JP2021069981A - Adsorbent for basic amino acid - Google Patents
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 53
- 239000003463 adsorbent Substances 0.000 title claims abstract description 28
- 239000004927 clay Substances 0.000 claims abstract description 64
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 239000011973 solid acid Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 238000005341 cation exchange Methods 0.000 claims description 5
- 239000004475 Arginine Substances 0.000 claims description 4
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 4
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 4
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 4
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 10
- 238000010306 acid treatment Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- -1 hydrogen ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000004278 EU approved seasoning Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 235000019658 bitter taste Nutrition 0.000 description 3
- 235000011194 food seasoning agent Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 244000294411 Mirabilis expansa Species 0.000 description 1
- 235000015429 Mirabilis expansa Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000020510 functional beverage Nutrition 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000013536 miso Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Abstract
Description
本発明は、新規な塩基性アミノ酸用吸着剤に関する。 The present invention relates to a novel adsorbent for basic amino acids.
アルギニン、ヒスチジン及びリジンは、いずれも側鎖にアミノ基を有するアミノ酸であり、これらは塩基性アミノ酸と呼ばれている。 Arginine, histidine and lysine are all amino acids having an amino group in the side chain, and these are called basic amino acids.
塩基性アミノ酸は、苦みを呈する成分として知られており、調味料や飲料などの風味改善のためには、塩基性アミノ酸を選択的に分離・除去することが望まれる。 Basic amino acids are known as components that exhibit bitterness, and it is desired to selectively separate and remove basic amino acids in order to improve the flavor of seasonings and beverages.
しかし、粘土鉱物によりアミノ酸溶液から不純物を除去する技術（特許文献１参照）や、アミノ酸を粘土鉱物に担持する技術（特許文献２参照）は検討されているものの（特許文献１参照）、複数種類のアミノ酸を含有する溶液から特定のアミノ酸を選択的に吸着する技術についてはほとんど検討されていないのが実情である。 However, although a technique for removing impurities from an amino acid solution with a clay mineral (see Patent Document 1) and a technique for supporting an amino acid on a clay mineral (see Patent Document 2) have been studied (see Patent Document 1), there are a plurality of types. The fact is that little research has been done on a technique for selectively adsorbing a specific amino acid from a solution containing the amino acid.
本発明の目的は、塩基性アミノ酸を含有する溶液から塩基性アミノ酸を選択的に吸着し得る吸着剤を提供することにある。 An object of the present invention is to provide an adsorbent capable of selectively adsorbing a basic amino acid from a solution containing a basic amino acid.
本発明によれば、ジオクタヘドラル型スメクタイト系粘土からなる塩基性アミノ酸用吸着剤であって、前記ジオクタヘドラル型スメクタイト系粘土のＳｉＯ２／Ａｌ２Ｏ３比が１０以下であることを特徴とする塩基性アミノ酸用吸着剤が提供される。 According to the present invention, it is an adsorbent for a basic amino acid composed of a dioctahedral type smectite type clay, and is characterized in that the SiO 2 / Al 2 O 3 ratio of the dioctahedral type smectite type clay is 10 or less. Amino acid adsorbents are provided.
本発明の塩基性アミノ酸用吸着剤においては、
（１）前記ジオクタヘドラル型スメクタイト系粘土のＨｏ≦−３．０の固体酸量が０．１０ｍｍｏｌ／ｇ−ｄｒｙ ｃｌａｙ以上であること、
（２）前記ジオクタヘドラル型スメクタイト系粘土のカチオン交換容量が２０ｍｍｏｌ／１００ｇ以上であること、
（３）前記ジオクタヘドラル型スメクタイト系粘土が酸処理物であること、
（４）前記ジオクタヘドラル型スメクタイト系粘土のＳｉＯ２／Ａｌ２Ｏ３比が７．５以下であること、
（５）前記塩基性アミノ酸がアルギニン又はヒスチジンであること、
が好適である。
In the adsorbent for basic amino acids of the present invention,
(1) The solid acid amount of Ho ≦ -3.0 of the dioctahedral type smectite clay is 0.10 mmol / g-dry clay or more.
(2) The cation exchange capacity of the dioctahedral type smectite clay is 20 mmol / 100 g or more.
(3) The dioctahedral type smectite clay is an acid-treated product.
