JPS63175637A - Adsorbent for purifying good - Google Patents

Abstract

PURPOSE:To adsorb and remove the impurities of food, by preparing an adsorbent containing synthetic laminar magnesium phillosilicate having not only a specific chemical composition and a specific X-ray diffraction peak but also a specific value such as a specific laminating irregular index. CONSTITUTION:An adsorbent for purifying good containing synthetic laminar magnesium phillosilicate, which has a composition represented by formula I (wherein n is an integer of 5 or less), X-ray diffraction peaks at spacings of 4.5-4.6Angstrom , 2.5-2.6Angstrom and 1.5-1.6Angstrom , a laminating irregular index defined by formula II (wherein theta1 is the angle formed by the peak perpendicular at an X-ray diffraction peak of spacing of 4.5-4.6Angstrom and a wide angle side peak tangential line and theta2 is the angle of the peak perpendicular at the peak and a wide angle side peak tangential line) of 30 or more, a BET specific surface area of 300m<2>/g or more and methylene blue decoloring force of 100ml/g or more, is prepared.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an adsorbent for food purification, and more specifically,
The present invention relates to an adsorbent useful for purifying liquid foods containing synthetic layered magnesium phyllosilicate having solid properties.

(Prior art and its problems) Conventionally, liquid seasonings such as raw fried soy sauce, heated soy sauce, sauces, and vinegar, clarified fruit juices from citrus fruits, ginger, grapes, etc., and liquid foods such as various soft drinks have been manufactured. For example, adsorbents such as activated carbon, silica gel, alumina gel, magnesia, talc, diatomaceous earth, etc. are used to remove and purify various impurities and impurities dissolved or suspended in them. The amount used is.

However, these conventional adsorbents have low adsorption performance and must be used in large quantities, which means that they either adsorb and remove the aromatic and flavor components inherent in liquid foods, or conversely, they adsorb and remove the aromatic and flavor components inherent in liquid foods. The drawback is that the agent imparts a characteristic odor to liquid foods. For liquid foods, subtle differences resulting from their aroma characteristics, taste characteristics, and their combinations are important factors that influence the value of liquid foods, and are important factors that affect the original aroma and taste of liquid foods. It is undesirable to use adsorbents that even slightly change the

Furthermore, some conventional adsorbents have poor filtration properties, and in this case, the filtration time is long, the quality of the liquid food deteriorates during that time, and the equipment becomes large.

(Object of the Invention) When the present invention is used in the am of a liquid food, it is possible to selectively adsorb and remove only impurities of the liquid food without changing the original flavor characteristics of the liquid food. It is an object of the present invention to provide an adsorbent that can change the flavor of liquid foods in a more favorable manner depending on the case, and that also has extremely excellent filtration properties.

(Structure of the Invention) The present invention has a composition in which the main component has the following formula % (in the formula, n is a number of 5 or less), and the interplanar spacing is 4.5 to 4.6X, 2.5 to 2.
It has X-ray diffraction peaks at 6 and 1.5-1.6X, and has the following formula % formula % (where θ1 is the angle between the perpendicular line and the included angle at the X-ray diffraction peak with a lattice spacing of 4.5-4.6X). The stacking irregularity index (1
,) is 3°0 or more, and BE of 300m/g or more
This adsorbent for Japanese food products is characterized by containing synthetic layered magnesium phyllosilicate having T specific surface area and methylene blue decolorizing power C5xs K-1470) of 100111/9 or more.

(Operation and Effect of the Invention) The synthetic layered magnesium phyllosilicate, which is one of the components of the adsorbent of the present invention, has the above-mentioned specific properties, which are not found at all in natural magnesium phyllosilicates such as Merck. It has an extremely large adsorption power that makes it impossible for liquid foods to be absorbed, and it also has the property of selectively adsorbing impurities in liquid foods, making it an excellent product that allows liquid foods to be purified using extremely small amounts. It has an effect. This is due to the fact that the synthetic layered magnesium phyllosilicate has a broad X-ray diffraction peak, has low crystallinity or fine crystallites, and has asymmetric peaks, which will be explained later. This is thought to be due to the irregularities in the stacking and the structure in which a uniform substance can easily enter between the layers.

Furthermore, activated carbon, which is another component of the adsorbent of the present invention, has a strong tendency to adsorb substances different from those which the synthetic layered magnesium phyllosilicate selectively adsorbs.

