WO2020021641A1 - Apparatus and method for removing salts from liquid food, and liquid food from which salts are removed - Google Patents

Apparatus and method for removing salts from liquid food, and liquid food from which salts are removed Download PDF

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Publication number
WO2020021641A1
WO2020021641A1 PCT/JP2018/027756 JP2018027756W WO2020021641A1 WO 2020021641 A1 WO2020021641 A1 WO 2020021641A1 JP 2018027756 W JP2018027756 W JP 2018027756W WO 2020021641 A1 WO2020021641 A1 WO 2020021641A1
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membrane
liquid food
potassium
anode
cathode
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PCT/JP2018/027756
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French (fr)
Japanese (ja)
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柳田　友隆
未来 中村
耀宗 江
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株式会社クレアテラ
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Priority to PCT/JP2018/027756 priority Critical patent/WO2020021641A1/en
Priority to PCT/JP2019/028932 priority patent/WO2020022357A1/en
Priority to JP2020532427A priority patent/JPWO2020022357A1/en
Publication of WO2020021641A1 publication Critical patent/WO2020021641A1/en

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/70—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter
    • A23L2/72—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by filtration
    • A23L2/74—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by filtration using membranes, e.g. osmosis, ultrafiltration
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/70—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter
    • A23L2/78—Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by ion-exchange
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/30—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation

Definitions

  • the present invention relates to an apparatus for removing salts by supplying electricity from a liquid, and a method for removing salts using the apparatus.
  • the present invention relates to a method and an apparatus for removing potassium from a liquid food such as juice, and a low potassium liquid food.
  • the amount of potassium available daily depends on the stage, but should be limited to 1500-2000 mg or less. This is because the target daily intake of potassium for adults is 3000 mg for men and 2600 mg for women according to the Japanese dietary intake standards (2015 version) set by the Ministry of Health, Labor and Welfare from the viewpoint of preventing the development of lifestyle-related diseases. This is equivalent to limiting to about 1/2 to 3/4.
  • Potassium is contained in almost all foods, and when it is necessary to limit potassium, it is necessary to reduce potassium intake by devising food selection and cooking methods.
  • Chronic kidney disease patients are subject to various restrictions on their dietary habits, including potassium intake, and daily dietary management places a heavy burden on the patients themselves and their families.
  • potassium can be removed by cooking methods such as boiling and exposing to water, but potassium cannot be removed from drinks.
  • Milk drinks, fruit juices, fruit / vegetable mixed juices and the like have a high potassium content of 100 mg or more per 100 g.
  • Green tea has a very high potassium content of 340 mg per 100 g of gyokuro.
  • gyokuro which has a high potassium content, it contains about 100 mg and 30 mg, and it is considered that a considerable amount of potassium is consumed from green tea in consideration of the normal dietary habits of Japanese people.
  • Patent Documents 1 to 5 disclose a method for producing a low potassium juice in which potassium is removed by treating the juice with a cation exchange resin and neutralized with calcium carbonate or calcium hydroxide.
  • Patent Document 4 discloses that a liquid food is immersed in an electrolytic solution in a state of being surrounded by a bag-shaped metal ion permeable membrane, an electric current is passed between a positive electrode and a negative electrode, and a metal component is electrolyzed to form a metal such as potassium. Methods for removing components are described.
  • Patent Document 4 in a method in which a food is surrounded by a bag-shaped metal ion permeable membrane and immersed in an electrolytic solution to energize to remove potassium, the food is contained in the electrolytic solution. Is immersed in the electrolyte, so that not only the food but also the immersed electrolyte is supplied with electricity. Therefore, there is a problem that the ion removal rate from the food is low.
  • Still another object of the present invention is to selectively remove anions instead of removing cations such as potassium from a liquid food.
  • the present invention relates to an apparatus for removing salts described below, a method for removing salts using the apparatus, and a low-potassium food produced using the apparatus.
  • a method for producing a liquid food in which cations or anions are removed from the liquid food wherein a membrane having a fixed pore size and an anode or a cathode are arranged to face each other, When removing the anode, the cathode is arranged on the opposite side of the surface of the membrane facing the anode, and when removing anions, the anode is located on the opposite side of the surface of the membrane facing the cathode.
  • a method for producing a liquid food wherein the liquid food is disposed so as to be in contact with the space, the space defined by the film is filled with the liquid food, and cations or anions are removed by applying a current.
  • a device for removing salts is a device for removing ions from a film in contact with an electrode by applying a current.
  • a membrane is disposed on the cathode side, and cations are removed together with a solvent from pores in the membrane.
  • the amount of anions does not change.
  • anions such as nitrate ions can be removed.
  • cations are not removed from the cathode side. That is, cations or anions can be selectively removed.
  • the liquid food in the present invention there is provided a food prescribed by Food Sanitation Law, it refers to viscosity of 10 0 from 10 5 mPa ⁇ s (cp) .
  • a food refers to viscosity of 10 0 from 10 5 mPa ⁇ s (cp) .
  • it refers to fruit juice, fruit mixed juice, fruit / vegetable mixed juice, vegetable juice such as green juice, green tea, black tea, coffee, soft drink, drinking water, liquid beverage such as wine.
  • Foods containing solids such as porridge, tomato ketchup, vegetable paste, fruit paste, surimi, liquid food, etc. are also included.
  • a membrane having a pore diameter of a certain size or less may be used.
  • the membrane having a pore diameter of a certain size or less include a microfiltration membrane, an ultrafiltration membrane, an ion exchange membrane, a reverse osmosis membrane, and a semipermeable membrane.
  • the material of the film may be an organic film using a polymer or an inorganic film using an inorganic material.
  • the material for the organic film include cellulose acetate, nitrocellulose, polyimide, polysulfone, polyacrylonitrile, Teflon (registered trademark), and polyester-based polymer alloy.
  • the material of the inorganic film include ceramic formed by mixing ceramic particles such as alumina, mullite, and titania, zeolite, metal, and carbon.
  • an ion-exchange membrane may be used.However, when removing cations such as potassium, use a cation-exchange membrane when removing anions such as nitrate ions. Requires the use of an anion exchange membrane.
  • the electrode it is preferable to use platinum or gold which does not cause electrolysis for the anode.
  • titanium may be plated with platinum and used.
  • the cathode stainless steel, titanium, or the like can be used in addition to platinum, gold, and the like.
  • a perforated electrode For example, a mesh electrode or the like can be preferably used.
  • the pH of the liquid By removing cations such as potassium, the pH of the liquid will be acidic. Sensory tests on foods such as fruit juices with acidic beverages with acidic pH revealed that potassium was removed and the pH was inclined to be acidic, so that it was not so bothersome. Therefore, it is not necessary to neutralize foods that are acidic in nature and have a sour taste unless the taste is uncomfortable.
  • cations are removed by applying electrophoresis, ions having a small radius such as potassium and sodium are removed first, and large ions are not easily removed. Therefore, as shown in the examples, the rate of decrease in pH is smaller than when cations are removed using an ion exchange resin.
  • the salt removing device 1 has a structure provided with a pair of electrodes in a tank 2.
  • a cathode 3 and an anode 4 are arranged in a tank 2 so as to face each other, and a liquid food 5 such as juice can be put in a space sandwiched between the electrodes.
  • a membrane 6 is disposed inside the cathode 3, and the liquid food 5 is separated by a membrane so as not to leak into a space 7 in a tank outside the membrane 6.
  • the membrane 6 arranged inside the cathode 3 is arranged so as to contact the cathode.
  • the cathode 3 Since the cathode 3 is in contact with the membrane 6, cations such as potassium can be positively removed from the pores opened in the membrane by energizing.
  • the anode When removing anions such as nitrate ions, the anode may be arranged so as to be in contact with the film. Furthermore, when removing cations and anions at the same time, both the cathode and the anode may be arranged so as to be in contact with the film, and may be removed at the same time.
  • the distance between the electrodes is large, the resistance will increase and a large amount of Joule heat will be generated, and the temperature of the liquid food will rise and deteriorate. Therefore, it is desirable that the distance between the electrodes is such that the food does not deteriorate due to the generation of Joule heat.
  • Embodiment 1 attracts a cation such as potassium to the cathode side by the principle of electrophoresis and discharges it from the pores of the membrane by energization by the electrophoresis principle. Therefore, it is not necessary to arrange a solvent such as water in the space 7 outside the membrane.
  • the salt can be removed by diffusion by adding water. The use of diffusion makes it possible to remove salts such as potassium very quickly.
  • the water placed in the space 7 outside the membrane uses stirring, running water, or removes cations outside the tank and circulates them again with a pump to quickly remove cations in the vicinity of the membrane. It is preferred to maintain a low concentration.
  • the space 7 When the space 7 is filled with water and used, if the interface of the liquid food 5 is slightly higher than the interface of the water filling the space 7, the membrane 6 and the cathode 3 adhere to each other by pressure. This is preferred. Water also contributes to cooling as well as rapid removal of potassium. The cooling may be performed by installing the device itself in a low-temperature environment such as a low-temperature room.
  • a membrane and an electrode are placed in the tank, and a device that puts liquid food such as juice into the area surrounded by the three walls of the membrane and the tank is used. May be arranged, an electrode may be arranged on the other side surface, and electricity may be supplied while flowing a liquid food through the flow path to remove salts.
  • the concentration of the anions such as organic acids and acidic amino acids contained in the liquid food is the same as that of the liquid food as the raw material even after the energization treatment.
  • Organic acids are formic, acetic, glycolic, lactic, gluconic, oxalic, malonic, succinic, fumaric, malic, tartaric, ⁇ -ketoglutanic, citric, Salicylic acid, p-coumaric acid, caffeic acid, ferulic acid, chlorogenic acid, quinic acid, orotic acid, etc .; acidic amino acids refer to aspartic acid and glutamic acid.
  • acidic amino acids refer to aspartic acid and glutamic acid.
  • the salt removing device 11 having a different shape will be described.
  • the salt removing apparatus 11 has two cathodes 13 and 13 ′ in a tank 12 and an anode 14 in the center. Films 15, 15 'are arranged inside the cathodes 13, 13'. Since it is divided by the two membranes 15 and 15 ', even if the liquid food 16 is put between the membranes 15 and 15', it does not leak to both sides.
  • Example 1 The results of removing potassium using various films using the apparatus of Embodiment 1 are shown below.