(4) The SiO 2 / Al 2 O 3 ratio of the dioctahedral type smectite clay is 7.5 or less.
(5) The basic amino acid is arginine or histidine.
Is preferable.
本発明において塩基性アミノ酸吸着剤として用いられるジオクタヘドラル型スメクタイト系粘土は、ＳｉＯ２／Ａｌ２Ｏ３比（質量比）が調整されている結果、塩基性アミノ酸を選択的に吸着することができる。 The dioctahedral type smectite clay used as the basic amino acid adsorbent in the present invention can selectively adsorb basic amino acids as a result of adjusting the SiO 2 / Al 2 O 3 ratio (mass ratio).
本発明の塩基性アミノ酸用吸着剤は、ＳｉＯ２／Ａｌ２Ｏ３比（質量比）が１０以下、好ましくは７．５以下のジオクタヘドラル型スメクタイト系粘土から成ることを特徴とするが、ＳｉＯ２／Ａｌ２Ｏ３比が当該範囲にあることに由来して、比較的強い固体酸性を示す。 Basic amino acid adsorbent of the present invention, SiO 2 / Al 2 O 3 ratio (mass ratio) is 10 or less, preferably is characterized in that it consists of 7.5 following dioctahedral smectite clay, SiO 2 Due to the / Al 2 O 3 ratio being in this range, it exhibits relatively strong solid acidity.
例えば、前記ジオクタヘドラル型スメクタイト系粘土のＨｏ≦−３．０の固体酸量は、０．１０ｍｍｏｌ／ｇ−ｄｒｙ ｃｌａｙ以上が好適であり、０．２０ｍｍｏｌ／ｇ−ｄｒｙ ｃｌａｙ以上がより好適であり、０．７０ｍｍｏｌ／ｇ−ｄｒｙ ｃｌａｙ以上が最も好適である。 For example, the solid acid amount of Ho ≦ −3.0 of the dioctahedral type smectite clay is preferably 0.10 mmol / g-dry clay or more, and more preferably 0.20 mmol / g-dry clay or more. 0.70 mmol / g-dry clay or more is most preferable.
このように前記ジオクタヘドラル型スメクタイト系粘土は比較的強い固体酸性を示すが、このことが、塩基性アミノ酸に対する優れた吸着性能を発揮する一因であるものと推察される。
即ち、塩基性アミノ酸は２つのアミノ基と１つのカルボン酸基を有するため、水溶液中では、陽イオン（２価）、陽イオン（１価）、双生イオン及び陰イオン（１価）が平衡状態にあり、水溶液中のｐＨ変化にしたがって平衡が移動する。
例えば、高ｐＨ（塩基性）条件下ではカルボン酸が陰イオンとなるため、平衡は陰イオン側に傾いている。ここに、比較的強い固体酸を含んでいる本発明の吸着剤を水溶液中に添加していくと、ｐＨが下がり、アミノ基が陽イオンとなり、塩基性アミノ酸の平衡は陽イオン側に移動する。従って、この塩基性アミノ酸の陽イオンが前記ジオクタヘドラル型スメクタイト系粘土の層間に有する負電荷により捕捉され、この結果、塩基性アミノ酸の吸着性が発現することとなる。
As described above, the dioctahedral type smectite clay exhibits relatively strong solid acidity, which is presumed to be one of the reasons for exhibiting excellent adsorption performance for basic amino acids.
That is, since a basic amino acid has two amino groups and one carboxylic acid group, cations (divalent), cations (monovalent), zwitterions and anions (monovalent) are in equilibrium in an aqueous solution. The equilibrium shifts as the pH changes in the aqueous solution.
For example, under high pH (basic) conditions, the carboxylic acid becomes an anion, so the equilibrium is inclined toward the anion. When the adsorbent of the present invention containing a relatively strong solid acid is added to the aqueous solution, the pH drops, the amino group becomes a cation, and the equilibrium of the basic amino acid shifts to the cation side. .. Therefore, the cations of this basic amino acid are captured by the negative charge between the layers of the dioctahedral type smectite clay, and as a result, the adsorptivity of the basic amino acid is exhibited.
