount of 25 parts by mass of polyethyleneimine, and an ethylene-vinyl alcohol copolymer is 75 in content. After mixing so as to be part by mass and kneading for a predetermined time, the resin composition was taken out. The obtained resin composition was pulverized with a pulverizer to form particles. The particles were subjected to a crosslinking treatment using ethylene glycol diglycidyl ether, dried, and classified into particles having a particle diameter of 212 μm to 500 μm using a sieve to obtain a target resin for purification of sugar solution. The evaluation results are shown in Table 1. In addition, the amino group introduction amount of the resin for purification of sugar solution was 5.7 mmol / g.

[Example 6]
An ethylene-vinyl alcohol copolymer (K101, manufactured by Kuraray Co., Ltd.) and polyallylamine having a weight average molecular weight of 15,000 (manufactured by Nittobo Co., Ltd., PAA-15C) were used. An ethylene-vinyl alcohol copolymer is melt-kneaded at 210 ° C. with a lab plast mill, and polyallylamine is contained therein in an amount of 20 parts by mass, and an ethylene-vinyl alcohol copolymer is 80 in content. After mixing so as to be part by mass and kneading for a predetermined time, the resin composition was taken out. The obtained resin composition was pulverized with a pulverizer to form particles. The particles were subjected to a crosslinking treatment using ethylene glycol diglycidyl ether, dried, and classified into particles having a particle diameter of 300 μm to 500 μm using a sieve to obtain a target resin for purification of sugar solution. The evaluation results are shown in Table 1. In addition, the amino group introduction amount of the resin for purification of sugar solution was 3.5 mmol / g.

[Example 7]
Ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., G156), polyethyleneimine having a weight average molecular weight of 10,000 (manufactured by Nippon Shokubai Co., Ltd., Epomin SP-200), and polyallylamine having a weight average molecular weight of 15,000 (Nitto Co., Ltd.) Spun, PAA-15C) was used. An ethylene-vinyl alcohol copolymer is melt-kneaded at 210 ° C. with a lab plast mill, and polyethyleneimine and polyallylamine are mixed therein, and the total content of polyethyleneimine and polyallylamine is 25 parts by mass (of polyethyleneimine and polyallylamine). 3 types of polymers were mixed and kneaded for a predetermined time so that the mass ratio of polyethyleneimine to the total was 80%) and the content of the ethylene-vinyl alcohol copolymer was 75 parts by mass, and then the resin composition was taken out It was. The obtained resin composition was pulverized with a pulverizer to form particles. The particles were subjected to a crosslinking treatment using ethylene glycol diglycidyl ether, dried, and classified into particles having a particle diameter of 212 μm to 425 μm using a sieve to obtain a target resin for purifying sugar solution. The evaluation results are shown in Table 1. In addition, the amino group introduction amount of the resin for purification of sugar solution was 5.4 mmol / g.

[Example 8]
A slurry was prepared by dispersing 4 parts by mass of fibrillated acrylic fiber bipal (manufactured by Toyobo Co., Ltd.) as a fibrous binder with respect to 100 parts by mass of the resin for purifying sugar solution obtained in Example 2. Next, the obtained slurry was put in a double tube container having an outer diameter of 75 mm, an inner diameter of 29 mm and a height of 255 mm having a large number of pores having a diameter of 3 mm, sucked at 350 mmHg, and then compressed at 120 ° C. without compression. It was dried for a time to obtain a hollow cylindrical sugar solution purification filter having an outer diameter of 65 mm, an inner diameter of 30 mm, and a height of 250 mm. This sugar liquid purification filter was loaded into a plastic housing (Advantech Toyo Co., Ltd., 1PP-1-FV) having a total width of 200 mm and a total height of 340 mm, and evaluated according to the evaluation method described above. The evaluation results are shown in Table 1.

