WO2011099345A1 - Method for producing hydrogenated fat or oil - Google Patents

Method for producing hydrogenated fat or oil Download PDF

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WO2011099345A1
WO2011099345A1 PCT/JP2011/051091 JP2011051091W WO2011099345A1 WO 2011099345 A1 WO2011099345 A1 WO 2011099345A1 JP 2011051091 W JP2011051091 W JP 2011051091W WO 2011099345 A1 WO2011099345 A1 WO 2011099345A1
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oil
temperature
oils
reaction
fat
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PCT/JP2011/051091
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French (fr)
Japanese (ja)
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義一 辻脇
浩志 山本
峰男 田原
敦則 熊西
真和 島田
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植田製油株式会社
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Priority to CN201180009485.5A priority Critical patent/CN102770521B/en
Publication of WO2011099345A1 publication Critical patent/WO2011099345A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
    • A23D9/04—Working-up

Definitions

  • the present invention relates to a method for producing hydrogenated fats and oils in which the production of a trans isomer (trans acid) is suppressed and a production apparatus therefor.
  • Solid fat is so-called hardened that is solidified by adding hydrogen to liquid oil and fat (hereinafter sometimes abbreviated as hydrogenation) in addition to natural and solid oil such as palm oil, beef tallow and lard. Oil and transesterified oil are often used.
  • hydrogenation liquid oil and fat
  • trans acids are prone to health problems and consumers tend to avoid using them.
  • frying oil may be hydrogenated to improve its oxidative stability, and consumers concerned about the formation of trans acid in this hydrogenation reaction are There is a tendency to refrain from using heavy oils and fats, especially in overseas countries where the trans acid content is indicated.
  • the melting point is generally lowered by selective hydrogenation.
  • the “selective” hydrogenation reaction indicates that there is a large difference in the reaction rate between so-called polyenoic acid having two or more double bonds and one monoenoic acid. Those with little difference are called “non-selective” hydrogenation reactions. The difference between “selective” and “non-selective” is relative. Usually, any hydrogenation reaction causes transation, but non-selective hydrogenation produces less transacid. .
  • the production of hardened oil by hydrogenation of edible oil is often produced batch-wise using a pressure vessel called an autoclave.
  • the pressure vessel has a capacity of 5 to 20 tons and has high airtightness and heat retention.
  • the reaction is carried out at a hydrogen pressure of about normal pressure to about 0.5 MPa.
  • Patent Document 1 As a method for producing hydrogenated fats and oils having a low trans fatty acid content, a method devised using a nickel catalyst using titanium oxide as a carrier is known (Patent Document 1).
  • Patent Document 3 a reaction temperature using a nickel catalyst
  • Patent Document 3 a method in which is carried out at 80 to 130 ° C.
  • Patent Document 4 a method for producing a hardened oil and fat in which a hydrogenation reaction is performed at 20 ° C. or more and less than 80 ° C. by selecting and using a well-known nickel catalyst having high active predetermined characteristics is disclosed.
  • the cited document also discloses that the hydrogenation reaction at a low temperature uses an emulsifier to carry out hydrogenation below the melting point of the fat.
  • a rare metal such as platinum is used as a catalyst and the reaction is performed at a high pressure, the cost becomes high and the practicality is low.
  • the supply amount of catalyst has also decreased.
  • the hydrogenation reaction is carried out at a high temperature of 80 ° C. or higher, and in this case, the hydrogenation reaction tends to be selective, so that the reduction in translation is sufficiently reduced. Or it was not easy to do reliably.
  • the hydrogenation technology capable of improving solid oil and oxidation stability using oil and fat margarine, shortening, etc. as a raw material has not been sufficiently improved without defects.
  • fat hydrogenation technology has the great advantage of improving the plasticity by partially reducing the unstable double bond of fats and oils and improving the oxidation stability, and further adjusting the melting point within a predetermined range.
  • it is an indispensable technology for the production of margarine and shortening the use of hydrogenated oils tends to be avoided by consumers due to a process involving an increase in trans fatty acids. .
  • the object of the present invention is to solve the problems in the conventional hydrogenation technology described above and to hydrogenate various fats and oils including polyunsaturated fatty acids in order to improve the plasticity and oxidation stability of the fats and oils.
  • a method for producing hydrogenated fats and oils that does not generate transacid as much as possible and a production method or a device for producing hydrogenated fats and oils that is highly practical.
  • the inventors of the present application conducted the production of hydrogenated oil at low temperatures and under strictly controlled conditions that exceeded conventional expectations, and by devising the equipment structure that enables it, This completes the invention relating to a method and an apparatus for producing a hardened oil with very little production.
  • the present invention hydrogenation is performed on fats and oils containing polyunsaturated fatty acids in the presence of a nickel catalyst (referred to as the catalyst being nickel (Ni); hereinafter the same).
  • the catalyst being nickel (Ni); hereinafter the same.
  • the oil temperature increase rate per unit of iodine value decreased by the hydrogenation reaction is 0.5 or less, and the temperature of the hydrogenation reaction is 60 to 75 ° C.
  • the method for producing hydrogenated fats and oils adjusts the amount of cooling heat or the amount of hydrogen supplied to the hydrogenation reaction system or both.
  • the rate of the hydrogenation reaction is controlled so as to keep the rate of increase in the fats and oils temperature as low as possible and to be below a predetermined value, that is, 0 to 0.5. Therefore, by carrying out the hydrogenation reaction under a condition controlled within a predetermined temperature range lower than the conventional hydrogenation temperature, the reaction can be made non-selective and the translation can be extremely reduced.
  • the amount of cooling heat for the hydrogenation reaction system is mainly adjusted so that the reaction is performed under a predetermined temperature condition, and if that is still insufficient, the amount of cooling heat is adjusted.
  • the oil temperature increase rate per unit of iodine value is 0.5 or less by controlling the cooling heat amount of the hydrogenation reaction system or controlling the hydrogen supply amount, or when the control of the reaction rate is insufficient in the one control, It is possible to control the oil / fat temperature rise rate and the predetermined temperature range of the hydrogenation reaction by adjusting both with the hydrogen supply amount.
  • the amount of cooling heat is adjusted, and if it is still insufficient, it is adjusted by adjusting both the amount of cooling heat and the amount of hydrogen supply to control the oil temperature rise rate and the predetermined temperature range of the hydrogenation reaction. Is preferred.
  • fats and oils containing polyunsaturated fatty acids applied to the present invention include beef tallow, lard (pig tallow), chicken tallow, fish oil, whale oil, palm oil, fractionated palm oil, soybean oil, rapeseed oil, sunflower oil, safflower oil.
  • oils and fats selected from flower oil, cottonseed oil and corn oil are employed in the above-described examples of fats and oils.
  • the hydrogenated fat and oil manufacturing apparatus that can be used in the manufacturing method as described above is a pressure-resistant structure in which a supply path for fat and oil containing polyunsaturated fatty acids and a supply path that can adjust the supply amount of the catalyst are connected.
  • a reaction vessel is provided, and a stirring device is attached to the reaction vessel to make a hydrogenated oil / fat manufacturing device that continuously performs a hydrogenation reaction while stirring, and a temperature sensor that senses the temperature in the reaction vessel in the manufacturing device
  • an electronic control means connected to the electronic control means, and the electronic control means is used to control the flow rate of refrigerant such as the amount of water in the cooler so as to adjust the amount of cooling heat from the reaction vessel. Can do.
  • the temperature information from the temperature sensor that senses the temperature in the reaction vessel is input to the electronic control means, and the temperature control information transmitted from this is input to the circulation pump of the cooler to control its operation.
  • the cooling heat amount of the appropriate reaction vessel determined in advance whereby the temperature of the hydrogenation reaction is, for example, 60 to 75 ° C., and the oil temperature per unit of iodine value that decreases
  • the increase rate can be adjusted to a specific condition of 0.5 or less, that is, 0 to 0.5.
  • the electronic control means is connected to a hydrogen supply device to a reaction vessel, and the hydrogen supply device in addition to the main adjustment for controlling the refrigerant flow rate of the cooler by the electronic control means. It is also possible to make an auxiliary adjustment for controlling the hydrogen supply amount.
  • the amount of heat of cooling and still insufficient is so low that the temperature of the hydrogenation reaction is within a predetermined range and the rate of increase in the oil temperature per unit of iodine value that decreases by the hydrogenation reaction is below a predetermined value.