  • the membrane used and the source are as follows. Nitrocellulose membrane (Toyo Roshi Kaisha, Ltd.), semipermeable membrane (cellophane), polyethylene membrane (Polywrap (registered trademark), Ube Film Co., Ltd.) having a pore size of 0.70 ⁇ m, 0.45 ⁇ m, or 0.10 ⁇ m. In Example 1, the area where the film was in contact with the juice was about 30% of the whole film.
  • a green juice beverage product a, manufactured by A company
  • vegetable and fruit juices manufactured using vegetables such as broccoli, celery, and cabbage was used.
  • Table 1 shows the results of applying electricity at a current density of 8 mA / cm 2 for 30 minutes or 45 minutes.
  • the distance between the electrodes is set to 2.5 cm.
  • the Joule heat generated by applying electricity to the juice and coffee used for the measurement was examined below, if the distance between the electrodes was 4.0 cm or less, preferably 3.5 cm, more preferably 2.5 cm or less. Even if Joule heat was generated, the food did not deteriorate.
  • the removal rate of potassium (K) from the undiluted solution, the solution temperature, the pH after energization, and the results of sensory tests are shown. Note that the potassium concentration of the stock solution was 153.8 to 170.2 mg / 100 g, depending on the product lot.
  • the amount of potassium removed from the raw beverage was measured and expressed as a removal rate (%).
  • Potassium was measured by atomic absorption spectrophotometry after drying and wet incineration of the sample.
  • the liquid temperature of the stock solution was 20 ° C., and the pH was 3.86.
  • the flavor of the processed juice was evaluated by 10 expert panelists having excellent flavor discrimination ability.
  • the evaluations are 5: the flavor does not change, 4: the flavor does not change much, 3: neither can be said, 2: the flavor slightly changes, 1: the flavor is greatly deteriorated, and the average is described.
  • the pore size of the semipermeable membrane is said to be 1 nm to 10 nm. Therefore, it is considered that a salt having a pore diameter of 1 nm or more can efficiently remove salts such as potassium.
  • a nitrocellulose membrane having a pore diameter of 0.70 ⁇ m since the beverage leaked to the outside of the membrane, it is necessary to use a membrane having a pore diameter of less than 0.70 ⁇ m.
  • the removal rate of potassium contained in a large amount is the highest, and calcium and magnesium with large atoms are hardly removed.
  • the liquid food from which potassium has been removed by the salt removing device has a low potassium content, and the calcium and magnesium contents have almost no difference from the food before removal. Therefore, a beverage from which potassium and sodium have been selectively removed can be provided.
  • Example 2 The amount of potassium removed was examined by changing the current density (Table 3). The treatment was carried out under the same conditions as in Example 1 except that the current-carrying density was increased to 12 mA / cm 2 , and the potassium removal rate, liquid temperature, and pH of the treated beverage were measured, and a sensory test was performed.
  • Example 3 Next, various beverages were energized under the conditions of a current density of 8 mA / cm 2 , a distance between electrodes of 2.5 cm, a current time of 30 minutes, and a 0.45 ⁇ m nitrocellulose membrane, the amount of cations was measured, and the removal rate was determined. . The following beverages were used as samples.
  • Orange juice (concentrated reduced orange juice, fruit juice 100%, product b1, manufactured by B company), apple juice (concentrated reduced apple juice, fruit juice 100%, product b2, manufactured by B company), vegetable / fruit beverage (green-yellow vegetable mixed juice, Vegetable juice 100%, product c, company C), tomato juice (concentrated and reduced tomato juice 100%, product d, company D), coffee (sugar-free, product e, company E).
  • potassium could be efficiently removed as 36.9 to 95.5% of the raw beverage by applying electricity for 8 minutes at an electric current density of 8 mA / cm 2 .
  • the potassium removal rate is as low as 36.9%, but about 100 mg of potassium is removed per 100 g. Comparing the amount of potassium removed before and after the treatment, about 100 mg / 100 g of potassium was removed in all of the beverages for 30 minutes.
  • Example 4 When cations are removed in the same manner as in Example 1, relatively large molecules such as amino acids are hardly removed compared to relatively small cations such as potassium and sodium. Using the apparatus of Embodiment 1, cations were extracted from a green juice beverage (product a, manufactured by Company A) containing vegetable and fruit juices using a nitrocellulose membrane having a pore size of 0.10 ⁇ m in the same manner as in Example 1. A test for removal was performed.
  • Electric current was applied at an electric current density of 8 mA / cm 2 for 60 minutes.
  • the distance between the electrodes is set to 3.5 cm.
  • the amount of potassium removed from the stock solution and the total amount of free amino acids were measured and expressed as the removal rate (%).
  • Potassium was measured by atomic absorption spectrometry after drying and wet incineration of the sample as described above.
  • the total free amino acid concentration was determined by heating a raw sample at 70 to 80 ° C. for 30 minutes and measuring the filtrate by a ninhydrin colorimetric method.
  • the potassium concentration, the potassium removal rate, the total free amino acid concentration, the total free amino acid removal rate, the solution temperature, and the pH of the stock solution and the treatment solution are shown.
  • Example 5 It is shown that the anion can be removed by replacing the anode and the cathode and using the electrode in contact with the membrane as the anode (Table 6).
  • a test for removing nitrate ions was performed by replacing the cathode and anode of the apparatus of Embodiment 1 so that the anode was in contact with the membrane.
  • the nitrate nitrogen content in foods varies from material to material.
  • spinach contains 0.2 g / 100 g and bok choy 0.5 g / 100 g, which is relatively large in leafy vegetables. Therefore, the test was carried out using potassium nitrate (Fuji Film Wako Pure Chemical Co., Ltd.) to prepare a solution having a nitric acid concentration (NO 3 ) of 100 mg / L (0.1 g / 100 g).
  • nitric acid concentration Using a nitrocellulose membrane having a pore size of 0.10 ⁇ m, current was applied at a current density of 4 mA / cm 2 for 10 minutes. The distance between the electrodes is set to 2.5 cm. Shows nitric acid concentration, removal rate from stock solution, liquid temperature, and pH. The removal rate (%) represents the amount of nitric acid removed from the stock solution in%. The nitric acid concentration was measured by a colorimetric method.
  • test solution did not contain fiber components such as pulp, 90% or more of nitric acid could be removed in a short time at a low current density. It was shown that even anions can be removed similarly to cations.
  • the nitrate content can be reduced to a desired concentration such as 50% or less of the liquid food as a raw material.
  • a desired concentration such as 50% or less of the liquid food as a raw material.
  • orange juice, tomato juice, and coffee are prepared by adding a dry weight of 5 g (wet weight of 7.53 g) of H-type ion exchange resin to 100 ml of a sample to produce a vegetable / fruit beverage, A green juice drink containing vegetable and fruit juices was added to a sample (100 ml) at a dry weight of 70 g (wet weight of 105.45 g), and after shaking for 30 minutes, a cation exchange resin was precipitated and the supernatant was measured.
  • Tomato juice has a large amount of pulp, is insufficiently separated from the resin, contains a large amount of resin, and cannot obtain an accurate measurement value.
  • Green juice drinks including orange juice and vegetable / fruit juice were able to obtain measurement results although resin was slightly mixed. Table 7 shows the results.
  • Potassium ions were very well removed at 95.3% to 99.7%.
  • calcium and magnesium are also removed at a high rate.
  • ions such as calcium and magnesium are also removed at a high rate regardless of the size of the mass.

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Abstract

Provided is a salt removing apparatus employing an electrophoresis principle. A membrane having a constant pore diameter is disposed so as to be in contact with an inner side of a cathode or an anode, and by filling a liquid food into a space between the opposing cathode and anode and passing an electric current therethrough, it is possible to remove salts from the liquid food.

Description

液体状の食品から塩類を除去する装置、方法、及び塩類が除去された液体状の食品Apparatus and method for removing salts from liquid food, and liquid food from which salts have been removed
　液体から通電することによって塩類を除去する装置、及び前記装置を用いて塩類を除去する方法に関する。特に、ジュースなどの液体状の食品からカリウムを除去する方法、装置及び低カリウム液体状食品に関する。 The present invention relates to an apparatus for removing salts by supplying electricity from a liquid, and a method for removing salts using the apparatus. In particular, the present invention relates to a method and an apparatus for removing potassium from a liquid food such as juice, and a low potassium liquid food.
　日本透析医学会の調査によれば、わが国の慢性透析患者は２０１６年には、約３３万人と１０００人あたり約２．６人が透析治療を受けていることになる。さらに、慢性腎臓病（ＣＫＤ）の患者は約１３３０万人、すなわち日本人成人の８人に１人が慢性腎臓病患者であるとも言われており、腎機能の低下は大きな問題と考えられている。腎機能が低下している患者ではカリウムの排泄機能が低下しており、致死性の不整脈による突然死をきたす高カリウム血症を引き起こしやすい。 According to a survey by the Japan Society for Dialysis Therapy, about 330,000 chronic dialysis patients in Japan will receive dialysis treatment in 2016, or about 2.6 out of 1,000. Furthermore, it is said that about 13.3 million patients with chronic kidney disease (CKD), that is, one out of eight Japanese adults have chronic kidney disease, and a decrease in renal function is considered to be a major problem. I have. Patients with impaired renal function have impaired potassium excretion and are more likely to cause hyperkalemia with sudden death due to fatal arrhythmias.
　そのため、慢性腎臓病患者には、カリウム制限の食事指導が継続して行われる必要がある。一日に摂取可能なカリウム量は病期によっても異なるが、１５００～２０００ｍｇ以下に制限する必要がある。これは、生活習慣病の発症予防などの観点から厚生労働省が定めた日本人の食事摂取基準（２０１５年版）における成人の１日のカリウム摂取量の目標量が男性３０００ｍｇ、女性２６００ｍｇであることから１／２から３／４程度に制限することに相当する。 Therefore, it is necessary to continuously provide dietary guidance on potassium restriction for patients with chronic kidney disease. The amount of potassium available daily depends on the stage, but should be limited to 1500-2000 mg or less. This is because the target daily intake of potassium for adults is 3000 mg for men and 2600 mg for women according to the Japanese dietary intake standards (2015 version) set by the Ministry of Health, Labor and Welfare from the viewpoint of preventing the development of lifestyle-related diseases. This is equivalent to limiting to about 1/2 to 3/4.
