JP2020158448A - Method for producing iron-polyphenol composite material - Google Patents

Abstract

To provide a method for producing iron-polyphenol composite material that consumes less energy, takes less time, and can be carried out in a small reactor.SOLUTION: Provided is a method for producing iron-polyphenol composite material comprising a step (X) in which an aqueous solution or dispersion (B) of iron or an iron compound (A) is brought into contact with a polyphenol source (C) to obtain a reaction product (P), and a step (Y) in which the reaction product (P) is heated to 70°C or higher and dried to a moisture content of 15% or less within 60 hours.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing an iron-polyphenol composite material, which consumes less energy and can be carried out in a small device in a short time.

Patent Document 1 describes coffee beans as a water-soluble iron feeder capable of reducing and maintaining ferric iron to divalent iron ions and stably supplying water-soluble iron ions (divalent iron ions) for a long period of time. Using the crushed roasted product and / or tea leaves of the above as a feedstock of the metal ion solubilizing component, the feedstock of the metal ion solubilizing component and the iron feedstock containing trivalent iron are mixed in the presence of water. A water-soluble iron feeder containing the obtained reaction product as an active ingredient is disclosed.
In Patent Document 2, crushed roasted coffee beans (particularly coffee cake) and tea leaves (particularly tea husks) are used as a feedstock for a reducing agent, and iron containing divalent or trivalent iron as a feedstock for the reducing ingredient. A Fenton reaction catalyst in which the feedstock is mixed in the presence of water and the obtained reaction product is used as an active ingredient, and a sterilization method characterized by generating hydroxyl radicals from hydrogen peroxide using this Fenton reaction catalyst. A method for decomposing pollutants and a method for emitting light using chemiluminescence are disclosed.

Japanese Unexamined Patent Publication No. 2011-21913 Japanese Unexamined Patent Publication No. 2011-212518

The method for producing a water-soluble iron feeder or Fenton reaction catalyst disclosed in these prior arts is to mix Akadama soil with coffee grounds, add and mix twice the total weight of water, and allow it to stand at a predetermined temperature for a predetermined time. It was unsuitable for industrial implementation, in which it was allowed to react by placing it and then air-dried. The problem to be solved by the present invention is to provide a more suitable method for industrial implementation.

The present invention includes the following.
[1] A step (X) of bringing an aqueous solution or dispersion (B) of iron or an iron compound (A) into contact with a polyphenol source (C) to obtain a reaction product (P), and the reaction product (P). ) Is heated to 70 ° C. or higher and dried to a moisture content of 15% or less within 60 hours (Y).
A method for producing an iron-polyphenol composite material, including.
[2] The method for producing an iron-polyphenol composite material according to [1], wherein the contact in the step (X) is performed by spraying the aqueous solution or the dispersion liquid (B) onto the polyphenol source (C).
[3] The iron-polyphenol composite according to [1] or [2], wherein the step (X) is carried out in a range where the mass ratio of (B): (C) is 0.1: 1 to 2.7: 1. Material manufacturing method.
[4] The method for producing an iron-polyphenol composite material according to any one of [1] to [3], wherein the step (X) is carried out while maintaining the water content at 30 to 70%.
[5] The iron-polyphenol composite material according to any one of [1] to [4], wherein the concentration of iron or iron compound (A) in the aqueous solution or dispersion (B) is more than 1% by mass. Production method.
[6] The iron-polyphenol composite material according to any one of [1] to [5], wherein the concentration of iron or iron compound (A) in the aqueous solution or dispersion (B) is less than 30% by mass. Production method.
[7] The iron according to any one of [1] to [6], wherein the step (Y) further comprises a step of promoting heat conduction (y1) and / or a step of promoting exhaust (y2). A method for producing a polyphenol composite material.
[8] The method for producing an iron-polyphenol composite material according to any one of [1] to [7], wherein the step (X) and the step (Y) are carried out continuously or in parallel.
[9] The method for producing an iron-polyphenol composite material according to any one of [1] to [8], wherein the step (X) is carried out for 2 to 48 hours.
[10] The method for producing an iron-polyphenol composite material according to any one of [1] to [9], wherein the step (X) is carried out at a temperature of 70 ° C. or higher.
[11] The method for producing an iron-polyphenol composite material according to any one of [1] to [10], wherein the iron or the iron compound (A) is a compound of ferric iron.
[12] The method for producing an iron-polyphenol composite material according to any one of [1] to [11], wherein the polyphenol source (C) is coffee or tea.