  • hydrogenated fats and oils are produced by adjusting both the amount of hydrogen supplied, so it becomes a method for producing hydrogenated fats and oils that do not generate transacid as much as possible for various fats and oils containing polyunsaturated fatty acids. There is an advantage that the manufacturing method becomes high.
  • the electronic control means is connected to a hydrogen supply device to the reaction vessel, and the electronic control means controls the refrigerant flow rate such as the amount of water in the cooler and the hydrogen supply device to reduce the heat of cooling. If it is not sufficient, it can be adjusted by both the refrigerant flow rate and the hydrogen supply amount of the cooler, so it can be adjusted to the appropriate cooling heat amount of the reaction vessel according to the temperature in the reaction vessel.
  • the temperature of the hydrogenation reaction is, for example, 60 to 75 ° C., and the rate of increase in fat / oil temperature per unit of iodine value is 0. It can be adjusted to specific strict reaction conditions such that it is 5 or less, and there is an advantage that hydrogenated fats and oils can be produced without generating transacid as much as possible.
  • the hydrogenation reaction temperature is 60 to 75 ° C. and the hydrogenation reaction is performed.
  • the amount of cooling heat and, if still insufficient, adjust the amount of hydrogen supplied so that the oil temperature increase rate per unit of the iodine value that decreases in 1 is 0.5 or less.
  • the fats and oils containing polyunsaturated fatty acids used in the present invention are well-known edible fats and oils that can be employed without any particular limitation, and as described above, animal fats such as beef tallow, lard, chicken fat, fish oil, whale oil and the like. , Palm oil, fractionated palm oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, cottonseed oil, corn oil and the like, or one or more oils and fats selected from these can also be employed.
  • the fats and oils containing said polyunsaturated fatty acid which contain 30 weight% or less of polyunsaturated acid (it may be hereafter called polyenoic acid) in 100 weight% of all fatty acids. More preferably, it is an oil containing 25% by weight or less of the amount of polyunsaturated acid.
  • polyunsaturated acid it may be hereafter called polyenoic acid
  • it is an oil containing 25% by weight or less of the amount of polyunsaturated acid.
  • Representative examples include, but are not limited to, palm oil, fractionated palm oil, lard, beef tallow, hyolein rapeseed oil, sunflower oil, and the like.
  • the catalyst used in the present invention may be a well-known one that can be used for producing a hardened oil.
  • a nickel catalyst as a curing catalyst for edible fats and oils approved by the Food Sanitation Act in Japan.
  • Nickel flakes and stabilized nickel are used, and commercially available products are flaky nickel manufactured by Sakai Chemical Co., Ltd. Examples include SO series of catalysts (SO-750, SO-450, etc.).
  • the temperature of the hydrogenation reaction is adjusted to 60 to 75 ° C. by a predetermined method. This is because at a reaction temperature of less than 60 ° C., the reaction rate becomes extremely slow, which is not practical. This is because at a high temperature exceeding 75 ° C., the increase in the trans isomer becomes too large, and the reaction rate increases in proportion to the temperature, making it difficult to control the temperature and the intended purpose cannot be achieved.
  • the oil-fat temperature rise rate per unit of the iodine value which falls by hydrogenation reaction may be 0.5 or less. This is because, in the state where the oil temperature rise rate per unit of iodine value exceeds 0.5, the increase in trans isomers becomes large and the intended purpose of the present invention cannot be achieved.
  • the amount of cooling heat and / or the amount of hydrogen supplied to the hydrogenation reaction system are adjusted.
  • the cooling heat quantity specifically, the oil temperature in the reaction vessel of the reaction apparatus is detected, and the water flow rate of the cooler is controlled accordingly.
  • the supplied hydrogen is stopped to control the reaction itself.
  • the hydrogen supply pressure of the pipe line leading to the reaction vessel that is, the hydrogen pressure in the reaction vessel is set to 0.5 Mp (gauge pressure) or less, and the reaction temperature is set to 60 to 75. Adjust to 0 ° C., preferably 65 to 75 ° C.
  • a hydrogenated fat and oil manufacturing apparatus includes a cooling coil in which a fat and oil supply path 1 and a catalyst supply path 2 containing polyunsaturated fatty acids are connected and piped in a coil shape of a heat exchanger. 3 and a cooler 5 having a chilling unit 4 and a pressure-resistant reaction vessel 7 provided with a hydrogen supply path 6 capable of adjusting the hydrogen supply amount per hour is provided. And a reaction system (mixture of raw oil and fat, catalyst, etc.) A is stirred, and the hydrogenation fat and oil production apparatus is made to continuously perform the hydrogenation reaction.
  • a reaction system mixture of raw oil and fat, catalyst, etc.
  • This manufacturing apparatus is provided with a temperature sensor 9 for sensing the temperature in the reaction vessel 7 and a pressure sensor 10 connected to the hydrogen supply path 6, and a control signal is transmitted based on these temperature information and pressure information.
  • Electronic controller 11 (manufactured by Yokogawa Electric Co., Ltd .: digital indicating controller) is provided, and the electronic controller 11 controls the operation of the circulation pump 17 and the operation of the flow control valve 15 to control the amount of cooling heat and the amount of hydrogen supplied to the reaction system A. Is an apparatus for producing hydrogenated fats and oils that can be adjusted.
  • the oil and fat used as the raw material is transferred to the oil and fat supply path 1 from a measuring tank (not shown) and drawn into the reaction vessel 7. After the pressure inside the reaction vessel 7 is sufficiently reduced by the vacuum pump 12, Is warmed to the reaction start temperature.
  • the nickel catalyst is charged from the catalyst hopper 2 a and supplied into the reaction vessel 7 and then sufficiently dispersed by the stirrer 8.
  • the stirrer 8 has a known structure such as providing a rotating stirring blade driven by an electric motor, and the hydrogenation reaction is started by increasing the rotational speed of the rotating blade.
  • Hydrogen used in the hydrogenation reaction is foamed from a tank (not shown) through a hydrogen flow meter 13 and further through a hydrogen supply path 6 and a flow rate adjusting valve 15 through a hydrogen blowing pipe 16 in the reaction vessel 7. And introduced into the liquid reaction system A.
  • the pressure sensor 10 reaches a predetermined pressure
  • the flow rate adjustment valve 15 is opened and closed by the control operation of the electronic controller 11 to adjust the hydrogen supply amount.
  • the progress of the hydrogenation reaction is integrated by the hydrogen counter 14 and is confirmed by the total amount of hydrogen supply.
  • the temperature sensor 9 senses the temperature rise due to the reaction heat, and a heat medium such as cooling water is supplied to the cooling coil 3 from the circulation pump 17 to the cooling coil 3 under the control of the electronic controller 11.
  • the reaction temperature is controlled.
  • the circulated cooling water is cooled by the chilling unit 4 and reused as cooling water.
  • the chilling unit 4 is a cooling device for a heat medium such as water in which a vapor compression device or the like is incorporated in one frame.
  • the hydrogenation reaction is terminated by lowering the rotational speed of the rotor blades of the agitator 8, and the hydrogenated fat is transferred to the filtration tank.
  • Examples 1 to 4, 6, 7 1 kg of raw oil / fat is charged into a reaction vessel (hereinafter referred to as autoclave) having a capacity of 2 liters, and a predetermined amount of flake nickel catalyst (manufactured by Sakai Chemical Co., Ltd .: SO-750, SO-450) is added to the reaction start temperature. Warmed up.
  • a reaction vessel hereinafter referred to as autoclave
  • SO-750, SO-450 flake nickel catalyst
  • the iodine value is based on the standard oil analysis test method 2.3.4.1-1996 iodine value (Wiis-cyclohexane method), and the amount of trans acid is based on the standard fat analysis method 17-2007 trans fatty acid content (capillary gas chromatograph). Method). However, the trans acid content of the refined fish oil and the hardened oil of the refined fish oil was measured in accordance with the standard oil analysis test method 9-2003 isolated trans isomer (difference infrared spectrum-cyclohexane method).
  • the increase in trans acid is the amount of trans acid that increases per unit of iodine value that decreases by the hydrogenation reaction, calculated by the following equation (1).
  • oil / fat temperature increase rate shown in the table indicates the oil / fat temperature increase rate per unit of iodine value, and the calculation formula is as shown in the following equation (2).
  • refined palm oil iodine value: 50.8, trans acid: 0.2%)
  • refined pork fat iodine value: 59.0, trans acid: 1.4%
  • refined fish oil Iodine value: 153.4, trans acid: 2.1%
  • refined hyolein rapeseed oil iodine value: 100.9, trans acid: 0.6%)
  • refined rapeseed oil iodine value: 114.0, trans acid: 1.1%) was used.
