JPS60197795A - Removal of caritenes from shea fat - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明は、シア脂中に含まれるカリテン類を有利に除去
する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for advantageously removing caritenes contained in shea butter.

シア脂は、アフリカ西海岸やナイジェリアに産するＢａ
５ｓｉａ　Ｐａｒｋｉｉ　という天然樹木の実から採取
される脂肪で、通常分画精製されたものがカカオ代用脂
として利用されている。この粗製シア脂は、国内入手段
階でかなり品質劣化が進んでいて酸価が３０に達するも
のもあり、また他の油脂には見られないカリテンと呼ば
れるポリイソプレン系化合物が多量台まれ、これがシア
脂両分中に残存していると該両分をカカオ代用脂として
使用したときチョコレート製造工程中のテンパリング処
理を阻害する原因になる。従って、シア脂をカカオ代用
脂として利用するとき、このようなカリテンを除去する
必要があるが、従来シア脂から低極性溶媒であるヘキサ
ンを用いてハードバター画分を分画処理する前に、該カ
リテンが極性溶媒、例えばアセトン（誘電率（８，２０
℃＞　２１．４）　、メチルエチルケトン（誘電率（８
，１７℃）　１７．８）或いはエチルアルコール（誘電
率（８，２０℃’）　２７．０）等の極性溶媒にＩＩＩ
溶であるという性質を利用して、シア脂を極性溶媒によ
り分画処理し、略テンパリング処理に支障がない程度の
量にまで該カリテンを除去したハードバター画分を分取
している。しかしながら、このような従来法では２種類
の溶媒を用いるので設備が拡大し、溶媒の蒸溜工程も２
工程必要となり効率的でないのみならず、極性溶媒中の
水分管理が煩雑であり、且つ熔媒楕留塔の設置が必要で
ある等種々の欠点を有する。一方、最近では膜を利用し
て各種の油脂を精製する方法が種々提案されており、例
えば特開昭５８−９３７９８号では特にナタネ油、大豆
油、サフラワー油、ヒマワリ油、綿実油等の比較的ガム
質含有量の多い植物性油脂からガム質を除去するという
簡便な方法が提案されている。しかしながら、これらの
植物性油脂中に含まれるガム質分は互いに凝集しその分
子が巨大化するため平均分画分子量の比較的大きいＩＮ
！　（目の粗い膜）の使用が可能であり、従ってｉガム
質分を容易に除去することができるのに対し、シア脂中
に含まれるカリテンは非乃至低極性溶媒中で殆ど凝集す
ることなく単分子の状態で存在し、且つそれぞれ分子量
が異なり分子量にかなりの幅を有するため膜を透過する
カリテン分が多く、テンパリング処理に支障をきたさな
い程度にまで該カリテンを除去するのは極めて困難であ
る。即ち、カリテン中の最小の分子量に合わせて膜の分
画分子量を設定すると、溶液の膜透過速度が極めて遅く
全く実用的でない。従って、分画分子量の大きい膜から
順次率さい膜へと数段階に分けて複数の膜処理を行うと
いう方法も考えられるが、かかる方法でも結局最終の膜
は分画分子量が小さい（膜目が細かい）ため処理速度が
遅く、圧力を上げれば膜が破損する等作業工程が煩雑に
なり、また仮令可能であるとしても装置が拡大するのみ
でなく、膜も多種類必要となる結果経済的にも費用がか
かるという欠点を有する。Shea butter is derived from Ba produced on the west coast of Africa and Nigeria.
It is a fat collected from the fruit of a natural tree called 5sia Parkii, and is usually fractionated and purified and used as a cacao substitute fat. The quality of this crude shea butter has deteriorated considerably when it is obtained domestically, with some having an acid value reaching 30. It also contains a large amount of a polyisoprene compound called caritene, which is not found in other fats and oils. If it remains in the fat content, it will cause inhibition of the tempering process during the chocolate manufacturing process when the fat content is used as a cacao substitute fat. Therefore, when using shea butter as a cocoa substitute, it is necessary to remove such caritene, but conventionally, before fractionating the hard butter fraction from shea butter using hexane, a low polar solvent, The caritene is a polar solvent such as acetone (dielectric constant (8,20
℃＞21.4), methyl ethyl ketone (dielectric constant (8
, 17℃) 17.8) or ethyl alcohol (dielectric constant (8, 20℃) 27.0).
Taking advantage of its soluble property, shea butter is fractionated using a polar solvent to obtain a hard butter fraction from which the caritene has been removed to an extent that does not interfere with tempering processing. However, since such conventional methods use two types of solvents, the equipment needs to be expanded, and the solvent distillation process also requires two types of solvents.
This method not only requires a process and is not efficient, but also has various drawbacks, such as complicated water management in the polar solvent and the need to install a solvent ellipsing column. On the other hand, recently, various methods have been proposed for refining various oils and fats using membranes. For example, JP-A-58-93798 specifically compares rapeseed oil, soybean oil, safflower oil, sunflower oil, cottonseed oil, etc. A simple method has been proposed to remove gum from vegetable oils and fats that have a high gum content. However, the gummy substances contained in these vegetable oils and fats aggregate with each other and their molecules become gigantic, so IN, which has a relatively large average molecular weight fraction,
! (coarse membrane) can be used, and therefore the i-gum content can be easily removed, whereas the caritene contained in shea butter hardly aggregates in non- to low polar solvents. Since it exists in a monomolecular state and each has a different molecular weight and a considerable range, a large amount of caritene passes through the membrane, and it is extremely difficult to remove this caritene to the extent that it does not interfere with the tempering process. be. That is, if the molecular weight cutoff of the membrane is set according to the minimum molecular weight in caritene, the permeation rate of the solution through the membrane is extremely slow, which is completely impractical. Therefore, it is possible to consider a method of performing multiple membrane treatments in several stages, starting with a membrane with a high molecular weight cut-off and proceeding to a membrane with a low molecular weight cut-off, but even with such a method, the final membrane will still have a small molecular weight cut-off (the membrane will have a smaller molecular weight). The processing speed is slow due to the fineness of the membranes (fine), and the work process is complicated as the membrane may be damaged if the pressure is increased.Also, even if it were possible to do so, not only would the equipment be expanded, but many different types of membranes would be required, resulting in economical problems. It also has the disadvantage of being expensive.

