JPH0132880B2 - - Google Patents
Info
- Publication number
- JPH0132880B2 JPH0132880B2 JP16128681A JP16128681A JPH0132880B2 JP H0132880 B2 JPH0132880 B2 JP H0132880B2 JP 16128681 A JP16128681 A JP 16128681A JP 16128681 A JP16128681 A JP 16128681A JP H0132880 B2 JPH0132880 B2 JP H0132880B2
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- urea
- adduct
- fatty acids
- impurities
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 88
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 79
- 229930195729 fatty acid Natural products 0.000 claims description 79
- 239000000194 fatty acid Substances 0.000 claims description 79
- 150000004665 fatty acids Chemical class 0.000 claims description 79
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 44
- 239000004202 carbamide Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 description 37
- 239000012535 impurity Substances 0.000 description 26
- 239000004094 surface-active agent Substances 0.000 description 15
- 238000006386 neutralization reaction Methods 0.000 description 14
- 238000007127 saponification reaction Methods 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 12
- 238000004821 distillation Methods 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 241001550224 Apha Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 2
- -1 polyoxyethylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- 241000195955 Equisetum hyemale Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
【発明の詳細な説明】
この発明は脂肪酸の精製法、さらに詳しくは油
脂の加水分解によつて得られる粗脂肪酸あるいは
この脂肪酸を分別して得られる固体酸ないし液体
酸からなる粗脂肪酸を精製して色相良好にしてか
つ高純度の脂肪酸を得る方法に関する。DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for refining fatty acids, and more specifically, to refining crude fatty acids obtained by hydrolyzing fats and oils, or solid acids or liquid acids obtained by fractionating these fatty acids. This invention relates to a method for obtaining highly purified fatty acids with good hue.
粗脂肪酸中に含まれる不純物の主なものは、
未分解のグリセリド(主としてジおよびモノグリ
セリド)、含酸素化合物(酸化生成物で水酸基
やカルボニル基を含有する)、たん白質に由来
する窒素や硫黄化合物、りん脂質に由来するり
ん化合物である。 The main impurities contained in crude fatty acids are:
They are undecomposed glycerides (mainly di- and monoglycerides), oxygenated compounds (oxidation products containing hydroxyl and carbonyl groups), nitrogen and sulfur compounds derived from proteins, and phosphorus compounds derived from phospholipids.
従来よりかかる粗脂肪酸を精製する方法として
一般的に採用されてきた蒸留法は、脂肪酸との沸
点差によつて前記不純物を除去するもので、これ
によれば色相良好でかつ比較的高純度の脂肪酸を
得ることができる。しかるに、近年蒸留操作に要
するエネルギー費の上昇に伴なつてコスト的な面
での改良が望まれ、また蒸留時脂肪酸の熱変性に
よる劣化という問題があることからこの解決も望
まれている。 The distillation method that has been commonly used to purify such crude fatty acids removes impurities based on the difference in boiling point with the fatty acids, and this method produces products with good color and relatively high purity. Fatty acids can be obtained. However, as the energy costs required for distillation operations have increased in recent years, improvements in terms of cost have been desired, and since there has been a problem of deterioration of fatty acids due to thermal denaturation during distillation, a solution to this problem is also desired.
古くから蒸留法に代わる脂肪酸の精製法が検討
され多々提案されてきた。しかし、単一手段によ
つて蒸留法と同等の精製効果が得られる方法は今
のところ見い出されておらず、また工業的実用性
に欠けるものがほとんどであつた。たとえば、粗
脂肪酸を硅酸ゲルや活性白土などの固体吸着剤に
接触させてこの吸着剤に不純物を吸着させて取り
除く方法がある。この方法は脂肪酸と不純物との
極性の差を利用して極性の大なる不純物を固体吸
着剤で吸着除去するものであるが、吸着処理に当
たつて大量の有機溶剤が必要とされ、その留去に
多大な熱エネルギーを消費し、また溶剤取り扱い
上の危険性を伴なうなど工業的実用性に著るしく
欠けるものであつた。 For a long time, methods for refining fatty acids as an alternative to distillation have been studied and many proposals have been made. However, no method has so far been found that achieves the same purification effect as the distillation method using a single method, and most of the methods lack industrial practicality. For example, there is a method in which crude fatty acids are brought into contact with a solid adsorbent such as silicic acid gel or activated clay, and impurities are adsorbed and removed by this adsorbent. This method utilizes the difference in polarity between fatty acids and impurities to adsorb and remove highly polar impurities with a solid adsorbent, but a large amount of organic solvent is required for the adsorption process, and the However, it consumes a large amount of thermal energy and is dangerous in handling the solvent, so it is extremely impractical for industrial use.