The method according to the present invention has an advantageous effect that energy consumption can be reduced, the required time can be shortened, and the reactor can be miniaturized.

It is a scheme diagram which compared the method which concerns on this invention with the conventional method. FIG. 2 is an image of a sample immediately after spraying an aqueous solution of iron (III) chloride on coffee in Example 2.

FIG. 1 compares each step between the conventional method and the method according to the present invention. The left side is a scheme of a typical example of the conventional method, the center is a scheme of a typical example of the method according to the present invention, and on the right side, each step is measured (I) and contacted (II) in chronological order. ), Warming reaction (III), drying (IV), and post-treatment (IV).

Comparing the conventional method and the method according to the present invention, there is a big difference in contact (II) and drying (IV).
In the conventional method, in the contact (II), a solid iron or iron compound (A) and a polyphenol source (C) which is also a solid are mixed in advance, water is added to the mixture, and further stirring is performed. Since it is carried out by performing, a large amount of energy and time are consumed for mixing the solids, and a large amount of energy and time are consumed for stirring even after water is added. In addition, since the amount of water input is large, a large reaction vessel is required, and a large amount of energy and time are required for drying.
On the other hand, in the method according to the present invention, the aqueous solution or dispersion (B) of iron or iron compound (A) is brought into contact with the polyphenol source (C), but the iron or iron compound (A) The aqueous solution or dispersion (B) can be prepared in a short time and with less energy. Further, by converting iron or the iron compound (A) into an aqueous solution or a dispersion liquid (B), a means called spray can be used as a means of contact, so that the amount of water used can be reduced. As a result, the reaction vessel can be miniaturized, and energy and time in drying (IV) can be saved.
As a result of these differences, the method according to the present invention has the advantages of reducing energy consumption, shortening the required time, and downsizing the reactor as compared with the conventional method for producing an iron-polyphenol composite material. It works.

[Iron or iron compound (A)]
In the present invention, any iron or iron compound can be used.
For example, metallic iron; water-soluble iron compounds such as iron (III) chloride and iron (III) sulfate; water-insoluble iron compounds such as iron (III) oxide, iron (III) nitrate and iron (III) hydroxide; Natural iron ores such as white iron ore, rhombic iron ore, magnetic iron ore, and needle iron ore; natural substances such as iron-containing soil, heme iron, and shells; and those obtained by dissolving these in acid.
Of these, compounds of ferric iron such as iron (III) chloride and iron (III) sulfate are preferable, and iron (III) chloride is more preferable.

[Aqueous solution or dispersion (B)]
In the present invention, the iron or the iron compound (A) is prepared and used as an aqueous solution or a dispersion (B). When the iron or the iron compound (A) is water-soluble, it is usually added to water, or water is added thereto, and the mixture is stirred until uniform to obtain an aqueous solution. When the iron or the iron compound (A) is water-insoluble, it is uniformly dispersed in water to obtain a dispersion liquid. If necessary, an auxiliary agent such as a surfactant may be added.
There is no particular limitation on the concentration of iron or the iron compound (A) in the aqueous solution or the dispersion (B). The concentration of iron or the iron compound (A) in the preferred aqueous solution or dispersion (B) is more than 1% by mass, or 5% by mass or more, less than 30% by mass, less than 20% by mass, or 16% by mass or less. Is.
There are no particular restrictions on the water used, and ordinary water may be used. For example, well water, river / lake water, seawater, tap water, agricultural water, industrial water, deionized water, distilled water and the like can be mentioned. It may contain a pH buffer, a salt (NaCl, KCl, etc.), an alcohol (ethanol, etc.), a saccharide, an acid, an alkali, etc., as long as it does not interfere with the advantageous effects of the present invention.
The method for mixing the iron or the iron compound (A) with water is not particularly limited, and a conventional mixing method is sufficient. For example, it can be done by a manual or automatic mixer, agitator, vortex, shaker and the like. The temperature at the time of mixing may be within the temperature range in which the water is in a liquid state (for example, 1 to 100 ° C.), and if the water is mixed at about room temperature (for example, 10 to 40 ° C.) without heating, in terms of energy. It is advantageous.

