JP3549123B2 - Method for producing edible fats and oils - Google Patents
Method for producing edible fats and oils Download PDFInfo
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- JP3549123B2 JP3549123B2 JP13101394A JP13101394A JP3549123B2 JP 3549123 B2 JP3549123 B2 JP 3549123B2 JP 13101394 A JP13101394 A JP 13101394A JP 13101394 A JP13101394 A JP 13101394A JP 3549123 B2 JP3549123 B2 JP 3549123B2
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- 239000003925 fat Substances 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000003921 oil Substances 0.000 title description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 32
- 238000005984 hydrogenation reaction Methods 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 239000008157 edible vegetable oil Substances 0.000 claims description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 16
- 239000011630 iodine Substances 0.000 claims description 16
- 229910052740 iodine Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 235000014593 oils and fats Nutrition 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 28
- 235000019197 fats Nutrition 0.000 description 27
- 238000000034 method Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000003549 soybean oil Substances 0.000 description 9
- 235000012424 soybean oil Nutrition 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
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- 150000004665 fatty acids Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000008173 hydrogenated soybean oil Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
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- 235000019485 Safflower oil Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 239000003240 coconut oil Substances 0.000 description 1
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- 235000005687 corn oil Nutrition 0.000 description 1
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- 235000012343 cottonseed oil Nutrition 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- Fats And Perfumes (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は食用油脂の水素添加方法に関し、更に詳しくは、白金触媒を用いて水素添加してトランス酸の少ない水素添加食用油脂を得る食用油脂の製造方法に関する。
【０００２】
【従来の技術】
油脂は、熱安定性を付与したり、マーガリンやショートニング用の油脂を得るため水素添加が行われる。水素添加により、油脂の構成脂肪酸の炭素・炭素間二重結合が水素化されるため、酸化が防止されて性状が安定化すると共に、マーガリンやショートニング等の原料油用としては形状保持性に優れ、最終製品の安定性が付与されるため、その後の貯蔵、取扱が容易となる。