　カリウムは、ほぼ全ての食品に含有されており、カリウム制限が必要な場合には、食品の選択や調理法を工夫することによってカリウム摂取量の低減を図る必要がある。慢性腎臓病患者は、カリウム摂取量をはじめ食生活において種々の制限を受けていることから、日々の食事管理は患者自身にとっても、家族にとっても負担が大きい。 (4) Potassium is contained in almost all foods, and when it is necessary to limit potassium, it is necessary to reduce potassium intake by devising food selection and cooking methods. Chronic kidney disease patients are subject to various restrictions on their dietary habits, including potassium intake, and daily dietary management places a heavy burden on the patients themselves and their families.
　食事に関しては、茹でこぼす、水にさらすなどの調理法によってカリウム除去を図ることができるが、「飲み物」からはカリウムを除去することができない。乳飲料、果実ジュース、果実・野菜ミックスジュースなどは、１００ｇあたりのカリウム含有量が１００ｍｇ以上とカリウムを多く含んでいる。また、緑茶は、玉露では１００ｇあたり３４０ｍｇとカリウム含有量が非常に高い。カリウム含有量の高い玉露以外でも１００ｇ３０ｍｇ程度含まれており、日本人の通常の食生活を考えると緑茶からもかなりの量のカリウムを摂取しているものと考えられる。 カ リ ウ ム As for meals, potassium can be removed by cooking methods such as boiling and exposing to water, but potassium cannot be removed from drinks. Milk drinks, fruit juices, fruit / vegetable mixed juices and the like have a high potassium content of 100 mg or more per 100 g. Green tea has a very high potassium content of 340 mg per 100 g of gyokuro. Other than gyokuro, which has a high potassium content, it contains about 100 mg and 30 mg, and it is considered that a considerable amount of potassium is consumed from green tea in consideration of the normal dietary habits of Japanese people.
　そこで、野菜ジュース、豆乳など液体状の食品から、カリウムを除去し、慢性腎臓病患者であっても安心して摂取することができる低カリウム飲料を製造する方法が提案されている（特許文献１～４）。特許文献１～３にはジュースを陽イオン交換樹脂によって処理することによってカリウムを除去し、炭酸カルシウム、あるいは水酸化カルシウムによって中和する低カリウムジュースの製造方法が記載されている。特許文献４は、液状の食品を袋状の金属イオン透過膜で包囲された状態にして電解液中に浸漬して、陽電極と陰電極間へ通電し、金属成分を電解しカリウム等の金属成分を除去する方法が記載されている。 Therefore, a method has been proposed in which potassium is removed from liquid foods such as vegetable juice and soy milk to produce a low-potassium beverage that can be safely consumed even by patients with chronic kidney disease (Patent Documents 1 to 5). 4). Patent Documents 1 to 3 disclose a method for producing a low potassium juice in which potassium is removed by treating the juice with a cation exchange resin and neutralized with calcium carbonate or calcium hydroxide. Patent Document 4 discloses that a liquid food is immersed in an electrolytic solution in a state of being surrounded by a bag-shaped metal ion permeable membrane, an electric current is passed between a positive electrode and a negative electrode, and a metal component is electrolyzed to form a metal such as potassium. Methods for removing components are described.
特開２０００－６９９４７号公報JP-A-2000-69947 特開２００１－１０３９４５号公報JP 2001-103945 A 特表２００３－５１１０５２号公報JP-T-2003-511052 特開平１０－１６５１１３号公報JP-A-10-165113
　しかしながら、陽イオン交換樹脂を使用する方法を用いた場合には、ジュースなどの液状食品に含まれるイオン濃度が高濃度であることから、陽イオン交換樹脂を頻繁に洗浄・再生したり、交換する必要があった。また、野菜ジュースなどパルプ成分の多いジュースでは、カラム式製法ではすぐに目詰まりを起こすため、パルプと分離した後にイオン交換樹脂と接触させなければならない。そのため、製造工程数が多くなるという問題が生じていた。また、バッチ式製法では、カリウムイオンを吸着させた後に樹脂をジュースと分離する際にパルプ成分との分離が困難であった。 However, when a method using a cation exchange resin is used, the cation exchange resin is frequently washed, regenerated, or replaced because the ion concentration contained in a liquid food such as juice is high. Needed. In addition, in the case of juice containing a large amount of pulp components such as vegetable juice, clogging occurs immediately in the column-type manufacturing method, so that it must be brought into contact with an ion exchange resin after being separated from pulp. Therefore, there has been a problem that the number of manufacturing steps is increased. Further, in the batch-type production method, when the resin is separated from the juice after the potassium ions are adsorbed, it is difficult to separate the resin from the pulp component.
　また、特許文献４に記載されているように、食品を袋状の金属イオン透過膜で包囲された状態にして電解液中に浸漬して通電しカリウムを除去する方法では、電解液中に食品を浸漬することから、食品だけではなく浸漬している電解液中も通電されることから、食品からのイオンの除去率が低いという問題があった。 Further, as described in Patent Document 4, in a method in which a food is surrounded by a bag-shaped metal ion permeable membrane and immersed in an electrolytic solution to energize to remove potassium, the food is contained in the electrolytic solution. Is immersed in the electrolyte, so that not only the food but also the immersed electrolyte is supplied with electricity. Therefore, there is a problem that the ion removal rate from the food is low.
　本発明は、工程が単純であり、かつ効率良く液体状の食品から塩類を除去する装置、及び方法を提供することを課題とする。特に、液状食品からカリウムを除去する装置、方法、及びこれにより製造された低カリウム液状食品を提供することを課題とする。さらに、本発明は、液体状の食品からカリウムなど陽イオンを除去する代わりに、陰イオンを選択的に除去することを課題とする。特に、ヒト体内で有害となる発がん性物質や、乳幼児においてメトヘモグロビン血症を引き起こす可能性のある亜硝酸に体内で還元される硝酸イオンを除去することを課題とする。 。 It is an object of the present invention to provide an apparatus and a method for removing salts from a liquid food efficiently with a simple process. In particular, it is an object of the present invention to provide an apparatus and a method for removing potassium from a liquid food, and a low potassium liquid food produced by the method. Still another object of the present invention is to selectively remove anions instead of removing cations such as potassium from a liquid food. In particular, it is an object of the present invention to remove carcinogenic substances that are harmful in the human body and nitrate ions that are reduced in the body to nitrite, which may cause methemoglobinemia in infants.
　本発明は、以下の塩類を除去する装置、及び前記装置を用いて塩類を除去する方法、これを用いて製造された低カリウム食品に関する。
（１）液体状の食品から陽イオン、又は陰イオンを除去する液体状の食品の製造方法であって、一定の孔径を備えた膜と、陽極、又は陰極を対向させて配置し、陽イオンを除去する場合には前記膜の前記陽極に対向する面の反対側に陰極を接するように配置し、陰イオンを除去する場合には前記膜の前記陰極に対向する面の反対側に陽極を接するように配置し、前記膜によって区切られた空間を液体状の食品で満たし、通電することによって陽イオン、又は陰イオンを除去する液体状の食品の製造方法。
（２）前記膜の孔径が１ｎｍ以上０．７μｍ未満であることを特徴とする（１）記載の液体状の食品の製造方法。
（３）対向する陰極と陽極を備え、前記陰極、又は陽極のいずれか一方の内側には一定の孔径を備えた膜が接するように配置されており、前記陽極と陰極間に通電することによって電気泳動によって液体状の食品から塩類を除去する装置。
（４）１対の陰極と陽極が設けられ、前記陰極、又は陽極は膜に接し、膜を介して陽極、又は陰極が対向するように設けられている（３）記載の液体状の食品から塩類を除去する装置。
（５）２つの陰極、又は２つの陽極が対向して配置され、前記２つの対向する陰極、又は陽極の中央に、陽極、又は陰極が設けられ、前記２つの対向する陰極、又は陽極は夫々膜を介して中央の陽極、又は陰極に対向している（３）記載の液体状の食品から塩類を除去する装置。
（６）前記膜の孔径が１ｎｍ以上０．７μｍ未満であることを特徴とする（３）～（５）いずれか１つ記載の液体状の食品から塩類を除去する装置。
（７）前記膜が接するように配置されている陰極、又は陽極が水に浸漬され、水を循環、及び／又は撹拌する手段を備えていることを特徴とする（３）～（６）いずれか１つ記載の液体状の食品から塩類を除去する装置。
（８）処理後のカリウム含有量が原料とする液体状の食品の５０％以下であり、少なくとも１つ以上の遊離酸性アミノ酸、及び／又は有機酸は原料とする液体状の食品とほぼ等量であることを特徴とする低カリウム化された液体状の食品。 The present invention relates to an apparatus for removing salts described below, a method for removing salts using the apparatus, and a low-potassium food produced using the apparatus.
(1) A method for producing a liquid food in which cations or anions are removed from the liquid food, wherein a membrane having a fixed pore size and an anode or a cathode are arranged to face each other, When removing the anode, the cathode is arranged on the opposite side of the surface of the membrane facing the anode, and when removing anions, the anode is located on the opposite side of the surface of the membrane facing the cathode. A method for producing a liquid food, wherein the liquid food is disposed so as to be in contact with the space, the space defined by the film is filled with the liquid food, and cations or anions are removed by applying a current.
(2) The method for producing a liquid food according to (1), wherein the membrane has a pore diameter of 1 nm or more and less than 0.7 μm.
(3) comprising a cathode and an anode facing each other, a membrane having a fixed pore size is disposed inside one of the cathode and the anode so as to be in contact with the cathode, and a current is passed between the anode and the cathode. A device that removes salts from liquid foods by electrophoresis.
(4) The liquid food according to (3), wherein a pair of a cathode and an anode are provided, and the cathode or the anode is in contact with the membrane, and the anode or the cathode is provided so as to face the membrane. Equipment for removing salts.
(5) Two cathodes or two anodes are arranged facing each other, and an anode or a cathode is provided at the center of the two facing cathodes or the anodes, and the two opposed cathodes or the anodes are respectively The apparatus for removing salts from liquid food according to (3), which is opposed to the central anode or cathode through the membrane.
(6) The apparatus for removing salts from a liquid food according to any one of (3) to (5), wherein the pore size of the membrane is 1 nm or more and less than 0.7 μm.