[Polyphenol source (C)]
The polyphenol source (C) used in the present invention is not particularly limited as long as it is a material containing polyphenol or a material capable of producing polyphenol. For example, wood or herbaceous materials or processed products thereof, grain raw materials such as malt, barley and wheat, coffee beans, tea leaves, hops and the like can be mentioned.
Preferably, coffee beans and tea leaves can be used. Further, both can be mixed and used.
As coffee beans, raw coffee beans, dried coffee beans, roasted coffee beans, roasted ground coffee beans, extracted components obtained by immersing them in water (coffee used for drinking), and extracted components were dried and powdered. Things, coffee beans, etc.
Examples of tea leaves include raw tea leaves, dried tea leaves, fermented tea leaves, extracted components obtained by immersing them in water (green tea, black tea, oolong tea, etc. used for drinking), dried powdered extracted components, tea leaves, etc. Be done.
It is highly possible that the iron content of coffee grounds and tea leaves after being used for drinking has been reduced by extraction. They may also require treatment to control the moisture content within acceptable limits before use in the methods of the invention to prevent spoilage during storage. On the other hand, the use of coffee or tea leaves before consumption may lead to competition for limited resources. Therefore, it is recommended from the viewpoint of effective use of resources to divert so-called non-standard products of coffee and tea that are not served as beverages out of the standard to the polyphenol source (C) used in the method of the present invention.

[Step (X)]
The contact between the aqueous solution or the dispersion (B) and the polyphenol source (C) can be carried out by conventional means. For example, the polyphenol source (C) may be put into the aqueous solution or the dispersion (B), or the aqueous solution or the dispersion (B) may be poured into the polyphenol source (C). From the viewpoint of utilizing the characteristic that the aqueous solution or the dispersion liquid (B) is a liquid, the contact in the step (X) is performed by spraying or spraying the aqueous solution or the dispersion liquid (B) on the polyphenol source (C). Is preferable. Spraying the aqueous solution or the dispersion (B) onto the polyphenol source (C) is particularly preferable because the device can be miniaturized and the amount of water used can be saved.

There is no particular limitation on the mass ratio of the aqueous solution or dispersion (B): polyphenol source (C). The preferred mass ratio range is 0.1: 1 or greater, 0.2: 1 or greater, or 0.3: 1 or greater, preferably 2.7: 1 or greater, or 2.6: 1 or greater, or 2.5: 1 or less.

In the step (X), since it is important to react the iron or the iron compound (A) with the polyphenol source (C), the step (X) is carried out while maintaining the water content. The preferred range of moisture content is 30% or more, 35% or more, or 40% or more, 70% or less, 65% or less, or 60% or less. In order to maintain the water content, the system may be sealed and sealed, or the water content lost during the reaction may be replenished at any time.

There is no particular limitation on the time during which step (X) is performed. The step (X) is usually carried out until the reaction between the iron or the iron compound (A) and the polyphenol source (C) is completed, but it may be rounded up in the middle of the reaction depending on the circumstances. The step (Y) may be started from the middle of the reaction. The time of the preferred step (X) is 2 hours or more, 3 hours or more, or 4 hours or more, 48 hours or less, 36 hours or less, or 24 hours or less.

There is no particular limitation on the temperature at which step (X) is performed. Room temperature is acceptable as long as the reaction proceeds. The temperature of the step (X), which is preferable from the viewpoint of increasing the reaction rate and increasing the productivity, is 70 ° C. or higher, 80 ° C. or higher, or 90 ° C. or higher. The temperature may be constant throughout step (X) or may be varied over time.

[Reaction product (P)]
The reaction product (P) obtained by the above step has a divalent iron ion (water-soluble iron ion) obtained by reducing trivalent iron derived from the iron or the iron compound (A).
Whether or not the iron-polyphenol composite is stably synthesized can be confirmed by subjecting the product to a pH stability test. The specific procedure will be described in the section of Examples described later.

[Step (Y)]
The step (Y) is a step of drying the reaction product (P). The step (Y) may be performed continuously with the step (X) or may be performed in parallel with the step (X). The former is, for example, an embodiment in which the reaction product (P) is not isolated and is carried out in the order of step (X) → step (Y). The latter is an embodiment in which, for example, by precisely controlling the water content and temperature, drying is performed at the same time as the reaction proceeds.