上記油脂の工業的水素添加は、従来、ニッケル触媒を用い、油脂中にニッケル触媒を分散させ水素ガスを吹込む方法で行われている。この場合の水素添加反応条件としては、通常、温度１３０〜２５０℃、圧力１〜５ｋｇ／ｃｍ２ Ｇ、反応時間０．５〜２時間である。ニッケル触媒としては、ケイソウ土やアルミナ等の細孔構造を有する担体にニッケル金属粒子を担持したものが用いられ、触媒量は、通常、油脂に対して０．０５〜０．１重量％の比率で添加されている。水素添加に用いられ活性の低下した触媒は、従来、再生することなくそのまま廃棄されることが多い。
【０００３】
上記水素添加処理される油脂は、一般に、３個の脂肪酸がグリセリンに結合したトリグリセライドである。脂肪酸としては、ステアリン酸（Ｃ１８：０）に代表される飽和脂肪酸と、リノレン酸（Ｃ１８：３）、リノール酸（Ｃ１８：２）、オレイン酸（Ｃ１８：１）等の不飽和脂肪酸との双方が含有されている。これら脂肪酸の記載において、例えばオレイン酸の場合、（Ｃ１８：１）と付記しているのは、炭素数が１８であり二重結合が１の枝分かれしていない脂肪酸を意味するものである。
また、二重結合を有する不飽和脂肪酸には、シス型とトランス型の異性体が存在することはよく知られているが、天然油脂中には一般にシス型しか存在しない。
【０００４】
【発明が解決しようとする課題】
しかしながら、上記した従来法による油脂の水素添加においては、トランス−オレフィン結合を有する不飽和脂肪酸（以下、単にトランス酸という）の生成が避けられず、水素添加された生成油（硬化油）中に約３０〜５０％のトランス酸が含有されるのが通常である。
これらトランス酸は、前記のように天然油脂中には存在せず、栄養的及び生物学的にみて一般にあまり好まれない。このため、トランス酸を生成することなく油脂を水素添加する方法が提案されている。例えば、特開昭５９−２１５３９７号や特開平２−２６３９００号がある。
【０００５】
前者は、低細孔容積で、低表面積のα−アルミナ担体に周期律表第ＶＩＩＩ族の金属、主にニッケルまたはコバルトを担持したα−アルミナ担持触媒を用いるものであり、トリエンからジエンへの転化の向上を図ると共にトランス酸の減少を図るものである。この方法は、従来法と比較してトランス酸量の減少が認められるものの、十分満足できるものでない。
一方、後者は、水素貯蔵合金を用い、トランス酸を減少させて水素添加生成物を得るものであるが、水素貯蔵合金に一旦水素を吸蔵させる等の操作条件が複雑となり取扱も簡便でない。
本発明は、上記従来の食用油脂の水素添加の状況を鑑み、トランス酸の生成を極力抑制し、且つ、操作等が簡便であり、触媒等の取扱も容易な食用油脂の水素添加処理方法の提供を目的とする。更に、廃棄物処理等の環境問題が深刻化する現代において、できる限り廃棄物を排出しない食用油脂の水素添加方法の提供を目的とする。
【０００６】
【課題を解決するための手段】
本発明によれば、ヨウ素価が６２〜９０であって、且つトランス酸含量が１０重量％以下の水素添加食用油脂を得る食用油脂の製造方法であって、食用油脂を、白金触媒の存在下（但し、アンモニアで処理した白金、及びアンモニアの存在下を除く）、水素圧３０〜７０ｋｇ／ｃｍ2Ｇで水素添加処理することを特徴とする食用油脂の製造方法が提供される。本発明において、白金触媒として、比表面積１０ｍ2／ｇ以上で、且つ、細孔容積０．１ｍｌ／ｇ以上の担体に、白金を元素基準で０．１〜１０重量％担持した触媒を用いて食用油脂の水素添加を行うのが好ましい。また、本発明の白金触媒は、好ましくは再生して使用する。
【０００７】
【作用】
本発明は上記のように構成され、白金触媒を用いることにより容易にトランス酸の生成を抑制することができる。生成トランス酸は、従来法の約１／３〜１／５に低減され約１０重量％以下とすることができる。
また、従来法の安価なニッケル触媒に比し、白金は高価であるが再生処理して用いることができ、工業性を損なうことがない。また、廃棄物処理問題上も好ましい。
【０００８】
以下、本発明について更に詳細に説明する。
本発明において水素添加処理する食用油脂としては、大豆油、綿実油、サンフラワー油、サフラワー油、菜種油、コーン油、椰子油、パーム油等の植物油が挙げられる。
【０００９】
本発明の白金触媒は、白金の単体、硫化物、塩化物等の化合物のいずれでもよく、それらを、単に反応物に懸濁等させたものでもよいし、また担体に担持させて用いてもよく、非担持触媒または担持触媒のいずれでもよいが、好ましくは担持触媒が用いられる。
本発明の白金触媒は、反応系含有量または担持量として、白金元素基準で０．１〜１０．０重量％であり、好ましくは０．５〜５．０重量％である。含有量または担持量が０．１重量％未満であると十分な活性が得られず、一方１０．０重量％を超えて用いても、それ以上の顕著な活性は向上は望めず経済的でない。
担持触媒の担体としては、アルミナ、シリカアルミナ、活性炭、マグネシア等の通常のよく知られている触媒担体が使用できる。この場合、比表面積が１０ｍ２ ／ｇ以上で、細孔容積が０．１ｍｌ／ｇ以上のものが好ましく、更に好ましくは比表面積が５０ｍ２ ／ｇ以上で、細孔容積が０．２ｍｌ／ｇ以上のものである。特に、γ−アルミナを担体に用いるのが好ましい。
触媒成分の白金の上記担体への担持は、従来公知のいずれの方法でも行うことができる。例えば、白金化合物の溶液を用い噴霧、浸漬等により担体に担持することができる。また、白金金属単体の担持は、上記したように白金化合物を担持した後、還元して白金金属単体が担持された状態にすることができる。