(7) The method according to any one of (3) to (6), wherein a cathode or an anode arranged so as to be in contact with the membrane is provided with means for immersing in water and circulating and / or stirring water. An apparatus for removing salts from a liquid food according to any one of the preceding claims.
(8) The potassium content after the treatment is 50% or less of the liquid food as the raw material, and at least one or more free acidic amino acids and / or organic acids are substantially equivalent to the liquid food as the raw material. A low-potassium liquid food product characterized by the following:
液体状の食品から塩類を除去する装置の例を示す図。The figure which shows the example of the apparatus which removes salts from liquid food.
　電気泳動によって液体状の食品から塩類を除去する方法、及び装置、また、これを用いて塩類が除去された食品を提供する。以下の実施例で示すように、塩類を除去する装置は通電することによって、電極と接している膜からイオンを除去する装置である。カリウムなどの陽イオンを除去する場合には、陰極側に膜を配置し、膜にある細孔から陽イオンを溶媒とともに除去する。このとき陽極側からはイオンを除去しないので、陰イオンの量は変化しない。また、陽極を膜と接するように配置すれば、硝酸イオンなどの陰イオンを除去することができる。このとき陰極側には膜を配置しないので、陰極側から陽イオンが除去されることはない。すなわち、陽イオン、あるいは陰イオンを選択的に除去することができる。 (4) A method and an apparatus for removing salts from liquid food by electrophoresis, and a food from which salts have been removed using the same. As shown in the following examples, a device for removing salts is a device for removing ions from a film in contact with an electrode by applying a current. When removing cations such as potassium, a membrane is disposed on the cathode side, and cations are removed together with a solvent from pores in the membrane. At this time, since no ions are removed from the anode side, the amount of anions does not change. If the anode is arranged so as to be in contact with the film, anions such as nitrate ions can be removed. At this time, since no film is disposed on the cathode side, cations are not removed from the cathode side. That is, cations or anions can be selectively removed.
　以下の実施例では、低カリウム食品を製造する目的で、果実ジュース、果実・野菜ミックスジュース、青汁などの飲料から塩類、特に野菜や果物に多く含まれているカリウムの除去について説明するが、実施例に限定されることなく、種々の液体からカリウムイオン、ナトリウムイオンなどの陽イオン、あるいは、クロライドイオン、硫酸イオンなどの陰イオンを除去することが可能である。 In the following examples, for the purpose of producing a low potassium food, fruit juice, fruit and vegetable mixed juice, salt from beverages such as green juice, the removal of potassium, which is particularly contained in vegetables and fruits, is described, Without being limited to the embodiments, it is possible to remove cations such as potassium ions and sodium ions or anions such as chloride ions and sulfate ions from various liquids.
　本発明で液体状の食品とは、食品衛生法で定める食品であって、粘度が１００から１０５ｍＰａ・ｓ（ｃｐ）であるものをいう。例えば、果実ジュース、果実ミックスジュース、果実・野菜ミックスジュース、青汁などの野菜汁、緑茶、紅茶、コーヒー、清涼飲料、飲料水、ワインなど液体状の飲料をいう。また、粥やトマトケチャップ、野菜ペースト、果物ペースト、すり身、流動食など固形分を含む食品も含まれる。 The liquid food in the present invention, there is provided a food prescribed by Food Sanitation Law, it refers to viscosity of 10 0 from 10 5 mPa · s (cp) . For example, it refers to fruit juice, fruit mixed juice, fruit / vegetable mixed juice, vegetable juice such as green juice, green tea, black tea, coffee, soft drink, drinking water, liquid beverage such as wine. Foods containing solids such as porridge, tomato ketchup, vegetable paste, fruit paste, surimi, liquid food, etc. are also included.
　以下の実施例で示すように、液体状の食品から塩類を除去するためには、一定以下の孔径の膜を使用すればよい。孔径が一定以下の膜としては、精密濾過膜、限外濾過膜、イオン交換膜、逆浸透膜、半透膜などがある。膜の素材としては、高分子を用いた有機膜でも、無機材料を用いた無機膜であってもよい。有機膜の素材としては、酢酸セルロース、ニトロセルロース、ポリイミド、ポリスルホン、ポリアクリロニトリル、テフロン(登録商標)、ポリエステル系ポリマーアロイなどがある。また、無機膜の素材としては、アルミナ、ムライト、チタニアなどのセラミック粒子を混合して成形するセラミックや、ゼオライト、金属、炭素などがある。 膜 As shown in the following examples, in order to remove salts from a liquid food, a membrane having a pore diameter of a certain size or less may be used. Examples of the membrane having a pore diameter of a certain size or less include a microfiltration membrane, an ultrafiltration membrane, an ion exchange membrane, a reverse osmosis membrane, and a semipermeable membrane. The material of the film may be an organic film using a polymer or an inorganic film using an inorganic material. Examples of the material for the organic film include cellulose acetate, nitrocellulose, polyimide, polysulfone, polyacrylonitrile, Teflon (registered trademark), and polyester-based polymer alloy. Examples of the material of the inorganic film include ceramic formed by mixing ceramic particles such as alumina, mullite, and titania, zeolite, metal, and carbon.
　また、用いる膜の孔径は、０．７μｍの孔径の膜を用いた場合には、ジュースが膜を通過してしまうことから、０．７μｍ未満の孔径の膜を使用する必要がある。また、１ｎｍ未満の孔径の膜では、ジュール熱が多量に発生し食品が変質してしまうことから、１ｎｍ以上の孔径の膜を使用する必要がある。この範囲の孔径を備えた膜であれば、どのような膜を使用してもよい。また、孔径がこの範囲の膜であれば、イオン交換膜を使用してもよいが、カリウムなど陽イオンを除去する場合には陽イオン交換膜を、硝酸イオンなどの陰イオンを除去する場合には陰イオン交換膜を使用する必要がある。 膜 In addition, when a membrane having a pore diameter of 0.7 μm is used, juice passes through the membrane, and therefore, it is necessary to use a membrane having a pore diameter of less than 0.7 μm. Further, in the case of a membrane having a pore diameter of less than 1 nm, a large amount of Joule heat is generated and the food is degraded, so it is necessary to use a membrane having a pore diameter of 1 nm or more. Any membrane having a pore size in this range may be used. If the pore size is within this range, an ion-exchange membrane may be used.However, when removing cations such as potassium, use a cation-exchange membrane when removing anions such as nitrate ions. Requires the use of an anion exchange membrane.
　電極は、陽極は電気分解が起こらない白金、金を使用することが好ましい。また、チタンに白金をメッキして用いてもよい。陰極は、白金、金などの他、ステンレス、チタンなどを使用することができる。また、陽イオンを除去する場合は陰極を、陰イオンを除去する場合は陽極を膜に接触させて通電することから、膜との接触面積の多い形状とすることが好ましい。また、膜から排出されたイオンを除去するために電極は有孔電極を用いる必要がある。例えば、網状の電極などを好ましく用いることができる。 For the electrode, it is preferable to use platinum or gold which does not cause electrolysis for the anode. Alternatively, titanium may be plated with platinum and used. As the cathode, stainless steel, titanium, or the like can be used in addition to platinum, gold, and the like. In addition, since the cathode is removed when removing cations, and the anode is removed when removing anions, the anode is brought into contact with the film, so that it is preferable that the shape has a large contact area with the film. Further, in order to remove ions discharged from the membrane, it is necessary to use a perforated electrode. For example, a mesh electrode or the like can be preferably used.
　以下低カリウム食品の製造方法、製造装置を中心に記載するが、硝酸イオンなどの陰イオンを除去する場合には、膜と接する極を陽極に代えて通電すればよい。低カリウム食品を製造する場合、腎臓病患者の食事制限がどの程度であるか、また、一日に摂取する量によって、カリウム除去率を適宜定めることが望ましい。腎臓病患者は病期によって、一日に摂取可能なカリウム量は異なっている。したがって、患者の必要に応じてジュース、あるいはコーヒーなどの原料食品に対して６５％以下、５０％以下、３０％以下と異なるカリウム含有量の低カリウム食品を提供することにより、異なる病期の患者に対して対応することができる。また、例えば、緑茶、コーヒーなど摂取する総量が多い飲料に関しては、含有するカリウム量を３０％以下にしておくことによって、カリウム量を気にせず安心して摂取することが可能となる。 Hereinafter, the method and apparatus for producing low potassium foods will be mainly described. In the case of removing anions such as nitrate ions, electricity may be supplied instead of the anode in contact with the membrane. When producing low potassium foods, it is desirable to appropriately determine the potassium removal rate depending on the dietary restrictions of patients with kidney disease and the daily intake. The amount of potassium that can be taken per day varies depending on the stage of kidney disease patients. Therefore, by providing low-potassium foods having a potassium content different from 65% or less, 50% or less, and 30% or less to raw materials such as juice or coffee as needed by patients, patients of different stages can be provided. Can be dealt with. In addition, for a beverage such as green tea or coffee that consumes a large amount of total, by setting the amount of potassium contained to 30% or less, it becomes possible to ingest with confidence without worrying about the amount of potassium.
　カリウムなど陽イオンを除去することによって、液体のｐＨは酸性に傾く。果実ジュースなど、原料飲料のｐＨが酸性の食品では、官能試験を行った結果、カリウムを除去しｐＨが酸性に傾いてもさほど気にならないことが明らかになった。したがって、もともと酸性であり、酸味がある食品では味に違和感がない限り中和する必要がない。電気泳動を応用して陽イオンを除去した場合には、カリウム、ナトリウムなど半径の小さいイオンから先に除去され、大きいイオンは除去されにくい。そのため、実施例で示すように、イオン交換樹脂を使用して陽イオンを除去した場合に比べてｐＨの低下率が少ない。一方、豆乳などｐＨが中性付近の飲料や、酸性になることによって凝集体が生じるものについては、味に違和感がなく、凝集体を生じない程度にカリウム除去率を抑えるか、炭酸カルシウム、水酸化カルシウム、水酸化マグネシウムなどのアルカリによって中和すればよい。以下に図面を用いて塩類を除去する装置について説明するが、実施態様で示した装置に限定されることがないのは言うまでもない。 By removing cations such as potassium, the pH of the liquid will be acidic. Sensory tests on foods such as fruit juices with acidic beverages with acidic pH revealed that potassium was removed and the pH was inclined to be acidic, so that it was not so bothersome. Therefore, it is not necessary to neutralize foods that are acidic in nature and have a sour taste unless the taste is uncomfortable. When cations are removed by applying electrophoresis, ions having a small radius such as potassium and sodium are removed first, and large ions are not easily removed. Therefore, as shown in the examples, the rate of decrease in pH is smaller than when cations are removed using an ion exchange resin. On the other hand, for beverages having a pH around neutrality, such as soy milk, and those in which aggregates are generated by becoming acidic, the taste is not uncomfortable and the potassium removal rate is suppressed to an extent that aggregates are not generated, or calcium carbonate, water, It may be neutralized with an alkali such as calcium oxide or magnesium hydroxide. Hereinafter, an apparatus for removing salts will be described with reference to the drawings, but it is needless to say that the apparatus is not limited to the apparatus shown in the embodiment.