前記ジオクタヘドラル型スメクタイト系粘土のＡｌ２Ｏ３比率は、９質量％以上が好適であり、１４質量％以上がより好適である。 The Al 2 O 3 ratio of the dioctahedral type smectite clay is preferably 9% by mass or more, and more preferably 14% by mass or more.
前記ジオクタヘドラル型スメクタイト系粘土のカチオン交換容量（ＣＥＣ）は、２０ｍｍｏｌ／１００ｇ以上が好適であり、４０ｍｍｏｌ／１００ｇ以上がより好適であり、５０ｍｍｏｌ／１００ｇ以上が最も好適である。 The cation exchange capacity (CEC) of the dioctahedral type smectite clay is preferably 20 mmol / 100 g or more, more preferably 40 mmol / 100 g or more, and most preferably 50 mmol / 100 g or more.
ここで、ジオクタヘドラル型スメクタイト系粘土について説明する。
ジオクタヘドラル型スメクタイト系粘土は、ＳｉＯ４四面体層−ＡｌＯ６八面体層−ＳｉＯ４四面体層からなり、且つこれらの四面体層と八面体層が部分的に異種金属で同形置換された三層構造を基本構造（単位層）としており、このような三層構造の積層層間には、Ｃａ、Ｋ、Ｎａ等の金属陽イオンや水素イオンとそれに配位している水分子が存在している。また、基本三層構造の八面体層中のＡｌの一部にＭｇやＦｅ（ＩＩ）が置換し、四面体層中のＳｉの一部にＡｌが置換しているため、結晶格子はマイナスの電荷を有しており、このマイナスの電荷が基本層間に存在する金属陽イオンや水素イオンにより中和されている。
Here, the dioctahedral type smectite clay will be described.
Dioctahedral smectite clay, SiO 4 tetrahedral layers -AlO 6 consists octahedral layer -SiO 4 tetrahedra layer and three layers of these tetrahedral layer and the octahedral layer are isomorphous substitution with partially different metals The structure is the basic structure (unit layer), and metal cations and hydrogen ions such as Ca, K, and Na and water molecules coordinated thereto are present between the laminated layers of such a three-layer structure. .. Further, since Mg and Fe (II) are substituted in a part of Al in the octahedral layer of the basic three-layer structure and Al is substituted in a part of Si in the tetrahedral layer, the crystal lattice is negative. It has an electric charge, and this negative charge is neutralized by metal cations and hydrogen ions existing between the basic layers.
このようなジオクタヘドラル型スメクタイト系粘土には、酸性白土、ベントナイト、フラーズアース等があり、基本層間に存在する金属陽イオンの種類や量、及び水素イオン量等によってそれぞれ異なる特性を示す。例えば、ベントナイトでは、基本層間に存在するＮａイオン量が多く、このため、水に懸濁分散させた分散液のｐＨが高くなる。一方、酸性白土では、基本層間に存在する水素イオン量が多く、このため、水に懸濁分散させた分散液のｐＨが低くなる。 Such dioctahedral type smectite clays include acid clay, bentonite, fraze earth, etc., and exhibit different characteristics depending on the type and amount of metal cations existing between the basic layers, the amount of hydrogen ions, and the like. For example, in bentonite, the amount of Na ions present between the basic layers is large, and therefore the pH of the dispersion liquid suspended and dispersed in water becomes high. On the other hand, in acid clay, the amount of hydrogen ions present between the basic layers is large, and therefore the pH of the dispersion liquid suspended and dispersed in water becomes low.
また、かかるジオクタヘドラル型スメクタイト系粘土は、粘土の成因、産地及び同じ産地でも埋蔵場所（切羽）等によっても相違するが、一般的には、酸化物換算で以下のような組成を有している。
ＳｉＯ２；５０〜７５質量％
Ａｌ２Ｏ３；１１〜２５質量％
Ｆｅ２Ｏ３；２〜２０質量％
ＭｇＯ；２〜７質量％
ＣａＯ；０．１〜３質量％
Ｎａ２Ｏ；０．１〜３質量％
Ｋ２Ｏ；０．１〜３質量％
その他の酸化物（ＴｉＯ２等）；２質量％以下
Ｉｇ−ｌｏｓｓ（１０５０℃）；５〜１１質量％
In addition, such dioctahedral type smectite clay differs depending on the origin of the clay, the place of origin, and the place of burial (face) even in the same place of origin, but generally has the following composition in terms of oxide. ..
