JP2016026492A - Method for concentrating liquid food - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for concentrating a liquid food that, when the liquid food is concentrated, can selectively and efficiently remove water from the liquid food to concentrate the liquid food at a high recovery rate while maintaining a state before the concentration, without decomposing substances to be concentrated, such as aroma components, Umami components, and functional components, and without removing a large amount of them together with water.SOLUTION: When a part of water is removed from a liquid food having a water content of 10 wt% or more to concentrate the liquid food, the liquid food is introduced to a molecular sieve membrane to separate and remove a part of water, whereby the liquid food is concentrated.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for concentrating liquid food, and more particularly, to a method for removing water in liquid food and concentrating it using a molecular sieve membrane.

  As a method of dehydrating and concentrating liquid foods containing a lot of water such as beverages and seasonings, conventionally, by utilizing the difference in boiling point, water which is a low boiling point component is distilled off by distillation, and it is a high molecular weight, high boiling point component. A method of concentrating a concentration target component has been performed.

For example, in patent document 1, after distilling the mash liquid part of shochu and distilling alcohol, the mash liquid concentrate is manufactured by further distilling the distillation residue under reduced pressure.
Further, in Patent Document 2, the roasted coffee beans are vaporized by heating and heating, and are rich in a substance group that is relatively less volatile than the aromatic component first distilled using a refrigerant at room temperature of 5 ° C. or higher. A composition having enhanced taste derived from roasted coffee beans is produced by a distillation process including concentrating and collecting the vaporized fraction.
However, concentration by distillation enables distillation by distilling off low-boiling components by performing vacuum distillation at a relatively low temperature, but the component composition inherent in the liquid food changes due to volatilization of umami components. There is a problem that the quality is greatly deteriorated.

  As a concentration method other than distillation, Patent Document 3 proposes a concentration method by ultrasonic atomization. However, this method has a problem that umami components and the like are also removed by entrainment of droplets.

  In patent document 4, it isolate | separates into the liquid mainly concentrated in the water | moisture content and ethanol by freeze concentration of sake. In freeze concentration, concentration can be performed without destroying umami components by performing separation at a low temperature, but ethanol is also contained in ice mainly composed of water, so that the ethanol recovery rate is low. In particular, when the ethanol concentration rate is increased, the ethanol recovery rate also decreases. In addition, since sugars other than ethanol, amino acids, organic acids, and the like are contained in ice mainly composed of water, the recovery rate of these components is low, resulting in a loss of taste balance.

  On the other hand, as a technique for separating an organic compound and water, a method using an inorganic separation membrane is known. As an inorganic separation membrane, for example, an inorganic porous support-zeolite membrane complex having a membrane composed of a zeolite crystal layer on the surface of the inorganic porous support as described in Patent Document 5 is known. This inorganic porous support-zeolite membrane composite is widely used, for example, as a dehydration process replacing the conventional azeotropic distillation method as described in Patent Document 6 and as a method for concentrating industrial alcohol. However, no application to liquid food has been reported.

JP 2006-109705 A International Publication WO2010 / 147222 Pamphlet JP-A-8-19735 Japanese Patent No. 4326526 JP 2012-67090 A JP 2010-207776 A

  In the concentration of the liquid food, the present invention selectively and efficiently removes water from the liquid food and decomposes substances to be concentrated such as aroma components, umami components, and functional components. It is an object of the present invention to provide a method for concentrating liquid food that can be concentrated while maintaining the state before concentration at a high recovery rate without being removed.

  As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by using a molecular sieve membrane capable of removing only water for concentration of liquid food, and the present invention has been achieved.

  That is, the gist of the present invention is as follows.

[1] A method of removing a part of water from a liquid food having a moisture content of 10% or more and concentrating the liquid food, introducing the liquid food into a molecular sieve membrane, A method for concentrating liquid food, characterized by separating and removing.

[2] The method for concentrating liquid food according to [1], wherein the molecular sieve membrane is a zeolite membrane formed on a porous support.

[3] The liquid food according to [1] or [2], wherein a deviation in concentration ratio of the substance to be concentrated in the liquid food before and after concentration as defined below is less than 40%. Concentration method.
Deviation in concentration ratio: “Concentration ratio” obtained by dividing the concentration of the substance to be concentrated in the liquid food after concentration by the concentration of the substance to be concentrated in the liquid food before concentration, and further dividing by the concentration factor And the absolute value of the difference between "standard value 1" and 100

[4] The recovery rate of main components other than water, aroma components, umami components, and functional components in the liquid food before and after concentration is 90% or more, [1] to [3] The concentration method of the liquid food in any one.

[5] The method for concentrating liquid food according to any one of [1] to [4], wherein at least one of the following conditions (1) to (4) is satisfied.
(1) (X1 / Y1) / (X2 / Y2) is 0.5 or more and 3 or less.
(2) (X1 / Z1) / (X2 / Z2) is 0.5 or more and 3 or less.
(3) {(Z1-Y1) / Z1} / {(Z2-Y2) / Z2} is 0.5 or more and 3 or less.
(4) (X1 / W1) / (X2 / W2) is 0.5 or more and 3 or less.
In the above formula, the meaning of each symbol is as follows.
X1: Any of the aromatic component, umami component, and functional component in the liquid food before concentration
Y1: Concentration of main components other than water in the liquid food before concentration Z1: Total concentration of all components other than water in the liquid food before concentration W1: Fragrance component in the liquid food before concentration , Umami ingredients and functional ingredients
Concentration of a component selected from components other than component X1 X2: Any of the aromatic component, umami component, and functional component in the liquid food after concentration
Y2: Concentration of main components other than water in the liquid food after concentration Z2: Total concentration of all components other than water in the liquid food after concentration W2: Fragrance component in the liquid food after concentration , Umami ingredients and functional ingredients
Concentrations of components selected from components other than X2 However, the components of X1 and X2 are the same. The components of W1 and W2 are the same.

  According to the present invention, when concentrating liquid food, water is selectively and efficiently removed from the liquid food, and substances to be concentrated such as aroma components, umami components, and functional components are decomposed, or these are combined with water. Without being removed in large quantities, it can be concentrated at a high recovery rate while maintaining the state before concentration.

It is process explanatory drawing which shows an example of the concentration method by the pervaporation method (PV method) which is one aspect | mode of embodiment of this invention. It is process explanatory drawing which shows another example of the concentration method by the pervaporation method (PV method) which is 1 aspect of embodiment of this invention.

  The embodiment of the method for concentrating liquid food according to the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention, and the present invention is the gist thereof. As long as the above is not exceeded, these contents are not specified.

  The method for concentrating liquid food according to the present invention is a method for concentrating the liquid food by removing a part of water from a liquid food having a water content of 10% by weight or more, and introducing the liquid food into a molecular sieve membrane Then, a part of water is separated and removed.

<Liquid food>
First, the liquid food will be described.
The liquid food targeted by the present invention is a food having a moisture content of 10% by weight or more. The concentration method of the present invention can be preferably applied to a liquid food having a moisture content of 10% by weight or more, but a liquid food having a certain amount of moisture is easier to apply, and the moisture content is 20% by weight or more. 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
In the present invention, by applying a molecular sieving membrane, even a liquid food product having a high water content that has a high energy load in distillation can be efficiently concentrated.

  The liquid food according to the present invention is not particularly limited as long as it is a liquid food containing water at the above moisture content, but the present invention does not require high-temperature heating such as distillation. It is particularly suitable for liquid foods containing vitamins such as vitamin C that are easily decomposed by heating, nutrients such as various amino acids, or flavor substances.

  The present invention can also be applied to liquid foods having a high viscosity and low fluidity, such as jelly-like foods such as ponzu jelly, but a liquid having a lower viscosity than such high-viscosity foods. The application to a food, for example, a liquid food having a viscosity at 20 ° C. of 100000 mPa · s or less is preferable in terms of concentration efficiency. The viscosity is preferably 10,000 mPa · s or less, more preferably 5000 mPa · s or less, still more preferably 1000 mPa · s or less, particularly preferably 500 mPa · s or less, and most preferably 100 mPa · s or less. When the viscosity is equal to or lower than the upper limit, the liquid food concentrated in the vicinity of the molecular sieve membrane is less likely to stay and the concentration rate is less likely to decrease, so that it is easy to increase the processing amount.

  More specifically, the liquid food includes various beverages, liquid seasonings, syrups, dashi, soups, dairy products, and mixtures or processed products thereof. Moreover, if it is substantially equivalent to these liquid foods, such as a drink, such as a raw material of ice confectionery, even if it is used as a food raw material, it is included.