Therefore, by using the above-mentioned synthetic layered phyllosilicic acid magnesium in combination with activated carbon, it becomes possible to efficiently adsorb and remove various impurities with a small amount of use.

(Preferred Embodiment of the Invention) The synthetic layered magnesium phyllosilicate having the above-mentioned specific properties, which is a component of the adsorbent for food purification of the present invention, is the one described in JP-A-61-10020. be.

That is, the synthetic layered magnesium phyllosilicate in the present invention has a chemical composition as a main component of the formula % (1). Water of hydration (nH2O) is usually 5
n is preferably within the range of 0.5 to 3, and this synthetic layered magnesium phyllosilicate is Mg04
It mainly has a three-layer structure in which two 8104 tetrahedral layers are sandwiched with an 8104 octahedral layer in between, and a two-layer structure in which a SiO4 tetrahedral layer and an Mgo6 octahedral layer are bonded in a layered manner. Those with a layered structure may be contained within the range that does not impair the essence of the three-layered structure, and unreacted silica components and magnesia components may be contained within the range that satisfies the characteristics described below. There is no problem even if it is.

The synthetic layered magnesium phyllosilicate in the present invention is
It has an X-ray diffraction image unique to the layered structure button described above. Figure 1 of the accompanying drawings shows the X-ray diffraction spectrum of the synthesized layered magnesium phyllosilicate according to the present invention using f-rays. Surface spacing 4.5~4.6X
([0201 page, (corresponds to 1103 page), 2.5-2.
61 ((corresponds to page 2001)).

It is clear that it has diffraction peaks at .

In the synthetic layered phyllosilicate magnet 9 of the present invention, each of the layers described above overlaps in parallel, but a certain unique irregularity is observed in the relative position of each layer. FIG. 2 of the accompanying drawings shows d=4. It is a diagram showing an enlarged diffraction peak near si. From FIG. 2, this peak has a relatively steep rise on the narrow angle side (the side where 2θ is small), and shows an asymmetric peak with a gentle slope on the wide angle side (the side where 2θ is large).

In a structure in which the layers are stacked regularly, this peak is symmetrical, and the asymmetric peak described above is due to the relative position of each layer.
indicates that an irregularity exists.

In this specification, the lamination irregularity index (r,) li of magnesium phyllosilicate is defined as follows.

That is, an X-ray diffraction chard as shown in FIG. 2 is obtained by the method described in the Examples described later. This d; 4.5-4.6
For the peak of Find the angle θ2t between the tangent and the perpendicular C.

Lamination irregularity index (I,) I, = -θ2/laaθ1
...Find it as the value of (2). This index (1,)#
i is 1.0 when the peak is completely symmetrical; the value increases as the degree of asymmetry increases.

The synthetic layered magnesium phyllosilicate in the present invention is
It has a novel laminated irregular structure in which the laminated irregularity index (!,) is 3.0 or more, particularly in the range of 3.5 to 6.0.

The synthetic layered magnesium phyllosilicate in the present invention is
It is also clearly distinguishable from natural layered phyllosilicates. First, in natural phyllosilicates, a large number of basic three-layer structures are accumulated in the C-axis direction, so d=9~15X (00
1) It shows a specific X-ray diffraction peak on the surface, but in the synthetic layered magnesium phyllosilicate in the present invention, d=9 to 15
No clear diffraction peak is observed in 1, which indicates that there is no regularity in the stacking of layers in the direction of the FiC axis.Also, in natural phyllosilicates, there is some asymmetry in the peak around d = 4.5i. Even if there is, the lamination irregularity index (k) is almost always 2 or less.

The synthetic layered magnesium phyllosilicate exhibits an extremely large specific surface area and methylene blue decolorizing power, which were not observed at all in known natural or synthetic phyllosilicates. That is, the synthetic layered magnesium phyllosilicate has a thickness of 300 m
It has a large ET specific surface area of /i or more, especially 500m2/1 or more, and has a JIS K-1470
Methylene blue decolorizing power measured with 100111171
It shows a large value of 7 or more, especially reaching 250 ml/g or more.

The synthetic layered magnesium phyllosilicate in the present invention is
Active silicic acid or active albanosilicic acid obtained by acid treatment of clay minerals and magnesium oxide, hydroxide, or a compound capable of forming said oxide or hydroxide under reaction conditions, It can be produced by a hydrothermal treatment method. For example, montmorillonite group clay minerals such as acid clay, bentonite, subbentonite, Frass earth, etc., or clay minerals such as paiprite, saponite, etc., are treated until the X-ray diffraction peak of plane index [0011 substantially disappears.
Treated with mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, or organic acids such as benzenesulfonic acid at a temperature of 60 to 300°C to produce active silicic acid or active aluminosilicate, and this and magnesium oxide or hydroxide. etc., into an aqueous slurry,
The synthetic layered magnesium phyllosilicate can be produced by hydrothermal treatment under pressure at a temperature of 110 to 200°C.