  • Examples were prepared by adjusting the oil temperature increase rate to 0.22 to 0.5 and adjusting the reaction temperature to 60 to 75 ° C. by flowing cooling water.
  • the trans acid content was in the range of 1.6 to 4.1%, and the cured oil was excellent.
  • Example 9 Hydrogenation was performed in the production apparatus described in the embodiment. 7t of refined palm oil (iodine value: 51.5, trans acid: 0.2%) as raw material fat is charged into an autoclave, and a predetermined amount of flake nickel catalyst (manufactured by Sakai Chemical Co., Ltd .: SO-750) is added to react. Warmed to start temperature. In the hydrogenation reaction, cooling water previously cooled to 10 ° C. is allowed to flow through the cooling coil of the autoclave so that the reaction takes place within the predetermined reaction temperature described in Table 2, and if it is still insufficient, pressurization is performed. The reaction rate was adjusted by adjusting to reduce the hydrogen pressure in the state, and the hydrogenation reaction was performed under such strict temperature control to prepare a hardened oil. The iodine value and the amount of trans acid of the obtained hardened oil are also shown in Table 2.
  • Example 3 7t of the same refined palm oil (iodine value: 51.5, trans acid: 0.2%) as in Example 9 was charged into the autoclave as a raw oil and fat, and a predetermined amount of flake nickel catalyst (SO-750: manufactured by Sakai Chemical Co., Ltd.) In addition, the reaction was heated to the reaction start temperature. Since the hydrogenation reaction was a reaction with a small decrease in iodine value, it was carried out at the reaction temperature and other various conditions described in Table 2 without cooling to produce a hardened oil. The iodine value and the amount of trans acid of the obtained hardened oil are also shown in Table 2.
  • the oil and fat temperature increase rate is adjusted to 0.5 by adjusting both the cooling heat amount and the hydrogen supply amount, and the reaction temperature is adjusted to 70 to 74 ° C.
  • the cured oil of Example 9 was an excellent cured oil having a low trans acid content of 2.5%.

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Abstract

Disclosed are a method for producing a hydrogenated fat or oil, whereby, in hydrogenating a fat or oil containing a polyvalent unsaturated fatty acid, the formation of a trans acid is minimized to improve the oxidation stability of the fat or oil, and a production device therefor. Specifically disclosed is a method for producing a hydrogenated fat or oil comprising hydrogenating a fat or oil containing a polyvalent unsaturated fatty acid in the presence of a nickel catalyst, wherein the hydrogenation is conducted at a reaction temperature of 60-75oC, and the fat/oil temperature-increasing ratio per unit of iodine value lowered by the aforesaid hydrogenation is regulated to 0.5 or below by controlling either or both of the heat amount for cooling and the hydrogen amount supplied to the hydrogenation system so that the amount of a trans acid formed per unit of iodine value lowered by the aforesaid hydrogenation is adjusted to 0.25 wt%. The regulation is conducted by controlling the operation of a circulating pump (17) and the operation of a flow rate-adjusting valve (15) by an electronic controller (11) based on the data of the temperature in a reaction container (7) and the data of the pressure in a hydrogen supply channel (6).

Description

水素添加油脂の製造方法Method for producing hydrogenated fats and oils
　この発明は、トランス異性体（トランス酸）の生成を抑制した水素添加油脂の製造方法およびその製造装置に関するものである。 The present invention relates to a method for producing hydrogenated fats and oils in which the production of a trans isomer (trans acid) is suppressed and a production apparatus therefor.
　通常、油脂をマーガリンやショートニングに使用する際に、固形脂を原料の一部または大部分に用いる必要がある。固形脂は、パーム油、牛脂、ラード等の天然で固形の油脂の他に、液体の油脂に水素を添加（以下、水添と略す場合がある。）することにより固形状化した、いわゆる硬化油やエステル交換油を用いることが多い。 Usually, when fats and oils are used for margarine and shortening, it is necessary to use solid fats for some or most of the raw materials. Solid fat is so-called hardened that is solidified by adding hydrogen to liquid oil and fat (hereinafter sometimes abbreviated as hydrogenation) in addition to natural and solid oil such as palm oil, beef tallow and lard. Oil and transesterified oil are often used.
　また、トランス酸は、健康上に問題のあることが喧伝され、消費者はその使用を敬遠する傾向がある。 Also, trans acids are prone to health problems and consumers tend to avoid using them.
　マーガリン、ショートニング以外にも、例えばフライ油等に対して、その酸化安定性を向上させるために水添する場合があり、この水素添加反応でもトランス酸が生成することを懸念する消費者はそのような油脂の使用を敬遠する傾向があり、特にトランス酸の含量表示がなされる海外では、その傾向は著しい。 In addition to margarine and shortening, for example, frying oil may be hydrogenated to improve its oxidative stability, and consumers concerned about the formation of trans acid in this hydrogenation reaction are There is a tendency to refrain from using heavy oils and fats, especially in overseas countries where the trans acid content is indicated.
　従来の水添工程では、耐圧容器に仕込んだ原料油脂にニッケル触媒０．０５～０．５重量％を加え、上層部の空気を水素に置換し、１２０℃程度に加熱すると、その後は水素添加の反応熱によって１５０～２００℃程度まで触媒含有の油脂温度は上昇し反応が継続する。 In the conventional hydrogenation process, 0.05 to 0.5% by weight of nickel catalyst is added to the raw oil and fat charged in the pressure vessel, the air in the upper layer is replaced with hydrogen, and heated to about 120 ° C. Due to the reaction heat, the temperature of the fat containing the catalyst increases to about 150 to 200 ° C., and the reaction continues.
　このような水素添加反応の発熱反応では、特に冷却操作をしない限り、ヨウ素価の１単位を低下させる毎に温度は１．６～１．７℃上昇する。また、油脂１トン当たりヨウ素価の１単位を低下させるためには水素は約１ｍ3必要とされる。水添工程では、吸収された水素量で希望の硬さになったかどうかを判断し、反応を停止して触媒を除去し、必要に応じて脱臭等の操作をして製品とし、これを工業用またはマーガリンやショートニングの原料またはフライ油等の食品に使用している。 In such an exothermic reaction of the hydrogenation reaction, the temperature rises by 1.6 to 1.7 ° C. every time one unit of iodine value is lowered unless a cooling operation is performed. In addition, about 1 m 3 of hydrogen is required to reduce one unit of iodine value per ton of fats and oils. In the hydrogenation process, it is determined whether the amount of absorbed hydrogen has reached the desired hardness, the reaction is stopped, the catalyst is removed, and if necessary, deodorization and other operations are performed to produce a product. Used for margarine and shortening ingredients or foods such as frying oil.
　因みに、同じ油脂を同じヨウ素価まで水添するとき、選択的に水添した方が一般的に融点は低くなる。また、二重結合に水素の付加する速度の比について、二重結合を２個以上持ついわゆるポリエン酸と１個のモノエン酸との反応速度の差が大きいことを「選択的」な水添反応といい、その差が少ないものを「非選択的」な水添反応という。「選択的」または「非選択的」の違いは相対的なものであり、通常、いずれの水添反応でもトランス化が起こっているが非選択的に水添する方が生成するトランス酸は少ない。 Incidentally, when hydrogenating the same fats and oils to the same iodine value, the melting point is generally lowered by selective hydrogenation. In addition, regarding the ratio of the rate at which hydrogen is added to the double bond, the “selective” hydrogenation reaction indicates that there is a large difference in the reaction rate between so-called polyenoic acid having two or more double bonds and one monoenoic acid. Those with little difference are called “non-selective” hydrogenation reactions. The difference between “selective” and “non-selective” is relative. Usually, any hydrogenation reaction causes transation, but non-selective hydrogenation produces less transacid. .
　また、実際に食用油の水添による硬化油の製造は、オートクレーブと呼ばれる耐圧容器を用いてバッチ式に製造される場合が多く、耐圧容器は５～２０トン容量で気密性も保温性も高いものであり、水素圧は常圧～０．５ＭＰａ程度で反応させている。 Actually, the production of hardened oil by hydrogenation of edible oil is often produced batch-wise using a pressure vessel called an autoclave. The pressure vessel has a capacity of 5 to 20 tons and has high airtightness and heat retention. The reaction is carried out at a hydrogen pressure of about normal pressure to about 0.5 MPa.