すなわち、一般に、珪酸ゲル、活性白土、モレ
キユラーシーブ、イオン交換樹脂などの固体吸着
剤で不純物を除去する場合、その除去効果は吸着
される分子の移動速度に大きく左右され、この移
動速度が大きくなければ充分な除去効果は得られ
ない。移動速度は系の粘度に関係し、たとえば吸
着処理温度で約1〜2センチポアズ以下の相当低
い粘度とされたときに除去効果を高めうるに充分
な移動速度が得られる。 In other words, in general, when removing impurities using solid adsorbents such as silicic acid gel, activated clay, molecular sieves, and ion exchange resins, the removal effect greatly depends on the movement speed of the adsorbed molecules. If it is not large, a sufficient removal effect cannot be obtained. The rate of migration is related to the viscosity of the system; for example, a fairly low viscosity of less than about 1-2 centipoise at the adsorption treatment temperature will provide sufficient migration rate to enhance the removal effect.
一方、粗脂肪酸は常温(25℃)で通常固体もし
くは10〜30センチポアズ付近の液体であるため、
これに含まれる不純物の移動速度を大にして吸着
除去効果を上げるためには、100℃以上に加熱す
るかあるいは有機溶剤を用いて溶解もしくは希釈
し系の粘度を前述の程度まで低下させなければな
らない。ところが、前者の加熱方式によると、固
体吸着剤に対する被吸着物たる不純物の脱着現象
を引きおこしやすく、また吸着剤の接触反応によ
つて脂肪酸が変質するなどの支障をきたすから、
この方法を採用することは適当でない。結局、後
者の有機溶剤の希釈方式を採用せざるをえず、こ
の場合かなり大量の有機溶剤が必要となり、前記
問題が生じてくる。 On the other hand, crude fatty acids are usually solid or liquid at around 10 to 30 centipoise at room temperature (25°C), so
In order to increase the transfer rate of the impurities contained in this and increase the adsorption removal effect, it is necessary to reduce the viscosity of the system to the above-mentioned level by heating it to 100°C or higher or by dissolving or diluting it with an organic solvent. It won't happen. However, the former heating method tends to cause desorption of impurities, which are adsorbed substances, from the solid adsorbent, and also causes problems such as deterioration of fatty acids due to catalytic reactions of the adsorbent.
It is not appropriate to adopt this method. In the end, the latter method of diluting the organic solvent has to be adopted, and in this case a considerably large amount of organic solvent is required, giving rise to the above-mentioned problem.
しかも、この発明者らの知見によれば、かかる
有機溶剤希釈方式をとつたとしても高純度の脂肪
酸を得ることは困難であつた。たとえば、粗脂肪
酸をn−ヘキサンで10倍に希釈したのち硅酸ゲル
カラムを通してみたところ、極性の非常に高い不
純物は吸着除去されるが、未分解のグリセリドの
如き極性の低い不純物はそのまま残留する。ため
に得られる精製脂肪酸の色相は比較的良好となる
ものの、(中和価/けん化価)×100(%)で表わさ
れる脂肪酸の純度は99.0%以下となり、蒸留法に
匹敵しうるような精製脂肪酸を得るには至らなか
つた。 Moreover, according to the findings of the inventors, it was difficult to obtain highly pure fatty acids even if such an organic solvent dilution method was used. For example, when crude fatty acids are diluted 10 times with n-hexane and passed through a silicic acid gel column, highly polar impurities are adsorbed and removed, but less polar impurities such as undecomposed glycerides remain. Although the color of the purified fatty acids obtained is relatively good, the purity of the fatty acids expressed as (neutralization value / saponification value) × 100 (%) is less than 99.0%, and the purification process is comparable to that of distillation. It was not possible to obtain fatty acids.
