JP6156978B2 - Production of strongly reducing sea salt - Google Patents
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- 235000002639 sodium chloride Nutrition 0.000 title claims description 61
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims description 26
- 239000011780 sodium chloride Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 31
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 31
- 241001330002 Bambuseae Species 0.000 claims description 31
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 31
- 239000011425 bamboo Substances 0.000 claims description 31
- 239000003610 charcoal Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 10
- 230000033116 oxidation-reduction process Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 description 35
- 238000003763 carbonization Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 230000003796 beauty Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021398 atomic carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 235000013402 health food Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 230000003248 secreting effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- -1 skin cleansers Substances 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Description
本発明は、海水から得られた強い還元力を有する塩の製法に関する。 The present invention relates to a process for the production of salt with a strong reducing power obtained from seawater.
通常市販されている塩の酸化還元電位（ＯＲＰ／Ｏｘｉｄａｔｉｏｎ−Ｒｅｄｕｃｔｉｏｎ Ｐｏｔｅｎｔｉａｌ）を計測すると、１２０〜３９０ｍＶの範囲の酸化力を示す。しかし、特殊な岩塩や特定の方法で加熱処理した塩は、ＯＲＰ値がマイナス、即ち還元力を示すものがあり、これらは還元性塩として、健康食品や美容・化粧品等として利用されている。 When the oxidation-reduction potential (ORP / Oxidation-Reduction Potential) of the salt marketed normally is measured, the oxidation power of the range of 120-390 mV is shown. However, some special rock salts and salts heat-treated by a specific method have a negative ORP value, that is, a reducing power. These are used as reducing salts as health foods, beauty / cosmetics, and the like.
例えば、ヒマラヤの岩塩や韓国の伝統製法竹塩等は還元性塩として知られている。ヒマラヤの岩塩は天然のままで還元性があるが、韓国の竹塩は、天然の海塩を輪切りにした竹に入れ、周囲を黄土で満たした後加熱する、という方法で古くから製造されているものである。そして、これらの還元性塩の還元性の指標としてのＯＲＰ値は、−１５０ｍＶ〜−２００ｍＶ程度で、比較的低いものであることが知られている。また、韓国の竹塩のごとき製造方法では長時間を要し、取得率も平均６０％程度と低いものである。 For example, Himalayan rock salt and Korean traditional bamboo salt are known as reducing salts. Himalayan rock salt is natural and reducible, but Korean bamboo salt has long been manufactured by a method in which natural sea salt is placed in a bamboo cut and filled with ocher and then heated. It is what. And it is known that the ORP value as an index of reducibility of these reducing salts is about -150 mV to -200 mV and relatively low. In addition, a manufacturing method such as Korean bamboo salt takes a long time, and the acquisition rate is as low as about 60% on average.
皮膚疾患の改善や美容、あるいは口腔衛生の改善のために、竹塩を用いることも提案されている（例えば、特許文献１〜３）。また、竹筒に詰めた塩を、竹チップを投入した還元雰囲気炭化炉で蒸し焼きする方法で、竹炭の微粒子を含む還元性の竹炭塩を製造する方法も提案されている（特許文献４）。しかし、かかる方法で得られた竹炭塩も、ＯＲＰ値が十分に低いものではない。 It has also been proposed to use bamboo salt to improve skin diseases, beauty, or oral hygiene (for example, Patent Documents 1 to 3). There has also been proposed a method for producing a reducing bamboo charcoal salt containing bamboo charcoal fine particles by steaming and baking the salt packed in the bamboo cylinder in a reducing atmosphere carbonization furnace containing bamboo chips (Patent Document 4). However, bamboo charcoal salt obtained by such a method is not sufficiently low in ORP value.
本発明者らは、従来の竹からの炭化反応に附随した生産法では、極めて時間がかかり、炭化乾留時の効果が全く反映されないことを改善し、工業的に有利な製法を開発することを試みた。 The present inventors have improved the fact that the conventional production method associated with carbonization reaction from bamboo is extremely time-consuming and does not reflect the effect of carbonization carbonization at all, and develop an industrially advantageous production method. Tried.
本発明者は、還元性付与に多孔質竹炭を用いることに着目し、海水塩（海洋塩）に強い還元性を付与されたものを木質類の炭化反応に頼ることなく作成することに成功した。 The present inventor paid attention to the use of porous bamboo charcoal for imparting reducibility, and succeeded in creating a product imparted with a strong reducibility to sea salt (marine salt) without depending on the carbonization reaction of wood. .