  As beverages, teas extracted from tea leaves and seeds such as green tea, sencha, matcha tea, oolong tea, black tea, strawberry tea, tochu tea, wheat tea, black bean tea, corn tea, sesame tea, and tea-based beverages processed from them; coffee Beverages; Cocoa drinks; Fruits such as orange, grapefruit, mandarin, grape, apple, acerola, mango, guava, lemon, lime, citron, peach, watermelon, melon, etc., vegetable juices such as kale, cabbage, carrot, tomato, etc. Non-alcoholic beverages such as juices such as concentrated liquids (concentrated reduced juice etc.) or diluted liquids; raw milk; processed milk; milk drinks; lactic acid bacteria drinks; soft drinks; carbonated drinks and mineral water. As beverages, whiskey, rum, vodka, gin, tequila, brandy, shochu and other beer-based beverages such as beer and sparkling liquor, wine, cider and other fruit wines, sake, Shaoxing sake, and mirin Examples include alcoholic beverages such as liquor, liqueurs and cocktails.

  As seasonings, vinegars such as vinegar, sushi vinegar and wine vinegar, sauces such as Worcester sauce, soy sauce, fish sauce, ketchup, mayonnaise, sauces, cooking liquor, mirin-style seasoning, fermented seasoning, Examples thereof include liquid seasonings such as flavoring seasonings such as amino acid solutions and vanilla essences.

  Examples of syrups include shaved ice syrup, gum syrup, and maple syrup.

  Examples of the soup stock include bonito soup, kelp soup, shiitake stock, noodle soup, a mixture thereof and a processed product thereof.

  Examples of soups include consomme, bouillon, and chicken soup.

  Dairy products include cream, coffee whitener, yogurt and the like.

  Among these, the present invention is particularly preferably applied to beverages, soups, soups, and liquid seasonings. Among them, it is particularly suitable to apply to teas and tea-based beverages, coffee beverages, cocoa beverages, juices, alcoholic beverages, vinegars, and soy sauces.

<Molecular sieve membrane>
Next, the molecular sieve film used in the present invention will be described.
A molecular sieve membrane is a membrane having the property of separating a target substance according to the size of the molecule. Specifically, dialysis membrane, microfiltration membrane (MF membrane), ultrafiltration membrane (UF membrane), nanofiltration membrane (NF membrane), reverse osmosis membrane (RO membrane), zeolite membrane, polymer membrane, zeolite, etc. Mixed matrix membrane (hereinafter referred to as MMM) to which is added. In the present invention, nanofiltration membranes, reverse osmosis membranes, zeolite membranes, and MMM are preferably used from the viewpoint of separation performance, and zeolite membranes are preferably used from the viewpoint of durability.

In the present invention, the zeolite membrane may be a single membrane of zeolite, or a zeolite membrane formed by dispersing zeolite powder in a polymer or other binder to form a membrane on various supports. It may be a fixed zeolite membrane composite (in the present invention, the porous support and the zeolite membrane formed on the surface thereof may be collectively referred to as “zeolite membrane composite”).
Among them, a zeolite membrane composite in which zeolite is fixed in a film form on a porous support is particularly preferable. That is, the zeolite membrane composite has a support that increases the mechanical strength, facilitates handling, allows various device designs, and, in particular, when an inorganic porous support is used, the zeolite membrane composite Since the body is composed entirely of inorganic substances, it is excellent in heat resistance, chemical resistance and durability, and can be used stably for a long time for concentration of liquid food.
Therefore, in the present invention, a zeolite membrane particularly suitable as a molecular sieve membrane is a zeolite membrane formed on the surface of an inorganic porous support.

  The porous support constituting the zeolite membrane composite has a chemical stability that allows the zeolite to be crystallized in the form of a membrane on its surface, etc., and is an inorganic porous support (inorganic porous support). For example, sintered ceramics (ceramics support) such as silica, α-alumina, γ-alumina, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, sintered metals such as iron, bronze, stainless steel, etc. Among them, a glass support, a carbon molding, and the like can be mentioned, and among these, a ceramic support is preferable.

  As described above, as the ceramic support, specifically, for example, a ceramic sintered body (ceramic support) containing silica, α-alumina, γ-alumina, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide, or the like. Among them, a ceramic support containing at least one of alumina, silica, and mullite is preferable.

  The shape of the porous support is not particularly limited as long as water can be efficiently separated from the liquid food. For example, the shape of the porous support is flat, tubular (for example, cylindrical tubular, rectangular tubular), honeycomb (for example, cylindrical) And honeycomb having a large number of cylindrical or prismatic holes), monoliths and the like. Among these, a tubular support is particularly preferable, and a cylindrical tubular support is particularly preferable.

The average pore diameter of the surface of the porous support is not particularly limited, but those having a controlled pore diameter are preferred, usually 0.02 μm or more, preferably 0.05 μm or more, and more preferably 0.00. It is 1 μm or more, particularly preferably 0.5 μm or more, and is usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less.
If the average pore diameter is too small, the amount of permeation tends to be small. If it is too large, the strength of the support itself may be insufficient, and the proportion of pores on the surface of the support will increase, forming a dense zeolite membrane. It may be difficult to be done.

The average thickness (wall thickness) of the porous support is usually at least 0.1 mm, preferably at least 0.3 mm, more preferably at least 0.5 mm, particularly preferably at least 0.7 mm, usually at most 7 mm. , Preferably 5 mm or less, more preferably 3 mm or less.
The support is used for the purpose of giving mechanical strength to the zeolite membrane. However, if the average thickness of the support is too thin, the porous support-zeolite membrane composite does not have sufficient strength- Zeolite membrane composites tend to be vulnerable to impacts and vibrations, causing problems in practical use. If the average thickness of the support is too thick, the diffusion of the permeated material tends to be poor and the permeation flux tends to be low.

  When the porous support is a cylindrical tube, the outer diameter of the cylindrical tube is usually 3 mm or more, preferably 5.5 mm or more, more preferably 9.5 mm or more, particularly preferably 11 mm or more, and usually 51 mm or less, preferably It is 31 mm or less, More preferably, it is 21 mm or less, More preferably, it is 17 mm or less, Most preferably, it is 15 mm or less.

Although the support is used for the purpose of giving mechanical strength to the zeolite membrane, when the support is a cylindrical tube, if the outer diameter is too small, the porous support-zeolite membrane composite does not have sufficient strength. There is a tendency that the porous support-zeolite membrane composite is susceptible to shock and vibration and causes problems in practice. When the support is a cylindrical tube, if the outer diameter is too large, the membrane area per volume will be small, so the volume of the membrane required to obtain the required membrane area will be large, and a large installation location will be required. There is a tendency to be economically disadvantageous because a large module is required.
The surface of the porous support is preferably smooth, and the surface may be polished with a file or the like as necessary.

The surface of the porous support means, for example, an inorganic porous support surface portion for crystallizing zeolite, and any surface of each shape may be used as long as it is a surface. Good. For example, in the case of a cylindrical tube support, it may be the outer surface or the inner surface, and in some cases both the outer and inner surfaces.
Further, the pore diameter of the porous support used in the present invention is not limited to the portion other than the surface of the porous support.

  The porosity of the porous support is usually 20% or more, preferably 25% or more, more preferably 30% or more, and usually 70% or less, preferably 60% or less, more preferably 50% or less.

  A zeolite membrane is formed on such a porous support to obtain a zeolite membrane composite.

  In addition to zeolite, the components constituting the zeolite membrane include inorganic binders such as silica and alumina, organic compounds such as polymers, or materials containing Si atoms that modify the zeolite surface as described in detail below (silylating agents) or their A reactant or the like may be included as necessary. Further, the zeolite membrane in the present invention may partially contain an amorphous component.

  The zeolite is preferably an aluminosilicate.

  The thickness of the zeolite membrane is not particularly limited, but is usually 0.1 μm or more, preferably 0.6 μm or more, more preferably 1.0 μm or more, and usually 100 μm or less, preferably 60 μm or less, more preferably 20 μm or less. It is. If the film thickness is too large, the amount of permeation tends to decrease, and if it is too small, the selectivity tends to decrease or the film strength tends to decrease.

The particle diameter of the zeolite is not particularly limited, but if it is too small, the grain boundary tends to increase, and the permeation selectivity tends to decrease. Therefore, it is usually 30 nm or more, preferably 50 nm or more, more preferably 100 nm or more, and the upper limit is the film thickness or less. Furthermore, it is particularly preferred that the zeolite particle size is the same as the membrane thickness.
The method for measuring the particle diameter is not particularly limited. For example, the particle diameter can be measured by observing the surface of the zeolite membrane by SEM, observing the cross section of the zeolite membrane by SEM, observing the zeolite membrane by TEM, or the like.