　トランス脂肪酸含量の低い水素添加油脂の製造方法としては、酸化チタンを担体とするニッケル触媒を用いて工夫した方法が知られている（特許文献１）。 As a method for producing hydrogenated fats and oils having a low trans fatty acid content, a method devised using a nickel catalyst using titanium oxide as a carrier is known (Patent Document 1).
　また、圧力を相当に１５０ｐｓｉｇ（重量ポンド毎平方インチ）（＝１．０３ＭＰａ）以上に高くし、温度を１２０～２４０℃程度にする方法（特許文献２）、また、ニッケル触媒を用いて反応温度を８０～１３０℃で行う方法（特許文献３）が知られている。 Also, a method in which the pressure is considerably increased to 150 psig (pound per square inch) (= 1.03 MPa) and the temperature is set to about 120 to 240 ° C. (Patent Document 2), and a reaction temperature using a nickel catalyst There is known a method (Patent Document 3) in which is carried out at 80 to 130 ° C.
　また、周知のニッケル触媒について、活性の高い所定特性であるものを選別して用いることにより、水素添加反応を２０℃以上８０℃未満で行なう硬化油脂の製造方法が開示されている（特許文献４）。同引用文献には、低温での水素添加反応では乳化剤を使用して油脂の融点以下で水素添加を行なうことも開示される。
　なお、白金等のレアメタルを触媒として、高圧で反応させると高コストになり実用性が低い。近年硬化油の製造が減少する中で、触媒の供給量も減少しているのが現状である。 In addition, a method for producing a hardened oil and fat in which a hydrogenation reaction is performed at 20 ° C. or more and less than 80 ° C. by selecting and using a well-known nickel catalyst having high active predetermined characteristics is disclosed (Patent Document 4). ). The cited document also discloses that the hydrogenation reaction at a low temperature uses an emulsifier to carry out hydrogenation below the melting point of the fat.
In addition, when a rare metal such as platinum is used as a catalyst and the reaction is performed at a high pressure, the cost becomes high and the practicality is low. In recent years, as the production of hydrogenated oil has decreased, the supply amount of catalyst has also decreased.
特開昭　５３－０９０１８９号公報JP-A-53-090189 特表平　０７－５０９７４６号公報Tokuheihei 07-509746 特開２００６－３２０２７５号公報JP 2006-320275 A 特開２０１０－００１３６６号公報JP 2010-001366 A
　しかしながら、特許文献１～３に記載される方法では、水素添加反応が８０℃以上の高温で行なわれ、その場合に水素添加反応は選択的なものになりやすいため、トランス化の低減を充分にまたは確実に行なうことは容易なことではなかった。 However, in the methods described in Patent Documents 1 to 3, the hydrogenation reaction is carried out at a high temperature of 80 ° C. or higher, and in this case, the hydrogenation reaction tends to be selective, so that the reduction in translation is sufficiently reduced. Or it was not easy to do reliably.
　また、特許文献４に記載される水素添加油脂の製造方法では、特定の活性を有するニッケル触媒を採用するにすぎないので、水素添加反応の速度を充分に制御できるものではなく、水素添加反応中に異性化を招く過剰な熱量を供給してしまう可能性がある。また、乳化剤を使用すると、対象の油種が大豆類や菜種油のような中性油に限定され、充分な効果も得られ難い。 Further, in the method for producing hydrogenated fats and oils described in Patent Document 4, since only a nickel catalyst having a specific activity is employed, the rate of the hydrogenation reaction cannot be sufficiently controlled, and the hydrogenation reaction is in progress. There is a possibility of supplying an excessive amount of heat that causes isomerization. In addition, when an emulsifier is used, the target oil type is limited to neutral oils such as soybeans and rapeseed oil, and it is difficult to obtain sufficient effects.
　このように油脂のマーガリン、ショートニングなどを原料として、固形油脂や酸化安定性を高めることの可能な水素添加技術は、充分に欠点のないものに改良されたものとはなっていない。
　すなわち、油脂の水素添加技術は、不安定な油脂の二重結合を部分的に減少させてその可塑性を改良する事や酸化安定性を向上させるという大きな利点があり、さらに所定範囲の融点の調整を可能にするため、マーガリンやショートニングの製造には欠かせない技術であるにもかかわらず、トランス脂肪酸の増加を伴う工程を経るため、水素添加油脂の使用が消費者に敬遠される傾向にある。 As described above, the hydrogenation technology capable of improving solid oil and oxidation stability using oil and fat margarine, shortening, etc. as a raw material has not been sufficiently improved without defects.
In other words, fat hydrogenation technology has the great advantage of improving the plasticity by partially reducing the unstable double bond of fats and oils and improving the oxidation stability, and further adjusting the melting point within a predetermined range. Although it is an indispensable technology for the production of margarine and shortening, the use of hydrogenated oils tends to be avoided by consumers due to a process involving an increase in trans fatty acids. .
　前述のトランス脂肪酸が高くなるという欠点さえ克服すれば、水素添加油脂の製造は、天然油脂が持つ特異的なトリアシルグリセロール構造の脂肪酸結合位置を変えることなく、その構成する脂肪酸の二重結合を減少させることで油脂の融点や硬度を任意に変化させることによって、エステル交換油にはない物性が得られるため、利点が大きく極めて有効な技術である。 As long as the above-mentioned disadvantage of high trans-fatty acids is overcome, the production of hydrogenated fats and oils does not change the fatty acid binding position of the specific triacylglycerol structure of natural fats and oils, without changing the fatty acid binding position of the constituent fatty acids. By changing the melting point and hardness of the fats and oils arbitrarily by decreasing, physical properties not found in the transesterified oil can be obtained, and this is a very effective technique with great advantages.
　また、前記したように水素添加油脂は、オートクレーブと呼ばれる耐圧容器を用いて大容量でバッチ式に製造されることが多いが、通常のニッケル触媒を用いて水添が開始されると急激に反応系の温度が上昇するため、通常は１８０℃付近を越えると冷却水で温度上昇を抑えて水素添加反応を継続させている。
　しかし、加速度的に上昇する反応温度を一定の範囲内に制御することは、非常に困難であり、いわゆる通常のニッケル触媒を用いた水素添加油脂の水素添加反応を８０℃未満の低温で行なうことは、実際に工業的に行なうことはできなかった。 In addition, as described above, hydrogenated fats and oils are often produced in a batch system with a large capacity using a pressure vessel called an autoclave. However, when hydrogenation is started using a normal nickel catalyst, the hydrogenated fats and oils react rapidly. Since the temperature of the system rises, normally, when the temperature exceeds about 180 ° C., the temperature increase is suppressed with cooling water and the hydrogenation reaction is continued.
However, it is very difficult to control the reaction temperature that increases at an accelerated rate within a certain range, and the hydrogenation reaction of hydrogenated fats and oils using a so-called ordinary nickel catalyst is performed at a low temperature of less than 80 ° C. Could not actually be carried out industrially.
　この発明の課題は、上記した従来の水素添加技術における問題点を解決して、油脂の可塑性や酸化安定性を高めるために多価不飽和脂肪酸を含む様々な油脂に対して水素添加を行なう際に、トランス酸を極力発生させない水素添加油脂の製造方法とすることであり、しかも実用性の高い製造方法または水素添加油脂の製造装置とすることである。 The object of the present invention is to solve the problems in the conventional hydrogenation technology described above and to hydrogenate various fats and oils including polyunsaturated fatty acids in order to improve the plasticity and oxidation stability of the fats and oils. In addition, a method for producing hydrogenated fats and oils that does not generate transacid as much as possible, and a production method or a device for producing hydrogenated fats and oils that is highly practical.
　本願の発明者らは、硬化油の製造条件を低温でありかつ従来の予想を超える厳密にコントロールされた条件下で行なうことにより、そしてそれを可能とする装置構造を工夫することによってトランス酸の生成が極めて少ない硬化油の製造方法および装置に係る発明を完成させたものである。 The inventors of the present application conducted the production of hydrogenated oil at low temperatures and under strictly controlled conditions that exceeded conventional expectations, and by devising the equipment structure that enables it, This completes the invention relating to a method and an apparatus for producing a hardened oil with very little production.