SiO 2 ; 50 to 75% by mass
Al 2 O 3 ; 11-25% by mass
Fe 2 O 3 ; 2 to 20% by mass
MgO; 2-7% by mass
CaO; 0.1 to 3% by mass
Na 2 O; 0.1 to 3% by mass
K 2 O; 0.1 to 3% by mass
Other oxides (TiO 2, etc.); 2% by mass or less Ig-loss (1050 ° C.); 5-11% by mass
前記ジオクタヘドラル型スメクタイト系粘土は、産地等によっては、石英等の不純物を多く含んでいることもある。従って、必要により石砂分離、浮力選鉱、磁力選鉱、水簸、風簸等の精製操作に賦して不純物をできるだけ除去した後に用いるのがよい。 The dioctahedral type smectite clay may contain a large amount of impurities such as quartz depending on the place of origin and the like. Therefore, if necessary, it should be used after removing impurities as much as possible by performing refining operations such as stone sand separation, buoyancy beneficiation, magnetic beneficiation, elutriation, and elutriation.
本発明で塩基性アミノ酸吸着剤として使用するジオクタヘドラル型スメクタイト系粘土は、特に限定されるものではないが、酸性白土を使用することが好適である。 The dioctahedral type smectite clay used as a basic amino acid adsorbent in the present invention is not particularly limited, but it is preferable to use acidic clay.
また、本発明の塩基性アミノ酸吸着剤としてとしては、酸性白土を酸処理したものを使用することがより好適である。この酸処理物は、活性白土と称されるものであり、ジオクタヘドラル型スメクタイト系粘土の基本層構造を破壊しない程度に酸処理したものである。酸処理により多孔度が上がるため、種々の物質の吸着に有利となる。 Further, as the basic amino acid adsorbent of the present invention, it is more preferable to use an acid-treated acid clay. This acid-treated product is called activated clay, and is acid-treated to the extent that the basic layer structure of dioctahedral type smectite clay is not destroyed. Since the porosity is increased by the acid treatment, it is advantageous for adsorption of various substances.
上記のような特性を有する活性白土は、夾雑物が取り除かれた酸性白土を所定の条件で酸処理することで製造される。
酸処理条件は、目的とする活性白土の物性（固体酸量など）に応じて適宜設定すればよく、例えば硫酸水溶液を使用する場合には、原料粘土中に含まれる水分も硫酸水溶液を構成するものとして算出した硫酸水溶液量が、通常、原料粘土１００質量部（１１０℃乾燥物として）当り２５０〜８００質量部、その時の硫酸水溶液の濃度が１５〜４５質量％になるような条件で行えばよい。
The activated clay having the above-mentioned characteristics is produced by treating acidic clay from which impurities have been removed with acid under predetermined conditions.
The acid treatment conditions may be appropriately set according to the physical properties (solid acid amount, etc.) of the target active clay. For example, when an aqueous sulfuric acid solution is used, the water contained in the raw material clay also constitutes the aqueous sulfuric acid solution. The amount of the sulfuric acid aqueous solution calculated as a product is usually 250 to 800 parts by mass per 100 parts by mass of the raw material clay (as a dried product at 110 ° C.), and the concentration of the sulfuric acid aqueous solution at that time is 15 to 45% by mass. Good.
さらに、本発明の塩基性アミノ酸吸着剤としてとしては、酸性白土を弱酸処理したものを使用することが特に好適である。以下、このような酸処理物を弱酸処理白土と呼ぶ。
かかる弱酸処理白土は、活性白土に比して弱い酸処理で得られるため、固体酸点として働くＡｌやＭｇの溶出が抑えられている。その一方で、固体酸点として働くＡｌやＭｇを覆っているＮａ分やＣａ分は除去されている。ゆえに、活性白土あるいは酸性白土に比して同等以上の固体酸量を示す。
Further, as the basic amino acid adsorbent of the present invention, it is particularly preferable to use an acid clay treated with a weak acid. Hereinafter, such an acid-treated product is referred to as a weak acid-treated white clay.
Since such weak acid-treated clay is obtained by a weak acid treatment as compared with active clay, elution of Al and Mg acting as solid acid points is suppressed. On the other hand, the Na and Ca components that cover Al and Mg that act as solid acid points are removed. Therefore, the amount of solid acid is equal to or higher than that of active clay or acid clay.