また、担持触媒の形状は特に制限されるものでなく、ペレット状、粒状、球状、柱状等の押出物等のいずれの形状でもよい。水素添加処理条件に応じて適宜選択することができる。
【００１０】
本発明の水素添加処理条件は、通常の水素添加と同様に行えばよく、温度を常温〜３００℃、好ましくは５０〜２００℃、水素圧を好ましくは５〜１５０ｋｇ／ｃｍ２Ｇとして、接触時間０．０１〜５時間、好ましくは０．０５〜２．０時間で、水素と接触処理することができる。また、接触処理形式としては、固定床、懸濁床、移動床、膨張床等の各種反応床で処理することができ、また、回分式または流通式のいずれの方式でも処理することができる。流通方式の場合は、被処理物の食用油脂と水素ガスとの接触時間が上記範囲内になるように、被処理油脂のＬＨＳＶ（液空間速度）等を調節して、食用油脂と水素ガスとを触媒床に並流または向流で流通して処理することができる。回分方式の場合は、反応装置内に触媒を充填、懸濁等配設し、被処理食用油脂を張込んだ状態で、水素ガスを供給し流通させて行うことができ、懸濁床の場合は攪拌して水素添加処理することもできる。水素ガスは、上記の水素圧となるように供給するが、いずれの方式においても過剰に水素ガスを供給し、処理装置から排出される水素ガスは再循環して用いるのが好ましい。
【００１１】
本発明において、上記のように食用油脂を水素添加処理することにより得られる水素添加食用油脂は、水素添加により不飽和脂肪酸の二重結合の一部が水素化されて飽和となり、同時に一部トランス酸が生成される。例えば、食用油脂としてよく用いられる大豆油では、水素添加処理前のヨウ素価は通常１３０前後であり、水素添加処理大豆油としては５０〜９０前後のものが一般に用いられている。本発明において、このような大豆油を水素添加処理した場合、得られる水素添加大豆油は、ヨウ素価を約７５としてもトランス酸含量１０重量％以下とトランス酸が著しく減少される。
これに対し、従来の水素添加処理法でヨウ素価を約７５となるように水素添加した水素添加大豆油のトランス酸含量は、通常、約３０重量％であり、本発明の水素添加処理がトランス酸の生成が極めて抑制され、食用油脂の水素添加に好適である。
【００１２】
【実施例】
以下、本発明を実施例に基づき詳細に説明する。但し、本発明は下記実施例により制限されるものでない。
なお、下記実施例において、トランス酸量は社団法人日本油化学協会制定の基準油脂分析試験法２．４．２４．１−８１（差赤外スペクトル法）で、ヨウ素価は同法２．４．５．１−７１（ウィイス法）で、それぞれ測定した。また、比表面積は窒素を用いＢＥＴ法で測定した。
実施例１〜９
内容量７０ｃｃの固定床流通式反応器に、エヌ・イーケムキャット社製の比表面積２５０ｍ２ ／ｇ、細孔容積０．５６ｃｃ／ｇのγ−アルミナに白金を２重量％担持した触媒を約３０ｃｃ充填し、水素気流中、温度３００℃で２時間還元処理した後、表１に示した種々の処理条件下において、大豆油（トランス酸含量：０％、ヨウ素価：１３０）を流通し水素添加処理した。得られた生成油について、それぞれトランス酸量及びヨウ素価を測定した。その結果を表１に示した。
【００１３】
【表１】
実施例１０〜１２
実施例１で用いたものと同一の白金触媒を、水素圧力２０ｋｇ／ｃｍ２ Ｇ、温度２００℃で２時間水素還元処理した。
次いで、内容量２５０ｃｃのオートクレーブ中に大豆油（トランス酸含量：０％、ヨウ素価：１２６）約２００ｃｃを仕込み、上記で得られた還元処理触媒を約１．５ｇ添加し、撹拌しながら温度７０℃、水素圧力７０ｋｇ／ｃｍ２ Ｇで、表２に示した処理時間でそれぞれ水素添加処理した。得られた各生成油のトランス酸量及びヨウ素価を測定し、その結果を表２に示した。
【００１５】
【表２】
実施例１３〜１５
粒度１００メッシュ以下に調整した白金ブラックを触媒として約１ｇ用い、内容量２５０ｃｃのオートクレーブに大豆油（トランス酸含量：０％、ヨウ素価：１３３）約２００ｃｃを仕込み、攪拌しながら温度１００℃、水素圧３０ｋｇ／ｃｍ２ Ｇで表３に示した処理時間でそれぞれ水素添加処理した。
得られた各生成油のトランス酸量及びヨウ素価を測定し、その結果を表３に示した。
【００１７】
【表３】
実施例１６
実施例１で用いたものと同一の白金触媒を、実施例１と同様に固定床流通反応器に充填し、硫黄濃度１重量％に調整したジターシャリーブチルジサルファイドのｎ−ヘキサン溶液を用いて、温度３００℃、ＬＨＳＶ＝１．０／時、水素圧２０ｋｇ／ｃｍ２ Ｇの条件で硫化処理した。その後、引き続き、実施例１で用いたものと同じ大豆油を用いて温度２５０℃、水素圧７０ｋｇ／ｃｍ２ Ｇ、ＬＨＳＶ＝２／時の条件下で水素添加処理した。
得られた各生成油のトランス酸量は７％で、ヨウ素価は７８であった。
【００１９】
比較例１〜６
内容量２５０ｃｃのオートクレーブ中に実施例１で用いたものと同じ大豆油約２００ｃｃを仕込み、ケイソウ土にＮｉを約５重量％担持した触媒を約１ｇ添加し、表４に示した処理条件下で水素添加処理した。得られた各生成油のトランス酸量及びヨウ素価を測定し、その結果を表４に示した。
【００２０】
【表４】
上記実施例より、本発明の方法によれば、ヨウ素価が低下してもトランス酸含量は相対的に増加することがなく、ヨウ素価７０以下であってもトランス酸が１０重量％以下とその生成が抑制されていることが明らかである。また、従来より低温の１００℃以下の反応温度で水素添加でき、操作上簡便化されることが分かる。