　すなわち、前記の課題を解決するために、この発明では、多価不飽和脂肪酸を含む油脂に対し、ニッケル触媒(触媒がニッケル(Ｎｉ)であるものをいう。以下同じ)の存在下で水素添加反応を行なう水素添加油脂の製造方法において、前記水素添加反応で低下するヨウ素価の１単位当りの油脂温度上昇率が０．５以下であり、かつ前記水素添加反応の温度が６０～７５℃であるように、水素添加反応系に対する冷却熱量もしくは水素供給量または両方を調整する水素添加油脂の製造方法としたのである。 That is, in order to solve the above-mentioned problems, in the present invention, hydrogenation is performed on fats and oils containing polyunsaturated fatty acids in the presence of a nickel catalyst (referred to as the catalyst being nickel (Ni); hereinafter the same). In the method for producing hydrogenated fats and oils for carrying out the reaction, the oil temperature increase rate per unit of iodine value decreased by the hydrogenation reaction is 0.5 or less, and the temperature of the hydrogenation reaction is 60 to 75 ° C. As described above, the method for producing hydrogenated fats and oils adjusts the amount of cooling heat or the amount of hydrogen supplied to the hydrogenation reaction system or both.
　上記した工程からなるこの発明の水素添加油脂の製造方法では、油脂温度の上昇率を可及的に押さえて所定値以下、すなわち０～０．５になるように水素添加反応の速度を制御し、そのために従来の水添処理温度よりも低温の所定温度の範囲内に制御された条件下で水素添加反応することにより、その反応を非選択的なものとしてトランス化を極めて少なくできる。 In the method for producing hydrogenated fats and oils of the present invention comprising the steps described above, the rate of the hydrogenation reaction is controlled so as to keep the rate of increase in the fats and oils temperature as low as possible and to be below a predetermined value, that is, 0 to 0.5. Therefore, by carrying out the hydrogenation reaction under a condition controlled within a predetermined temperature range lower than the conventional hydrogenation temperature, the reaction can be made non-selective and the translation can be extremely reduced.
　このように水素添加反応の速度を充分厳密に制御するには、所定温度条件下で反応させるように、主として水素添加反応系に対する冷却熱量を調整し、それでもなお不十分な場合は冷却熱量の調整と共に、水素供給量の水素供給圧力を０．５Ｍｐ（ゲージ圧）以下に調整することが好ましい。 Thus, in order to control the rate of the hydrogenation reaction sufficiently closely, the amount of cooling heat for the hydrogenation reaction system is mainly adjusted so that the reaction is performed under a predetermined temperature condition, and if that is still insufficient, the amount of cooling heat is adjusted. At the same time, it is preferable to adjust the hydrogen supply pressure of the hydrogen supply amount to 0.5 Mp (gauge pressure) or less.
　水素添加反応系の冷却熱量の制御または水素供給量の制御によってヨウ素価の１単位当りの油脂温度上昇率を０．５以下にし、または前記一方の制御では反応速度の制御が不足する場合は、水素供給量と両方で調整して前記油脂温度上昇率および水素添加反応の所定温度範囲に制御することができる。特に、冷却熱量を調整し、それでもなお不十分な場合は、冷却熱量の調整と水素供給量の調整との両方で調整し、前記油脂温度上昇率および水素添加反応の所定温度範囲に制御することが好ましい。 When the oil temperature increase rate per unit of iodine value is 0.5 or less by controlling the cooling heat amount of the hydrogenation reaction system or controlling the hydrogen supply amount, or when the control of the reaction rate is insufficient in the one control, It is possible to control the oil / fat temperature rise rate and the predetermined temperature range of the hydrogenation reaction by adjusting both with the hydrogen supply amount. In particular, the amount of cooling heat is adjusted, and if it is still insufficient, it is adjusted by adjusting both the amount of cooling heat and the amount of hydrogen supply to control the oil temperature rise rate and the predetermined temperature range of the hydrogenation reaction. Is preferred.
　この発明に適用される多価不飽和脂肪酸を含む油脂の例としては、牛脂、ラード（豚脂）、鶏脂、魚油、鯨油、パーム油、分別パーム油、大豆油、菜種油、ヒマワリ油、サフラワー油、綿実油およびコーン油から選ばれる１種以上の油脂である。
　この発明に適用される多価不飽和脂肪酸を含む油脂としては、上記した油脂の例において、さらに全脂肪酸１００重量％に多価不飽和酸量を３０重量％以下含有する油脂を採用する。 Examples of fats and oils containing polyunsaturated fatty acids applied to the present invention include beef tallow, lard (pig tallow), chicken tallow, fish oil, whale oil, palm oil, fractionated palm oil, soybean oil, rapeseed oil, sunflower oil, safflower oil. One or more oils and fats selected from flower oil, cottonseed oil and corn oil.
As the fats and oils containing polyunsaturated fatty acids applied to the present invention, fats and oils that contain 30% by weight or less of polyunsaturated acids in 100% by weight of all fatty acids are employed in the above-described examples of fats and oils.
　このような油脂に対して水素添加を行なう際、この水素添加反応系に対する冷却熱量の調整もしくは水素供給量の調整または両調整を行なうことにより、上記したトランス酸を極力発生させない水素添加油脂の製造方法の特徴が充分に発揮される。このような調整は、製造された水素添加油脂が、反応中に低下したヨウ素価の１単位当りにおけるトランス酸の発生量が０．２５重量％以下になるように調整されることである。すなわち水添反応中に異性化に必要な過剰な熱量を供給させないで脂肪酸の異性化を極力抑えるものである。 When hydrogenation is performed on such fats and oils, production of hydrogenated fats and oils that do not generate the above-mentioned trans acid as much as possible by adjusting the amount of cooling heat for this hydrogenation reaction system or adjusting the amount of hydrogen supply or both adjustments. The characteristics of the method are fully exhibited. Such adjustment is that the produced hydrogenated fat is adjusted so that the amount of trans acid generated per unit of iodine value decreased during the reaction is 0.25% by weight or less. That is, the isomerization of fatty acids is suppressed as much as possible without supplying an excessive amount of heat necessary for isomerization during the hydrogenation reaction.
　また、上記したような製造方法に用いることのできる水素添加油脂の製造装置は、多価不飽和脂肪酸を含む油脂の供給路および触媒の供給量を調整可能な供給路が接続された耐圧性の反応容器を設け、この反応容器に攪拌装置を付設して攪拌しながら水素添加反応を連続的に行なわせる水素添加油脂の製造装置とし、この製造装置に前記反応容器内の温度を感知する温度センサーおよびこれに接続された電子制御手段を設け、この電子制御手段により冷却器の水量などの冷媒流量を制御して反応容器からの冷却熱量を調整可能とした水素添加油脂の製造装置を採用することができる。 In addition, the hydrogenated fat and oil manufacturing apparatus that can be used in the manufacturing method as described above is a pressure-resistant structure in which a supply path for fat and oil containing polyunsaturated fatty acids and a supply path that can adjust the supply amount of the catalyst are connected. A reaction vessel is provided, and a stirring device is attached to the reaction vessel to make a hydrogenated oil / fat manufacturing device that continuously performs a hydrogenation reaction while stirring, and a temperature sensor that senses the temperature in the reaction vessel in the manufacturing device And an electronic control means connected to the electronic control means, and the electronic control means is used to control the flow rate of refrigerant such as the amount of water in the cooler so as to adjust the amount of cooling heat from the reaction vessel. Can do.
　反応容器内の温度を感知する温度センサーからの温度情報を電子制御手段に入力し、これから発信される温度制御情報を冷却器の循環ポンプに入力してその動作を制御するので、反応容器内の温度に応じて、予め決められた適切な反応容器の冷却熱量に調整可能であり、これにより水素添加反応の温度を、例えば６０～７５℃とし、かつ低下するヨウ素価の１単位当りの油脂温度上昇率が０．５以下、すなわち０～０．５である特定の条件に調整できる。 The temperature information from the temperature sensor that senses the temperature in the reaction vessel is input to the electronic control means, and the temperature control information transmitted from this is input to the circulation pump of the cooler to control its operation. Depending on the temperature, it is possible to adjust the cooling heat amount of the appropriate reaction vessel determined in advance, whereby the temperature of the hydrogenation reaction is, for example, 60 to 75 ° C., and the oil temperature per unit of iodine value that decreases The increase rate can be adjusted to a specific condition of 0.5 or less, that is, 0 to 0.5.
　またこのような水素添加油脂の製造装置において、前記電子制御手段を反応容器への水素供給装置に接続し、前記電子制御手段で冷却器の冷媒流量を制御する主調整に加えて前記水素供給装置の水素供給量を制御する補助調整を可能とすることもできる。 Further, in such a hydrogenated oil production apparatus, the electronic control means is connected to a hydrogen supply device to a reaction vessel, and the hydrogen supply device in addition to the main adjustment for controlling the refrigerant flow rate of the cooler by the electronic control means. It is also possible to make an auxiliary adjustment for controlling the hydrogen supply amount.