このような弱酸処理白土のＳｉＯ２／Ａｌ２Ｏ３比（質量比）は、７．５以下が好適である。 The SiO 2 / Al 2 O 3 ratio (mass ratio) of such a weak acid-treated white clay is preferably 7.5 or less.
このような弱酸処理白土のＨｏ≦−３．０の固体酸量は、０．７０ｍｍｏｌ／ｇ−ｄｒｙ ｃｌａｙ以上が好適である。 The amount of solid acid of Ho ≦ −3.0 of such a weak acid-treated clay is preferably 0.70 mmol / g-dry clay or more.
このような弱酸処理白土のＡｌ２Ｏ３比率は、１４質量％以上が好適である。 The Al 2 O 3 ratio of such weak acid-treated white clay is preferably 14% by mass or more.
上記のような特性を有する弱酸処理白土は、夾雑物が取り除かれた酸性白土を所定の条件で弱酸処理することにより製造される。
かかる弱酸処理は、従来公知の活性白土や半活性白土を製造する際の酸処理に比してマイルドな条件下で行われる。例えば硫酸水溶液を使用する場合には、原料粘土中に含まれる水分も硫酸水溶液を構成するものとして算出した硫酸水溶液量が、原料粘土１００質量部（１１０℃乾燥物として）当り２５０〜８００質量部、その時の硫酸水溶液の濃度が１〜１５質量％程度になるような条件で酸処理を行えばよい。酸処理にあたっては、必要により２５〜９５℃程度に加熱することもできる。このようにして、原料の組成、用いる酸水溶液の酸濃度、処理温度等によって、ＳｉＯ２／Ａｌ２Ｏ３比が所定の範囲となる程度の時間（０．５〜１２時間程度、好ましくは０．５〜８時間程度、特に好ましくは０．５〜４時間程度）、酸処理を行えばよい。
The weak acid-treated clay having the above-mentioned characteristics is produced by treating the acid clay from which impurities have been removed with a weak acid under predetermined conditions.
Such a weak acid treatment is carried out under mild conditions as compared with the acid treatment in producing conventionally known active clay or semi-active clay. For example, when an aqueous sulfuric acid solution is used, the amount of the aqueous sulfuric acid solution calculated assuming that the water content in the raw material clay also constitutes the aqueous sulfuric acid solution is 250 to 800 parts by mass per 100 parts by mass of the raw material clay (as a dried product at 110 ° C.). The acid treatment may be carried out under the condition that the concentration of the sulfuric acid aqueous solution at that time is about 1 to 15% by mass. In the acid treatment, it can be heated to about 25 to 95 ° C. if necessary. In this way, depending on the composition of the raw material, the acid concentration of the acid aqueous solution used, the treatment temperature, etc., the time (about 0.5 to 12 hours, preferably about 0) that the SiO 2 / Al 2 O 3 ratio falls within a predetermined range The acid treatment may be carried out for about 5 to 8 hours, particularly preferably about 0.5 to 4 hours).
本発明の吸着剤は、塩基性アミノ酸を含有する溶液から塩基性アミノ酸を選択的に吸着することができる。 The adsorbent of the present invention can selectively adsorb basic amino acids from a solution containing basic amino acids.
本発明の吸着剤は、塩基性アミノ酸の中でも、アルギニン又はヒスチジンを好適に吸着することができる。 Among the basic amino acids, the adsorbent of the present invention can preferably adsorb arginine or histidine.
本発明の吸着剤により調味料や飲料から塩基性アミノ酸を選択的に除去することで、塩基性アミノ酸由来の苦みを低減させることができる。例えば、醤油、味噌、魚介エキス、肉エキス又は酵母エキスなどの調味料や、アミノ酸含有の機能性飲料などの苦み低減に利用することができる。 By selectively removing basic amino acids from seasonings and beverages with the adsorbent of the present invention, bitterness derived from basic amino acids can be reduced. For example, it can be used for reducing bitterness of seasonings such as soy sauce, miso, seafood extract, meat extract or yeast extract, and functional beverages containing amino acids.