The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite membrane itself is usually 0.5 or more, preferably 5 or more, more preferably 7.5 or more, still more preferably 8 or more, particularly preferably 10 or more, and particularly preferably 12 Or more, preferably 2000 or less, more preferably 1000 or less, further preferably 500 or less, particularly preferably 100 or less, particularly preferably 50 or less. When the SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite membrane is within this range, the zeolite membrane has excellent hydrophilicity, acid resistance and water resistance, and is suitable for concentration of liquid foods by separating water. It is done.

The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite membrane itself is a numerical value obtained by scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX). In SEM-EDX, information of only a film of several microns can be obtained by measuring the acceleration voltage of X-rays at about 10 kV. Since the zeolite membrane is uniformly formed, the SiO ₂ / Al ₂ O ₃ molar ratio of the membrane itself can be determined by this measurement.

  The main zeolite constituting the zeolite membrane preferably contains a zeolite having a pore structure having an oxygen 12-membered ring or less, more preferably contains a zeolite having a pore structure having an oxygen 10-membered ring or less, and an oxygen 8-membered ring. Those containing a zeolite having the following pore structure are more preferred, and those containing a zeolite having a 6- to 8-membered oxygen pore structure are particularly preferred. Here, the value of n of the zeolite having an oxygen n-membered ring has the largest number of oxygen in the pores composed of oxygen forming the zeolite skeleton and T element (element other than oxygen constituting the skeleton). Show things. For example, when there are 12-membered and 8-membered pores of oxygen, such as MOR type zeolite, it is regarded as a 12-membered ring zeolite.

  Examples of the zeolite having a pore structure having an oxygen 12-membered ring or less include AEI, AEL, AFI, AFG, ANA, ATO, BEA, BRE, CAS, CDO, CHA, CON, DDR, DOH, EAB, EPI, ERI , ESV, EUO, FAR, FAU, FER, FRA, HEU, GIS, GIU, GME, GOO, ITE, KFI, LEV, LIO, LOS, LTA, LTL, LTN, MAR, MEP, MER, MEL, MFI, MON , MOR, MSO, MTF, MTN, MTW, MWW, NON, NES, OFF, PAU, PHI, RHO, RTE, RTH, RUT, SGT, SOD, STI, STT, TOL, TON, TSC, UFI, VNI, WEI , YUG and the like.

  Among these, as a zeolite having a pore structure having an oxygen 10-membered ring or less, for example, AEI, AEL, AFG, ANA, BRE, CAS, CDO, CHA, DDR, DOH, EAB, EPI, ERI, ESV, EUO , FAR, FER, FRA, HEU, GIS, GIU, GOO, ITE, KFI, LEV, LIO, LOS, LTA, LTN, MAR, MEP, MER, MEL, MFI, MON, MSO, MTF, MTN, MWW, NON , NES, PAU, PHI, RHO, RTE, RTH, RUT, SGT, SOD, STI, STT, TOL, TON, TSC, UFI, VNI, WEI, YUG and the like.

  Furthermore, as a zeolite having a pore structure having an oxygen 8-membered ring or less, for example, AEI, AFG, ANA, BRE, CAS, CDO, CHA, DDR, DOH, EAB, EPI, ERI, ESV, FAR, FRA, GIS , GIU, GOO, ITE, KFI, LEV, LIO, LOS, LTA, LTN, MAR, MEP, MER, MON, MSO, MTF, MTN, NON, PAU, PHI, RHO, RTE, RTH, RUT, SGT, SOD , TOL, TSC, UFI, VNI, YUG and the like.

  Among these, as the zeolite having an oxygen 6-8 membered ring structure, for example, AEI, AFG, ANA, CHA, EAB, ERI, ESV, FAR, FRA, GIS, ITE, KFI, LEV, LIO, LOS, LTA, Examples include LTN, MAR, PAU, RHO, RTH, SOD, TOL, and UFI.

  In addition, in this specification, the structure of a zeolite is shown by the code | symbol which prescribes | regulates the structure of the zeolite which International Zeolite Association (IZA) defines as above-mentioned.

The oxygen n-membered ring structure determines the pore size of the zeolite, and the zeolite smaller than the oxygen 6-membered ring has a smaller pore size than the kinetic diameter of the H ₂ O molecule, so the water permeability is reduced. It may not be practical. Moreover, when it is larger than the oxygen 8-membered ring structure, the pore diameter becomes large, and the amount of components other than water that permeate and are removed together with water increases, and the object of the present invention may not be achieved.

The framework density (T / 1000 ³ ) of the main zeolite constituting the zeolite membrane is not particularly limited, but is usually 17 or less, preferably 16 or less, more preferably 15.5 or less, and particularly preferably 15 or less. Usually, it is 10 or more, preferably 11 or more, more preferably 12 or more.
The framework density means the number of elements (T element) other than oxygen constituting the framework per 1000 ³ of the zeolite, and this value is determined by the structure of the zeolite. The relationship between the framework density and the structure of zeolite is shown in ATLAS OF ZEOLITE FRAMEWORK TYPES Sixth Revised Edition 2007 ELSEVIER.

  When the framework density is equal to or higher than the above lower limit, the structure of the zeolite is prevented from becoming fragile, the durability of the zeolite membrane is increased, and it is easy to apply to various uses. Further, when the framework density is less than or equal to the above upper limit, the permeation flux of the zeolite membrane tends to increase without hindering the diffusion of substances in the zeolite, which is economically advantageous.

  In the present invention, preferred structures of the main zeolite constituting the zeolite membrane are AEI, AFG, CHA, EAB, ERI, ESV, FAR, FRA, GIS, ITE, KFI, LEV, LIO, LOS, LTN, MAR, PAU, RHO, RTH, SOD, TOL, UFI, more preferable structures are AEI, CHA, ERI, KFI, LEV, PAU, RHO, RTH, UFI, and more preferable structures are CHA, LEV, RHO, The most preferred structure is CHA.

Next, the CHA type zeolite will be described. The CHA-type zeolite preferably used in the present invention is a code that defines the structure of zeolite defined by International Zeolite Association (IZA) and indicates a CHA structure. It is a zeolite having a crystal structure equivalent to that of naturally occurring chabasite. The CHA-type zeolite has a structure characterized by having three-dimensional pores composed of 8-membered oxygen rings having a diameter of 3.8 × 3.8 mm, and the structure is characterized by X-ray diffraction data.
The framework density of the CHA-type zeolite used in the present invention is 14.5 T / 1000 kg.

  The zeolite membrane in the present invention may partially contain an amorphous component or the like, but is preferably a zeolite membrane substantially composed only of zeolite. Preferably, it is a zeolite membrane containing CHA-type zeolite as a main component, and may contain a part of zeolite of other structure such as mordenite type and MFI type, or may contain an amorphous component, etc. Preferably, the zeolite membrane is substantially composed of only CHA-type zeolite.

  In the present invention, when the zeolite membrane contains a CHA-type zeolite, the intensity of the peak around 2θ = 17.9 ° is the peak intensity around 2θ = 20.8 ° in the X-ray diffraction pattern. The size is preferably 0.5 times or more.

Here, the peak intensity refers to a value obtained by subtracting the background value from the measured value.
The peak intensity ratio represented by (the intensity of the peak around 2θ = 17.9 °) / (the intensity of the peak around 2θ = 20.8 °) (hereinafter this may be referred to as “peak intensity ratio A”). In general, it is usually 0.5 or more, preferably 1 or more, more preferably 1.5 or more, more preferably 2.0 or more, more preferably 2.5 or more, still more preferably 3.0 or more, particularly preferably. It is 3.5 or more, most preferably 4.0 or more. Although an upper limit is not specifically limited, Usually, it is 1000 or less.

  When the zeolite membrane contains CHA-type zeolite, the intensity of the peak around 2θ = 9.6 ° is twice the intensity of the peak around 2θ = 20.8 ° in the X-ray diffraction pattern. It is preferable that it is the above magnitude | size.

  Peak intensity ratio represented by (Intensity of peak near 2θ = 9.6 °) / (Intensity of peak near 2θ = 20.8 °) (hereinafter this may be referred to as “peak intensity ratio B”) In other words, it is usually 2 or more, preferably 2.5 or more, more preferably 3 or more, more preferably 4 or more, still more preferably 6 or more, particularly preferably 8 or more, and most preferably 10 or more. Although an upper limit is not specifically limited, Usually, it is 1000 or less.