　［実施態様１］
　一対の電極間に液体状の食品を配置し、塩類を除去する装置、及び方法について説明する（図１（Ａ））。塩類除去装置１は、槽２の中に、１対の電極を備えた構造となっている。塩類除去装置１は、槽２に陰極３と陽極４が対向して配置され、電極間に挟まれた空間にジュースなどの液体状の食品５を入れることができる。陰極３の内側には膜６が配置されており、液体状の食品５は膜６の外側の槽内の空間７には漏れ出ないように膜で空間が区切られている。陰極３の内側に配置されている膜６は、陰極に接触するように配置されている。陰極３が膜６に接触していることから、通電することによって、膜に開いている細孔から、カリウムなどの陽イオンを積極的に除去することができる。また、硝酸イオンなどの陰イオンを除去する場合には、陽極を膜に接するように配置すればよい。さらに、陽イオンと陰イオンを同時に除去する場合には、陰極、陽極の両方を膜に接するように配置し、同時に除去する構成としてもよい。 [Embodiment 1]
An apparatus and a method for disposing a liquid food between a pair of electrodes and removing salts will be described (FIG. 1A). The salt removing device 1 has a structure provided with a pair of electrodes in a tank 2. In the salt removing device 1, a cathode 3 and an anode 4 are arranged in a tank 2 so as to face each other, and a liquid food 5 such as juice can be put in a space sandwiched between the electrodes. A membrane 6 is disposed inside the cathode 3, and the liquid food 5 is separated by a membrane so as not to leak into a space 7 in a tank outside the membrane 6. The membrane 6 arranged inside the cathode 3 is arranged so as to contact the cathode. Since the cathode 3 is in contact with the membrane 6, cations such as potassium can be positively removed from the pores opened in the membrane by energizing. When removing anions such as nitrate ions, the anode may be arranged so as to be in contact with the film. Furthermore, when removing cations and anions at the same time, both the cathode and the anode may be arranged so as to be in contact with the film, and may be removed at the same time.
　電極間の距離が離れていると抵抗が高くなりジュール熱が多量に発生し、液状食品の温度が上昇し変質する。したがって、電極間の距離は、ジュール熱の発生により食品が変質しない程度の距離とすることが望ましい。 と If the distance between the electrodes is large, the resistance will increase and a large amount of Joule heat will be generated, and the temperature of the liquid food will rise and deteriorate. Therefore, it is desirable that the distance between the electrodes is such that the food does not deteriorate due to the generation of Joule heat.
　実施態様１で示している脱塩装置は、通電することによって、電気泳動の原理で、陰極側にカリウムなどの陽イオンを引き寄せ、膜の細孔から排出させる。したがって、膜の外側の空間７には水などの溶媒を配置する必要はない。しかし、水を入れておくことによって拡散によっても塩類を除去することができる。拡散の利用によって、非常に迅速にカリウムなどの塩類の除去が可能となる。膜の外側の空間７に配置する水は、撹拌、流水を使用する、あるいは、槽外で陽イオンを除去し、再度ポンプで循環させることによって、膜近傍の陽イオンを速やかに除去し、常に低濃度に維持することが好ましい。 脱 The desalination apparatus shown in Embodiment 1 attracts a cation such as potassium to the cathode side by the principle of electrophoresis and discharges it from the pores of the membrane by energization by the electrophoresis principle. Therefore, it is not necessary to arrange a solvent such as water in the space 7 outside the membrane. However, the salt can be removed by diffusion by adding water. The use of diffusion makes it possible to remove salts such as potassium very quickly. The water placed in the space 7 outside the membrane uses stirring, running water, or removes cations outside the tank and circulates them again with a pump to quickly remove cations in the vicinity of the membrane. It is preferred to maintain a low concentration.
　空間７に水を満たして使用する場合、液体状の食品５の界面が、空間７を満たしている水の界面よりも幾分高くなるようにすれば、圧力により膜６と陰極３が密着することから好ましい。また、水はカリウムの迅速な除去だけではなく、冷却にも寄与する。冷却は、装置自体を低温室などの低温環境に設置することによって行ってもよい。 When the space 7 is filled with water and used, if the interface of the liquid food 5 is slightly higher than the interface of the water filling the space 7, the membrane 6 and the cathode 3 adhere to each other by pressure. This is preferred. Water also contributes to cooling as well as rapid removal of potassium. The cooling may be performed by installing the device itself in a low-temperature environment such as a low-temperature room.
　また、ここでは槽内に膜と電極を配置し、膜と槽の三方の壁に囲まれた領域にジュースなどの液体食品を入れる装置にしているが、流路の片側に膜と接した電極を配置し、他方の側面に電極を配置し、流路内を液体食品を流しながら通電し、塩類を除去する構成としてもよい。 Also, here, a membrane and an electrode are placed in the tank, and a device that puts liquid food such as juice into the area surrounded by the three walls of the membrane and the tank is used. May be arranged, an electrode may be arranged on the other side surface, and electricity may be supplied while flowing a liquid food through the flow path to remove salts.
　陽極４は液体状の食品５に浸漬されているので、陰イオンが排除されることはない。そのため、塩類除去装置１では陽イオンのみが除去される。したがって、液体状の食品に含まれている有機酸などの陰イオン、酸性アミノ酸は、通電処理を行った後でも原料となる液体状の食品と同等の濃度である。有機酸とは、食品成分表に記載されているギ酸、酢酸、グリコール酸、乳酸、グルコン酸、シュウ酸、マロン酸、コハク酸、フマル酸、リンゴ酸、酒石酸、α-ケトグルタン酸、クエン酸、サリチル酸、p－クマル酸、コーヒー酸、フェルラ酸、クロロゲン酸、キナ酸、オロト酸などをいい、酸性アミノ酸とはアスパラギン酸、グルタミン酸をいうが、これらの量を測定しても通電前後で変化することはない。また、後述するように、カリウムなど小さなイオンは除去されるものの、マグネシウム、カルシウムは除去されるのに時間がかかる。アミノ酸も分子量が大きいことから、塩基性アミノ酸であるアルギニン、リジンは正電荷を有しているが除去されにくい。 (4) Since the anode 4 is immersed in the liquid food 5, anions are not eliminated. Therefore, in the salt removing device 1, only cations are removed. Therefore, the concentration of the anions such as organic acids and acidic amino acids contained in the liquid food is the same as that of the liquid food as the raw material even after the energization treatment. Organic acids are formic, acetic, glycolic, lactic, gluconic, oxalic, malonic, succinic, fumaric, malic, tartaric, α-ketoglutanic, citric, Salicylic acid, p-coumaric acid, caffeic acid, ferulic acid, chlorogenic acid, quinic acid, orotic acid, etc .; acidic amino acids refer to aspartic acid and glutamic acid. Never. Further, as described later, although small ions such as potassium are removed, it takes time to remove magnesium and calcium. Since amino acids also have a large molecular weight, arginine and lysine, which are basic amino acids, have a positive charge but are not easily removed.
　電気泳動を応用した方法によりカリウムなどの陽イオンを除去した場合には、負に帯電している分子は除去されにくい。そのため、遊離アミノ酸のうちでもアスパラギン酸、グルタミン酸、また、中性アミノ酸は除去されにくい。したがって、陽イオンを除去した場合には、少なくとも１つ以上の酸性アミノ酸や中性アミノ酸、又は有機酸を測定することによって、陽イオン交換樹脂など、他の方法で陽イオンを除去した食品との区別をすることが可能となる。特に、実施態様で示す塩類除去装置は、陽イオンを選択的に除去できることから、陰イオンの量や組成は原料飲料と大きく変動することはない。したがって、複数の有機酸、アミノ酸を測定し、その量や組成を解析することで、他の方法でカリウム等の陽イオンを除去した食品と区別することができる。 場合 When cations such as potassium are removed by a method using electrophoresis, negatively charged molecules are not easily removed. Therefore, among the free amino acids, aspartic acid, glutamic acid, and neutral amino acids are not easily removed. Therefore, when cations are removed, by measuring at least one or more acidic amino acids or neutral amino acids, or organic acids, the cations can be exchanged with other foods, such as cation exchange resins, from which cations have been removed. It is possible to make a distinction. In particular, since the salt removing apparatus described in the embodiment can selectively remove cations, the amount and composition of the anions do not greatly vary from those of the raw material beverage. Therefore, by measuring a plurality of organic acids and amino acids and analyzing the amounts and compositions thereof, it is possible to distinguish the food from the cations such as potassium which have been removed by other methods.
［実施態様２］
　異なる形状の塩類除去装置１１について説明する。図１（Ｂ）に示すように、塩類除去装置１１は、槽１２内に２つの陰極１３、１３’と中央に陽極１４が配置されている。陰極１３、１３’の内側には膜１５、１５’が配置されている。２つの膜１５、１５’で仕切られていることから、膜１５、１５’の間に液体状の食品１６を入れても両側に漏れることがない。 [Embodiment 2]
The salt removing device 11 having a different shape will be described. As shown in FIG. 1 (B), the salt removing apparatus 11 has two cathodes 13 and 13 ′ in a tank 12 and an anode 14 in the center. Films 15, 15 'are arranged inside the cathodes 13, 13'. Since it is divided by the two membranes 15 and 15 ', even if the liquid food 16 is put between the membranes 15 and 15', it does not leak to both sides.