この発明は、上記の観点から、固体吸着剤によ
る精製法に不可欠とされるような有機溶剤を全く
使用することなく、他の単一手段で蒸留法と同等
ないしそれ以上の精製効果を得ることができ、そ
のうえ蒸留法の如き熱エネルギーや熱劣化の問題
を生じない工業的有用な脂肪酸の精製法を提供す
ることを目的とする。 From the above point of view, the present invention aims to obtain a purification effect equivalent to or better than that of a distillation method using another single method, without using any organic solvents, which are indispensable for purification methods using solid adsorbents. The object of the present invention is to provide an industrially useful method for refining fatty acids that does not cause the problems of thermal energy and thermal deterioration that occur in distillation methods.
すなわち、この発明は、(a)陰イオン性界面活性
剤またはHLB10以上の非イオン性界面活性剤を
含ませた尿素またはチオ尿素の水溶液に粗脂肪酸
を加えて脂肪酸の尿素付加体またはチオ尿素付加
体を生成する工程と、(b)上記の付加体を別した
のち陰イオン性界面活性剤またはHLB10以上の
非イオン性界面活性剤を含ませた尿素またはチオ
尿素の飽和水溶液で洗浄する工程と、(c)洗浄され
た上記の付加体を分解して脂肪酸を再生する工程
とを含むことを特徴とする脂肪酸の精製法に係る
ものである。 That is, the present invention provides (a) adding a crude fatty acid to an aqueous solution of urea or thiourea containing an anionic surfactant or a nonionic surfactant with an HLB of 10 or more to form a urea adduct or thiourea adduct of a fatty acid. (b) After separating the adduct, washing with a saturated aqueous solution of urea or thiourea containing an anionic surfactant or a nonionic surfactant with an HLB of 10 or more; and (c) a step of decomposing the washed adduct to regenerate the fatty acid.
このように、この発明においては、脂肪酸と尿
素ないしチオ尿素とが付加体を生成する性質を利
用し、粗脂肪酸から付加体を生成したのち別す
ることにより付加体生成に関与しない不純物を取
り除き、別された付加体を分解して脂肪酸を再
生するという方式を採用したものであり、これに
よれば蒸留法の如き熱エネルギーや熱劣化の問題
を回避でき、付加体生成という単一手段で高度の
精製効果を得ることが可能となる。また、上記付
加体の生成を尿素ないしチオ尿素の水溶液中で行
なわせるようにしているから、前記固体吸着剤に
よる精製に不可避とされていた有機溶剤に起因し
た問題も生じない。 In this way, the present invention takes advantage of the property of fatty acids and urea or thiourea to form adducts, generates adducts from crude fatty acids, and then separates them to remove impurities that do not participate in adduct formation. This method uses a method of decomposing separated adducts to regenerate fatty acids. This method avoids the problems of thermal energy and thermal deterioration that occur in distillation methods, and allows highly advanced production by a single method of adduct generation. It becomes possible to obtain the purification effect of Furthermore, since the adduct is produced in an aqueous solution of urea or thiourea, problems caused by organic solvents, which are considered inevitable in purification using the solid adsorbent, do not occur.
ところで、脂肪酸と尿素ないしチオ尿素との付
加体の生成を利用した脂肪酸の精製法はすでに公
知である。この方法は粗脂肪酸と尿素ないしチオ
尿素とを有機溶剤に加熱溶解したのち冷却し、こ
の冷却で析出生成する付加体を有機溶剤溶液から
別し、分解再生するものである。明らかなよう
に、かかる方法は有機溶剤を大量に使用するもの
であるため、固体吸着剤を使用する場合と同様の
問題がある。 Incidentally, a method for purifying fatty acids that utilizes the production of adducts between fatty acids and urea or thiourea is already known. In this method, crude fatty acids and urea or thiourea are heated and dissolved in an organic solvent and then cooled, and the adducts that precipitate out during this cooling are separated from the organic solvent solution and decomposed and regenerated. As is clear, such methods involve the use of large amounts of organic solvents and therefore suffer from the same problems as when using solid adsorbents.