The temperature at which the reaction product (P) is dried is 70 ° C. or higher, preferably 80 ° C. or higher, and more preferably 90 ° C. or higher. The upper limit of the drying temperature is not particularly limited, but is usually 200 ° C. or lower, preferably 120 ° C. or lower, 110 ° C. or lower, or 100 ° C. or lower.

The time for drying the reaction product (P) to a water content of 15% or less shall be 60 hours or less. The preferred drying time is within 48 hours, or within 24 hours, or within 12 hours, or within 6 hours. The shortest drying time is the time required to reduce the moisture content of the reaction product (P) to 15% or less, depending on various factors such as the amount of the reaction product (P), the initial moisture content, and the ability of the drying means. Can fluctuate. The water content can be easily measured with a commercially available moisture meter. Alternatively, when most of the volatile components are water, it can be easily measured by measuring the weight before and after drying.

The means for drying the reaction product (P) is a means capable of heating the reaction product (P) to 70 ° C. or higher and drying the reaction product (P) to a moisture content of 15% or less, preferably 12% or less within 60 hours. If there is, there is no particular limitation. In the step (Y), the step of heating to 70 ° C. or higher is indispensable, and a dryer can be exemplified as a means for that purpose. The dryer may be a batch type dryer in which the product is taken in and out each time, or may be a continuous type dryer in which the product passes through the product over a predetermined time. In order to complete the drying step within a predetermined time, it is preferable that the step (Y) further includes a step (y1) for promoting heat conduction and / or a step (y2) for promoting exhaust. For that purpose, it is preferable to equip the dryer with a hot air circulation mechanism, a forced exhaust mechanism, and the like.

[Post-process]
The iron-polyphenol composite (crude product) obtained in step (Y) can be finished into a final product by conventional means. Such post-processes include, but are not limited to, purification, pulverization, sieving, support treatment on a carrier such as silica sand, and tableting.

[Use]
The iron-polyphenol composite can be used for the production of water-soluble iron ion feeders for plant cultivation by processing into forms commonly used in the field of agriculture and horticulture such as powders, granules and concentrates. In addition, the iron-polyphenol composite material can be used for the production of a water-soluble iron ion feeder for oral ingestion by processing it into a form commonly used in food and pharmaceutical applications such as powders, granules and concentrates. In addition, iron-polyphenol composites can also be used to produce pollutant decomposing agents that decompose pollutants contained in contaminated water and contaminated soil. Further, the iron-polyphenol composite material can be used for producing a luminescent agent using chemiluminescence in combination with a luminescent substrate such as luminol, loffin, lucigenin, diphenyl oxalate, oxalyl chloride, and lucigenin.

The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited by the following Examples and Comparative Examples.

The measurement method used is as follows.
[Phenanthroline-silver colorimetric method]
(1) Reagent
1 g of 0.2% phenanthroline solution is dissolved in 500 mL of 10% acetic acid solution of commercially available α, α'-phenanthroline.
10% Hydroxylamine Hydroxylamine Solution Dissolve 10 g of hydroxylamine hydrochloride in distilled water to make 100 mL.
136.1 g of sodium acetate buffer is dissolved in 750 mL of distilled water, the pH is adjusted to 5.5 with glacial acetic acid, and the pH is adjusted to 1 L.
100pm iron (II) standard solution Mohr's salt placed precisely weighed a _{((NH 4) 2 SO 4} · FeSO 4 · 6H 2 O) 0.7022g, sulfate (1: 5) of distilled water containing 10 mL (pH 1.0 After dissolving in (below), the volume is adjusted to 1000 mL.
(2) Preparation of calibration curve 10 ppm iron standard solution is placed in a 0, 0.8, 1.6, 2.4, 3.2, 4.0 mL, 20 mL volumetric flask. Add 2 mL of 10% hydroxylamine hydrochloride solution, 2 mL of phenanthroline solution, and 5 mL of acetate buffer solution in that order, mix well, and then adjust to 20 mL with distilled water. After leaving it for about 20 to 30 minutes, the absorbance is measured at a wavelength of 510 nm.
(3) Measurement of sample Take 0.20 mL of the sample into a 20 mL volumetric flask. Add 2 mL of 10% hydrokiluamine hydrochloride (added when quantifying the total amount of iron, not added when quantifying only the amount of iron (II)), 2 mL of phenanthroline solution, and 5 mL of acetate buffer, and mix well. After that, the volume is adjusted to 20 mL with distilled water. After leaving it for about 20 to 30 minutes, the absorbance is measured at a wavelength of 510 nm.