また、本発明の吸着剤は、吸着した塩基性アミノ酸を適宜溶媒で抽出・精製し利用することもできる。 Further, the adsorbent of the present invention can also be used by appropriately extracting and purifying the adsorbed basic amino acid with a solvent.
本発明の吸着剤は、溶液に含有される塩基性アミノ酸１質量部あたり０．１〜１００質量部以上、好ましくは１〜１０質量部の量で使用される。この投入量が少ないと、当然のことながら、塩基性アミノ酸の吸着量が不十分となってしまう。また、投入量が必要以上に多い場合には、コストの点で不利となってしまう。 The adsorbent of the present invention is used in an amount of 0.1 to 100 parts by mass or more, preferably 1 to 10 parts by mass, per 1 part by mass of the basic amino acid contained in the solution. If this input amount is small, the adsorption amount of basic amino acids will naturally be insufficient. In addition, if the input amount is larger than necessary, it will be disadvantageous in terms of cost.
塩基性アミノ酸を吸着した本発明の吸着剤は、遠心分離や濾過等公知の方法により分離され、取り出される。分離の方法としては、有効成分のロスが少ないという観点から、濾過が好ましい。 The adsorbent of the present invention adsorbing basic amino acids is separated and taken out by a known method such as centrifugation or filtration. As a separation method, filtration is preferable from the viewpoint of less loss of the active ingredient.
本発明の優れた効果を、次の実施例により説明する。 The excellent effects of the present invention will be described with reference to the following examples.
（実施例１）
新潟県胎内市産のジオクタヘドラル型スメクタイト系粘土ペレット７００ｇを９０℃に加熱した５質量％硫酸水溶液１０００ｍｌに投入した。液温９０℃に維持した状態で撹拌し、３０分間酸処理を行った。酸処理終了後、水で洗浄したペレットを１１０℃にて乾燥し、粉砕、分級して弱酸処理白土粉末を得た。
(Example 1)
700 g of dioctahedral type smectite clay pellets produced in Tainai City, Niigata Prefecture were put into 1000 ml of a 5 mass% sulfuric acid aqueous solution heated to 90 ° C. The mixture was stirred while the liquid temperature was maintained at 90 ° C., and acid-treated for 30 minutes. After completion of the acid treatment, the pellets washed with water were dried at 110 ° C., pulverized and classified to obtain a weak acid-treated white clay powder.
（実施例２）
水澤化学工業（株）製活性白土（Ａ）
(Example 2)
Activated clay (A) manufactured by Mizusawa Industrial Chemicals Co., Ltd.
（実施例３）
水澤化学工業（株）製酸性白土
(Example 3)
Mizusawa Industrial Chemicals Co., Ltd. Acid clay
（比較例１）
水澤化学工業（株）製活性白土（Ｂ）
(Comparative Example 1)
Activated clay (B) manufactured by Mizusawa Industrial Chemicals Co., Ltd.
（１）元素分析
元素分析については、（株）リガク社製Ｒｉｇａｋｕ ＺＳＸ ｐｒｉｍｕｓ ＩＩを用い、定量ソフトＥｚスキャンにより各元素の酸化物量（質量％）の測定を行った。
(1) Elemental analysis For elemental analysis, the amount of oxide (mass%) of each element was measured by Rigaku ZSX primus II manufactured by Rigaku Co., Ltd. by quantitative software Ez scan.
（２）カチオン交換容量
ショーレンベルガー法に準拠し試料１００ｇ当たりのカチオン交換容量を測定した（参考文献「日本ベントナイト工業会標準試験方法」）。結果を表１に示す。
(2) Cation exchange capacity The cation exchange capacity per 100 g of the sample was measured according to the Schorenberger method (reference "Japan Bentonite Industry Association Standard Test Method"). The results are shown in Table 1.
（３）固体酸量
ｎ−ブチルアミン滴定法にてＨｏ≦−３．０の固体酸量を測定した。尚、試料はあらかじめ１５０℃で３時間乾燥したものを用いた｛参考文献：「触媒」Ｖｏｌ．１１，Ｎｏ６，Ｐ２１０−２１６（１９６９）｝。結果を表１に示す。
(3) Amount of solid acid The amount of solid acid with Ho ≦ −3.0 was measured by the n-butylamine titration method. The sample used was previously dried at 150 ° C. for 3 hours. {Reference: "Catalyst" Vol. 11, No6, P210-216 (1969)}. The results are shown in Table 1.