これに対し、この発明では、脂肪酸と尿素ない
しチオ尿素との付加体を水中で生成させるもので
あり、この点において上記公知の方法とは本質的
な差異を有している。一方、かかる水中での生成
は、生成した付加体と不純物との分離に難点を有
している。すなわち、有機溶剤系では不純物が有
機溶剤に溶解するから、析出生成した付加体と上
記不純物との分離は容易である。しかし、水系で
は脂肪酸および不純物が共に水中で分散された状
態にあり、かかる状態下で付加体を生成するもの
であるため、この付加体と不純物との分離は容易
でなく、一般に付加体中に不純物が混入してくる
のをさけられない。 On the other hand, in this invention, an adduct of fatty acid and urea or thiourea is produced in water, and in this point, there is an essential difference from the above-mentioned known method. On the other hand, such production in water has difficulties in separating the produced adduct and impurities. That is, in an organic solvent system, since impurities are dissolved in the organic solvent, it is easy to separate the precipitated adduct from the impurities. However, in aqueous systems, fatty acids and impurities are both dispersed in water, and adducts are formed under such conditions. Therefore, it is not easy to separate these adducts from impurities; Impurities cannot be avoided.
この発明者らは、上記の問題を尿素またはチオ
尿素の水溶液中に界面活性剤を加えることにより
解決できることを見い出した。すなわち、界面活
性剤によつて粗脂肪酸を充分に乳化分散させた状
態で付加体を生成すると、この付加体と不純物と
のからまりあいが可及的に阻止される。また、こ
のように不純物の混入を抑止して水中から別し
た付加体を、さらに上記同様の界面活性剤を含む
尿素またはチオ尿素の飽和溶液で洗浄することに
より、付加体表面に付着する不純物をほぼ取り除
くことができ、これによつて不純物の分離が実質
的に可能となることが見い出された。 The inventors have discovered that the above problem can be solved by adding a surfactant to an aqueous solution of urea or thiourea. That is, if an adduct is produced with the crude fatty acid sufficiently emulsified and dispersed by a surfactant, entanglement between the adduct and impurities can be prevented as much as possible. In addition, by washing the adduct separated from water with impurities inhibited in this way with a saturated solution of urea or thiourea containing the same surfactant as above, impurities adhering to the surface of the adduct can be removed. It has been found that substantially all of the impurities can be removed, thereby making it possible to substantially separate the impurities.
すなわち、上記方法で不純物を除去した付加体
から分離再生される脂肪酸は、その特性面で蒸留
法で得られるものと全く遜色がなく、色相良好に
してかつ99.0重量%以上の高純度品であり、精製
脂肪酸として工業的有利に利用することができ
る。 In other words, the fatty acids separated and regenerated from the adducts from which impurities have been removed by the above method are completely comparable in properties to those obtained by distillation, have good color, and are highly pure products with a purity of 99.0% by weight or more. , can be advantageously used industrially as a purified fatty acid.
この発明におけるa工程では、まず、界面活性
剤を含ませた尿素またはチオ尿素の水溶液を調製
する。この水溶液は所定温度たとえば50〜80℃程
度に加温されるが、この温度で溶解しうるだけの
尿素またはチオ尿素が添加される。一般には30〜
80重量%程度である。また、これに含ませる界面
活性剤としては、粗脂肪酸に対する反応性を有し
ないものであればよく、通常はHLB10以上の非
イオン性界面活性剤や硫酸塩もしくはスルホン酸
塩型の陰イオン性界面活性剤が好ましく用いられ
る。界面活性剤の含有量は、通常0.2〜5重量%、
好適には0.5〜2.0重量%である。 In step a in this invention, first, an aqueous solution of urea or thiourea containing a surfactant is prepared. This aqueous solution is heated to a predetermined temperature, for example, about 50 to 80°C, and as much urea or thiourea as can be dissolved at this temperature is added. Generally 30~
It is about 80% by weight. In addition, the surfactant to be included may be one that does not have reactivity with crude fatty acids, and is usually a nonionic surfactant with an HLB of 10 or higher, or an anionic surfactant of the sulfate or sulfonate type. Activators are preferably used. The content of surfactant is usually 0.2 to 5% by weight,
It is preferably 0.5 to 2.0% by weight.