本発明の塩分濃度２０％の水溶液における酸化還元電位（ＯＲＰ）値が、−３００ｍＶ以下の値を呈する強還元性海塩は、海水塩１００重量部と多孔質の竹炭１０重量部以上とからなる配合物又は混合物を、空気遮断し、８００〜１２００℃で加熱することによって得られる。 The strongly reducing sea salt having an oxidation-reduction potential (ORP) value of -300 mV or less in an aqueous solution having a salt concentration of 20% according to the present invention comprises 100 parts by weight of sea salt and 10 parts by weight or more of porous bamboo charcoal. It is obtained by blocking the air and heating the formulation or mixture at 800-1200 ° C.
本発明によれば、強還元性海塩を、比較的短い作成時間及び加熱時間で得ることができ、且つ、８０％以上の高収率で作成することができる。そして、得られた還元性海塩のＯＲＰ値は、２０％水溶液で−３００ｍＶ以下に及び、還元力の持続性も極めて良好である。 According to the present invention, a strongly reducing sea salt can be obtained with a relatively short production time and heating time, and can be produced with a high yield of 80% or more. And the ORP value of the obtained reducing sea salt is -300mV or less with 20% aqueous solution, and the sustainability of a reducing power is also very favorable.
本発明の強還元性海塩は、塩分濃度２０％の水溶液における酸化還元電位（ＯＲＰ）値が、−３００ｍＶ以下、好ましくは−４００ｍＶ以下の値を呈するものである。そして、かかる強還元性海塩は、海水から得られる海水塩１００重量部と多孔質の竹炭１０重量部以上とからなる配合物又は混合物を、空気遮断し、８００〜１２００℃、好ましくは８００〜１０００℃で加熱することによって得られる。 The strongly reducing sea salt of the present invention exhibits a redox potential (ORP) value in an aqueous solution having a salinity of 20% of -300 mV or less, preferably -400 mV or less. And this strong reducible sea salt air-blocks the compound or mixture which consists of 100 weight part of sea salt obtained from seawater, and 10 weight part or more of porous bamboo charcoal, 800-1200 degreeC, Preferably it is 800- Obtained by heating at 1000 ° C.
本発明の強還元性海塩は、海水塩と多孔質の竹炭を、重量比で１０対１以上の比率で、炭化装置や電気還元炉等の中に入れ、空気を遮断して、８００〜１２００℃に加熱することによって得られる。本発明では、還元剤として従来知られていた竹ではなく多孔質の竹炭を使用するので、還元力が強く、かつ、海水塩と固体の炭粉との接触面積が増加するので、還元反応が非常に進みやすくなり、それらの結果、比較的短時間にＯＲＰ値の低いものが得られるという特徴がある。 The strongly reducing sea salt of the present invention is a mixture of sea salt and porous bamboo charcoal in a weight ratio of 10 to 1 or more in a carbonization device, an electric reduction furnace, etc. Obtained by heating to 1200 ° C. In the present invention, porous bamboo charcoal is used instead of bamboo, which has been conventionally known as a reducing agent. Therefore, the reducing power is strong and the contact area between seawater salt and solid charcoal powder increases. It is very easy to proceed, and as a result, a product having a low ORP value can be obtained in a relatively short time.
本発明において原料として用いる海水塩は、海水から得られるいわゆる粗塩を意味し、市販されている食用等の精製塩とは異なる。 The sea salt used as a raw material in the present invention means a so-called crude salt obtained from sea water, and is different from commercially available purified salts such as food.
本発明において用いられる多孔質の竹炭とは、竹を高温〜中温（４００〜７００℃）で人為的に炭化させた微細孔が多数存在する炭である。微細孔はその半径が１５〜２７ｎｍのものであり、通常の木炭などに比べて小さいものである。竹炭の炭化温度によってその表面積は異なり、通常、竹炭１ｇ中の孔の表面積は、炭化温度２００℃で１．７ｍ２、８００℃で７２４．８ｍ２程度であることが知られている。本発明においては、４００〜７００℃で炭化させた多孔質の竹炭が好ましく用いられる。 The porous bamboo charcoal used in the present invention is charcoal having many fine pores obtained by artificially carbonizing bamboo at a high temperature to a medium temperature (400 to 700 ° C.). The fine holes have a radius of 15 to 27 nm and are smaller than ordinary charcoal. Unlike its surface area by the carbonization temperature of the charcoal, usually, the surface area of pores in the charcoal 1g, it is known at the carbonization temperature 200 ° C. is 1.7 m 2, 800 2 approximately 724.8m at ° C.. In the present invention, porous bamboo charcoal carbonized at 400 to 700 ° C. is preferably used.