（４）ｐＨ
イオン交換水に試料濃度が５質量％になるように吸着剤粉末を添加し、３０分間撹拌した後、東亜ディーケーケー製ｐＨメーターＨＭ−３０Ｒにて測定を行った。結果を表１に示す。
(4) pH
The adsorbent powder was added to the ion-exchanged water so that the sample concentration was 5% by mass, and the mixture was stirred for 30 minutes, and then measured with a pH meter HM-30R manufactured by Toa DKK. The results are shown in Table 1.
（５）吸着試験
富士フイルム和光純薬（株）製アミノ酸混合標準液（Ｈ型）５ｍｌに対して試料０．０５ｇを投入し振盪した後、冷蔵庫内に静置した。１０分おきに冷蔵庫から取り出して振盪し、合計３０分間静置したところで、上澄みをメンブランフィルター（アドバンテック製、フィルター孔径０．４５μｍ）で濾過し、試料液を得た。得られた試料液についてアミノ酸自動分析計により、試料液１００ｇあたりの各アミノ酸の含有量（ｍｇ）を測定した。結果を表２に示す。尚、カッコ内は未処理標準液とのアミノ酸含有量（ｍｇ）の差である。
(5) Adsorption test 0.05 g of a sample was added to 5 ml of an amino acid mixed standard solution (H type) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., shaken, and then allowed to stand in a refrigerator. The sample was taken out of the refrigerator every 10 minutes, shaken, and allowed to stand for a total of 30 minutes. The supernatant was filtered through a membrane filter (manufactured by Advantech, filter pore size 0.45 μm) to obtain a sample solution. The content (mg) of each amino acid per 100 g of the sample solution was measured with respect to the obtained sample solution by an automatic amino acid analyzer. The results are shown in Table 2. The values in parentheses are the difference in amino acid content (mg) from the untreated standard solution.
Claims (6)
前記ジオクタヘドラル型スメクタイト系粘土のＳｉＯ２／Ａｌ２Ｏ３比が１０以下であることを特徴とする塩基性アミノ酸用吸着剤。 An adsorbent for basic amino acids made of dioctahedral smectite clay.
An adsorbent for basic amino acids, characterized in that the SiO 2 / Al 2 O 3 ratio of the dioctahedral type smectite clay is 10 or less.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10182142A (en) * | 1996-10-23 | 1998-07-07 | Osaki Kogyo Kk | Metallic fine particle/solid carrier composition, its use and production |
| JP2000344513A (en) * | 1999-06-01 | 2000-12-12 | Mizusawa Ind Chem Ltd | Activated clay shaped particle, its production and its utilization |
| JP2005104959A (en) * | 2003-01-23 | 2005-04-21 | Nippon Soda Co Ltd | Agricultural and horticultural water dispersible granule |
| US20060276333A1 (en) * | 2003-05-25 | 2006-12-07 | Ulrich Sohling | Agent for adsorbing protein from protein-containing liquids in the foood sector |
| JP2010011858A (en) * | 2009-09-03 | 2010-01-21 | Kao Corp | Tea extract |
| JP2017136584A (en) * | 2016-01-28 | 2017-08-10 | 水澤化学工業株式会社 | Absorbent for purine body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10182142A (en) * | 1996-10-23 | 1998-07-07 | Osaki Kogyo Kk | Metallic fine particle/solid carrier composition, its use and production |
| JP2000344513A (en) * | 1999-06-01 | 2000-12-12 | Mizusawa Ind Chem Ltd | Activated clay shaped particle, its production and its utilization |
| JP2005104959A (en) * | 2003-01-23 | 2005-04-21 | Nippon Soda Co Ltd | Agricultural and horticultural water dispersible granule |
| US20060276333A1 (en) * | 2003-05-25 | 2006-12-07 | Ulrich Sohling | Agent for adsorbing protein from protein-containing liquids in the foood sector |
| JP2010011858A (en) * | 2009-09-03 | 2010-01-21 | Kao Corp | Tea extract |
| JP2017136584A (en) * | 2016-01-28 | 2017-08-10 | 水澤化学工業株式会社 | Absorbent for purine body |
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