[Measurement of polyphenol amount by Foreign Dennis method]
(1) Reagent
Foreign Dennis Reagent 25 g of sodium tungstate, 5 g of phosphomolybdic acid, 12.5 mL of phosphoric acid, and 188 mL of water are mixed and boiled for 2 hours, and then water is added to prepare 1000 mL.
10% Sodium Carbonate 10 g of sodium carbonate is dissolved in 100 mL of water.
(2) Sample preparation 90 mL of hot water (around 95 ° C.) is added to 1 g of the measurement sample, and the mixture is stirred and extracted for 1 hour. After allowing to cool, transfer to a 100 mL volumetric flask and settle in water. This liquid is used for color development.
(3) Preparation of calibration curve The standard solution is chlorogenic acid for coffee and ethyl gallate for tea. Add 0, 0.4, 0.8, 1.2, 1.6 mL of 100 ppm standard solution to a 20 mL volumetric flask. Add 5 mL of Foreign Dennis Reagent to this. After 3 minutes, add 5 mL of sodium carbonate solution. The volume is adjusted to 20 mL with pure water. After 60 minutes, remove the supernatant and measure the absorbance at 700 nm.
(4) Analytical operation Add an arbitrary amount (for example, 0.1 mL) of a sample to a 20 mL volumetric flask. Add 5 mL of Foreign Dennis Reagent to this. After 3 minutes, add 5 mL of sodium carbonate solution. The volume is adjusted to 20 mL with pure water. After 60 minutes, remove the supernatant and measure the absorbance at 700 nm.

The method for preparing the pH buffer used is as follows.
Acetic acid-sodium acetate buffer Add 700 mL of water to 136.1 g of sodium acetate (manufactured by Kishida Chemical Industries, Ltd.) and adjust to pH 4.0 and pH 5.0 with acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) to 1000 mL. did.
21.325 g of sodium hydroxide-MES buffer 2-morpholinoethanesulfonic acid monohydrate (MES, manufactured by Dojin Chemical Laboratory Co., Ltd.) is dissolved in 300 to 400 mL of water. Then, the volume was adjusted to 1000 mL, an appropriate amount was taken, and the pH was adjusted to 6.0, pH 7.0, and pH 8.0 with sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.).
Ammonia-ammonium chloride buffer solution 570 mL of ammonia water was added to 67.5 g of ammonium chloride to make 1000 mL of water, and the pH was adjusted to 9.0 and 10.0.

5.231 g of Bis-Tris reagent (bis (2-hydroxyethyl) iminotris (hydroxymethyl) methane, manufactured by Dojin Chemical Laboratory Co., Ltd.) was taken in a 300 mL beaker of Bis-Tris buffer , and 100 mL of ion-exchanged water was added to dissolve it. After that, the whole volume was adjusted to 250 mL (referred to as solution A). 2.25 mL of hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 300 mL beaker, and the total volume was adjusted to 250 mL with ion-exchanged water (referred to as solution B). Solution B was added to solution A to adjust the pH to 6.0 and 7.0.
Take 20.729 g of CHES (N-cyclohexyl-2-aminoethanesulfonic acid, manufactured by Dojin Chemical Laboratory Co., Ltd.) in a 1000 mL beaker of CHES buffer solution , completely dissolve it in 300 to 400 mL of ion-exchanged water, and then use ion-exchanged water. The total volume was 1000 mL (solution A). After dissolving 4 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) in 200 to 300 mL of ion-exchanged water, the whole volume was adjusted to 1000 mL with ion-exchanged water (referred to as solution B). Solution B was added to solution A to adjust the pH to 9.0 and 10.0.
POPSO buffer solution Since the free acid of POPSO is poorly soluble, a monosodium salt solution is prepared and used.
39.237 g of POPSO (piperazin-1,4-bis (2-hydroxy-3-propanesulfonic acid) dihydrate, manufactured by Dojin Chemical Laboratory Co., Ltd.) and 4 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) ) Is completely dissolved in 300 to 400 mL of ion-exchanged water, and then the whole volume is made 1000 mL with ion-exchanged water (referred to as solution A). After dissolving 4 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) in 200 to 300 mL of ion-exchanged water, make the whole volume 1000 mL with ion-exchanged water (referred to as solution B). Solution B was added to solution A to adjust the pH to 8.0.