上記の加温された水溶液に、好ましくは同温度
ないしそれに近い温度に加温された粗脂肪酸を加
えて撹拌混合する。粗脂肪酸の添加量は、水溶液
に対し通常5〜20重量%、好ましくは8〜10重量
%である。添加後、撹拌を続けながら所定温度ま
で徐々に冷却すると、尿素またはチオ尿素が飽和
溶解度に達して析出してくると同時に水中に分散
された脂肪酸との付加体を生成し、スラリー化す
る。このとき、水中に含ませた界面活性剤が付加
体中への不純物の混入を効果的に抑止する。 The crude fatty acid, preferably heated to the same temperature or close to it, is added to the above-mentioned heated aqueous solution and mixed with stirring. The amount of crude fatty acid added is usually 5 to 20% by weight, preferably 8 to 10% by weight based on the aqueous solution. After the addition, when the mixture is gradually cooled to a predetermined temperature while stirring, urea or thiourea reaches a saturated solubility and precipitates, at the same time forming an adduct with the fatty acid dispersed in water to form a slurry. At this time, the surfactant contained in the water effectively prevents impurities from being mixed into the adduct.
この発明のb工程では、上記生成した付加体を
別したのち、界面活性剤を含ませた尿素または
チオ尿素の飽和水溶液によつて洗浄する。この洗
浄は必要に応じて数回繰り返され、付加体表面に
付着する不純物を取り除く。界面活性剤の使用は
上記不純物の除去に不可欠であり、これを用いな
ければ洗浄の効果は得られない。界面活性剤の種
類、含有量は、前記a工程の場合と同様である。
なお、このb工程で用いる洗浄液を尿素またはチ
オ尿素の飽和水溶液としたのは、付加体の破壊を
防ぐためである。 In step b of the present invention, the adduct produced above is separated and then washed with a saturated aqueous solution of urea or thiourea containing a surfactant. This washing is repeated several times as necessary to remove impurities adhering to the surface of the adduct. The use of a surfactant is essential for removing the above-mentioned impurities, and without its use no cleaning effect can be obtained. The type and content of the surfactant are the same as in step a above.
Note that the reason why the washing liquid used in step b is a saturated aqueous solution of urea or thiourea is to prevent destruction of the adduct.
つぎに、c工程において、上述の如く洗浄され
た付加体を適宜の温度たとえば60℃程度の温度に
加温して分解し、脂肪酸を再生するとともに尿素
またはチオ尿素を分離する。再生分離された脂肪
酸を60〜80℃程度で湯洗し、脱水処理することに
より、目的とする色相良好でかつ高純度の精製脂
肪酸製品が得られる。 Next, in step c, the adduct washed as described above is decomposed by heating to an appropriate temperature, for example, about 60°C, to regenerate fatty acids and separate urea or thiourea. By washing the regenerated and separated fatty acids with hot water at about 60 to 80°C and dehydrating them, a purified fatty acid product with the desired color and high purity can be obtained.
つぎに、この発明の実施例を記載してより具体
的に説明する。なお、以下において部および%と
あるは重量部および重量%を意味するものであ
る。また、以下に記述する色相は、社団法人 日
本油化学協会により制定されたた基準油脂分析試
験法4.3.1.1(ガードナー法)および4.3.1.2(APHA
法)により測定した。 Next, examples of the present invention will be described in more detail. In the following, parts and % mean parts by weight and % by weight. In addition, the hues described below are based on standard oil and fat analysis test methods 4.3.1.1 (Gardner method) and 4.3.1.2 (APHA method) established by the Japan Oil Chemists' Association.
method).