本発明者は如上の諸欠点を解決すべく種々研究を繰り返
した結果、特定の処理を施した半透膜を使用することに
より問題なく容易にカリテン類を除去できるという知見
を得て本発明を完成するに至った。即ち本発明は、シア
脂中に含まれるカリテン類を除去するに際して、非乃至
低極性溶媒で希釈した生成溶液を、加圧下に予や該溶液
を接触させてカリテン類が殆ど透過しなくなるまで目づ
まりを起こさせた半透膜と接触させミ膜透過画分と不透
過画分とに分離し、この膜透過画分、を脱溶剤して精製
物を回収することを骨子とするものである。As a result of repeated research in order to solve the above-mentioned drawbacks, the present inventor obtained the knowledge that caritenes can be easily removed without any problems by using a semipermeable membrane that has been subjected to a specific treatment, and has developed the present invention. It was completed. That is, in the present invention, when removing caritenes contained in shea butter, the resulting solution diluted with a non- to low polarity solvent is brought into contact with the solution under pressure until almost no caritene permeates through. The main idea is to bring it into contact with a clogged semipermeable membrane to separate it into a membrane-permeable fraction and an impermeable fraction, and to remove the solvent from this membrane-permeable fraction to recover a purified product.

本発明は、このように極性溶媒を使用せず非乃至低極性
溶媒を用い、特定の処理を施した半透膜を単独使用する
のみでシア脂から簡便且つ有利にカリテン類を分画除去
する方法を提供するものである。As described above, the present invention uses a non- to low polarity solvent without using a polar solvent, and simply uses a semipermeable membrane subjected to a specific treatment to easily and advantageously fractionate caritenes from shea butter. The present invention provides a method.

本発明において、原料シア脂としては搾油したままの粗
製原油、或いはアルカリ精製した脱酸油を用いることが
できる。非乃至低極性溶媒としては誘電率（８，２０℃
）が２．５以下のものが適用でき、例へばヘキサン（誘
電率（８，２０℃）　１．８５）が代表的に例示できる
。これに対し、アセトン等の極性溶媒では、その油脂溶
解度が低いため、高濃度の希釈溶液を得ることができず
効率的な作業とならない。In the present invention, as the raw material shea butter, crude crude oil as-extracted or deacidified oil refined with an alkali can be used. As a non- to low polarity solvent, dielectric constant (8, 20℃
) is 2.5 or less, and a typical example is hexane (dielectric constant (8, 20° C.) 1.85). On the other hand, polar solvents such as acetone have low solubility in fats and oils, making it impossible to obtain highly concentrated diluted solutions and resulting in inefficient work.