[Example 1]
(1) Production of iron-polyphenol composite material
Take 106 g of non-standard coffee (before use, particle size 0.1 to 3 mm) as a polyphenol source in an A4 size SUS bat, and add 107.5 g of a 16% aqueous solution of iron (III) chloride (manufactured by Wako Pure Chemical Industries, Ltd.). Mixing while spraying (spray time 5 minutes). (Moisture content of coffee when the entire amount of the aqueous solution is mixed = (0.84 × 107.5 g) / (106 g + 107.5 g) = 42.3%) Then, the iron-polyphenol composite material is dried at 70 ° C. for 5 hours in a dryer. Got

(2) Measurement of pH stability A pH stability test was conducted as a method for determining whether or not the iron-polyphenol composite material was stably synthesized.
Take 1 g of a sample from the iron-polyphenol composite material obtained above, make 100 g with purified water, stir for 1 hour, filter with filter paper (model: No. 1, φ125 mm, manufactured by Advantech), and extract the filtrate as a sample. It was made into a liquid. The Fe concentration of the sample extract was measured. The sample extract was diluted so that the Fe concentration became 40 ppm, 10 mL of the diluted solution was added to the sample bottle (Laboran screw tube bottle manufactured by AS ONE Corporation), and 10 mL of each pH buffer solution was added, and the change over time was observed. .. The results of measuring the pH of each sample when the buffer solutions of pH 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0 were added were pH 4.7 and 6, respectively. It was 2, 7.0, 7.4, 8.5, 9.3.
As a result of observation, the extract was stable until a precipitate was observed in the sample having a pH of 9.0 and 10.0 after 17 hours, and then a precipitate was also observed in the sample having a pH of 6.0 after 41 hours.

(3) Measurement of Fe (II) / [Fe (II) + Fe (III)] concentration ratio Measurement of the concentration ratio of Fe (II) to the total amount of Fe (II) and Fe (III) in the sample extract. , A spectrophotometer (model: U-1800, manufactured by Hitachi High-Technologies Co., Ltd.) was used to perform phenanthroline colorimetric quantification. As a result, the concentration ratio of Fe (II) / [Fe (II) + Fe (III)] was 94.5%.
It was confirmed that trivalent Fe was reduced to almost divalent by the production of iron-polyphenol.

[Example 2]
(1) Production of iron-polyphenol composite material 20 g of the non-standard coffee (before use, without beans) was taken as a polyphenol source in an A4 size SUS bat, and iron (III) chloride (III) at the concentration shown in Table 1 below was taken. Wako Pure Chemical Industries, Ltd.) While spraying the aqueous solution, the mixture was mixed (within a spray time of 10 minutes or less). An image of the sample immediately after spraying is shown in FIG. Then, it is dried in a dryer at 70 ° C. for 5 hours (only in the case of a 1% aqueous solution of iron (III) chloride, an additional 90 ° C. for 2 hours), or at 95 ° C. for 2.5 hours, and the iron-polyphenol composite is dried. I got the wood.

(2) Measurement of pH stability A pH stability test was conducted as a method for determining whether or not the iron-polyphenol composite material was stably synthesized.
Take 1 g of a sample from the iron-polyphenol composite material obtained above, make 100 g with purified water, stir for 1 hour, filter with filter paper (model: No. 1, φ125 mm, manufactured by Advantech), and extract the filtrate as a sample. It was made into a liquid. The Fe concentration of the sample extract was measured. The sample extract was diluted so that the Fe concentration became 40 ppm, 10 mL of the diluted solution was added to the sample bottle (Laboran screw tube bottle manufactured by AS ONE Corporation), and 10 mL of each pH buffer solution was added, and the change over time was observed. ..
As a result of observation, the extract was stable until a precipitate was observed in the sample having a pH of 6.0 to 8.0 after 22 hours.