一方、従来法と同様にニッケル担持触媒を用いた比較例においては、１００℃以下では水素添加することができず、また、トランス酸含量が１０重量％以下にならないことが分かる。
【００２２】
【発明の効果】
本発明の食用油脂の水素添加方法は、自然界に存在しないためその影響が問われつつあるトランス酸の生成を著しく抑制して、食用油脂を水素添加処理してトランス酸含量の少ない水素添加食用油脂を得ることができると共に、水素添加条件を緩和することができ、工業上極めて有用である。[0001]
[Industrial applications]
It relates hydrogenation process of the present invention is an edible oil or fat, further particularly, relates to the production how edible oils and fats to obtain a small hydrogenated edible fats of trans acid by hydrogenation using a platinum catalyst.
[0002]
[Prior art]
Fats and oils are subjected to hydrogenation to impart thermal stability and to obtain fats and oils for margarine and shortening. Hydrogenation hydrogenates the carbon-carbon double bonds of the constituent fatty acids of fats and oils, thereby preventing oxidation and stabilizing the properties, and has excellent shape retention properties for raw oils such as margarine and shortening. Since the stability of the final product is imparted, subsequent storage and handling become easier.
Conventionally, the industrial hydrogenation of the above-mentioned fats and oils is performed by using a nickel catalyst, dispersing the nickel catalyst in the fats and oils, and blowing hydrogen gas. The hydrogenation reaction conditions in this case are usually a temperature of 130 to 250 ° C., a pressure of 1 to 5 kg / cm 2 G, and a reaction time of 0.5 to 2 hours. As the nickel catalyst, a catalyst in which nickel metal particles are supported on a carrier having a pore structure such as diatomaceous earth or alumina is used, and the amount of the catalyst is usually 0.05 to 0.1% by weight with respect to fats and oils. It is added in. Conventionally, a catalyst with reduced activity used for hydrogenation is conventionally discarded without regeneration.
[0003]
The fats and oils subjected to the hydrogenation treatment are generally triglycerides in which three fatty acids are bonded to glycerin. As fatty acids, saturated fatty acids represented by stearic acid ( C18: 0 ) and unsaturated fatty acids such as linolenic acid ( C18: 3 ), linoleic acid ( C18: 2 ) and oleic acid ( C18: 1 ) Both fatty acids are included. In the description of these fatty acids, for example, in the case of oleic acid, the notation (C 18: 1 ) means an unbranched fatty acid having 18 carbon atoms and one double bond.