　このように電子制御手段で冷却器の冷媒流量および水素供給装置を制御すれば、反応容器内の温度および水素圧を精密に制御することが可能となり、トランス酸を極力発生させないで水素添加油脂を製造することができる。 Thus, by controlling the refrigerant flow rate and the hydrogen supply device of the cooler with the electronic control means, it becomes possible to precisely control the temperature and hydrogen pressure in the reaction vessel, and the hydrogenated oil and fat can be removed without generating transacid as much as possible. Can be manufactured.
　この発明は、水素添加反応の温度が所定範囲でありかつ前記水素添加反応で低下するヨウ素価の１単位当りの油脂温度上昇率を所定値以下であるように、冷却熱量およびそれでもなお不十分な場合は水素供給量と両方で調整して水素添加油脂を製造するので、多価不飽和脂肪酸を含む様々な油脂に対して、トランス酸を極力発生させない水素添加油脂の製造方法となり、しかも実用性の高い製造方法となるという利点がある。 In the present invention, the amount of heat of cooling and still insufficient is so low that the temperature of the hydrogenation reaction is within a predetermined range and the rate of increase in the oil temperature per unit of iodine value that decreases by the hydrogenation reaction is below a predetermined value. In this case, hydrogenated fats and oils are produced by adjusting both the amount of hydrogen supplied, so it becomes a method for producing hydrogenated fats and oils that do not generate transacid as much as possible for various fats and oils containing polyunsaturated fatty acids. There is an advantage that the manufacturing method becomes high.
　また、水素添加油脂の製造装置において、前記電子制御手段を反応容器への水素供給装置に接続し、前記電子制御手段で冷却器の水量などの冷媒流量および水素供給装置を制御して冷却熱量を調整し、不十分な場合は冷却器の冷媒流量と水素供給量との両方で調整可能としたので、反応容器内の温度に応じて、予め決められた適切な反応容器の冷却熱量に調整可能であり、またヨウ素価の１単位当りの油脂温度上昇率であるように、水素添加反応の温度を、例えば６０～７５℃であり、かつヨウ素価の１単位当りの油脂温度上昇率が０．５以下であるように特定の厳密な反応条件に調整でき、これによりトランス酸を極力発生させないで水素添加油脂を製造できる利点がある。 Further, in the hydrogenated oil production apparatus, the electronic control means is connected to a hydrogen supply device to the reaction vessel, and the electronic control means controls the refrigerant flow rate such as the amount of water in the cooler and the hydrogen supply device to reduce the heat of cooling. If it is not sufficient, it can be adjusted by both the refrigerant flow rate and the hydrogen supply amount of the cooler, so it can be adjusted to the appropriate cooling heat amount of the reaction vessel according to the temperature in the reaction vessel. In addition, the temperature of the hydrogenation reaction is, for example, 60 to 75 ° C., and the rate of increase in fat / oil temperature per unit of iodine value is 0. It can be adjusted to specific strict reaction conditions such that it is 5 or less, and there is an advantage that hydrogenated fats and oils can be produced without generating transacid as much as possible.
水素添加油脂の製造装置の概略構成を示す説明図Explanatory drawing which shows schematic structure of the manufacturing apparatus of hydrogenated fats and oils
　この発明の水素添加油脂の製造方法およびそれを実施するために使用可能な水素添加油脂の製造装置を以下に、図面を参照しながら説明する。
　先ず、多価不飽和脂肪酸を含む油脂に対し、触媒の存在下で水素添加反応を行なう水素添加油脂の製造方法においては、前記水素添加反応の温度が６０～７５℃でありかつ前記水素添加反応で低下するヨウ素価の１単位当りの油脂温度上昇率が０．５以下であるように、冷却熱量およびそれでもなお不十分な場合は水素供給量と両方で調整する。 The method for producing hydrogenated fats and oils of the present invention and the apparatus for producing hydrogenated fats and oils that can be used to implement the method will be described below with reference to the drawings.
First, in the method for producing hydrogenated fats and oils in which a hydrogenation reaction is performed on fats and oils containing polyunsaturated fatty acids in the presence of a catalyst, the hydrogenation reaction temperature is 60 to 75 ° C. and the hydrogenation reaction is performed. The amount of cooling heat and, if still insufficient, adjust the amount of hydrogen supplied so that the oil temperature increase rate per unit of the iodine value that decreases in 1 is 0.5 or less.
　ここで、この発明に用いる多価不飽和脂肪酸を含む油脂としては、特に限定せずに採用できる周知の食用油脂であり、前記したように牛脂、ラード、鶏脂、魚油、鯨油等の動物油脂、パーム油、分別パーム油、大豆油、菜種油、ヒマワリ油、サフラワー油、綿実油、コーン油などであり、またはこれらから選ばれる１種以上の油脂も採用できる。 Here, the fats and oils containing polyunsaturated fatty acids used in the present invention are well-known edible fats and oils that can be employed without any particular limitation, and as described above, animal fats such as beef tallow, lard, chicken fat, fish oil, whale oil and the like. , Palm oil, fractionated palm oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, cottonseed oil, corn oil and the like, or one or more oils and fats selected from these can also be employed.
　また、この発明では、上記の多価不飽和脂肪酸を含む油脂において、全脂肪酸１００重量％に多価不飽和酸（以下、ポリエン酸と称する場合がある。）量を３０重量％以下含有する油脂であることが好ましく、より好ましくは多価不飽和酸量を２５重量％以下含有する油脂である。代表的なものとしてはパーム油、分別されたパーム油、ラード、牛脂、ハイオレインの菜種油、ヒマワリ油などがあるがこれらに限定されるものではない。 Moreover, in this invention, in the fats and oils containing said polyunsaturated fatty acid, the fats and oils which contain 30 weight% or less of polyunsaturated acid (it may be hereafter called polyenoic acid) in 100 weight% of all fatty acids. More preferably, it is an oil containing 25% by weight or less of the amount of polyunsaturated acid. Representative examples include, but are not limited to, palm oil, fractionated palm oil, lard, beef tallow, hyolein rapeseed oil, sunflower oil, and the like.
　また、この発明に用いる触媒は、硬化油の製造に使用可能な周知なものであってもよい。但し、我国の食品衛生法で認可されている食用油脂の硬化触媒としてニッケル触媒があり、ニッケルのフレーク状のものや安定化ニッケルが使用され、市販品としては、堺化学社製のフレーク状ニッケル触媒のＳＯシリーズ（ＳＯ－７５０、ＳＯ－４５０など）などが挙げられる。 Further, the catalyst used in the present invention may be a well-known one that can be used for producing a hardened oil. However, there is a nickel catalyst as a curing catalyst for edible fats and oils approved by the Food Sanitation Act in Japan. Nickel flakes and stabilized nickel are used, and commercially available products are flaky nickel manufactured by Sakai Chemical Co., Ltd. Examples include SO series of catalysts (SO-750, SO-450, etc.).
　この発明の水素添加油脂の製造方法においては、前記水素添加反応の温度を６０～７５℃に所定の方法で調整する。なぜなら、６０℃未満の反応温度では、反応速度が極端に遅くなり実用的ではない。７５℃を越える高温ではトランス異性体の増加が大きくなりすぎ、かつまた反応速度が温度に比例して速くなり温度コントロールが困難になって所期の目的を達せられないからである。 In the method for producing hydrogenated fats and oils of the present invention, the temperature of the hydrogenation reaction is adjusted to 60 to 75 ° C. by a predetermined method. This is because at a reaction temperature of less than 60 ° C., the reaction rate becomes extremely slow, which is not practical. This is because at a high temperature exceeding 75 ° C., the increase in the trans isomer becomes too large, and the reaction rate increases in proportion to the temperature, making it difficult to control the temperature and the intended purpose cannot be achieved.
　また、この発明では、水素添加反応で低下するヨウ素価の１単位当りの油脂温度上昇率が０．５以下であるように所定の方法で調整する。なぜなら、ヨウ素価の１単位当りの油脂温度上昇率が０．５を超える状態では、トランス異性体の増加が大きくなりこの発明の所期の目的を達せられないからである。 Moreover, in this invention, it adjusts with a predetermined | prescribed method so that the oil-fat temperature rise rate per unit of the iodine value which falls by hydrogenation reaction may be 0.5 or less. This is because, in the state where the oil temperature rise rate per unit of iodine value exceeds 0.5, the increase in trans isomers becomes large and the intended purpose of the present invention cannot be achieved.