(3) Measurement of Fe (II) / [Fe (II) + Fe (III)] concentration ratio Fe (II) with respect to the total amount of Fe (II) and Fe (III) in the sample extract as in Example 1. The concentration ratio of (1) was measured by a spectrophotometer (model: U-1800, manufactured by Hitachi High-Technologies Co., Ltd.) by a phenanthroline specific color quantification method. The results are also shown in Table 1.

It was found that an iron polyphenol composite material containing Fe (II) iron can be produced with the water content, drying temperature, and drying time immediately after spraying as shown in Table 1.

[Example 3]
(1) Production of iron-polyphenol composite material Take 17.7 g of the nonstandard coffee powder (before use) as a polyphenol source in a 150 mL glass sample bottle, and iron (III) chloride (manufactured by Kanto Chemical Co., Inc.) 2. An aqueous solution having a concentration of 5.4% in which 3 g was dissolved in 40 g of water was sprayed onto coffee powder at room temperature for about 2 minutes by a spray (manufactured by AS ONE Co., Ltd., capacity 500 mL). The water content of the entire coffee powder immediately after spraying was 67%.
The sample bottle was wrapped and the lid was closed. Three samples prepared in this way were prepared, placed in a hot air dryer (manufactured by Tabie Spec Co., Ltd., model: PH-200) set at 95 ° C., and 1 each according to the heating time shown in Table 2 below. It was heated (heated) for 2 hours and 3 hours. After heating, remove the wrap of the sample bottle, open the lid, take out the contents from the bottle to a bat (dimensions 23 cm x 29 cm x depth 5 cm), dry in a hot air dryer set at 70 ° C for 3 hours, and iron. -A polyphenol composite was obtained.
The water content of this iron-polyphenol composite material was measured using a moisture meter (infrared moisture meter manufactured by Kett Scientific Research Institute, Inc., model: FD-220). The results are also shown in Table 2.
To 1 g of the obtained iron-polyphenol composite material, 99 g of ion-exchanged water was added, the mixture was stirred for 1 hour, and the extracted solution was used as an extract and subjected to the following tests.

(2) Measurement of pH stability To 1 g of the iron-polyphenol composite obtained above, 99 g of ion-exchanged water was added, stirred for 1 hour, and the extracted solution was used as an extract to test the pH stability. ..
As a result of observation, no precipitation was observed until after 168 hours.

(3) Measurement of Fe (II) / [Fe (II) + Fe (III)] concentration ratio Fe (II) with respect to the total amount of Fe (II) and Fe (III) in the sample extract as in Example 1. The concentration ratio of the above was measured by a spectrophotometer (model: U-1800, Hitachi High-Technologies Co., Ltd.) by the phenanthroline specific color quantification method. The results are also shown in Table 2.

(4) Measurement of Polyphenol Amount by Foreign Dennis Method The polyphenol amount in the sample extract was measured by the method described above. The results are also shown in Table 2.

[Comparative Example 4]
Put 17.7 g of the non-standard coffee powder (before use), 2.3 g of iron (III) chloride (manufactured by Kanto Chemical Co., Inc.), and 50 g of water as a polyphenol source in a 150 mL glass sample bottle, and use a spatula for about 1 minute. , Manually stirred and mixed. The water content of the entire coffee powder immediately after mixing was 71%.
The sample bottle was wrapped and the lid was closed. Six samples prepared in this way were prepared, the bottles were covered, and placed in a hot air dryer (manufactured by Tabie Spec Co., Ltd., model: PH-200) set at 70 ° C., and shown in Table 4 below. According to the heating time, it was heated (heated) for 7, 16, 24, and 30 hours. After heating, remove the wrap of the sample bottle, open the lid, take out the contents from the bottle to a bat (dimensions 23 cm x 29 cm x depth 5 cm), and dry in a hot air dryer set at 70 ° C for 3.5 hours. , An iron-polyphenol composite was obtained.
The weight of the sample before and after drying was measured, and the water content after drying was obtained as follows.

Comparing Example 3 and Comparative Example 4, in Example 3, the moisture content before heating is 67%, the moisture content after heating is 1-3 hours, and the moisture content after drying is 4.5 to 5.3% in 3 hours. On the other hand, in Comparative Example 4, the moisture content before heating was 71% to 7 to 30 hours after heating, and the moisture content after drying was 5.95% or more even after 3.5 hours of drying.