It is well known that cis- and trans-isomers exist in unsaturated fatty acids having a double bond, but generally only cis-form exists in natural fats and oils.
[0004]
[Problems to be solved by the invention]
However, in the hydrogenation of fats and oils according to the conventional method described above, the production of unsaturated fatty acids having a trans-olefin bond (hereinafter simply referred to as trans acid) is unavoidable, and the hydrogenated product oil (hardened oil) Typically, it contains about 30-50% trans acid.
As mentioned above, these trans acids are not present in natural fats and oils and are generally less preferred nutritionally and biologically. For this reason, a method of hydrogenating fats and oils without generating trans acid has been proposed. For example, there are JP-A-59-215397 and JP-A-2-263900.
[0005]
The former uses an α-alumina supported catalyst in which a metal of Group VIII of the periodic table, mainly nickel or cobalt is supported on an α-alumina support having a low pore volume and a low surface area, and a triene to a diene is used. It is intended to improve conversion and reduce trans acid. In this method, although the amount of trans acid is reduced as compared with the conventional method, it is not sufficiently satisfactory.
On the other hand, the latter uses a hydrogen storage alloy to obtain a hydrogenation product by reducing trans acid, but the operation conditions such as temporarily storing hydrogen in the hydrogen storage alloy are complicated, and handling is not easy.
The present invention, in view of the above-mentioned conventional hydrogenation of edible oils and fats, minimizes the production of trans acid, and is simple in operation and the like, and a method for hydrogenating edible oils and fats in which handling of catalysts and the like is easy. For the purpose of providing. Furthermore, in the present age when environmental problems such as waste disposal are becoming more serious, it is another object of the present invention to provide a method for hydrogenating edible oils and fats that does not discharge waste as much as possible.
[0006]
[Means for Solving the Problems]
According to the present invention, there is provided a Yo c iodine value 62-90, and a process for the preparation of edible fats and oils content of trans acids to obtain a 10% by weight of hydrogenated edible fats, edible oils and fats, of a platinum catalyst A method for producing an edible oil and fat is provided, which comprises subjecting to hydrogenation treatment in the presence (excluding the presence of platinum treated with ammonia and ammonia ) at a hydrogen pressure of 30 to 70 kg / cm 2 G. In the present invention, a platinum catalyst having a specific surface area of 10 m 2 / g or more and having a pore volume of 0.1 ml / g or more and having platinum supported on the carrier in an amount of 0.1 to 10% by weight on an elemental basis is used. Preferably, the edible fat is hydrogenated. Further, the platinum catalyst of the present invention is preferably used after being regenerated .
[0007]
[Action]
The present invention is configured as described above, and the production of trans acid can be easily suppressed by using a platinum catalyst. The generated trans acid can be reduced to about 1/3 to 1/5 of the conventional method to about 10% by weight or less.
Platinum is more expensive than conventional inexpensive nickel catalysts, but can be used after regenerating, and does not impair industrial properties. It is also preferable in terms of waste disposal.
[0008]
Hereinafter, the present invention will be described in more detail.
The edible oils and fats to be hydrogenated in the present invention include vegetable oils such as soybean oil, cottonseed oil, sunflower oil, safflower oil, rapeseed oil, corn oil, coconut oil, and palm oil.
[0009]
The platinum catalyst of the present invention may be any of compounds such as simple substance of platinum, sulfide, chloride and the like, and may be those simply suspended in a reaction product or used by being supported on a carrier. The catalyst may be either an unsupported catalyst or a supported catalyst, but preferably a supported catalyst is used.
The platinum catalyst of the present invention is used in an amount of 0.1 to 10.0% by weight, preferably 0.5 to 5.0% by weight, based on platinum element, as a reaction system content or a supported amount. If the content or the supported amount is less than 0.1% by weight, sufficient activity cannot be obtained. On the other hand, if it is used in excess of 10.0% by weight, further remarkable activity cannot be expected to be improved and it is not economical. .
As the carrier of the supported catalyst, a commonly known catalyst carrier such as alumina, silica alumina, activated carbon, and magnesia can be used. In this case, it is preferable that the specific surface area is 10 m 2 / g or more and the pore volume is 0.1 ml / g or more, more preferably the specific surface area is 50 m 2 / g or more and the pore volume is 0.2 ml / g. That's all. In particular, it is preferable to use γ-alumina for the carrier.