実施例 1
中和価196.4、けん化価201.2、脂肪酸純度97.6
%、色相ガードナー11の牛脂加水分解粗脂肪酸
100部を60℃に加温し、同様に60℃に加温された
1%のドデシル硫酸ナトリウムを含有する尿素水
溶液(尿素61%含有)1000部中に撹拌しながら加
えた。加え終つてから、撹拌を続けながら25℃ま
で1.5時間を要して冷却した。この時点で系内は
脂肪酸の尿素付加体を含有するスラリー状となつ
た。Example 1 Neutralization value 196.4, saponification value 201.2, fatty acid purity 97.6
%, Hue Gardner 11 Beef Tallow Hydrolyzed Crude Fatty Acid
100 parts were heated to 60°C and added with stirring to 1000 parts of an aqueous urea solution (containing 61% urea) containing 1% sodium dodecyl sulfate, which had also been heated to 60°C. After the addition was completed, the mixture was cooled to 25° C. over 1.5 hours while stirring was continued. At this point, the inside of the system became a slurry containing urea adducts of fatty acids.
この尿素付加体を別したのち、1%のドデシ
ル硫酸ナトリウムを含有する25℃での尿素飽和水
溶液250部に入れ、25℃で30分間撹拌したのち
別した。この操作を再度繰り返し充分に洗浄し
た。つぎに、付加体を60℃に加温して脂肪酸を再
生し、尿素と分離したのち70℃で湯洗した。その
ご脱水処理して93.6部の精製脂肪酸を得た。この
脂肪酸は、中和価201.8、けん化価202.3、脂肪酸
純度99.8%、色相APHA140(ガードナー1)であ
つた。 After the urea adduct was separated, it was poured into 250 parts of a saturated aqueous solution of urea at 25°C containing 1% sodium dodecyl sulfate, stirred at 25°C for 30 minutes, and then separated. This operation was repeated again to thoroughly wash. Next, the adduct was heated to 60°C to regenerate fatty acids, separated from urea, and then washed with hot water at 70°C. The dehydration treatment yielded 93.6 parts of purified fatty acids. This fatty acid had a neutralization value of 201.8, a saponification value of 202.3, a fatty acid purity of 99.8%, and a hue of APHA 140 (Gardner 1).
なお、通常法で前記の粗脂肪酸を蒸留すると、
93.9部の精製脂肪酸が得られ、その特性は、中和
価202.2、けん化価203.0、脂肪酸純度99.6%、色
相APHA160であつた。 In addition, when the above crude fatty acid is distilled by the usual method,
93.9 parts of purified fatty acid was obtained, and its characteristics were a neutralization value of 202.2, a saponification value of 203.0, a fatty acid purity of 99.6%, and a hue of APHA 160.
参考例 1
付加体生成に際して用いた尿素水溶液にドデシ
ル硫酸ナトリウムを含有させなかつた以外は、実
施例1と同様にして脂肪酸を得た。この脂肪酸は
その色相がガードナー6であつた。これより、付
加体生成段階での界面活性剤の使用は、この発明
において不可欠なものであることが判る。Reference Example 1 A fatty acid was obtained in the same manner as in Example 1, except that sodium dodecyl sulfate was not contained in the urea aqueous solution used for adduct production. The hue of this fatty acid was Gardner 6. This shows that the use of a surfactant in the adduct formation step is essential in this invention.
実施例 2
中和価191.2、けん化価200.8、脂肪酸純度95.2
%、色相ガードナー18の牛脂加水分解粗脂肪酸を
固液分別して得た粗液体酸100部を55℃に加温し、
70℃に加温された1.5%のポリオキシエレン(20
モル付加)オクチルフエニルエーテル(HLB=
16)を含有する尿素水溶液(尿素65%含有)850
部中に、撹拌しながら加えた。以下、実施例1と
同様の操作にて、90.6部の精製液体酸を得た。た
だし、洗浄用の尿素飽和水溶液に含ませた界面活
性剤は1.5%のポリオキシエチレン(20モル付加)
オクチルフエニルエーテル(HLB=16)である。
この液体酸は、中和価202.0、けん化202.3、脂肪
酸純度99.9%、色相APHA200(ガードナー1〜
2)であつた。Example 2 Neutralization value 191.2, saponification value 200.8, fatty acid purity 95.2
%, Hue: 100 parts of crude liquid acid obtained by solid-liquid separation of beef tallow hydrolyzed crude fatty acid of Gardner 18 was heated to 55℃,
1.5% polyoxyethylene (20
molar addition) octyl phenyl ether (HLB=
16) Aqueous urea solution (containing 65% urea) 850
was added to the solution while stirring. Thereafter, in the same manner as in Example 1, 90.6 parts of purified liquid acid was obtained. However, the surfactant included in the urea saturated aqueous solution for cleaning is 1.5% polyoxyethylene (20 moles added).