また、半透膜としては市販の耐溶媒性半透膜、例えばダ
イセル＠製の０１１５−４０　（商品名、平均分画分子
量４００００、ポリエーテルスルホン系）、或いは日東
電工■製のＮＴＵ−４２０８（商品名、平均分画分子量
８０００　、ポリイミド重合体）又はＮＴＵ−４２２０
（同、平均分画分子量２００００）が例示でき、分画分
子量として５０００〜５ｏｏｏｏ好ましくはａｏｏｏｏ
〜５００００のものが適用できる。分画分子量が５００
０未満では透過流速が極端に遅く実用的でない。また、
分画分子量が５００００を越えると膜目に目づまりを起
こさせることができにくく、殆どのカリテン類が透過す
るので目的を達成し難い。本発明を実施するには原料シ
ア脂を非乃至低極性溶媒に油脂分として５〜５０％（重
量基準、以下同じ）となるように希釈するのがよい。油
脂分が５％未満であれば処理量が少なすぎて効率的でな
く、また５０％を越えるとミセラの粘度が高く経済的な
透過流速が得られず、同様に効率的でない。このような
希釈溶液を２０〜７０℃好ましくは３０〜６０℃に加温
し、１〜１０ｋｇ　／　ｃｔの加圧下に、１２１−１２
０１７ｃｄ／時間の流速で膜と接触させる。ここで初期
に透過する両分の一定量を力；ノドする必要があり、こ
の量は膜処理の条件によって一概に規定することはでき
ないが、カリテンの沃素価が油脂に比べて異常に高い（
２５０〜３５０）という点を利用して、膜透過画分の油
脂の沃素価を測定し、対称油（例えばアセトンで処理し
た油脂）の沃素価と比較することによって容易に決定す
ることができる。本発明者の実験によれば、上記の処理
条件において約５〜１０分程度透過する分の量をカント
すればよいようである。この操作を実施しないと膜透過
画分中にカリテン類が混入したままとなって、満足する
品質が得られない。即ち本発明は、膜透過初期段階にお
いて比較的低分子量のカリテン類が透過する程度の半透
膜を用い、予め一定量の溶媒希釈溶液を透過させること
によって、膜目に目づまりを起こさせた後、目的とする
膜透過処理を実施する方法である。なお、初期段階にお
いてカントし−た膜透過溶液は再び元の希釈溶液に戻す
のが有利である。本発明を実施するに際して、少量を処
理する場合は平膜を用いればよいが、大量を連続処理す
る場合にはモジュール膜を用いてもよい。この場合、希
釈溶液の濃度が高くなって処理し難いようであるならば
、新たに溶媒を追加して濃度を調整する。In addition, as a semipermeable membrane, commercially available solvent-resistant semipermeable membranes such as 0115-40 (trade name, average molecular weight cut off 40,000, polyether sulfone type) manufactured by Daicel@, or NTU-4208 (trade name, manufactured by Nitto Denko ■) Product name, average molecular weight cut off: 8000, polyimide polymer) or NTU-4220
(same, average molecular weight cut off 20000), and the cut off molecular weight is 5000 to 5oooo, preferably aooooo
~50,000 are applicable. Molecular weight cut off is 500
If it is less than 0, the permeation flow rate is extremely slow and is not practical. Also,
When the molecular weight cutoff exceeds 50,000, it is difficult to cause the membrane to become clogged, and most of the caritenes permeate, making it difficult to achieve the objective. In order to carry out the present invention, raw shea butter is preferably diluted in a non- to low polar solvent so that the fat content becomes 5 to 50% (by weight, the same applies hereinafter). If the fat content is less than 5%, the amount of treatment is too small and is not efficient, and if it exceeds 50%, the micellar viscosity is high and an economical permeation flow rate cannot be obtained, which is also not efficient. Such a diluted solution is heated to 20-70°C, preferably 30-60°C, and under a pressure of 1-10 kg/ct, 121-12
Contact the membrane at a flow rate of 0.017 cd/hr. At this point, it is necessary to remove a certain amount of both components that initially permeate, and although this amount cannot be determined unconditionally depending on the membrane treatment conditions, the iodine value of caritene is abnormally high compared to fats and oils (
250 to 350), the iodine value of the oil or fat in the membrane-permeable fraction can be easily determined by measuring the iodine value and comparing it with the iodine value of a symmetrical oil (for example, acetone-treated oil or fat). According to experiments conducted by the present inventors, it appears that it is sufficient to cant the amount that permeates for approximately 5 to 10 minutes under the above processing conditions. If this operation is not carried out, caritenes remain mixed in the membrane-permeable fraction, making it impossible to obtain a satisfactory quality. That is, the present invention uses a semi-permeable membrane that allows relatively low-molecular-weight caritenes to pass through in the initial stage of membrane permeation, and then allows a certain amount of a diluted solvent solution to pass through the membrane in advance to cause clogging of the membrane. This is a method for carrying out the desired membrane permeation treatment. Note that it is advantageous to return the membrane-permeable solution that was canted in the initial stage to the original diluted solution. When carrying out the present invention, a flat membrane may be used when a small amount is to be treated, but a module membrane may be used when a large amount is to be continuously treated. In this case, if the concentration of the diluted solution becomes too high to be processed, a new solvent is added to adjust the concentration.