The loading of the catalyst component platinum on the carrier can be performed by any conventionally known method. For example, it can be carried on a carrier by spraying, dipping, or the like using a solution of a platinum compound. In addition, after loading the platinum compound as described above, the loading of the platinum metal simple substance can be reduced to a state where the platinum metal simple substance is supported.
The shape of the supported catalyst is not particularly limited, and may be any shape such as an extrudate such as a pellet, a granule, a sphere, and a column. It can be appropriately selected according to the hydrogenation treatment conditions.
[0010]
Hydrogenation treatment conditions of the present invention may be performed in the same manner as conventional hydrogenation, the temperature normal temperature to 300 ° C., preferably as 50 to 200 ° C., the good Mashiku hydrogen pressure 5~150kg / cm 2 G, The contact treatment with hydrogen can be performed for a contact time of 0.01 to 5 hours, preferably 0.05 to 2.0 hours. In addition, as a contact treatment type, treatment can be carried out in various reaction beds such as a fixed bed, a suspension bed, a moving bed, and an expansion bed, and treatment can be carried out in any of a batch system and a flow system. In the case of the circulation method, LHSV (liquid hourly space velocity) and the like of the oil and fat to be treated are adjusted so that the contact time between the edible oil and fat of the article and the hydrogen gas is within the above range, and the edible oil and hydrogen and the hydrogen gas are mixed. Can be treated by flowing through the catalyst bed in cocurrent or countercurrent. In the case of a batch system, the reaction can be carried out by supplying and flowing hydrogen gas in a state in which the edible fat or oil is filled with the catalyst filled in the reactor, suspended, etc. Can be subjected to a hydrogenation treatment with stirring. The hydrogen gas is supplied so as to have the above-mentioned hydrogen pressure. However, in any of the methods, it is preferable to supply an excessive amount of the hydrogen gas and recycle the hydrogen gas discharged from the processing apparatus.
[0011]
In the present invention, the hydrogenated edible oil / fat obtained by hydrogenating the edible oil / fat as described above is partially saturated with hydrogenation by partially hydrogenating unsaturated fatty acids by hydrogenation. An acid is produced. For example, in soybean oil often used as edible oils and fats, the iodine value before hydrogenation treatment is usually around 130, and as hydrogenation-treated soybean oil, one having around 50 to 90 is generally used. In the present invention, when such a soybean oil is subjected to a hydrogenation treatment, the resulting hydrogenated soybean oil has a trans acid content of 10% by weight or less, even if the iodine value is about 75, and the trans acid is remarkably reduced.
On the other hand, the trans acid content of hydrogenated soybean oil hydrogenated by a conventional hydrogenation treatment method so as to have an iodine value of about 75 is usually about 30% by weight, and the hydrogenation treatment of the present invention has a transacid content of about 30% by weight. The generation of acid is extremely suppressed and is suitable for hydrogenation of edible fats and oils.
[0012]
【Example】
Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited by the following examples.
In the following examples, the amount of trans acid was determined by the standard oil and fat analysis test method 2.4.24.1-81 (differential infrared spectroscopy) established by the Japan Oil Chemical Association, and the iodine value was determined by the same method as 2.4. 5.5.1-71 (Wijs method). The specific surface area was measured by a BET method using nitrogen.
Examples 1 to 9
Approximately 30 cc of a catalyst in which 2 wt% of platinum is supported on γ-alumina having a specific surface area of 250 m 2 / g and a pore volume of 0.56 cc / g, manufactured by N-Chemcat Co., Ltd., in a fixed-bed flow reactor having an inner volume of 70 cc. After filling and reducing in a hydrogen stream at a temperature of 300 ° C. for 2 hours, under various treatment conditions shown in Table 1, soybean oil (trans acid content: 0%, iodine value: 130) was passed and hydrogenated. Processed. About the obtained product oil, the trans-acid amount and the iodine value were measured, respectively. The results are shown in Table 1.