本発明の強還元性海塩は、海水塩１００重量部と多孔質の竹炭１０重量部以上とからなる配合物又は混合物を、空気遮断し、８００〜１２００℃、好ましくは８００〜１０００℃で加熱・炭化することによって得られる。空気を遮断して加熱するための装置は、特別なものである必要はなく、空気を遮断して、配合物又は混合物を焼成でき、かつ、加熱温度を容易にコントロールできるものであれば、どのようなものでもかまわない。 The strongly reducing sea salt of the present invention shields air from a mixture or mixture comprising 100 parts by weight of sea salt and 10 parts by weight or more of porous bamboo charcoal, and heats at 800 to 1200 ° C., preferably 800 to 1000 ° C. • Obtained by carbonization. The apparatus for shutting off and heating the air does not need to be special, and any apparatus can be used as long as it can shut off the air, fire the compound or mixture, and easily control the heating temperature. It doesn't matter.
海水塩と多孔質の竹炭の配合又は混合割合は、海水塩１００重量部当たり多孔質の竹炭が１０重量部以上、好ましくは２０〜５０重量部である。 The blending ratio or mixing ratio of sea salt and porous bamboo charcoal is 10 parts by weight or more, preferably 20 to 50 parts by weight of porous bamboo charcoal per 100 parts by weight of sea salt.
本発明において、海水塩と多孔質の竹炭の配合物又は混合物は、空気遮断して、通常の単槽釜又は二重槽釜からなる炭化容器で電気還元炉に配置し焼成される。８００℃以上に加熱することによって、多孔質竹炭の加熱によって原子状炭素や一酸化炭素ガスを発生させつつ、塩を溶融還元し、高収率（９０％程度にもなる）で、塩水が低濃度でもＯＲＰ値が−３００ｍＶ以下の強還元塩を得ることができる。加熱時間は４〜９時間が適当である。 In the present invention, the mixture or mixture of sea salt and porous bamboo charcoal is air-blocked and placed in an electric reduction furnace in a carbonization vessel comprising a normal single tank or double tank and fired. By heating to 800 ° C or higher, the porous bamboo charcoal is heated to generate atomic carbon and carbon monoxide gas, and the salt is melt-reduced, resulting in high yield (about 90%) and low salt water. A strongly reduced salt having an ORP value of −300 mV or less can be obtained even at a concentration. The heating time is suitably 4-9 hours.
炭化容器の材質・形状は、特に限定されるものではないが、例えば、外容器の中に内容器が配置された二重容器（２重槽釜）が適当である。この場合、外容器は銅製又はステンレス製のものが好ましく、内容器としては、炭化ケイ素製、アルミナ製、セラミック製、又は素焼き陶磁器製のものが好ましく用いられる。 The material and shape of the carbonization container are not particularly limited, but, for example, a double container (double tank pot) in which the inner container is arranged in the outer container is suitable. In this case, the outer container is preferably made of copper or stainless steel, and the inner container is preferably made of silicon carbide, alumina, ceramic, or unglazed ceramic.
化学的には、市販の純粋なＮａＣｌ塩は還元されないが、海水塩には、硫酸塩・硝酸塩などが含まれており、これらも本発明の方法で還元され、例えば、ＳＯ４→ＳＯ３→Ｓ２Ｏ３など複雑な複合還元性塩になっている還元塩が得られるものと考えられる。 Chemically, commercially pure NaCl salts are not reduced, but seawater salts include sulfates and nitrates, which are also reduced by the method of the present invention, for example, SO 4 → SO 3 → It is considered that a reduced salt that is a complex complex reducing salt such as S 2 O 3 can be obtained.
本発明の還元力のある塩は、酸化還元電位測定計で大きなマイナス値を示す還元性の塩であるから、体表の皮膚や毛根から、酸化すると悪臭を発する分泌皮脂の酸化を防止するものと考えられる。また、生体内あるいは食品中のフリーラジカル捕促効果に優れているので、人の美容や健康に寄与するものと考えられる。特に老化や疾病の元凶である体内で発生する活性酸素（フリーラジカル）の捕促効果によって、人の健康増進を図ることができるとも言われている。以下、実施例により本発明を詳述する。 The reducing salt of the present invention is a reducing salt that shows a large negative value in the oxidation-reduction potential meter, and therefore prevents oxidation of secretory sebum that produces a bad odor when oxidized from the skin or hair root of the body surface. it is conceivable that. Moreover, since it is excellent in the free radical scavenging effect in the living body or in food, it is considered to contribute to human beauty and health. In particular, it is said that the promotion of active oxygen (free radicals) generated in the body, which is the cause of aging and disease, can promote human health. Hereinafter, the present invention will be described in detail by way of examples.