本発明により、従来シア脂中に含まれるカリテン類を極
性溶媒で分画処理して除去した後、非乃至低極性溶媒を
用いてハードバター画分を分画処理していたのに対し、
全て初めから非乃至低極性溶媒の使用に一本化でき、且
つ特定の処理膜を単独で使用するのみで目的が達成でき
るので、作業性が著しく改善されるという効果を有する
。According to the present invention, whereas conventionally the caritene contained in shea butter was removed by fractionation treatment with a polar solvent, the hard butter fraction was fractionated using a non- to low polar solvent.
Since all processes can be integrated into the use of non- to low polarity solvents from the beginning and the purpose can be achieved only by using a specific treatment membrane alone, it has the effect of significantly improving workability.

以下に実施例を例示するが、本発明の精神はこれに限定
されるものではない。Examples are illustrated below, but the spirit of the invention is not limited thereto.

実施例１ 沃素価６２．７　、鹸化価１７６．７、酸１ｊ６１．８
４のシア脂脱酸油をＮ−ヘキサンに混合し、油脂分が２
０％である希釈溶液を得た。この溶液を４０℃に加温し
、分画分子量が４００００の膜（ダイセル−製ＤＵＳ−
４０）を用いて５ｋｇ／ａａの加圧下に７５．６６／ｎ
ｆ／時間の流速にて接触させ、１０分間の初期膜透過画
分を元の希釈溶液に戻した後、あとはそのまま膜処理を
続行して透過画分及び不透過画分を脱溶剤し、以下の性
状を有した両分を得た。Example 1 Iodine number 62.7, saponification number 176.7, acid 1j61.8
The shea fat deoxidized oil from step 4 is mixed with N-hexane, and the fat content is 2.
A diluted solution was obtained which was 0%. This solution was heated to 40°C, and a membrane with a molecular weight cutoff of 40,000 (DUS-manufactured by Daicel) was
75.66/n under a pressure of 5 kg/aa using
After contacting at a flow rate of f/hour and returning the initial membrane-permeable fraction for 10 minutes to the original diluted solution, the membrane treatment is continued as it is to remove the solvent of the permeable fraction and non-permeable fraction, Both fractions were obtained with the following properties.

透過画分　不透過画分 収率（％）　９５．２　４．８ 沃素価　５４．２　２８０．０ 鹸化価　１８１．８　− 酸価　２．４１　一 対称として、同じ原料シア脂１０％のアセトン溶液を４
５℃に加温し不熔解物を濾別し脱溶剤して、以下の性状
の両分を得た。Permeable fraction Impermeable fraction yield (%) 95.2 4.8 Iodine value 54.2 280.0 Saponification value 181.8 - Acid value 2.41 As a symmetry, an acetone solution of 10% of the same raw material shea butter 4
The mixture was heated to 5° C., undissolved matter was filtered off, and the solvent was removed to obtain both components with the following properties.

濾液側　不溶解物 収率（％）　９５．７　４．３ 沃素価　５４．０　３１１．８ 鹸化価　１８１．５　− 酸価　１．９− 以上の結果より、本発明法によって得たシア脂の膜透過
画分中にはカリテンが従来の方法と同程度除去されてい
ることがわかる。Filtrate side Insoluble matter yield (%) 95.7 4.3 Iodine value 54.0 311.8 Saponification value 181.5 - Acid value 1.9 - From the above results, the shea butter obtained by the method of the present invention It can be seen that caritene was removed from the membrane-permeable fraction to the same extent as in the conventional method.

実施例２ 沃素価６１．６　、鹸化価１７７．４、酸価１．６９の
シア脂脱酸油をＮ−ヘキサンに混合し、油脂分が１０％
である希釈溶液を調整した。この溶液を４０℃に加温し
、分画分子量がａｏｏｏの膜（日東電工■ｆ！！ＮＴＵ
−４２０８）を用いて５　ｋｇ　／　ａｄの圧力下に１
５．６１１／　ｏｒ／時間の流速にて接触させ、１０分
間の初期膜透過画分をカットした後、膜処理を続行して
透過画分及び不透過画分を得、脱溶剤して以下の性状を
有する両分を得た。Example 2 Shea fat deoxidized oil with an iodine value of 61.6, a saponification value of 177.4, and an acid value of 1.69 was mixed with N-hexane, and the fat content was 10%.
A diluted solution was prepared. This solution was heated to 40°C, and a membrane with a molecular weight cut-off of aooo (Nitto Denko f!!NTU)
-4208) under a pressure of 5 kg/ad.
After contacting at a flow rate of 5.611/or/hour and cutting the initial membrane permeation fraction for 10 minutes, membrane treatment was continued to obtain a permeation fraction and a non-permeation fraction, and the solvent was removed and the following Both parts with properties were obtained.