[Example 9]
A slurry was prepared by dispersing fibrillated acrylic fiber bipal (manufactured by Toyobo Co., Ltd.) as a fibrous binder in water at a ratio of 5 parts by mass with respect to 100 parts by mass of the resin for purifying sugar solution obtained in Example 5. Next, the obtained slurry was put in a double tube container having an outer diameter of 75 mm, an inner diameter of 29 mm and a height of 255 mm having a large number of pores having a diameter of 3 mm, sucked at 350 mmHg, and then compressed at 120 ° C. without compression. It was dried for a time to obtain a hollow cylindrical sugar solution purification filter having an outer diameter of 65 mm, an inner diameter of 30 mm, and a height of 250 mm. This sugar liquid purification filter was loaded into a plastic housing (Advantech Toyo Co., Ltd., 1PP-1-FV) having a total width of 200 mm and a total height of 340 mm, and evaluated according to the evaluation method described above. The evaluation results are shown in Table 1.

[Comparative Example 1]
A commercially available ethylene-vinyl alcohol copolymer (F101, manufactured by Kuraray Co., Ltd.) was pulverized and then classified into particles having a particle diameter of 212 μm to 425 μm using a sieve to obtain a target resin for purifying sugar solution. . The evaluation results are shown in Table 1.

[Comparative Example 2]
Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA205) and polyethyleneimine having a weight average molecular weight of 10,000 (manufactured by Nippon Shokubai Co., Ltd., Epomin SP-200) were used. A 5% by mass aqueous solution of polyvinyl alcohol was prepared, and polyethyleneimine was mixed therewith so that the content of polyethyleneimine was 25 parts by mass and the content of polyvinyl alcohol was 75 parts by mass, and cast onto a PET film. Thereafter, the film was dried at 20 ° C. for one week, and further dried overnight in a vacuum drier to obtain a film having a thickness of about 150 μm. The film was pulverized with a pulverizer to form particles. The particles were subjected to a crosslinking treatment using ethylene glycol diglycidyl ether, dried, and classified into particles having a particle diameter of 150 μm to 300 μm using a sieve to obtain a target resin for purification of sugar solution. However, when the resin for purifying sugar solution was packed in a column and immersed in a thermostatic bath, volume swelling was remarkable and particles were dissolved and disintegrated.

[Comparative Example 3]
The performance was evaluated using a commercially available strong basic ion exchange resin Amberlite IRA400 (manufactured by Organo Corporation, styrene resin, gel type). The evaluation results are shown in Table 1.

  As is clear from Table 1, the resin for purifying a sugar solution of the present invention has excellent decolorization performance, and since the decrease in performance is small even when the liquid flow rate increases, the time for decolorization treatment can be shortened. . In addition, it is possible to provide a sugar solution purifying filter that exhibits high performance even when processed into a filter shape and is excellent in handleability. On the other hand, as in Comparative Example 1, an ethylene-vinyl alcohol copolymer having no amino group does not exhibit decolorization performance. As in Comparative Example 2, when a hydrophilic resin is used as the base material, the sugar liquid refining resin swells and partially dissolves upon contact with the high-temperature sugar liquid, and the shape cannot be maintained. As in Comparative Example 3, the ion exchange resin based on the hydrophobic resin is not only inferior in the decolorization performance, but also the performance is significantly lowered when the liquid passing speed is increased.

  ADVANTAGE OF THE INVENTION According to this invention, the novel resin for refine | purifying a sugar solution which is excellent in decoloring performance and can be used industrially can be provided. The sugar liquid refining resin can be handled more easily, for example, by processing it into a filter.

As described above, the preferred embodiments of the present invention have been described. However, various additions, modifications, or deletions are possible without departing from the spirit of the present invention, and such modifications are also included in the scope of the present invention. It is.

Claims (7)

  A resin for purifying a sugar solution into which an amino group is introduced, based on an ethylene-vinyl alcohol copolymer.   The resin for purifying a sugar solution according to claim 1, wherein the amino group introduction amount is 2.0 mmol / g to 15 mmol / g.   The resin for refining a sugar solution according to claim 1 or 2, which has a particle shape and a particle diameter of 10 to 3000 µm.   The resin for purifying a sugar solution according to any one of claims 1 to 3, which is porous and has an average pore diameter formed on the surface thereof in a range of 0.01 to 50 µm.   A filter for purifying a sugar solution comprising 2 to 100 parts by mass of a binder with respect to 100 parts by mass of the resin for purifying a sugar solution according to any one of claims 1 to 4.   A housing in which the sugar liquid purification filter according to claim 5 is loaded.   A method for purifying a sugar solution using the housing according to claim 6.