　また、この発明では、水素添加反応系に対する冷却熱量もしくは水素供給量または両方を調整する。
　冷却熱量を調整するには、具体的には反応装置の反応容器中の油温を検出し、それに対応して冷却器の水流量を制御する。その制御能力が限界に近くなる場合は供給する水素を停止して反応自体を制御する。
　反応装置を用いて水素供給量を調整するには、反応容器内に通じる管路の水素供給圧力、すなわち反応容器内の水素圧を０．５Ｍｐ（ゲージ圧）以下とし、反応温度を６０～７５℃、好ましくは６５～７５℃に調整する。 In the present invention, the amount of cooling heat and / or the amount of hydrogen supplied to the hydrogenation reaction system are adjusted.
In order to adjust the cooling heat quantity, specifically, the oil temperature in the reaction vessel of the reaction apparatus is detected, and the water flow rate of the cooler is controlled accordingly. When the control ability is close to the limit, the supplied hydrogen is stopped to control the reaction itself.
In order to adjust the hydrogen supply amount using the reaction apparatus, the hydrogen supply pressure of the pipe line leading to the reaction vessel, that is, the hydrogen pressure in the reaction vessel is set to 0.5 Mp (gauge pressure) or less, and the reaction temperature is set to 60 to 75. Adjust to 0 ° C., preferably 65 to 75 ° C.
　ここで、水素添加油脂の製造装置の構成およびその使用について説明する。
　図１に示すように、水素添加油脂の製造装置は、多価不飽和脂肪酸を含む油脂の供給路１および触媒の供給路２が接続され、かつ熱交換器のコイル状に配管された冷却コイル３およびチリングユニット４を有する冷却器５が付設され、かつ時間当たりの水素供給量を調整可能な水素の供給路６が付設された耐圧性の反応容器７を設け、この反応容器７に攪拌機８を設けて反応系（原料油脂と触媒等の混合物）Ａを攪拌しながら水素添加反応を連続的に行なわせる水素添加油脂の製造装置である。 Here, the structure of the manufacturing apparatus of hydrogenated fats and its use are demonstrated.
As shown in FIG. 1, a hydrogenated fat and oil manufacturing apparatus includes a cooling coil in which a fat and oil supply path 1 and a catalyst supply path 2 containing polyunsaturated fatty acids are connected and piped in a coil shape of a heat exchanger. 3 and a cooler 5 having a chilling unit 4 and a pressure-resistant reaction vessel 7 provided with a hydrogen supply path 6 capable of adjusting the hydrogen supply amount per hour is provided. And a reaction system (mixture of raw oil and fat, catalyst, etc.) A is stirred, and the hydrogenation fat and oil production apparatus is made to continuously perform the hydrogenation reaction.
　そして、この製造装置には、反応容器７内の温度を感知する温度センサー９および水素の供給路６に接続された圧力センサー１０を設け、これらの温度情報および圧力情報に基づいて制御信号を発信する電子コントローラ１１（横河電気社製：デジタル指示調節計）を設け、この電子コントローラ１１により循環ポンプ１７の動作および流量調整弁１５の動作を制御して反応系Ａに対する冷却熱量および水素供給量を調整可能とした水素添加油脂の製造装置である。 This manufacturing apparatus is provided with a temperature sensor 9 for sensing the temperature in the reaction vessel 7 and a pressure sensor 10 connected to the hydrogen supply path 6, and a control signal is transmitted based on these temperature information and pressure information. Electronic controller 11 (manufactured by Yokogawa Electric Co., Ltd .: digital indicating controller) is provided, and the electronic controller 11 controls the operation of the circulation pump 17 and the operation of the flow control valve 15 to control the amount of cooling heat and the amount of hydrogen supplied to the reaction system A. Is an apparatus for producing hydrogenated fats and oils that can be adjusted.
　ここで、前記した原料となる油脂は、図外の計量槽より油脂の供給路１に移送されて反応容器７に引き込まれ、反応容器７内は真空ポンプ１２により充分に減圧された後、油脂は反応開始温度まで加温される。 Here, the oil and fat used as the raw material is transferred to the oil and fat supply path 1 from a measuring tank (not shown) and drawn into the reaction vessel 7. After the pressure inside the reaction vessel 7 is sufficiently reduced by the vacuum pump 12, Is warmed to the reaction start temperature.
　ニッケル触媒は、触媒ホッパー２ａから投入されて反応容器７内に供給され、次いで攪拌機８により充分に分散される。攪拌機８は、電動モータで駆動され回転する攪拌翼を供えるなどの周知構造のものであり、回転翼の回転速度を上げることにより水素添加反応が開始される。 The nickel catalyst is charged from the catalyst hopper 2 a and supplied into the reaction vessel 7 and then sufficiently dispersed by the stirrer 8. The stirrer 8 has a known structure such as providing a rotating stirring blade driven by an electric motor, and the hydrogenation reaction is started by increasing the rotational speed of the rotating blade.
　水添反応に用いる水素は、図外のタンクから水素流量計１３を経由し、さらに水素の供給路６および流量調整弁１５を経由して反応容器７内の水素吹き込み管１６より泡状となって液状の反応系Ａ内に導入される。圧力センサー１０が所定の圧力になると電子コントローラ１１の制御動作により流量調整弁１５が開閉され水素供給量は調整される。また、水素添加反応の進行度合いは、水素カウンター１４により積算され、水素供給量の総量によって確認される。 Hydrogen used in the hydrogenation reaction is foamed from a tank (not shown) through a hydrogen flow meter 13 and further through a hydrogen supply path 6 and a flow rate adjusting valve 15 through a hydrogen blowing pipe 16 in the reaction vessel 7. And introduced into the liquid reaction system A. When the pressure sensor 10 reaches a predetermined pressure, the flow rate adjustment valve 15 is opened and closed by the control operation of the electronic controller 11 to adjust the hydrogen supply amount. The progress of the hydrogenation reaction is integrated by the hydrogen counter 14 and is confirmed by the total amount of hydrogen supply.
　水素添加反応が開始されると、反応熱による温度上昇を温度センサー９が感知し、電子コントローラ１１の制御により、冷却水などの熱媒体が循環ポンプ１７より冷却コイル３に所要流量だけ供給されて反応温度が制御される。また、循環された冷却水はチリングユニット４で冷却され、冷却水として再使用される。因みにチリングユニット４は、蒸気圧縮装置などを１台の架台に組み込んだ水などの熱媒体の冷却装置である。 When the hydrogenation reaction is started, the temperature sensor 9 senses the temperature rise due to the reaction heat, and a heat medium such as cooling water is supplied to the cooling coil 3 from the circulation pump 17 to the cooling coil 3 under the control of the electronic controller 11. The reaction temperature is controlled. The circulated cooling water is cooled by the chilling unit 4 and reused as cooling water. Incidentally, the chilling unit 4 is a cooling device for a heat medium such as water in which a vapor compression device or the like is incorporated in one frame.
　また、水などの熱媒体による温度制御が不十分な場合に限って、電子コントローラ１１の制御により水素の流量調整弁を調整して反応に使用される水素の量を減らし、水などの熱媒体による温度制御と連動した複合的な温度制御を行なっても良い。 In addition, only when temperature control using a heat medium such as water is insufficient, the amount of hydrogen used in the reaction is reduced by adjusting the hydrogen flow rate adjusting valve under the control of the electronic controller 11, so that the heat medium such as water is used. Combined temperature control in conjunction with temperature control by may be performed.
　反応を終了させるには、攪拌機８の回転翼の回転速度を下げることにより水素添加反応は終了され、水素添加された油脂は濾過タンクへと移送される。 To terminate the reaction, the hydrogenation reaction is terminated by lowering the rotational speed of the rotor blades of the agitator 8, and the hydrogenated fat is transferred to the filtration tank.