  The X-ray diffraction pattern referred to here is obtained by irradiating the surface on which zeolite is mainly attached with X-rays using CuKα as a radiation source and setting the scanning axis to θ / 2θ. As the shape of the sample to be measured, any shape that can irradiate the surface of the zeolite membrane composite on which the zeolite is mainly attached with X-rays can be used. The zeolite membrane composite as it is or one cut into an appropriate size restricted by the apparatus is preferable.

  The X-ray diffraction pattern here may be measured by fixing the irradiation width using an automatic variable slit when the surface of the zeolite membrane composite is a curved surface. An X-ray diffraction pattern using an automatic variable slit refers to a pattern subjected to variable → fixed slit correction.

  Here, the peak in the vicinity of 2θ = 17.9 ° refers to the maximum of the peaks present in the range of 17.9 ° ± 0.6 ° among the peaks not derived from the porous support as the base material. .

  The peak in the vicinity of 2θ = 20.8 ° refers to the maximum peak in the range of 20.8 ° ± 0.6 ° among the peaks not derived from the porous support that is the base material.

  The peak in the vicinity of 2θ = 9.6 ° refers to the maximum of the peaks present in the range of 9.6 ° ± 0.6 ° among the peaks not derived from the porous support as the base material.

  The peak near 2θ = 9.6 ° in the X-ray diffraction pattern is rhombohedral setting according to COLLECTION OF SIMULATED XRD POWDER PATTERNS FOR ZEOLITE Third Revised Edition 1996 ELSEVIER (hereinafter sometimes referred to as “Non-Patent Document 1”). In space group

(No. 166), it is a peak derived from the plane having an index of (1, 0, 0) in the CHA structure.

  In addition, according to Non-Patent Document 1, the peak near 2θ = 17.9 ° in the X-ray diffraction pattern indicates the space group by rhombohedral setting.

(No. 166) is a peak derived from the (1,1,1) index in the CHA structure.

  According to Non-Patent Document 1, the peak near 2θ = 20.8 ° in the X-ray diffraction pattern is a space group in the rhombohedral setting.

(No. 166) is a peak derived from the (2, 0, -1) index in the CHA structure.

  A typical ratio (peak intensity ratio B) of the peak intensity from the (1, 0, 0) plane and the peak intensity from the (2, 0, -1) plane (peak intensity ratio B) is described in Halil Kalipcilar et al., “Synthesis and Separation Performance of SSZ-13 according to Zeolite Membranes on Tubular Supports ", Chem. Mater. 2002, 14, 3458-3464 (hereinafter sometimes referred to as" Non-Patent Document 2 ").

  Therefore, this ratio of 2 or more means that, for example, the zeolite crystal is oriented so that the (1,0,0) plane when the CHA structure is rhombohedral setting is oriented almost parallel to the surface of the membrane composite. It is thought that it means growing in an oriented manner. Orientation and growth of zeolite crystals in the zeolite membrane composite is advantageous in that a dense membrane with high separation performance can be formed.

  A typical ratio (peak intensity ratio A) of the peak intensity derived from the (1,1,1) plane and the peak intensity derived from the (2,0, -1) plane is 0 according to Non-Patent Document 2. Less than .5.

  Therefore, this ratio of 0.5 or more means, for example, that the (1, 1, 1) plane when the CHA structure is a rhombohedral setting is oriented so that the orientation is almost parallel to the surface of the membrane composite. It is thought to mean that the crystals are oriented and growing. Orientation and growth of zeolite crystals in the zeolite membrane composite is advantageous in that a dense membrane with high separation performance can be formed.

  As described above, the fact that one of the peak intensity ratios A and B is a value within the above-mentioned specific range means that the zeolite crystals are oriented and grow, and a dense zeolite membrane with high separation performance is formed. It shows that.

  The peak intensity ratios A and B indicate that the larger the value, the stronger the degree of orientation, and generally the stronger the degree of orientation, the more dense the film is formed. In general, the stronger the orientation, the higher the separation performance tends to be. However, the optimum degree of orientation in which the separation performance becomes higher differs depending on the mixture to be separated. It is desirable to select and use the membrane complex.

  Such a zeolite membrane can be produced by a conventionally known method, but it is particularly preferred to produce it by hydrothermal synthesis in order to produce a uniform membrane.

A specific method for producing a zeolite membrane composite is as described in the Examples section below, but for the zeolite membrane composites suitably used as molecular sieve membranes in the present invention, Examples For the film to be baked, measured by the method described in 1., the air permeation amount after baking and for the film not to be baked is usually 1400 L / (m ² · h) or less, preferably 1000 L / ( m ² · h) or less, more preferably 700 L / (m ² · h) or less, even more preferably 600 L / (m ² · h) or less, particularly preferably 500 L / (m ² · h) or less, more preferably 300 L. / (M ² · h) or less, most preferably 200 L / (m ² · h) or less. The lower limit of the air permeation quantity is not particularly limited, usually 0.01L / ^(m 2 · h) or more, preferably 0.1L / ^(m 2 · h) or more, more preferably 1L / ^(m 2 · h) or higher It is.

Here, the air permeation amount is the air permeation amount [L / (m ² · h)] when the zeolite membrane composite is connected to a vacuum line having an absolute pressure of 5 kPa, as described in detail in the Examples.
When the air permeation amount of the zeolite membrane composite is smaller than the above upper limit, the zeolite membrane composite has few defects, and components other than water hardly permeate to the permeation side during concentration. The smaller the air permeation amount, the higher the separation performance, which is desirable. However, when the air permeation amount is smaller than the above lower limit, the water removal efficiency during concentration may deteriorate in some cases.

<Concentration method>
Hereinafter, a method for concentrating liquid food according to the present invention using the above-described zeolite membrane, particularly a zeolite membrane complex, as a molecular sieve membrane will be described. However, the molecular sieve membrane used in the present invention is not limited to a zeolite membrane. It is not a thing.

  “Concentration” in the present invention is to remove a part of water in a liquid food.

  Specifically, the liquid food to be concentrated is brought into contact with the porous support side or zeolite membrane side of the zeolite membrane composite, and the opposite side is set to a pressure lower than the side with which the liquid food is in contact. Permeate water selectively from liquid food. Thereby, water can be separated from the liquid food. As a result, the liquid food can be concentrated by increasing the concentration of the component to be concentrated in the liquid food. A separation / concentration method called a pervaporation method (pervaporation method, PV method) or a vapor permeation method (vapor permeation method, VP method) is one embodiment.

Further, when the liquid food is concentrated using a molecular sieve membrane, particularly a zeolite membrane composite, the liquid food may be pretreated if necessary.
Examples of the pretreatment include a treatment for removing insoluble matters such as fibers, starches and suspended matters and high molecular weight compounds by passing liquid food through a filtration membrane. The insoluble matter such as fiber, starch, suspended matter and high molecular weight compound removed by the pretreatment may or may not be returned to the concentrated solution after concentration by the zeolite membrane composite.
In addition, pretreatment can be performed using the above-described film as a molecular sieve film. Specifically, liquid food is subjected to membrane separation treatment using one or more of MF membrane, UF membrane, NF membrane, and RO membrane, and the liquid that has permeated the membrane is brought into contact with the zeolite membrane complex and concentrated. The method etc. are mentioned. In this case as well, the substance that has not permeated the previous membrane may or may not be mixed with the concentrated solution with the zeolite membrane composite.
By performing these pretreatments, it is possible to reduce fouling of the membrane used for the subsequent treatment and concentration, or to suppress clogging, and to improve the permeation amount of the membrane used for the subsequent treatment and concentration. In some cases, effects such as increasing the efficiency and extending the life of the film may be obtained.
In addition, two or more types of molecular sieve membranes can be used for concentration of liquid foods. For example, one or more types of molecular sieve membranes such as MF membranes, UF membranes, NF membranes, and RO membranes can be used for membrane separation. The concentrated solution obtained by the treatment may be brought into contact with the zeolite membrane composite to be concentrated. Further, the liquid concentrated by contacting with the zeolite membrane composite may be further treated with a molecular sieve membrane such as an MF membrane, UF membrane, NF membrane, or RO membrane.
Alternatively, two or more types of zeolite membrane composites may be used, and the concentrated solution of the previous zeolite membrane composite may be further concentrated with the subsequent zeolite membrane composite.

  In the PV method, liquid food is brought into contact with the zeolite membrane to allow water to permeate. That is, this method is also referred to as a pervaporation method or an osmosis vaporization method, and the liquid food (feed liquid) is evaporated through the zeolite membrane, and at that time, only the water is permeated to concentrate the liquid food. Since the supply liquid is cooled by the heat of vaporization, a heating means for supplementing it is necessary.