　陰極１３、１３’と陽極１４間で通電することによって、液体状の食品中の陽イオンが陰極１３、１３’に泳動し、膜１５、１５’の細孔から溶媒とともに除去される。槽１２の膜の外側の空間１６、１６’を水で満たしておけば、膜の細孔から排出された陽イオンを迅速に除去することができる。実施態様２の装置を使用することにより、実施態様１の装置の２倍の容量の液状食品を処理することができるので、大量の食品を処理することができる。なお、陰イオンを除去する場合には、陽極と陰極の位置を入れ替えて、膜の外側に1対の陽極を配置すればよい。 By energizing between the cathodes 13, 13 ’and the anode 14, cations in the liquid food migrate to the cathodes 13, 13’ and are removed from the pores of the membranes 15, 15 ’together with the solvent. If the spaces 16, 16 'outside the membrane of the tank 12 are filled with water, the cations discharged from the pores of the membrane can be quickly removed. By using the apparatus of the second embodiment, a liquid food having twice the capacity of the apparatus of the first embodiment can be processed, so that a large amount of food can be processed. When removing anions, the positions of the anode and the cathode may be switched, and a pair of anodes may be arranged outside the film.
［実施例１］
　実施態様１の装置を使用して、種々の膜を用い、カリウムを除去した結果を以下に示す。使用した膜、及び入手先は以下のとおりである。０．７０μｍ、０．４５μｍ、又は０．１０μｍの孔径のニトロセルロース膜（東洋濾紙株式会社）、半透膜（セロファン）、ポリエチレン膜（ポリラップ（登録商標）、宇部フィルム株式会社）。なお、実施例１において、膜がジュースと接している面積は膜全体の約３０％である。また、試料としては、ブロッコリー、セロリ、キャベツなどの野菜を用いて製造されている野菜・果実汁を含む青汁飲料（商品ａ、Ａ社製）を用いた。 [Example 1]
The results of removing potassium using various films using the apparatus of Embodiment 1 are shown below. The membrane used and the source are as follows. Nitrocellulose membrane (Toyo Roshi Kaisha, Ltd.), semipermeable membrane (cellophane), polyethylene membrane (Polywrap (registered trademark), Ube Film Co., Ltd.) having a pore size of 0.70 μm, 0.45 μm, or 0.10 μm. In Example 1, the area where the film was in contact with the juice was about 30% of the whole film. In addition, as a sample, a green juice beverage (product a, manufactured by A company) containing vegetable and fruit juices manufactured using vegetables such as broccoli, celery, and cabbage was used.
　通電密度８ｍＡ／ｃｍ２で３０分、又は４５分通電した結果を表１に示す。電極間距離は２．５ｃｍに設定している。なお、以下で測定に用いたジュース、コーヒーで、通電により発生するジュール熱を検討したところ、電極間の距離が４．０ｃｍ以下、好ましくは３．５ｃｍ、より好ましくは２．５ｃｍ以下であれば、ジュール熱が発生したとしても食品が変質することはなかった。原液からのカリウム（Ｋ）の除去率、通電後の液温、ｐＨ、及び官能試験結果を示す。なお、原液のカリウム濃度は、製品のロットによって異なり１５３．８～１７０．２ｍｇ／１００ｇであった。原料の飲料から除去されたカリウムの量を測定し、除去率（％）として表している。カリウムは、試料を乾燥・湿式灰化後、原子吸光光度法により測定した。なお、原液の液温は２０℃、ｐＨは３．８６であった。 Table 1 shows the results of applying electricity at a current density of 8 mA / cm 2 for 30 minutes or 45 minutes. The distance between the electrodes is set to 2.5 cm. In addition, when the Joule heat generated by applying electricity to the juice and coffee used for the measurement was examined below, if the distance between the electrodes was 4.0 cm or less, preferably 3.5 cm, more preferably 2.5 cm or less. Even if Joule heat was generated, the food did not deteriorate. The removal rate of potassium (K) from the undiluted solution, the solution temperature, the pH after energization, and the results of sensory tests are shown. Note that the potassium concentration of the stock solution was 153.8 to 170.2 mg / 100 g, depending on the product lot. The amount of potassium removed from the raw beverage was measured and expressed as a removal rate (%). Potassium was measured by atomic absorption spectrophotometry after drying and wet incineration of the sample. The liquid temperature of the stock solution was 20 ° C., and the pH was 3.86.
　また、処理後のジュースを風味識別能力に優れた専門パネラー１０名によって風味の評価を実施した。評価は５：風味が変わらない、４：風味があまり変わらない、３：どちらともいえない、２：風味がやや変化、１：風味が大きく劣化の５段階評価とし、平均を記載している。 ジ ュ ー ス Furthermore, the flavor of the processed juice was evaluated by 10 expert panelists having excellent flavor discrimination ability. The evaluations are 5: the flavor does not change, 4: the flavor does not change much, 3: neither can be said, 2: the flavor slightly changes, 1: the flavor is greatly deteriorated, and the average is described.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、０．４５μｍ、０．１０μｍの孔径のニトロセルロース膜、半透膜液を使用した場合には、通電４５分という短時間で、８０～９０％のカリウムを飲料から除去することができた。このときのｐＨは原料の清涼飲料と比較して１．０から１．２ほど低下している。また、通電３０分では、原料からカリウムを５割から７割ほど除去することができた。この場合のｐＨの低下は０．７程度であった。 As shown in Table 1, when a nitrocellulose membrane having a pore diameter of 0.45 μm or 0.10 μm or a semipermeable membrane liquid is used, 80 to 90% of potassium is removed from the beverage in a short time of 45 minutes. We were able to. At this time, the pH is lower by about 1.0 to 1.2 as compared with the soft drink as the raw material. Further, in 30 minutes of energization, about 50 to 70% of potassium was removed from the raw material. In this case, the decrease in pH was about 0.7.
　いずれの通電条件でも、官能試験の結果、評価は４．５であり、風味が原料飲料とほとんど変わらなかったことを示している。カリウムが８０％以上除去されている通電４５分の条件であっても、官能試験結果は、元のジュースと比べて遜色ない風味であることを示しており、中和処理を行う必要がない。従来のカリウム除去法では、処理後に中和する必要があったが、膜を用いた除去法では中和の必要がない場合も多い。 で も Under any of the energizing conditions, the result of the sensory test was 4.5, indicating that the flavor was almost the same as that of the raw beverage. Even under the condition of 45 minutes of energization in which 80% or more of potassium has been removed, the sensory test result shows that the flavor is comparable to that of the original juice, and there is no need to perform a neutralization treatment. In the conventional potassium removal method, it was necessary to neutralize after the treatment, but in many cases, the removal method using a membrane does not require neutralization.
　孔径０．７０μｍの膜を用いた場合には、細孔からジュースが膜の外側に漏れ出るのが観察されたため、測定を行わなかった。また、不透膜であるポリエチレンフィルムを用いた場合には、３０分の通電で液温が５２℃と高くなり、これ以上通電すると液温がさらに上昇すると考えられたので、通電４５分の試験は行わなかった。 測定 When a membrane having a pore size of 0.70 μm was used, the measurement was not performed because juice was observed to leak out of the membrane from the pores. When a polyethylene film, which is an impermeable membrane, was used, the liquid temperature was raised to 52 ° C. by energizing for 30 minutes, and the liquid temperature was considered to rise further when energizing for more than 30 minutes. Did not do.
　以上のように、半透膜を用いた場合には、カリウム除去を行うことができた。半透膜の孔径は１ｎｍ～１０ｎｍと言われている。したがって、１ｎｍ以上の孔径の膜であれば効率良くカリウムなどの塩類を除去することができると考えられる。また、孔径０．７０μｍのニトロセルロース膜では飲料が膜の外側に漏れ出たことから、孔径０．７０μｍ未満の膜を使用する必要がある。 カ リ ウ ム As described above, when the semipermeable membrane was used, potassium could be removed. The pore size of the semipermeable membrane is said to be 1 nm to 10 nm. Therefore, it is considered that a salt having a pore diameter of 1 nm or more can efficiently remove salts such as potassium. In the case of a nitrocellulose membrane having a pore diameter of 0.70 μm, since the beverage leaked to the outside of the membrane, it is necessary to use a membrane having a pore diameter of less than 0.70 μm.
　次に、０．４５μｍ、０．１０μｍの孔径のニトロセルロース膜、半透膜について、実施例１の通電３０分の条件で陽イオン除去を行い、カリウム、ナトリウム（Ｎａ）、カルシウム（Ｃａ）、マグネシウム（Ｍｇ）量を測定した。ナトリウム、カルシウム、及びマグネシウムの測定はカリウムと同様、試料を乾燥・湿式灰化後、原子吸光光度法により測定した（表２）。 Next, for the nitrocellulose membrane and the semipermeable membrane having pore diameters of 0.45 μm and 0.10 μm, cations were removed under the conditions of 30 minutes of energization of Example 1, and potassium, sodium (Na), calcium (Ca), The amount of magnesium (Mg) was measured. As in the case of potassium, sodium, calcium, and magnesium were measured by atomic absorption spectrophotometry after drying and wet incineration of the sample (Table 2).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　いずれの膜を使用して陽イオン除去を行った場合でも、多量に含まれているカリウムの除去率が最も高く、原子の大きいカルシウム、マグネシウムはほとんど除去されていない。このように、塩類除去装置でカリウムを除去した液状食品は、カリウム含有量が少なく、カルシウム、マグネシウム含有量は除去前の食品とほとんど差がない。したがって、カリウム、ナトリウムを選択的に除去した飲料を提供することができる。 陽 Regardless of which membrane is used to remove cations, the removal rate of potassium contained in a large amount is the highest, and calcium and magnesium with large atoms are hardly removed. As described above, the liquid food from which potassium has been removed by the salt removing device has a low potassium content, and the calcium and magnesium contents have almost no difference from the food before removal. Therefore, a beverage from which potassium and sodium have been selectively removed can be provided.