炭化容器としては、図１に示したようなものを用いた。蓋付きのセラミック製あるいはＳＵＳ３１６Ｌ製の外容器１の内部に、上部は開口した銅製の内容器２を入れ、両容器の隙間には竹炭３を配置し、海水塩４を内容器に入れ、全体を加熱炉（図示せず）中に置き９００℃で５時間加熱した。なお、内容器の側壁と底面には、必要に応じてガス透過性の小孔を多数開けておいた。なお、竹炭の配置の位置や状態は特に限定されるものではないが、一部を内容器に配置しておくとより効率的ではある。
As the carbonization vessel, the one shown in FIG. 1 was used. Inside the outer container 1 made of ceramic with a lid or made of SUS316L, put the inner container 2 made of copper open at the top, place bamboo charcoal 3 in the gap between both containers, put
佐賀県産及び沖縄産の海洋塩と多孔質高温〜中温竹炭を、適切な比率の小型の炭化試験装置内に入れ空気は遮断し、窒素を１５０ｍｌ／分で流しながら、所定温度で６時間、多孔質竹炭の加熱によって原子状炭素や一酸化炭素ガスを発生させつつ塩を溶融還元した。生成したすべての還元塩で収率は、８０〜９０％程度で良好で、それらの還元性ＯＲＰ値（２０％及び１％水道水溶液）測定を行い、その還元性の強度と持続性について測定し、結果を表１（佐賀県産）と表２（沖縄産）に示した。比較のために示した水道水は、微量の酸化性の塩素を含んでいるために、約６００ｍＶのＯＲＰ値（ｐＨ＝７．６）を示していた。 Put marine salt from Saga and Okinawa and porous high-temperature to medium-temperature bamboo charcoal in a small carbonization test device at an appropriate ratio, shut off the air, and flow nitrogen at 150 ml / min for 6 hours at the specified temperature. Salt was melt-reduced while generating atomic carbon and carbon monoxide gas by heating porous bamboo charcoal. Yields of all the reduced salts are good at about 80-90%, their reducible ORP values (20% and 1% tap water) are measured, and the strength and sustainability of the reducibility are measured. The results are shown in Table 1 (from Saga Prefecture) and Table 2 (from Okinawa). The tap water shown for comparison had an ORP value of about 600 mV (pH = 7.6) because it contained a trace amount of oxidizing chlorine.
表より、８００〜１２００℃で塩と炭の比が４：１以上の場合に、還元力の優れた還元塩が得られていることが分かる。また、ＯＲＰ値が、溶解直後と７時間又は１００時間放置した後でも、余り変わらないことから、本発明の還元塩の還元力の持続力も優れていることが分かる。なお、ｐＨとＯＲＰ値の上段は溶解直後の測定値で、下段は溶解７時間（塩分濃度１％のとき）又は１００時間（塩分濃度２０％のとき）後の測定値である。また、海水塩は、前処理として１００℃で約１２時間、予備乾燥したものを使用した。 From the table, it can be seen that when the ratio of salt to charcoal is 4: 1 or more at 800 to 1200 ° C., a reduced salt with excellent reducing power is obtained. Further, since the ORP value does not change so much even after being left for 7 hours or 100 hours immediately after dissolution, it can be seen that the reducing power of the reducing salt of the present invention is excellent in sustainability. The upper part of pH and ORP values are measured values immediately after dissolution, and the lower part are measured values after dissolution for 7 hours (when the salt concentration is 1%) or 100 hours (when the salt concentration is 20%). The sea salt used was predried at 100 ° C. for about 12 hours as a pretreatment.
本発明の製法によって得られる塩は、還元性食品、栄養補助食品、入浴剤、石鹸添加剤、皮膚洗浄剤、食品保存剤等に利用することができる。 The salt obtained by the production method of the present invention can be used for reducing foods, nutritional supplements, bathing agents, soap additives, skin cleansers, food preservatives and the like.
１ 外容器（蓋付）
２ 内容器
３ 竹炭
４ 海水塩
1 Outer container (with lid)
2 Inner container 3 Bamboo
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