Hereinafter, a method for concentrating liquid food by the PV method will be described with reference to FIG.
In the process shown in FIG. 1, two concentrators (1) and (2) are arranged in series by a zeolite membrane (zeolite membrane composite) (1M) and (2M), the interior of which is divided into a concentrating chamber and a permeating chamber. Then, the liquid food as the supply liquid is supplied to the first concentrator (1) via the heater (11) by the supply pump (51). Water (gas) permeated through the zeolite membrane (zeolite membrane composite) (1M) is introduced into the cooler (3), cooled and liquefied, and then stored in the tank (4). The liquid food concentrated without passing through the zeolite membrane (zeolite membrane complex) (1M) is circulated through the heater (11) to the concentration chamber of the first concentration device (1) for concentration treatment.

The concentrated liquid taken out from the circulation path of the first concentrator (1) is supplied to the second concentrator (2) via the intermediate heater (21). In the same manner as above, the water (gas) that has passed through the zeolite membrane (zeolite membrane composite) (2M) is introduced into the cooler (3), cooled and liquefied, and then stored in the tank (4). The liquid food concentrated without passing through the membrane (zeolite membrane composite) (2M) is circulated through the intermediate heater (21) to the concentration chamber of the second concentration device (2) for concentration treatment.
Then, the finally concentrated liquid food is taken out from the circulation path of the second concentrator (2) with the discharge valve (63) opened.

  Circulation of the liquid in the first concentrator (1) and the second concentrator (2) is performed by circulation pumps (52) and (53). The vacuum required for driving the concentrators (1) and (2) is given by a vacuum pump (54), and the degree of vacuum in the permeation chamber of each concentrator (1) and (2) is the pressure provided in the middle of the piping. Controlled by control valves (61) and (62). The water stored in the tank (4) is discharged by a discharge pump (55).

Although the PV method shown in FIG. 1 adopts a circulation method, a non-circulation method may be adopted. In addition, the driving of the concentrating device may employ a sweep gas method in which nitrogen, dry air, or the like is supplied to the permeation chamber instead of the vacuum method shown in FIG. The number of concentrators to be installed is appropriately selected according to conditions, and may be one or may be two or more as shown. Furthermore, before supplying liquid food to a concentration apparatus, you may provide the filter for removing the solid substance in liquid food.
In the VP method, liquid food vapor is brought into contact with the zeolite membrane to permeate water. That is, this method is also called a vapor permeation method, in which liquid food (feed liquid) is heated or decompressed, or steam is generated by combining heating and decompression, the steam is brought into contact with the zeolite membrane, Concentrate liquid food by allowing only permeation. By contacting only the vapor with the zeolite membrane, insoluble matter such as fibers, starch, and suspended matter and high molecular weight compounds can be prevented from coming into contact with the zeolite membrane, reducing membrane fouling and clogging. In some cases, such effects as increasing the permeation amount of the membrane to increase the processing efficiency and extending the lifetime of the membrane may be obtained.

Next, the operating conditions of the concentrator will be described.
The optimum range of operating conditions of the concentrator cannot be determined unconditionally because it varies depending on the type of liquid food supplied to the concentrator, but general conditions such as temperature and operating pressure are the range of conditions of known operating methods. Is appropriately selected from the following ranges.

  For example, the temperature of the liquid food supplied to the concentrator is usually 70 ° C. or lower, preferably 40 ° C. or lower, more preferably 30 ° C. or lower, and further preferably 25 ° C. or lower. If the temperature of the liquid food is too high, there is a concern that the components in the liquid food may be decomposed. Therefore, the temperature is preferably as low as possible. However, if the temperature of the liquid food is excessively low, the liquid food may not be maintained in a liquid state. Therefore, the temperature of the liquid food is usually −10 ° C. or higher, preferably 0 ° C. or higher. As described above, in the PV method, the liquid food is cooled by the heat of vaporization when water permeates. Therefore, in order to compensate for the heat of vaporization, in the process of FIG. 1, the liquid food is obtained by the heaters (11) and (21). Is heating up.

The operating pressure (the degree of vacuum in the permeation chamber of the concentrator) is usually 0.1 to 1.5 MPa, preferably 0.2 to 0.8 MPa.
There is no particular restriction on the atmosphere during concentration, but substances to be concentrated such as fragrance, umami, and functional components may be easily oxidized, so an inert gas atmosphere such as nitrogen may be appropriately used. preferable.

<Concentration effect>
According to the concentration method of the present invention, water in liquid food can be removed, and main components (components having the highest concentration (weight%) in liquid food) other than water can be concentrated. At this time, substances to be concentrated such as aroma components, umami components, and functional components are not easily decomposed or removed together with water in a large amount, and can be concentrated while maintaining almost the state before concentration. That is, before and after concentration, the contents of main components other than water, and substances to be concentrated such as aroma components, umami components, and functional components hardly change. Therefore, a high recovery rate can be realized for the main components other than water, and substances to be concentrated, such as aroma components, umami components, and functional components. In addition, the main components other than water may be substances to be concentrated such as aroma components, umami components, and functional components.

Here, the fragrance component is any compound that is perceived as having a characteristic odor by stimulating the sense of smell or taste, and may be referred to as a flavor component, a fruit fragrance component, a coffee fragrance component, an alcoholic beverage. Examples include aromatic components.
More specifically, isothiocyanates, indoles, ethers, esters, aldehydes, ketones, alcohols, fatty acids, aliphatic higher hydrocarbons, terpenes, thioethers, thiols, phenols, Examples include phenol ethers, furfural and derivatives thereof, and lactones.

  Examples of the umami component include glutamic acid, which is an amino acid, tasty nucleotides such as inosinic acid, guanylic acid, and xanthylic acid, which are nucleotides of nucleic acid constituents, succinic acid, which is another organic acid, and salts thereof. .

  Functional ingredients are components with physiologically active functions such as disease risk reduction, blood pressure lowering action, lipid metabolism improvement, antioxidant action, etc., minerals, vitamins, iridoids, catechins, polyphenols, quercetins, Examples include amino acids, gallic acid derivatives, flavone derivatives, isoflavone derivatives, caffeine, γ-aminobutyric acid, γ-oryzanol, tocophenol, folic acid, collagen, coenzyme, and nobiletin.

  According to the method of the present invention, with respect to substances to be concentrated such as main components, aroma ingredients, umami ingredients, functional ingredients in liquid foods other than water, the abundance after concentration is usually higher than the abundance before concentration. It can be 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more. That is, the present invention is economically superior because the content of the substance to be concentrated does not change before and after the concentration, a high recovery rate can be realized, and the loss amount of the main component is small. In addition, aromatic components, umami components, functional components and the like are hardly lost during the concentration process.

  More specifically, the deviation of the concentration ratio of each component that is the concentration target substance is usually less than 50%, preferably less than 40%, more preferably less than 30%, still more preferably less than 20%, and particularly preferably 10%. Less than, most preferably less than 5%. Thus, according to the method of the present invention, the content of the substance to be concentrated hardly changes before and after the concentration. When the concentration ratio shift is less than or equal to the above upper limit, the composition balance of the main component, aroma component, umami component, functional component and the like does not change, and the same flavor and taste as the liquid food before concentration can be realized. The lower limit of the deviation of the concentration ratio is 0%.

Here, the concentration ratio refers to a value obtained by dividing the concentration of the substance to be concentrated in the liquid food after concentration by the concentration of the substance to be concentrated in the liquid food before concentration, and further dividing by the concentration ratio. Here, the deviation (%) of the concentration ratio is a value obtained by multiplying 100 by the absolute value of the difference between the “concentration ratio” and the “reference value 1”.
That is, for example, when the content of the A component in the liquid food before concentration is Ao wt%, the content of the A component in the liquid food after concentration is Ax wt%, and the concentration factor is x times The ratio deviation (%) is calculated as follows.
Deviation in concentration ratio (%) = | 1− (Ax / Ao) / x | × 100
The smaller the value of the “concentration ratio deviation”, the smaller the change in the composition balance of the component in the liquid food before and after the concentration. Conversely, the greater the value of the “concentration ratio deviation”, the greater the value before and after the concentration. The change with respect to the composition balance in the liquid food of an ingredient is large.

  In particular, it is preferable that the deviation of the concentration ratio of main components other than water, free amino acids, catechins, and the like is in the above range. Furthermore, among free amino acids, Asp, Thr, Ser, Asn, Glu, Gln, Gly, Ala, Val, Cys2, Met, Ile, Leu, Tyr, Phe, Trp, Lys, His, Arg, and Pro are concentrated. The ratio deviation is preferably in the above range. In particular, when the concentration method of the present invention is used for a tea-based beverage, it is preferable that the deviation in the concentration ratio of Theanine and / or caffeine is in the above range.