[Example 5]
(1) Manufacture of iron-polyphenol composite material On the drum of a coating machine (KC-152 (S) manufactured by Keibunsha Co., Ltd.), the nonstandard coffee (before use) is applied as a polyphenol source according to Table 4 below. I prepared it. While operating the coating machine and rotating the drum, a 10% aqueous solution of iron (III) chloride (Kanto Chemical Co., Inc.) was sprayed onto coffee from a spray container for spraying pesticides, and the entire amount of the aqueous solution was sprayed within about 10 minutes. This coffee was taken out into a bat with a plastic bag, wrapped in a 45 L plastic bag together with the bat, and the mouth of the plastic bag was tied. This package was placed in a hot air dryer set at 95 ° C. and heated for 3 hours. After the heating time had elapsed, the plastic bag was removed, and the coffee on the vat was dried at 95 ° C. for 52 hours in a hot air dryer to obtain an iron-polyphenol composite material.
The water content of this iron-polyphenol composite material was measured using a moisture meter (infrared moisture meter manufactured by Kett Scientific Research Institute, Inc., model: FD-220). These results are shown in Table 4.

(2) Measurement of pH stability A pH stability test was conducted in the same manner as in Example 2.
As a result of observation, no precipitation was observed until after 168 hours.

(3) Measurement of Fe (II) / [Fe (II) + Fe (III)] concentration ratio Fe (II) with respect to the total amount of Fe (II) and Fe (III) in the sample extract as in Example 1. The concentration ratio of iris was measured by a spectrophotometer (U-1800, Hitachi High-Technologies) by the phenanthroline colorimetric quantification method. The results are also shown in Table 4.

From the results in Table 4, it was found that an iron-polyphenol composite material containing iron in which Fe (II) / [Fe (II) + Fe (III)] was about 90% could be obtained on the order of kg.

The method for producing an iron-polyphenol composite material of the present invention has an advantageous effect that energy consumption can be reduced, the required time can be shortened, and the reactor can be miniaturized as compared with the conventional method.

Claims (12)

The step (X) of bringing the aqueous solution or dispersion (B) of iron or the iron compound (A) into contact with the polyphenol source (C) to obtain the reaction product (P), and the reaction product (P) are described. Step (Y) of heating to 70 ° C. or higher and drying to a moisture content of 15% or less within 60 hours.
A method for producing an iron-polyphenol composite material, including. The method for producing an iron-polyphenol composite material according to claim 1, wherein the contact in the step (X) is performed by spraying the aqueous solution or the dispersion liquid (B) onto the polyphenol source (C). The method for producing an iron-polyphenol composite material according to claim 1 or 2, wherein the step (X) is carried out in a range where the mass ratio of (B): (C) is 0.1: 1 to 2.7: 1. The method for producing an iron-polyphenol composite material according to any one of claims 1 to 3, wherein the step (X) is carried out while maintaining the water content at 30 to 70%. The method for producing an iron-polyphenol composite material according to any one of claims 1 to 4, wherein the concentration of iron or iron compound (A) in the aqueous solution or dispersion (B) is more than 1% by mass. The method for producing an iron-polyphenol composite material according to any one of claims 1 to 5, wherein the concentration of iron or iron compound (A) in the aqueous solution or dispersion (B) is less than 30% by mass. The iron-polyphenol composite material according to any one of claims 1 to 6, wherein the step (Y) further includes a step (y1) for promoting heat conduction and / or a step (y2) for promoting exhaust. Manufacturing method. The method for producing an iron-polyphenol composite material according to any one of claims 1 to 7, wherein the step (X) and the step (Y) are carried out continuously or in parallel. The method for producing an iron-polyphenol composite material according to any one of claims 1 to 8, wherein the step (X) is carried out for 2 to 48 hours. The method for producing an iron-polyphenol composite material according to any one of claims 1 to 9, wherein the step (X) is performed at a temperature of 70 ° C. or higher. The method for producing an iron-polyphenol composite material according to any one of claims 1 to 10, wherein the iron or the iron compound (A) is a compound of ferric iron. The method for producing an iron-polyphenol composite material according to any one of claims 1 to 11, wherein the polyphenol source (C) is coffee or tea.