It is octyl phenyl ether (HLB=16).
This liquid acid has a neutralization value of 202.0, a saponification value of 202.3, a fatty acid purity of 99.9%, and a hue of APHA 200 (Gardner 1 to
2) It was.
なお、通常法で前記の粗液体酸を蒸留すると、
90.8部の精製液体酸が得られ、その特性は、中和
価202.4、けん化価203.5、脂肪酸純度99.5%、色
相APHA250であつた。 In addition, when the above crude liquid acid is distilled by the usual method,
90.8 parts of purified liquid acid was obtained, and its properties were a neutralization value of 202.4, a saponification value of 203.5, a fatty acid purity of 99.5%, and a hue of APHA 250.
参考例
付加体を別したのちの界面活性剤を含む尿素
飽和水溶液による洗浄を行なわなかつた以外は、
実施例2と同様にして97.4部の脂肪酸を得た。こ
の脂肪酸は、中和価193.3、けん化価201.2、脂肪
酸純度96.1%、色相ガードナー12であつた。これ
より、付加体を生成したのち界面活性剤を含む尿
素飽和水溶液による洗浄は、この発明において不
可欠なものであることが判る。Reference example Except for not washing with a urea saturated aqueous solution containing a surfactant after separating the adduct,
97.4 parts of fatty acid were obtained in the same manner as in Example 2. This fatty acid had a neutralization value of 193.3, a saponification value of 201.2, a fatty acid purity of 96.1%, and a hue of Gardner 12. This shows that washing with a saturated aqueous urea solution containing a surfactant after producing the adduct is essential in the present invention.
実施例 3
中和価192.5、けん化価196.7、脂肪酸純度97.9
%、色相ガードナー8のハイオレイツクサフラワ
ー油加水分解粗脂肪酸100部を60℃に加温し、同
様に60℃に加温された0.5%のドデシルベンゼン
スルホン酸ナトリウムを含有する尿素水溶液(尿
素61%含有)900部中に、撹拌しながら加えた。
以下、実施例1と同様の操作にて、92.6部の精製
脂肪酸を得た。ただし、洗浄用の尿素飽和水溶液
に含ませた界面活性剤は0.5%のドデシルベンゼ
ンスルホン酸ナトリウムである。得られた精製脂
肪酸は、中和価193.1、けん化価194.9、脂肪酸純
度99.1%、色相APHA180(ガードナー1)であつ
た。Example 3 Neutralization value 192.5, saponification value 196.7, fatty acid purity 97.9
%, Hue Gardner 8, 100 parts of hydrolyzed crude fatty acids in high oleic horsetail flower oil were heated to 60°C, and a urea aqueous solution containing 0.5% sodium dodecylbenzenesulfonate (urea 61% (containing 61%) was added with stirring.
Thereafter, in the same manner as in Example 1, 92.6 parts of purified fatty acid was obtained. However, the surfactant included in the urea saturated aqueous solution for cleaning is 0.5% sodium dodecylbenzenesulfonate. The obtained purified fatty acid had a neutralization value of 193.1, a saponification value of 194.9, a fatty acid purity of 99.1%, and a hue of APHA 180 (Gardner 1).
なお、通常法で前記の粗脂肪酸を蒸留すると、
92.9部の精製脂肪酸が得られ、その特性は、中和
価193.9、けん化価195.3、脂肪酸純度99.3%、色
相APHA200であつた。 In addition, when the above crude fatty acid is distilled by the usual method,
92.9 parts of purified fatty acid was obtained, and its characteristics were a neutralization value of 193.9, a saponification value of 195.3, a fatty acid purity of 99.3%, and a hue of APHA 200.