In the method of the present invention, the concentration of the substance to be concentrated in the liquid food is hardly changed before and after the concentration, and only the concentration is increased. As a result, according to the present invention, the water after the concentration before the concentration is concentrated. Concentration can be achieved with almost no change in the composition ratio of the main component, aroma component, umami component, and functional component.
As an index indicating that the composition ratio of the main component other than the concentrated water, the aromatic component, the umami component, and the functional component is almost the same as that before the concentration, the following conditions (1) to (4) may be mentioned: In the present invention, it is preferable to satisfy at least one of the following conditions (1) to (4), more preferably to satisfy two of the following conditions (1) to (4). It is more preferable to satisfy three of the conditions (1) to (4), and it is particularly preferable to satisfy all of the following conditions (1) to (4).

(1) (X1 / Y1) / (X2 / Y2) is 0.5 or more and 3 or less.
(2) (X1 / Z1) / (X2 / Z2) is 0.5 or more and 3 or less.
(3) {(Z1-Y1) / Z1} / {(Z2-Y2) / Z2} is 0.5 or more and 3 or less.
(4) (X1 / W1) / (X2 / W2) is 0.5 or more and 3 or less.
In the above formula, the meaning of each symbol is as follows.
X1: Any of the aromatic component, umami component, and functional component in the liquid food before concentration
Y1: Concentration of main components other than water in the liquid food before concentration Z1: Total concentration of all components other than water in the liquid food before concentration W1: Fragrance component in the liquid food before concentration , Umami ingredients and functional ingredients
Concentration of a component selected from components other than component X1 X2: Any of the aromatic component, umami component, and functional component in the liquid food after concentration
Y2: Concentration of main components other than water in the liquid food after concentration Z2: Total concentration of all components other than water in the liquid food after concentration W2: Fragrance component in the liquid food after concentration , Umami ingredients and functional ingredients
Concentrations of components selected from components other than X2 However, the components of X1 and X2 are the same. The components of W1 and W2 are the same.

  The value of (X1 / Y1) / (X2 / Y2) in (1) is more preferably 0.8 or more and 1.2 or less. The value of (X1 / Z1) / (X2 / Z2) in (2) is more preferably 0.8 or more and 1.2 or less. Moreover, the value of {(Z1-Y1) / Z1} / {(Z2-Y2) / Z2} in (3) is more preferably 0.8 or more and 1.2 or less. The value of (X1 / W1) / (X2 / W2) in (4) is more preferably 0.8 or more and 1.2 or less.

  The above conditions (1), (2), and (4) may be satisfied for one or more of the aroma component, umami component, and functional component in the liquid food. As described above, it is particularly preferable that all components are satisfied. However, the concentrations X1, X2, W1, and W2 of the fragrance component, the umami component, and the functional component may be calculated using components that can be quantified and do not need to be covered. As X1, X2, W1, and W2, the concentrations of amino acids and / or catechins and / or polyphenols and / or caffeine are preferably used, and specific measurement methods thereof are described in the Examples section below. It is as described in.

  When the conditions of the above (1) to (4) are satisfied and the values of the respective formulas are in the above range before and after concentration, the main components, aromatic components, umami components, functional components, etc. in the liquid food after concentration The composition balance does not change, and the same flavor and taste as the liquid food before concentration can be realized.

  As described above, the present invention can be concentrated at a low temperature, so that the substance to be concentrated can be prevented from being decomposed by heat, and it can be concentrated while containing a low-boiling component. Therefore, it is suitably applied to the concentration of liquid food containing a substance having a decomposition temperature of usually 150 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower as a concentration target substance. Further, as a substance to be concentrated, a component having a boiling point of usually 100 ° C. or lower, preferably 80 ° C. or lower, more preferably 60 ° C. or lower, further preferably 50 ° C. or lower, particularly preferably 40 ° C. or lower, particularly preferably 30 ° C. or lower is contained. It is preferably applied to the concentration of liquid food.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless the gist of the present invention is exceeded.
In the following examples, X-ray diffraction (XRD) measurement, SEM-EDX measurement, catechin concentration measurement, and amino acid concentration measurement were performed by the following methods.

[X-ray diffraction (XRD) measurement]
XRD measurement of the zeolite membrane was performed under the following conditions.
-Device name: X'PertPro MPD manufactured by PANalytical, the Netherlands
Optical system specifications Incident side: Enclosed X-ray tube (CuKα)
Soller Slit (0.04 rad)
Divergence Slit (Variable Slit)
Sample stage: XYZ stage
Light receiving side: Semiconductor array detector (X 'Celerator)
Ni-filter
Soller Slit (0.04 rad)
Goniometer radius: 240mm
Measurement conditions X-ray output (CuKα): 45 kV, 40 mA
Scanning axis: θ / 2θ
Scanning range (2θ): 5.0-70.0 °
Measurement mode: Continuous
Reading width: 0.05 °
Counting time: 99.7 sec
Automatic variable slit (Automatic-DS): 1 mm (irradiation width)
Lateral divergence mask: 10 mm (irradiation width)

X-rays were irradiated in a direction perpendicular to the axial direction of the cylindrical tubular membrane composite. Also, X-rays are not the sample table surface but the sample line surface of the two lines where the cylindrical tubular zeolite membrane composite placed on the sample table and the surface parallel to the sample table surface are in contact with each other so that noise and the like are not introduced as much as possible. It was made to hit mainly on the other line above the table surface.
In addition, the irradiation width was fixed to 1 mm by an automatic variable slit and measured, and Materials Data, Inc. XRD analysis software JADE 7.5.2 (Japanese version) was used to perform variable slit → fixed slit conversion to obtain an XRD pattern.

[SEM-EDX measurement]
SEM-EDX measurement of the zeolite membrane was performed under the following conditions.
-Device name: SEM: FE-SEM Hitachi: S-4800
EDX: EDAX Genesis
・ Acceleration voltage: 10 kV
The entire field of view (25 μm × 18 μm) at a magnification of 5000 was scanned, and X-ray quantitative analysis was performed.
By this SEM-EDX measurement, the SiO ₂ / Al ₂ O ₃ molar ratio of the produced zeolite membrane itself was determined.

[Measurement of catechin and caffeine concentration]
The concentration of catechin and caffeine was measured based on the following conditions.
Column: Unison UK-C18 (3 μm, 4.6 × 75 mm, Imtakt),
40 ° C
Mobile phase: A 0.1% H ₃ PO ₄ / water B CH ₃ CN, 1.0 ml / min
Method B (%) 5% (0 min) → 50% (15 min)
→ 80% (15.1 min) → 80% (20 min)
Detector: PDA (280mm)
Injection volume: 5 μl
The sample solution was analyzed after being filtered through a 0.45 μm filter. Comparison of the amount of catechin and caffeine was performed by LC area ratio.

[Amino acid concentration measurement]
The amino acid concentration was measured based on the following conditions.
Apparatus: Hitachi Amino Acid Analyzer L-8900
Analysis conditions: Bioamino acid separation conditions-Ninhydrin coloring method Standard product: PF (Wako amino acid mixed solution AN2 type 0.8 ml + B type 0.8 ml → 10 ml)
Injection volume: 10 μl
Quantitative calculation: Pro is 440 nm, other amino acids are from 570 nm peak area
Calculated by one-point external standard method.
For Theanine, a Gln calibration curve was used.

[Example 1]
<Preparation of zeolite membrane composite>
A zeolite membrane composite was prepared by hydrothermal synthesis of CHA-type zeolite directly on an inorganic porous support.
The following was prepared as an aqueous reaction mixture for hydrothermal synthesis.
A solution of 693 g of 1 mol / L-KOH aqueous solution and 680 g of water was added to 23.6 g of aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich) and dissolved by mixing and stirring. To this was added 149 g of colloidal silica (Snowtech-40, Nissan Chemical Co., Ltd.) and stirred for 2 hours to obtain an aqueous reaction mixture for hydrothermal synthesis.
The composition (molar ratio) of this mixture was SiO ₂ / Al ₂ O ₃ / KOH / H ₂ O = 1 / 0.125 / 0.7 / 80 / and SiO ₂ / Al ₂ O ₃ = 8.

  As the inorganic porous support, a cylindrical tubular porous alumina tube (outer diameter 12 mm, inner diameter 9 mm, length 800 mm, porosity 40%) was used.

A mixture of 10.0 g of proton-type Y zeolite (HY (SAR = 5), produced by Catalyst Kasei Kogyo Co., Ltd.) and 5.00 g of NaOH and 100 g of water is heated at 100 ° C. for 7 days, filtered, washed and dried. As a result, FAU type zeolite was obtained. The FAU type _{D 50} was measured particle size distribution of the zeolite 1.73Myuemu, maximum value 1.32 .mu.m, was 2.98Myuemu (particle size: about 2 [mu] m). This FAU type zeolite was used as a seed crystal.