　電気泳動法によって、カリウムを除去した場合には、カルシウム、マグネシウムがほとんど除去されないことから、イオン交換樹脂によるカリウム除去法に比べて、ｐＨが低下する割合が少ない。したがって、果実ジュースなど原料とする飲料が酸性の場合にはほとんど中和する必要がない。しかし、中性付近の飲料、例えば緑茶などからカリウムを除去する場合には、酸性だと味に違和感が生じることから、水酸化ナトリウム、炭酸カルシウム、水酸化カルシウム、水酸化マグネシウムなどのｐＨ調整剤を用いて中和する必要がある。電気泳動によってカリウムを除去し、中和する場合には、除去されたカリウムによるｐＨ低下に見合った量のアルカリ塩を加える必要がある。そのため、ナトリウム、カルシウム、又はマグネシウム量が原料とする飲料よりも多く含まれることになる。 (4) When potassium is removed by electrophoresis, calcium and magnesium are hardly removed, so that the rate of decrease in pH is smaller than in the potassium removal method using an ion exchange resin. Therefore, when a beverage as a raw material such as fruit juice is acidic, it is hardly necessary to neutralize the beverage. However, in the case of removing potassium from beverages near neutrality, for example, green tea, etc., the taste may be uncomfortable if it is acidic, and therefore, pH adjusters such as sodium hydroxide, calcium carbonate, calcium hydroxide, and magnesium hydroxide. It is necessary to neutralize using. When potassium is removed by electrophoresis and neutralized, it is necessary to add an alkali salt in an amount commensurate with the decrease in pH due to the removed potassium. Therefore, the amount of sodium, calcium, or magnesium is larger than that of the beverage used as the raw material.
［実施例２］
　通電密度を変えて、カリウム除去量を検討した（表３）。通電密度を１２ｍＡ／ｃｍ２に上げたほかは実施例１と同じ条件で処理を行い、処理後の飲料のカリウム除去率、液温、ｐＨを測定し、官能試験を実施した。 [Example 2]
The amount of potassium removed was examined by changing the current density (Table 3). The treatment was carried out under the same conditions as in Example 1 except that the current-carrying density was increased to 12 mA / cm 2 , and the potassium removal rate, liquid temperature, and pH of the treated beverage were measured, and a sensory test was performed.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　通電密度を上げて通電することにより、より短時間でカリウムを除去することができた。いずれの膜を使用した場合でも３０分で７５％以上のカリウムを飲料から除去することができる。しかし、液温上昇のためか、カリウム除去に要する時間は短かったものの、官能試験の結果は、通電３０分でいずれの膜でも３．５、通電４５分では１と通電密度８ｍＡ／ｃｍ２の場合と比較して風味が劣化していた。通電密度を上げることによる液温の上昇は避けることができないことから、通電密度を上げる場合には、槽を低温室に設置して通電する、あるいは槽内に冷却水を入れたり、冷却装置を設けるなど冷却しながら通電する必要がある。 By increasing the current density and energizing, potassium could be removed in a shorter time. Regardless of which membrane is used, more than 75% of potassium can be removed from the beverage in 30 minutes. However, although the time required for removing potassium was short due to an increase in the liquid temperature, the results of the sensory test showed that any of the films had a current density of 3.5 mA for 30 minutes and a current density of 8 mA / cm 2 for 45 minutes. The flavor was deteriorated as compared with the case. Since the rise of the liquid temperature due to the increase in the current density cannot be avoided, when increasing the current density, place the tank in a low-temperature room and energize it, put cooling water in the tank, or install a cooling device. It is necessary to energize while cooling, such as by providing.
［実施例３］
　次に種々の飲料を通電密度８ｍＡ／ｃｍ２、電極間距離２．５ｃｍ、通電時間３０分、０．４５μｍニトロセルロース膜の条件で通電し、陽イオンの量を測定し、除去率を求めた。試料は以下の飲料を用いた。オレンジジュース（濃縮還元オレンジジュース、果汁１００％、商品ｂ１、Ｂ社製）、アップルジュース（濃縮還元アップルジュース、果汁１００％、商品ｂ２、Ｂ社製）、野菜・果実飲料（緑黄色野菜ミックスジュース、野菜汁果汁１００％、商品ｃ、Ｃ社製）、トマトジュース（濃縮還元トマトジュース１００％、商品ｄ、Ｄ社製）、コーヒー（無糖、商品ｅ、Ｅ社製）。 [Example 3]
Next, various beverages were energized under the conditions of a current density of 8 mA / cm 2 , a distance between electrodes of 2.5 cm, a current time of 30 minutes, and a 0.45 μm nitrocellulose membrane, the amount of cations was measured, and the removal rate was determined. . The following beverages were used as samples. Orange juice (concentrated reduced orange juice, fruit juice 100%, product b1, manufactured by B company), apple juice (concentrated reduced apple juice, fruit juice 100%, product b2, manufactured by B company), vegetable / fruit beverage (green-yellow vegetable mixed juice, Vegetable juice 100%, product c, company C), tomato juice (concentrated and reduced tomato juice 100%, product d, company D), coffee (sugar-free, product e, company E).
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　いずれの飲料を用いた場合でも、通電密度８ｍＡ／ｃｍ２、３０分の通電で、原料飲料の３６．９～９５．５％と効率良くカリウムを除去することができた。トマトジュースのように、元の飲料に含まれるカリウム量が多い場合には、カリウム除去率では３６．９％と低い値を示しているが、１００ｇあたり約１００ｍｇのカリウムが除去されている。カリウム除去量を処理前後で比較すると、いずれの飲料でも３０分の通電で１００ｍｇ／１００ｇ程度のカリウムが除去されている。 Regardless of which beverage was used, potassium could be efficiently removed as 36.9 to 95.5% of the raw beverage by applying electricity for 8 minutes at an electric current density of 8 mA / cm 2 . When the amount of potassium contained in the original beverage is large, such as in tomato juice, the potassium removal rate is as low as 36.9%, but about 100 mg of potassium is removed per 100 g. Comparing the amount of potassium removed before and after the treatment, about 100 mg / 100 g of potassium was removed in all of the beverages for 30 minutes.
［実施例４］
　実施例１と同様にして陽イオンを除去した場合には、カリウム、ナトリウムなどの比較的小さい陽イオンに比べて、アミノ酸など比較的大きい分子は除去されにくいことを示す。実施態様１の装置を使用して、実施例１と同様に、０．１０μｍの孔径のニトロセルロース膜を用い、野菜・果実汁を含む青汁飲料（商品ａ、Ａ社製）から陽イオンを除去する試験を行った。 [Example 4]
When cations are removed in the same manner as in Example 1, relatively large molecules such as amino acids are hardly removed compared to relatively small cations such as potassium and sodium. Using the apparatus of Embodiment 1, cations were extracted from a green juice beverage (product a, manufactured by Company A) containing vegetable and fruit juices using a nitrocellulose membrane having a pore size of 0.10 μm in the same manner as in Example 1. A test for removal was performed.
　通電密度８ｍＡ／ｃｍ２で６０分通電した。電極間距離は３．５ｃｍに設定している。原液から除去されたカリウム量、全遊離アミノ酸量を測定し、除去率（％）として表している。カリウムは、上記と同様に試料を乾燥・湿式灰化後、原子吸光光度法により測定した。全遊離アミノ酸濃度は、生試料を７０～８０℃で３０分間加温し、ろ過液をニンヒドリン比色法により測定した。原液、処理液のカリウム濃度、カリウム除去率、全遊離アミノ酸濃度、全遊離アミノ酸除去率、液温、ｐＨを示す。 Electric current was applied at an electric current density of 8 mA / cm 2 for 60 minutes. The distance between the electrodes is set to 3.5 cm. The amount of potassium removed from the stock solution and the total amount of free amino acids were measured and expressed as the removal rate (%). Potassium was measured by atomic absorption spectrometry after drying and wet incineration of the sample as described above. The total free amino acid concentration was determined by heating a raw sample at 70 to 80 ° C. for 30 minutes and measuring the filtrate by a ninhydrin colorimetric method. The potassium concentration, the potassium removal rate, the total free amino acid concentration, the total free amino acid removal rate, the solution temperature, and the pH of the stock solution and the treatment solution are shown.
　表５に示すように、カリウムが８４％除去されたが、全遊離アミノ酸は１２％しか除去されなかった。カリウムが８０％以上除去されている条件であっても、アミノ酸は１０％程度しか除去されておらず、処理前後で野菜・果汁飲料、ジュースなどの食品に含まれるアミノ酸の量や組成に大きな変化はないと考えられる。特に、陽イオンが除去される条件では、酸性アミノ酸、あるいは中性アミノ酸はほとんど除去されていないと考えられる。通電処理によって塩類を除去した場合は、イオン交換樹脂によって塩類を除去した場合と比較して、小さいイオンが選択的に除去され、質量の大きいイオン、分子は除去されにくい。したがって、アミノ酸などの量や組成は変化しにくい。また、上記で示したように、酸などの陰イオンの除去は起こらないことから、処理前後でジュースなどの食品に含まれる酸の組成にも大きな変化はない。 カ リ ウ ム As shown in Table 5, 84% of potassium was removed, but only 12% of total free amino acids were removed. Even under conditions in which potassium is removed by 80% or more, only about 10% of amino acids are removed, and the amount and composition of amino acids contained in foods such as vegetables, fruit juice drinks, and juices before and after treatment significantly change. It is thought that there is no. In particular, it is considered that acidic or neutral amino acids are hardly removed under the conditions for removing cations. When the salts are removed by the energization treatment, small ions are selectively removed and ions and molecules having a large mass are hardly removed as compared with the case where the salts are removed by an ion exchange resin. Therefore, the amount and composition of amino acids and the like are unlikely to change. In addition, as described above, since the removal of anions such as acids does not occur, there is no significant change in the composition of acids contained in foods such as juice before and after the treatment.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
［実施例５］
　陽極と陰極を入れ替え、膜に接する電極を陽極とすることによって、陰イオンが除去できることを示す（表６）。実施態様１の装置の陰極と陽極を入れ替え、膜に陽極が接するようにして硝酸イオンの除去試験を行った。 [Example 5]
It is shown that the anion can be removed by replacing the anode and the cathode and using the electrode in contact with the membrane as the anode (Table 6). A test for removing nitrate ions was performed by replacing the cathode and anode of the apparatus of Embodiment 1 so that the anode was in contact with the membrane.
　食品中の硝酸性窒素含量は材料により異なる。日本食品標準成分表（七訂）によれば、ほうれんそうでは０．２ｇ／１００ｇ、チンゲンサイでは０．５ｇ／１００ｇと葉物野菜に比較的多量に含まれている。そこで、試験は硝酸カリウム（富士フィルム和光純薬株式会社）を用いて、１００ｍｇ／Ｌ（０．１ｇ／１００ｇ）の硝酸濃度（ＮＯ３）の溶液を作製して実施した。 The nitrate nitrogen content in foods varies from material to material. According to the Japanese Food Standard Composition Table (Seventh Edition), spinach contains 0.2 g / 100 g and bok choy 0.5 g / 100 g, which is relatively large in leafy vegetables. Therefore, the test was carried out using potassium nitrate (Fuji Film Wako Pure Chemical Co., Ltd.) to prepare a solution having a nitric acid concentration (NO 3 ) of 100 mg / L (0.1 g / 100 g).