[0013]
[Table 1]
Examples 10 to 12
The same platinum catalyst as used in Example 1 was subjected to hydrogen reduction treatment at a hydrogen pressure of 20 kg / cm 2 G and a temperature of 200 ° C. for 2 hours.
Then, about 200 cc of soybean oil (trans acid content: 0%, iodine value: 126) was charged into an autoclave having a content of 250 cc, and about 1.5 g of the above-mentioned reduction treatment catalyst was added thereto. Each hydrogenation treatment was performed at a temperature of 70 ° C. and a hydrogen pressure of 70 kg / cm 2 G for the treatment time shown in Table 2. The trans acid amount and iodine value of each of the resulting oils were measured, and the results are shown in Table 2.
[0015]
[Table 2]
Examples 13 to 15
About 1 g of platinum black adjusted to a particle size of 100 mesh or less was used as a catalyst, and about 200 cc of soybean oil (trans acid content: 0%, iodine value: 133) was charged into an autoclave having a content of 250 cc. Hydrogenation treatment was performed at a pressure of 30 kg / cm 2 G for the treatment time shown in Table 3.
The trans acid content and iodine value of each of the resulting oils were measured, and the results are shown in Table 3.
[0017]
[Table 3]
Example 16
The same platinum catalyst as used in Example 1 was charged into a fixed bed flow reactor in the same manner as in Example 1, and a di-tert-butyl disulfide solution of n-hexane adjusted to a sulfur concentration of 1% by weight was used. Sulfidation treatment was performed under the conditions of a temperature of 300 ° C., an LHSV of 1.0 / hour, and a hydrogen pressure of 20 kg / cm 2 G. Thereafter, the same soybean oil as that used in Example 1 was subjected to a hydrogenation treatment under the conditions of a temperature of 250 ° C., a hydrogen pressure of 70 kg / cm 2 G, and an LHSV of 2 / hour.
The resulting product oil had a trans acid content of 7% and an iodine value of 78.
[0019]
Comparative Examples 1 to 6
About 200 cc of the same soybean oil as used in Example 1 was charged into an autoclave having a content of 250 cc, and about 1 g of a catalyst having about 5% by weight of Ni supported on diatomaceous earth was added. Hydrogenation treatment was performed. The amount of trans acid and iodine value of each of the obtained product oils were measured, and the results are shown in Table 4.
[0020]
[Table 4]
According to the above examples, according to the method of the present invention, even if the iodine value decreases, the trans acid content does not relatively increase, and even if the iodine value is 70 or less, the trans acid content is 10% by weight or less. It is clear that production is suppressed. In addition, it can be seen that hydrogenation can be performed at a reaction temperature of 100 ° C. or lower, which is lower than conventional, and the operation is simplified.
On the other hand, in the comparative example using the nickel-supported catalyst as in the conventional method, hydrogenation cannot be performed at 100 ° C. or less, and the trans acid content does not become 10% by weight or less.
[0022]
【The invention's effect】
The method for hydrogenating edible fats and oils of the present invention is a hydrogenated edible fat and oil having a low trans acid content by hydrogenating edible fats and oils, which significantly suppresses the production of trans acid, which is not naturally occurring and its effects are being questioned. Can be obtained, and the hydrogenation conditions can be relaxed, which is extremely useful industrially.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13101394A JP3549123B2 (en) | 1994-05-20 | 1994-05-20 | Method for producing edible fats and oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13101394A JP3549123B2 (en) | 1994-05-20 | 1994-05-20 | Method for producing edible fats and oils |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07316585A JPH07316585A (en) | 1995-12-05 |
| JP3549123B2 true JP3549123B2 (en) | 2004-08-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13101394A Expired - Fee Related JP3549123B2 (en) | 1994-05-20 | 1994-05-20 | Method for producing edible fats and oils |
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| Country | Link |
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| JP (1) | JP3549123B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100913850B1 (en) * | 2006-12-29 | 2009-08-26 | 우석대학교 산학협력단 | Method for the production of edible oil having rich and deep buttery flavor with very low content of trans fatty acid and edible oil prepared by the same |
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1994
- 1994-05-20 JP JP13101394A patent/JP3549123B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07316585A (en) | 1995-12-05 |
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