The synthetic layered magnesium phyllosilicate is dried, pulverized 5
It is classified and generally has a particle size of less than 200 Messier on a Tyler standard sieve.

The adsorbent of the present invention may contain activated carbon in addition to the synthetic layered magnesium phyllosilicate. Examples of the activated carbon include wood chips, sawdust, rice husk, coconut shell, lignin, coal, and lignite. Activated carbon obtained by carbonizing, peat, petroleum pitch, etc. can be used.

Activated carbon may be in any form such as powder, crushed or granulated material.

When the adsorbent of the present invention contains a synthetic layered magnesium phyllosilicate and activated carbon, the mixing ratio of the two is such that the weight ratio of the synthetic layered magnesium phyllosilicate to the activated carbon is 1:
The ratio is preferably 0.1 to 1:10, particularly 1:0.3 to 1:3. There are no particular restrictions on the method of mixing the above two.

The synthetic layered magnesium phyllosilicate has excellent filtration properties, and even when combined with activated carbon, which has poor filtration properties, the filtration properties are improved. Alternatively, it can be used in combination with activated carbon, and in addition, silica dal, alumina dal, titanate chloride, and porous resin can be used in combination or in combination as other adsorbents, but if necessary,
It can also be used in combination with or mixed with suitable filter aids such as diatomaceous earth, china clay, etc.

The adsorbent of the present invention has excellent filtration properties as described above, so it can be used in powder form for purifying liquid foods.
1 is preferred for increasing adsorption efficiency and adsorption rate.
The adsorbent of the present invention may be used alone or a mixture of the adsorbent and the filter aid may be granulated into particles or tablets of appropriate size.

A method for purifying liquid foods using the adsorbent of the present invention is as follows: 1. Adding and mixing powder or granules containing the adsorbent of the present invention to liquid foods, and then stirring at an appropriate temperature for a required period of time to prepare liquid foods. There is a method of purifying the food and then filtering or settling the powder or granules to obtain a purified liquid food. In addition, as another method, the liquid food is purified by passing the liquid food through a packed bed of granules containing the adsorbent of the present invention while maintaining it at an appropriate temperature, and the purified liquid food is used as the passed liquid. There are ways to get it.

The temperature and processing time during purification of liquid foods cannot be uniformly prescribed because they vary depending on the type of liquid food, but they can be easily determined by a simple experiment by a drafter.

Furthermore, the amount of the adsorbent of the present invention to be used for a liquid food product varies depending on the type of liquid food product, the content of impurities, etc., and cannot be determined by law, but it can be easily determined by a simple trial.

Example 1 A synthetic layered magnesium phyllosilicate as an adsorbent was prepared as follows.

Acidic clay from Nakajo Town, Niigata Prefecture is roughly crushed and then shaped into columns (
Diameter: 3 m) L, t 25011, the total duram equivalent number of basic metal components such as aluminum, magnesium, calcium, iron, sodium, potassium, titanium, etc. contained in the clay (1 t/1.14 grams) 100
Sulfuric acid equivalent to 3.5 times the gram equivalent number of JI [excellent],
That is, add 700% of 34-thiosulfuric acid and 1
The mixture was heated for 5 hours and treated with acid. Washed with water by filtration,
Nine got the cake.

A small amount of the cake was dried at 110°C, pulverized, and quantitatively analyzed, the sto□ fraction was 92.71 (110°C dry matter m)
Met. Put the resulting cake in a pot mill, add water and make Korean? - Wet grinding with 8102 minutes for 15 minutes
1. Obtain a slurry containing 1.

Next, the obtained slurry 200 Ii (8102 minutes: 3
0g) and magnesium hydroxide (Reagent-M) 22Q-I
A hydrothermal synthesis reaction was carried out at 160° C. for 5 hours under stirring conditions of 500 revolutions/min. After cooling, the reaction product was filtered out, filtered and water was separated, dried at 130° C., and the dried product was ground in a small tabletop sample mill to obtain a fine white powder.