　０．１０μｍの孔径のニトロセルロース膜を用い、通電密度４ｍＡ／ｃｍ２で１０分通電した。電極間距離は２．５ｃｍに設定している。硝酸の濃度、原液からの除去率、液温、ｐＨを示す。除去率（％）は、原液から除去された硝酸の量を％で表している。硝酸濃度は、比色法により測定した。 Using a nitrocellulose membrane having a pore size of 0.10 μm, current was applied at a current density of 4 mA / cm 2 for 10 minutes. The distance between the electrodes is set to 2.5 cm. Shows nitric acid concentration, removal rate from stock solution, liquid temperature, and pH. The removal rate (%) represents the amount of nitric acid removed from the stock solution in%. The nitric acid concentration was measured by a colorimetric method.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　試験溶液には、パルプなどの繊維成分が含まれていないことから、低い通電密度、かつ短時間で９０％以上の硝酸を除去することができた。陰イオンであっても、陽イオンと同様に除去できることが示された。 (4) Since the test solution did not contain fiber components such as pulp, 90% or more of nitric acid could be removed in a short time at a low current density. It was shown that even anions can be removed similarly to cations.
　上記処理によって、原料とする液状食品の５０％以下など、所望の濃度に硝酸塩含有量を低減させることができる。硝酸イオンなどの陰イオンを除去する場合には、液体食品からは陽イオンは除去されにくい。したがって、遊離アミノ酸のうち、塩基性アミノ酸及び中性アミノ酸は除去されにくい。 By the above treatment, the nitrate content can be reduced to a desired concentration such as 50% or less of the liquid food as a raw material. When removing anions such as nitrate ions, cations are not easily removed from liquid foods. Therefore, of the free amino acids, basic amino acids and neutral amino acids are not easily removed.
［参考例３］従来法との比較
　ジュース、豆乳からカリウムを除去する方法として従来から用いられているイオン交換樹脂によるカリウム除去法と実施例で開示している方法との比較を行った。用いた試料は下記の飲料である。オレンジジュース（商品ｂ１、Ｂ社製）、野菜・果実飲料（商品ｃ、Ｃ社製）、トマトジュース（商品ｄ、Ｄ社製）、コーヒー（商品ｅ、Ｅ社製）、野菜・果実汁を含む青汁飲料（商品ａ、Ａ社製） [Reference Example 3] Comparison with conventional method As a method for removing potassium from juice and soy milk, a comparison was made between a potassium removal method using a conventional ion exchange resin and a method disclosed in the examples. The samples used are the following beverages. Orange juice (product b1, manufactured by Company B), vegetable / fruit drink (product c, manufactured by Company C), tomato juice (product d, manufactured by Company D), coffee (product e, manufactured by Company E), vegetable / fruit juice Green juice beverage (product a, manufactured by Company A)
　特許文献３に記載の方法に沿って、オレンジジュース、トマトジュース、コーヒーは、試料１００ｍｌに対し、乾燥重量５ｇ（湿重量７．５３ｇ）のＨ型イオン交換樹脂を添加し、野菜・果実飲料、野菜・果実汁を含む青汁飲料は試料１００ｍｌに対し、乾燥重量７０ｇ（湿重量１０５．４５ｇ）を添加し、３０分間振盪した後に陽イオン交換樹脂を沈殿させ、上澄み液を測定した。トマトジュースはパルプが多く、樹脂との分離が不十分であり樹脂が多量に混入し、正確な測定値を得ることができなかったので測定結果からは除いている。オレンジジュース、野菜・果実汁を含む青汁飲料はわずかに樹脂が混入したが測定結果を得ることができた。結果を表７に示す。 In accordance with the method described in Patent Literature 3, orange juice, tomato juice, and coffee are prepared by adding a dry weight of 5 g (wet weight of 7.53 g) of H-type ion exchange resin to 100 ml of a sample to produce a vegetable / fruit beverage, A green juice drink containing vegetable and fruit juices was added to a sample (100 ml) at a dry weight of 70 g (wet weight of 105.45 g), and after shaking for 30 minutes, a cation exchange resin was precipitated and the supernatant was measured. Tomato juice has a large amount of pulp, is insufficiently separated from the resin, contains a large amount of resin, and cannot obtain an accurate measurement value. Green juice drinks including orange juice and vegetable / fruit juice were able to obtain measurement results although resin was slightly mixed. Table 7 shows the results.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　カリウムイオンは９５．３％～９９．７％と非常に良く除去されていた。また、樹脂を使用する方法では、カルシウム、マグネシウムも高率に除去されている。イオン交換樹脂を用いた場合には、質量の大きさによらずカルシウム、マグネシウムなどのイオンも高率に除去される。 Potassium ions were very well removed at 95.3% to 99.7%. In the method using a resin, calcium and magnesium are also removed at a high rate. When an ion exchange resin is used, ions such as calcium and magnesium are also removed at a high rate regardless of the size of the mass.
　また、バッチ式で樹脂と試料を混合し、カリウムを除去した場合には、試料から樹脂を除くのが非常に困難であった。特にパルプの多いトマトジュースでは、樹脂とジュースを分離することは困難であった。電気泳動による方法では、パルプの多い飲料や、流動食であっても、３０分程度の短時間でカリウムを除去することが可能である。 In addition, when the resin and the sample were mixed in a batch system to remove potassium, it was very difficult to remove the resin from the sample. In particular, in the case of tomato juice containing a large amount of pulp, it was difficult to separate the resin from the juice. In the method by electrophoresis, potassium can be removed in a short time of about 30 minutes even in a beverage containing a lot of pulp or a liquid food.
１、１１…塩類除去装置、２、１２…槽、３、１３、１３’…陰極、４、１４…陽極、５、１６…液体状の食品、６、１５、１５’…膜 1, 11: salt removal device, 2, 12, tank, 3, 13, 13 '... cathode, 4, 14 ... anode, 5, 16 ... liquid food, 6, 15, 15' ... membrane

Claims (8)

  1. 　液体状の食品から陽イオン、又は陰イオンを除去する液体状の食品の製造方法であって、
    　一定の孔径を備えた膜と、
    　陽極、又は陰極を対向させて配置し、
    　陽イオンを除去する場合には前記膜の前記陽極に対向する面の反対側に陰極を接するように配置し、
    　陰イオンを除去する場合には前記膜の前記陰極に対向する面の反対側に陽極を接するように配置し、
    　前記膜によって区切られた空間を液体状の食品で満たし、
    　通電することによって陽イオン、又は陰イオンを除去する液体状の食品の製造方法。     A method for producing a liquid food for removing cations or anions from the liquid food,
    A membrane with a fixed pore size,
    Anode or cathode is placed facing,
    When removing cations, a cathode is placed on the opposite side of the surface of the membrane facing the anode,
    When anions are removed, an anode is disposed on the opposite side of the surface of the membrane facing the cathode,
    Fill the space separated by the membrane with liquid food,
    A method for producing a liquid food in which cations or anions are removed by energizing.
  2. 　前記膜の孔径が１ｎｍ以上０．７μｍ未満であることを特徴とする請求項１記載の液体状の食品の製造方法。 (4) The method for producing a liquid food according to (1), wherein the membrane has a pore diameter of 1 nm or more and less than 0.7 μm.
  3. 　対向する陰極と陽極を備え、
    　前記陰極、又は陽極のいずれか一方の内側には一定の孔径を備えた膜が接するように配置されており、
    　前記陽極と陰極間に通電することによって電気泳動によって液体状の食品から塩類を除去する装置。     With opposing cathode and anode,
    The cathode, or a membrane having a certain pore diameter is arranged to be in contact with the inside of either one of the anode,
    An apparatus for removing salts from liquid food by electrophoresis by energizing between the anode and the cathode.
  4. 　１対の陰極と陽極が設けられ、
    　前記陰極、又は陽極は膜に接し、
    　膜を介して陽極、又は陰極が対向するように設けられている請求項３記載の液体状の食品から塩類を除去する装置。     A pair of cathode and anode are provided,
    The cathode, or the anode is in contact with the membrane,
    The apparatus for removing salts from a liquid food according to claim 3, wherein the anode or the cathode is provided so as to face the membrane.
  5. 　２つの陰極、又は２つの陽極が対向して配置され、
    　前記２つの対向する陰極、又は陽極の中央に、陽極、又は陰極が設けられ、
    　前記２つの対向する陰極、又は陽極は夫々膜を介して中央の陽極、又は陰極に対向している請求項３記載の液体状の食品から塩類を除去する装置。     Two cathodes or two anodes are arranged facing each other,
    At the center of the two opposed cathodes or anodes, an anode or cathode is provided,
    4. The apparatus for removing salts from a liquid food according to claim 3, wherein the two opposed cathodes or anodes face the central anode or cathode through a membrane, respectively.
  6. 　前記膜の孔径が１ｎｍ以上０．７μｍ未満であることを特徴とする請求項３～５いずれか１項記載の液体状の食品から塩類を除去する装置。 (6) The apparatus for removing salts from a liquid food according to any one of (3) to (5), wherein the pore size of the membrane is 1 nm or more and less than 0.7 μm.
  7. 　前記膜が接するように配置されている陰極、又は陽極が水に浸漬され、
    　水を循環、及び／又は撹拌する手段を備えていることを特徴とする請求項３～６いずれか１項記載の液体状の食品から塩類を除去する装置。     A cathode, or an anode, in which the membrane is arranged to be in contact, is immersed in water,
    The apparatus for removing salts from a liquid food according to any one of claims 3 to 6, further comprising means for circulating and / or stirring water.
  8. 　処理後のカリウム含有量が原料とする液体状の食品の５０％以下であり、
    　少なくとも１つ以上の遊離酸性アミノ酸、及び／又は有機酸は原料とする液体状の食品とほぼ等量であることを特徴とする低カリウム化された液体状の食品。     The potassium content after the treatment is 50% or less of the liquid food as a raw material,
    A low-potassium liquid food, wherein at least one or more free acidic amino acids and / or organic acids are substantially equivalent to a liquid food as a raw material.
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