The support was immersed in a dispersion of 0.5% by weight of this seed crystal in water for a predetermined time, and then dried at 100 ° C. for 5 hours or more to attach the seed crystal. The weight of the attached seed crystal was 0.4 g / m ² .
The support to which the seed crystal is attached is inserted into a Teflon (registered trademark) inner cylinder (1700 ml) containing the aqueous reaction mixture for hydrothermal synthesis in the cylinder axis direction and immersed in the aqueous reaction mixture for hydrothermal synthesis. Thereafter, the autoclave was sealed, and the temperature was raised from room temperature to 180 ° C. over 5 hours. After completion of the temperature increase, it was heated at 180 ° C. for 24 hours in a stationary state under an autogenous pressure. The mixture was allowed to cool after a predetermined time, and the zeolite membrane composite was taken out of the aqueous reaction mixture, washed, and dried at 100 ° C. for 4 hours.

After drying, one end of the cylindrical tubular zeolite membrane composite is sealed, the other end is connected to a 5 kPa vacuum line, the inside of the tube is depressurized, and air is passed through a mass flow meter installed between the vacuum line and the zeolite membrane composite. The flow rate of was 4 L / (m ² · h).
The weight of the CHA-type zeolite crystallized on the support, determined from the difference between the weight of the dried zeolite membrane composite and the weight of the support, was 120 g / m ² .

<Concentration of green tea>
The zeolite membrane composite obtained by the above method was cut into a length of 80 mm, and the PV method was used to concentrate water selectively through green tea at 40 ° C. in a nitrogen atmosphere. The specifications of the green tea used for concentration are as follows.
<Green tea>
AEON Co., Ltd. Food Classification (Soft Drinks)
Ingredients: green tea (domestic), antioxidant (vitamin C)
Nutritional components (per 100 mL): Energy 1 kcal, protein 0 g, lipid 0 g, carbohydrate 0.2 g, sodium 7 mg, polyphenol 90 mg
Water content: 90% by weight or more

The green tea (tea-based beverage) 95 g is immersed in a cylindrical tubular zeolite membrane composite with one end sealed in the vertical direction, and the green tea is stirred in a nitrogen atmosphere by the PV method in which the hollow portion of the cylindrical tube is evacuated. The solution was concentrated at a liquid temperature of 40 ° C. and an operating pressure of 1 KPa.
A schematic diagram of the concentrator used in the PV method is shown in FIG. In FIG. 2, the inside of the zeolite membrane composite 73 is depressurized by a vacuum pump 77, and the pressure difference is about 1 atm with the outside where the liquid to be separated 72 is in contact. Due to this pressure difference, the permeated water in the liquid to be separated 72 permeates and permeates the zeolite membrane composite 73. The permeated material is collected by the cold trap 75. On the other hand, substances to be concentrated such as main components other than water, aroma components, umami components, and functional components in the liquid to be separated 72 stay outside the zeolite membrane complex 73. 71 is a hot water bath and 74 is a nitrogen bag.
Concentration was performed for 35 hours. The concentrated green tea was 54 g, and 41 g was removed and concentrated 1.76 times (concentration factor 1.76 times).
Amino acid concentration measurement and catechin concentration measurement of green tea before concentration, and amino acid concentration measurement and catechin concentration measurement of green tea after concentration were performed.

  Table 1 shows the results of amino acid concentration measurement of green tea before concentration and green tea after concentration.

From Table 1, it was confirmed that the concentration was carried out with almost no change in the balance of various amino acids. In addition, the concentration of total amino acids increased 1.74 times before and after concentration.
From the measurement results of amino acid concentration and the weight of green tea, it was confirmed that green tea before concentration contained 3.81 mg of amino acid, and green tea after concentration contained 3.78 mg of amino acid. The recovery rate of the amino acid after concentration was 99.1%. From this result, it was confirmed that according to the present concentration method, concentration can be performed with almost no loss of amino acids.

  Table 2 shows the results of measurement of catechin and caffeine concentrations of green tea before concentration and green tea after concentration.

  From Table 2, the concentration of caffeine is 1.70 times before and after concentration, and as can be seen from comparison with the concentration ratio (1.76 times) of green tea, caffeine is concentrated with almost no loss. It was confirmed.

As the concentration ratio, the free amino acid concentration, the catechin concentration and the LC area considered to be proportional to the caffeine concentration contained in the green tea after concentration in Example 1, the free amino acid concentration and the catechin LC area in the green tea before concentration, A value obtained by dividing by the caffeine LC area and further by each concentration ratio was calculated.
A value obtained by multiplying the absolute value of the difference between the “concentration ratio” and the “reference value 1” by 100 was defined as “concentration ratio deviation (%)”. That is, the smaller this “concentration ratio deviation” value, the smaller the change in the ratio of the component in green tea before and after concentration, and conversely, the greater the “concentration ratio deviation” value, the greater the value before and after concentration. The ratio change in green tea of the ingredient is large.
The results are shown in Table 3.

  From Table 3, it can be seen that the deviation of the concentration ratio of each amino acid, catechin and caffeine in Example 1 is less than 20%. Moreover, it turns out that the shift | offset | difference of the concentration ratio of the total amino acid is less than 1%. It can also be seen that the deviation in the concentration ratio of caffeine is less than 5%.

  Moreover, when the value of the formula of the above-mentioned condition (4) is calculated for the component amino acids and caffeine in green tea, X1 = 40.11 mg / L, X2 = 60.11 mg / L (amino acid concentration), W1 = 95428, Since W2 = 1621952 (LC area considered to be proportional to the concentration of caffeine), the value of the expression of the condition (4) is 1.1.

[Example 2]
<Preparation of zeolite membrane composite>
A zeolite membrane composite was prepared by hydrothermal synthesis of CHA-type zeolite directly on an inorganic porous support.

The following was prepared as a reaction mixture for hydrothermal synthesis.
10.8 g of 1 mol / L-NaOH aqueous solution, 7.0 g of 1 mol / L-KOH aqueous solution and 100.0 g of water were added to 0.88 g of aluminum hydroxide (containing 53.5% by weight of Al ₂ O ₃ , manufactured by Aldrich). Stir and dissolve to give a clear solution. As an organic template, 2.36 g of an aqueous N, N, N-trimethyl-1-adamantanammonium hydroxide (TMADAOH) solution (containing 25% by weight of TMADAOH, manufactured by Seychem) was added, and colloidal silica (Snowtech manufactured by Nissan Chemical Co., Ltd.) was added. −40) 10.5 g was added and stirred for 2 hours to prepare an aqueous reaction mixture for hydrothermal synthesis.
The composition (molar ratio) of this mixture was SiO ₂ / Al ₂ O ₃ / NaOH / KOH / H ₂ O / TMADAOH = 1 / 0.066 / 0.15 / 0.1 / 100 / 0.04, SiO ₂ / Al ₂ O ₃ = 15.

  As the inorganic porous support, a cylindrical porous ceramic tube (outer diameter 12 mm, inner diameter 9 mm) was cut to a length of 80 mm, washed with an ultrasonic cleaner and dried.

Prior to hydrothermal synthesis, SiO ₂ / Al ₂ O ₃ / NaOH / H ₂ O / TMADAOH = 1 / 0.033 / 0.1 / 40 / 0.1 is formed on the support by the same method as described above. The above support was placed for a predetermined time on a 0.5% by weight seed crystal of CHA zeolite having a gel composition of 160 ° C. and crystallized by hydrothermal synthesis for 2 days for about 0.5 μm. After soaking, seed crystals were adhered by drying at 100 ° C. for 5 hours or more. The weight of the attached seed crystal was about 0.4 g / m ² .

  The support to which the seed crystals are attached is inserted into the Teflon (registered trademark) inner cylinder containing the aqueous reaction mixture for hydrothermal synthesis in the cylinder axis direction and immersed in the aqueous reaction mixture for hydrothermal synthesis, and then the autoclave. Was sealed and heated at 160 ° C. for 48 hours under autogenous pressure. After elapse of a predetermined time, the zeolite membrane composite was taken out of the aqueous reaction mixture after being allowed to cool, washed, and dried at 100 ° C. for 5 hours or more.

After drying, the mass flow is set between the vacuum line and the zeolite membrane composite by sealing one end of the unfired cylindrical tubular zeolite membrane composite and connecting the other end to a 5 kPa vacuum line to reduce the pressure inside the tube. When the flow rate of air was measured with a meter, it was 0 L / (m ² · h).