The resulting nine-white fine powder was analyzed by X-ray diffraction, and found to be
Surface spacing 4.5-4.6X, 2.5-2.6X and 1.5
It has an X-ray diffraction peak at ~1.6X, the product no irregularity index (E@) defined above is 4.3, and the BET specific surface area is 5.
26m”/11, and methylene blue decolorizing power is 280
1R1/i layered magnesium phyllosilicate.

In addition, the stacking irregularity index (Is) i! : Calculated using the following method.

The peak tangents (a, b) are plotted so that the absolute value of the slope is maximum on the narrow-angle side and the wide-angle side of the peak obtained by X-ray diffraction and has an order diffraction angle (2θ) of 19.5° to 19.71'.
), then drop the perpendicular C from the intersection of the narrow-angle side peak tangent a and the wide-angle side peak tangent s, and find the angle θ between the tangent a and the perpendicular C, and the angle θ2 between the tangent IvJlb and the perpendicular C.

Find the irregularity index (work 1) using the following formula.

The decolorizing power of methylene blue was determined using the method specified in JIS K1470 activated carbon test method.

Example 2゜Synthetic layered magnesium phyllosilicate powder and activated carbon (
An adsorbent was prepared by thoroughly mixing the adsorbent with the adsorbent (manufactured by Kurade Yakuhin Kogyo Co., Ltd., Jyoku Shirasagi) at a weight ratio of 6:1.

Example 3 An adsorbent was produced in the same manner as in Example 2, except that the weight ratio of synthetic layered magnesium phyllosilicate to activated carbon was 3:1.

Example 4 Synthesis An adsorbent was produced in the same manner as in Example 3, except that the weight ratio of layered magnesium phyllosilicate to activated carbon was 1:2.

Application Examples Using the adsorbents obtained in Examples 1, 2.3, and 4, extracts of seafood such as bonito, clams, scallops, and scallions, and sake (
The adsorption treatment was carried out for unprocessed sake) and soy sauce under the conditions shown in Table 1, and then the adsorbent was separated and the purified liquids were collected, and their taste and odor were compared by a panel consisting of five people. A sensory evaluation was conducted using the method.

For all except sake, the collected aS liquids with BX concentrations of 25 to 40' were diluted to BXa degrees of 56, heated to 50 to 60 @CK, and used as test solutions.

Table 1: As a comparative example, BX concentration is 2 for each other than sake.
Untreated concentrates of 0 to 40@ were prepared, each diluted to a BXg degree of 5'' and heated to 50 to 60' to provide comparative test solutions Al, Bl, CI, Di, El and Fl.

As a result, the taste and odor were ranked second. The friends shown in Table 3, No. 2. The numbers in Table 3 indicate the number of panelists who answered that the recovered and purified sample solution had a better taste or depth than the untreated comparative sample solution.

Table 2 Table 3

[Brief explanation of the drawing]

FIG. 1 is an X-ray diffraction spectrum of nine synthetic layered magnesium phyllosilicates prepared according to Example I using α-rays for Cu-. Figure 2 shows d=4 in the X-ray diffraction spectrum of Figure 1.
．． This is an enlarged diagram of the diffraction peak near sl, and it shows the θ1. The following diagram shows how to obtain θ2. Patent applicant: Mizusawa Chemical Industry Co., Ltd.

Claims (3)

[Claims] (1) The main component is the following formula Mg_3Si_4O_1_0(OH)_2・nH_2O
(In the formula, n is a number of 5 or less).
It has X-ray diffraction peaks at 6 Å and 1.5-1.6 Å, and has the following formula I_s = tan θ_2/tan θ_1 (where θ_1 is the peak perpendicular and narrow line in the X-ray diffraction peak with a lattice spacing of 4.5-4.6 Å. The stacking irregularity index (I_s) defined by the angle formed by the corner side peak tangent line, θ_2 is the angle formed between the peak perpendicular line at the peak and the wide angle side peak tangent line is 3.0 or more, and 300 m^2 /g or more BET specific surface area and 10
Methylene blue decolorizing power of 0ml/g or more (JISK-1
470) An adsorbent for food purification, comprising a synthetic layered magnesium phyllosilicate. (2) The adsorbent for food purification according to claim 1, wherein the adsorbent comprises a combination of the synthetic layered magnesium phyllosilicate and activated carbon. (3) The adsorbent for food purification according to claim 2, wherein the weight ratio of the synthetic layered magnesium phyllosilicate to activated carbon is 1:0.1 to 1:10.