透過画分　不透過画分 収率（％）　９５．５　４．５ 沃素価　５３．５　２９５．２ 鹸化価　１７９．７　− 酸価　２．４１　− なお、比較のため初期膜透過画分をカットせずに実施し
たものは以下のとおりであった。Permeated fraction Impermeable fraction yield (%) 95.5 4.5 Iodine value 53.5 295.2 Saponification value 179.7 - Acid value 2.41 - For comparison, the initial membrane permeation fraction was cut The following were carried out without this.

透過画分　不透過画分 収率（％）　９６．０　４．０ 沃素価　５５．７　３０４．１ 鹸化価　１７８．５　− 酸価　２．３０　一 対称として同原料シア脂を実施例１と同様に１０％アセ
トン溶液とし、４５℃に加温した後不溶解物を濾別し脱
溶剤して、以下の性状の画分を得た。Permeable fraction Impermeable fraction yield (%) 96.0 4.0 Iodine value 55.7 304.1 Saponification value 178.5 - Acid value 2.30 As one symmetry, the same raw material shea butter was used as in Example 1. The mixture was made into a 10% acetone solution, heated to 45°C, and undissolved matter was filtered off and the solvent was removed to obtain a fraction with the following properties.

濾液側　不溶解物 収率（％）９５．８　４．２ 沃素価　５３．８　３１４．０ 鹸化（ｉｌｉ　１８０．０　− 酸価　１．８２　− 以上の結果より、本発明法によって得たシア脂の膜透過
画分中には、カリテン類が従来の方法と同程度除去され
ていることが明らかである。Filtrate side Insoluble matter yield (%) 95.8 4.2 Iodine value 53.8 314.0 Saponification (ili 180.0 - Acid value 1.82 - From the above results, the shea butter obtained by the method of the present invention It is clear that caritenes are removed from the membrane-permeable fraction to the same extent as in the conventional method.

特許出願人　不二製油株式会社 代理人　弁理士　門　脇　清Patent applicant: Fuji Oil Co., Ltd. Agent: Patent Attorney Kiyoshi Kadowaki

Claims (5)

【特許請求の範囲】[Claims] （１）、シア脂中に含まれるカリテン類を除去するに際
して、非乃至低極性溶媒で希釈した生成溶液を、加圧下
に予め該溶液を接触させてカリテン類が殆ど透過しなく
なるまで目づまりを起こさせた半透膜と接触させ、Ｉｆ
！透過画分と不透過画分とに分離し、この膜透過画分を
脱溶剤して精製物を回収することを特徴とするシア脂の
カリテン類除去法。(1) When removing caritenes contained in shea butter, the resulting solution diluted with a non- to low polarity solvent is brought into contact with the solution under pressure to cause clogging until almost no caritene permeates through. If
! A method for removing caritenes from shea butter, which comprises separating into a permeable fraction and an impermeable fraction, and recovering a purified product by removing solvent from the membrane permeable fraction. （２）、非乃至低極性溶媒かヘキ号ンである特許請求の
範囲第（１１項に記載の方法。(2) The method according to claim 11, wherein a non- to low polarity solvent is used. （３）、希釈した生成溶液の油脂濃度が５〜５０％（重
量基準）である特許請求の範囲第（１）項又は第（２）
項に記載の方法(3) Claim (1) or (2), wherein the oil and fat concentration of the diluted product solution is 5 to 50% (by weight)
The method described in section （４）、半透膜の分画分子量が５０００〜５００００好
ましくは３００００〜５００００である特許請求の範囲
第（１）項乃至第（３）項の何れかに記載の方法。(4) The method according to any one of claims (1) to (3), wherein the semipermeable membrane has a molecular weight cutoff of 5,000 to 50,000, preferably 30,000 to 50,000. （５）、予め目づまりを起こさせるまで接触させた初期
の膜透過画分を原希釈溶液に戻す特許請求の範囲第（１
）項乃至第（４）項の何れかに記載の方法。(5) The initial membrane-permeable fraction, which has been brought into contact with each other until clogging is caused, is returned to the original diluted solution (claim 1).
) to (4).