実施例 4
中和価197.0、けん化価200.2、脂肪酸純度98.4
%、色相ガードナー10の豚脂加水分解粗脂肪酸
100部を60℃に加温し、同様に60℃に加温された
1%のドデシル硫酸ナトリウムを含有するチオ尿
素水溶液(チオ尿素35%含有)1000部中に、撹拌
しながら加えた。以下、実施例1と同様の操作に
て、93.2部の精製脂肪酸を得た。ただし、別さ
れた付加体の洗浄液としては、1%のドデシル硫
酸ナトリウムを含有する25℃でのチオ尿素飽和水
溶液を用いた。得られた精製脂肪酸は、中和価
201.1、けん化価201.9、脂肪酸純度99.6%、色相
APHA130(ガードナー1)であつた。Example 4 Neutralization value 197.0, saponification value 200.2, fatty acid purity 98.4
%, Hue Gardner 10 pork fat hydrolyzed crude fatty acids
100 parts were heated to 60°C and added with stirring to 1000 parts of a thiourea aqueous solution (containing 35% thiourea) containing 1% sodium dodecyl sulfate, which had also been heated to 60°C. Thereafter, in the same manner as in Example 1, 93.2 parts of purified fatty acid was obtained. However, as a washing solution for the separated adduct, a saturated aqueous solution of thiourea containing 1% sodium dodecyl sulfate at 25° C. was used. The obtained purified fatty acids have a neutralization value
201.1, saponification value 201.9, fatty acid purity 99.6%, hue
It was APHA130 (Gardner 1).
なお、通常法で前記の粗脂肪酸を蒸留すると、
93.8部の精製脂肪酸が得られ、その特性は、中和
価200.7、けん化価201.5、脂肪酸純度99.6%、色
相APHA130であつた。 In addition, when the above crude fatty acid is distilled by the usual method,
93.8 parts of purified fatty acid was obtained, and its characteristics were a neutralization value of 200.7, a saponification value of 201.5, a fatty acid purity of 99.6%, and a hue of APHA 130.
Claims (1)
上の非イオン性界面活性剤を含ませた尿素また
はチオ尿素の水溶液に粗脂肪酸を加えて脂肪酸
の尿素付加体またはチオ尿素付加体を生成する
工程と、 (b) 上記の付加体を別したのち陰イオン性界面
活性剤またはHLB10以上の非イオン性界面活
性剤を含ませた尿素またはチオ尿素の飽和水溶
液で洗浄する工程と、 (c) 洗浄された上記の付加体を分解して脂肪酸を
再生する工程 とを含むことを特徴とする脂肪酸の精製法。[Scope of Claims] 1 (a) A crude fatty acid is added to an aqueous solution of urea or thiourea containing an anionic surfactant or a nonionic surfactant with an HLB of 10 or more to produce a urea adduct of fatty acid or thiourea. (b) a step of separating the adduct and washing it with a saturated aqueous solution of urea or thiourea containing an anionic surfactant or a nonionic surfactant with an HLB of 10 or more; and (c) a step of decomposing the washed adduct to regenerate the fatty acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16128681A JPS5861192A (en) | 1981-10-09 | 1981-10-09 | Fatty acid purification |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16128681A JPS5861192A (en) | 1981-10-09 | 1981-10-09 | Fatty acid purification |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5861192A JPS5861192A (en) | 1983-04-12 |
JPH0132880B2 true JPH0132880B2 (en) | 1989-07-10 |
Family
ID=15732215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16128681A Granted JPS5861192A (en) | 1981-10-09 | 1981-10-09 | Fatty acid purification |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5861192A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT399716B (en) * | 1993-04-06 | 1995-07-25 | Wimmer Theodor | METHOD FOR THE FRACTIONATION OF FATTY ACID ESTER MIXTURES |
-
1981
- 1981-10-09 JP JP16128681A patent/JPS5861192A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5861192A (en) | 1983-04-12 |
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