Next, the zeolite membrane composite was baked in an electric furnace at 500 ° C. for 5 hours to remove the template TMADAOH. The weight of the CHA zeolite crystallized on the support determined from the difference between the weight of the zeolite membrane composite after calcination and the weight of the support was 130 g / m ² .
When XRD of the produced membrane was measured, it was found that CHA-type zeolite was produced. From the XRD pattern, (the intensity of the peak near 2θ = 17.9 °) / (the intensity of the peak near 2θ = 20.8 °) = 4.9, and the XRD of the CHA zeolite of the powder used for the seed crystal The peak intensity around 2θ = 17.9 ° was remarkably larger than that in FIG. 2, and the orientation to the (1,1,1) plane in the rhombohedral setting was estimated.
Further, by SEM-EDX, was measured _SiO 2 / _Al 2 _{O 3} molar ratio of the zeolite membrane was 17.
Further, the air flow rate measured in the same manner as described above for the sintered zeolite membrane composite was 22 L / m ² · h.

<Concentration of vinegar>
Using the zeolite membrane composite after calcination obtained by the above method, concentration by selectively allowing water to permeate from 70 ° C. vinegar was performed by a PV method under a nitrogen atmosphere. The specifications of the vinegar subjected to concentration are as follows.

<Vinegar>
Made by Mitsukan Co., Ltd. Grain vinegar Ingredients: Cereals (wheat, rice, corn), alcohol, sake lees Acidity: 4.2%
Nutritional components (per 15 mL): energy 3.8 kcal, protein 0 g, lipid 0 g, carbohydrates 1.1 g, sodium 0-1 mg
Water content: 90% by weight or more

40.6 g of the above vinegar (hereinafter, undiluted solution) was placed between the outer periphery of the zeolite membrane composite and the inner surface of the glass vessel equipped with the zeolite membrane composite, and stirred at 70 ° C. with a stirrer. Heated. Using a vacuum pump, the inside of the zeolite composite was depressurized to 0.2 kPa, whereby the components that permeated the zeolite composite were vaporized and collected with a trap for collection.
The permeate was collected every hour, and vinegar (stock solution) having a weight corresponding to the collected weight was added to the glass container, so that the volume in the glass container was kept constant, and concentration was performed for 8 hours.

[Comparative Example 1]
Concentration was performed by evaporating water from vinegar at 100 ° C. using a glass distillation apparatus.
The same vinegar (stock solution) 120.0 g as in Example 2 was placed in a 200 ml two-necked flask and heated to 100 ° C. in an oil bath while stirring with a stir bar. The generated vapor was passed through a 20 cm Vigreux fractionation tube attached to a two-necked flask, and then cooled with a Liebig condenser to collect condensed components. Distillation was performed for 6 hours.

[Contrast of concentration results of Example 2 and Comparative Example 1]
The concentration of free amino acids contained in the stock solution and the concentrates obtained in Example 2 and Comparative Example 1 were measured.
The concentrate was diluted 10-fold with ultrapure water, filtered through an ultrafiltration membrane (MWCO 10,000, manufactured by Millipore), and the filtrate was subjected to the above-described measurement of amino acid concentration.

(1) Concentration magnification The concentration magnification was a value obtained by dividing the weight of the used vinegar (stock solution) by the weight of the concentrated solution.
The total amount of vinegar used in Example 2 was 127.8 g, and the concentrated liquid recovered from the glass container was 25.7 g. That is, the concentration factor was 5.0 times.
On the other hand, the vinegar (stock solution) used in Comparative Example 1 was 120.0 g, and the concentrated liquid recovered from the two-necked flask was 13.7 g. That is, the concentration factor was 8.8 times.

(2) Measurement results of free amino acid concentration Table 4 shows the measurement results of free amino acid concentration in Example 2 and Comparative Example 1.

(3) Concentration ratio As the concentration ratio, each free amino acid concentration contained in the concentrates of Example 2 and Comparative Example 1 was divided by each free amino acid concentration in the stock solution, and further divided by the respective concentration magnifications. Calculated.
A value obtained by multiplying the absolute value of the difference between the “concentration ratio” and the “reference value 1” by 100 was defined as “concentration ratio deviation (%)”. That is, the smaller the value of the “concentration ratio deviation”, the smaller the change in the ratio of the component in the vinegar before and after the concentration. On the contrary, the greater the value of the “concentration ratio deviation”, the greater the value before and after the concentration. It shows that the ratio change in vinegar of ingredients is large.
The results are shown in Table 5.

From Table 5, the deviation of the concentration ratio of each amino acid in Example 2 is less than 40%, whereas the deviation of the concentration ratio of each amino acid in Comparative Example 1 is large, and especially aspartic acid (Asp) is 53. %, Asparagine (Asn) was 56%, and glutamic acid (Glu) was 60%.
That is, it was found that the amino acid balance of the vinegar stock solution was maintained by concentration with the zeolite membrane, but the amino acid balance of the vinegar stock solution was greatly changed by distillation.

Moreover, since the main components other than the water in vinegar in Example 2 are acetic acid, they are Y1 = 42g / L and Y2 = 239g / L.
Moreover, since it is X1 = 0.453g / L and X2 = 2.484g / L when the value of the formula of said conditions (1)-(2) is calculated about the component amino acid in vinegar, conditions (1) The value of the formula is 1.04.
Moreover, since the main components other than water in vinegar in the comparative example 1 are acetic acid, they are Y1 = 42 g / L and Y2 = 131 g / L.
Moreover, since it is X1 = 0.453g / L and X2 = 3.573g / L when the value of the formula of the above-mentioned conditions (1)-(2) is calculated about the component amino acid in vinegar, condition (1) The value of the equation is 0.40.

1 First Concentrator 1M Zeolite Membrane (Zeolite Membrane Complex)
2 Second Concentrator 2M Zeolite Membrane (Zeolite Membrane Complex)
DESCRIPTION OF SYMBOLS 3 Cooler 4 Tank 11 Heater 21 Intermediate heater 51 Supply pump 52 Circulation pump 53 Circulation pump 54 Vacuum pump 55 Discharge pump 61,62 Pressure control valve 63 Discharge valve 71 Hot water bath 72 Separation liquid 73 Zeolite membrane complex 74 Nitrogen bag 75 Cold trap 76 Pressure gauge 77 Vacuum pump

Claims (5)

A method of removing a part of water from a liquid food having a water content of 10% by weight or more and concentrating the liquid food,
A method for concentrating liquid food, wherein the liquid food is introduced into a molecular sieve membrane to separate and remove a part of water.   2. The method for concentrating liquid food according to claim 1, wherein the molecular sieve membrane is a zeolite membrane formed on a porous support. The method for concentrating liquid food according to claim 1 or 2, wherein a deviation in concentration ratio of the concentration target substance in the liquid food before and after concentration defined below is less than 50%.
Deviation in concentration ratio: “Concentration ratio” obtained by dividing the concentration of the substance to be concentrated in the liquid food after concentration by the concentration of the substance to be concentrated in the liquid food before concentration, and further dividing by the concentration factor And the absolute value of the difference between "standard value 1" and 100   The amount of the main component other than water in the liquid food, the aroma component, the umami component, and the functional component after concentration is 70% by weight or more with respect to the amount before concentration. The concentration method of the liquid food as described in any one of Claims 1 thru | or 3. The method for concentrating liquid food according to claim 1, wherein at least one of the following conditions (1) to (4) is satisfied.
(1) (X1 / Y1) / (X2 / Y2) is 0.5 or more and 3 or less.
(2) (X1 / Z1) / (X2 / Z2) is 0.5 or more and 3 or less.
(3) {(Z1-Y1) / Z1} / {(Z2-Y2) / Z2} is 0.5 or more and 3 or less.
(4) (X1 / W1) / (X2 / W2) is 0.5 or more and 3 or less.
In the above formula, the meaning of each symbol is as follows.
X1: Any of the aromatic component, umami component, and functional component in the liquid food before concentration
Y1: Concentration of main components other than water in the liquid food before concentration Z1: Total concentration of all components other than water in the liquid food before concentration W1: Fragrance component in the liquid food before concentration , Umami ingredients and functional ingredients
Concentration of a component selected from components other than component X1 X2: Any of the aromatic component, umami component, and functional component in the liquid food after concentration
Y2: Concentration of main components other than water in the liquid food after concentration Z2: Total concentration of all components other than water in the liquid food after concentration W2: Fragrance component in the liquid food after concentration , Umami ingredients and functional ingredients
Concentrations of components selected from components other than X2 However, the components of X1 and X2 are the same. The components of W1 and W2 are the same.

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