［実施例１～４、６、７］
　容量２リットルの反応容器（以下、オートクレーブと称する。）に原料油脂１ｋｇを仕込み、フレーク状のニッケル触媒（堺化学株式会社製：ＳＯ－７５０、ＳＯ－４５０）を所定量加えて反応開始温度まで加温した。水素添加反応においては、表１中に示す所定の反応温度範囲内にて反応させるために、オートクレーブのジャケットへ冷却水を流し、表１中に示す反応温度範囲、温度上昇率などの反応条件における水素添加反応を厳密な管理下で行なって硬化油を製造し、得られた硬化油のヨウ素価およびトランス酸含量を表１中に併記した。 [Examples 1 to 4, 6, 7]
1 kg of raw oil / fat is charged into a reaction vessel (hereinafter referred to as autoclave) having a capacity of 2 liters, and a predetermined amount of flake nickel catalyst (manufactured by Sakai Chemical Co., Ltd .: SO-750, SO-450) is added to the reaction start temperature. Warmed up. In the hydrogenation reaction, in order to make the reaction within the predetermined reaction temperature range shown in Table 1, cooling water is allowed to flow through the jacket of the autoclave, and the reaction temperature range and temperature increase rate shown in Table 1 are satisfied. The hydrogenation reaction was performed under strict control to produce a hardened oil, and the iodine value and trans acid content of the obtained hardened oil are also shown in Table 1.
　なお、ヨウ素価は基準油脂分析試験法２．３．４．１－１９９６ヨウ素価（ウィイス－シクロヘキサン法）により、トランス酸量は、基準油脂分析試験法暫１７－２００７トランス脂肪酸含量（キャピラリーガスクロマトグラフ法）に従い測定した。但し、精製魚油および精製魚油の硬化油のトランス酸含量は、基準油脂分析試験法暫９－２００３孤立トランス異性体（差赤外スペクトル－シクロヘキサン法）に従い測定した。 The iodine value is based on the standard oil analysis test method 2.3.4.1-1996 iodine value (Wiis-cyclohexane method), and the amount of trans acid is based on the standard fat analysis method 17-2007 trans fatty acid content (capillary gas chromatograph). Method). However, the trans acid content of the refined fish oil and the hardened oil of the refined fish oil was measured in accordance with the standard oil analysis test method 9-2003 isolated trans isomer (difference infrared spectrum-cyclohexane method).
　表中、トランス酸上昇は、水素添加反応で低下するヨウ素価の１単位当りに増加するトランス酸の量を以下の数１の式により算出したものである。 In the table, the increase in trans acid is the amount of trans acid that increases per unit of iodine value that decreases by the hydrogenation reaction, calculated by the following equation (1).
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　また、表中に示す油脂温度上昇率とは、ヨウ素価の１単位当りの油脂温度上昇率を示し、その計算式は、以下の数２の式に示される通りである。 In addition, the oil / fat temperature increase rate shown in the table indicates the oil / fat temperature increase rate per unit of iodine value, and the calculation formula is as shown in the following equation (2).
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　なお、原料油脂としては、精製パーム油（ヨウ素価：５０．８、トランス酸：０．２％）、精製豚脂（ヨウ素価：５９．０、トランス酸：１．４％）、精製魚油（ヨウ素価：１５３．４、トランス酸：２．１％)、精製ハイオレイン菜種油（ヨウ素価：１００．９、トランス酸：０．６％）、精製菜種油（ヨウ素価：１１４.０、トランス酸：１.１％）を用いた。 In addition, as raw material fats and oils, refined palm oil (iodine value: 50.8, trans acid: 0.2%), refined pork fat (iodine value: 59.0, trans acid: 1.4%), refined fish oil ( Iodine value: 153.4, trans acid: 2.1%), refined hyolein rapeseed oil (iodine value: 100.9, trans acid: 0.6%), refined rapeseed oil (iodine value: 114.0, trans acid: 1.1%) was used.
［比較例１、２］
　表１に示す原料油脂１ｋｇを容量２リットルのオートクレーブに仕込み、フレーク状のニッケル触媒（堺化学株式会社製：ＳＯ－７５０）を所定量加えて反応開始温度まで加温した。水素添加反応においては、反応温度が異常に高くなると油脂の劣化や反応が制御不能となり製造上危険を伴うため、ヨウ素価の低下が大きい反応においてはオートクレーブのジャケットへ冷却水を流すことにより反応温度上昇を抑え、ヨウ素価の低下が小さい反応においては冷却せずに表１に記載の各種条件で水素添加反応を行い、硬化油を作成した。得られた硬化油のヨウ素価、トランス酸量を表１中に示した。 [Comparative Examples 1 and 2]
1 kg of raw oil and fat shown in Table 1 was charged into a 2 liter autoclave, and a predetermined amount of flaky nickel catalyst (manufactured by Sakai Chemical Co., Ltd .: SO-750) was added and heated to the reaction start temperature. In the hydrogenation reaction, if the reaction temperature becomes abnormally high, the deterioration of the oil and fats and the reaction become uncontrollable and there is a risk in manufacturing.Therefore, the reaction temperature is increased by flowing cooling water through the jacket of the autoclave in the reaction with a large decrease in iodine value. In the reaction in which the increase was suppressed and the decrease in iodine value was small, the hydrogenation reaction was carried out under various conditions shown in Table 1 without cooling to prepare a hardened oil. Table 1 shows the iodine value and trans acid amount of the obtained hardened oil.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１の結果からも明らかなように、冷却水を流すことにより油脂温度上昇率を０．２２～０．５に調整し、かつ反応の温度を６０～７５℃に調整して製造した実施例１～４、６、７の硬化油では、トランス酸含有量は１．６～４．１％の範囲で低く優れた硬化油となった。 As can be seen from the results in Table 1, Examples were prepared by adjusting the oil temperature increase rate to 0.22 to 0.5 and adjusting the reaction temperature to 60 to 75 ° C. by flowing cooling water. In the cured oils of 1-4, 6, and 7, the trans acid content was in the range of 1.6 to 4.1%, and the cured oil was excellent.
　一方、反応温度が所定範囲を超える高温であり、かつヨウ素価の１単位当りの油脂温度上昇率が所定値より高い比較例１、２では、トランス酸含有量は１３．４～３９．１％という高い硬化油であった。 On the other hand, in Comparative Examples 1 and 2 in which the reaction temperature is a high temperature exceeding a predetermined range and the oil temperature rise rate per unit of iodine value is higher than the predetermined value, the trans acid content is 13.4 to 39.1%. It was a high hydrogenated oil.
［実施例９］
　実施形態にて説明した製造装置にて水素添加を行った。原料油脂として精製パーム油（ヨウ素価： ５１．５ 、トランス酸：０．２％)７ｔをオートクレーブに仕込み、フレーク状のニッケル触媒（堺化学株式会社製：ＳＯ－７５０）を所定量加えて反応開始温度まで加温した。水素添加反応は、表２中に記載した所定の反応温度内その他の条件で反応するように、オートクレーブの冷却コイルへあらかじめ１０℃に冷却された冷却水を流し、それでも不充分な場合は加圧状態にある水素圧を低下させる調整をすることによって反応速度を調整し、このような厳密な温度管理の下で水素添加反応を行って硬化油を作成した。得られた硬化油のヨウ素価、トランス酸量を表２中に併記した。 [Example 9]
Hydrogenation was performed in the production apparatus described in the embodiment. 7t of refined palm oil (iodine value: 51.5, trans acid: 0.2%) as raw material fat is charged into an autoclave, and a predetermined amount of flake nickel catalyst (manufactured by Sakai Chemical Co., Ltd .: SO-750) is added to react. Warmed to start temperature. In the hydrogenation reaction, cooling water previously cooled to 10 ° C. is allowed to flow through the cooling coil of the autoclave so that the reaction takes place within the predetermined reaction temperature described in Table 2, and if it is still insufficient, pressurization is performed. The reaction rate was adjusted by adjusting to reduce the hydrogen pressure in the state, and the hydrogenation reaction was performed under such strict temperature control to prepare a hardened oil. The iodine value and the amount of trans acid of the obtained hardened oil are also shown in Table 2.
［比較例３］
　原料油脂として実施例９と同じ精製パーム油（ヨウ素価：５１．５ 、トランス酸：０．２％）７ｔをオートクレーブに仕込み、フレークニッケル触媒（ＳＯ－７５０ ：堺化学株式会社製）を所定量加えて反応開始温度まで加温した。水素添加反応は、ヨウ素価の低下が小さい反応であったため、冷却を行わずに表２中に記載した反応温度その他の各種条件で行なって硬化油を製造した。得られた硬化油のヨウ素価、トランス酸量を表２中に併記した。 [Comparative Example 3]
7t of the same refined palm oil (iodine value: 51.5, trans acid: 0.2%) as in Example 9 was charged into the autoclave as a raw oil and fat, and a predetermined amount of flake nickel catalyst (SO-750: manufactured by Sakai Chemical Co., Ltd.) In addition, the reaction was heated to the reaction start temperature. Since the hydrogenation reaction was a reaction with a small decrease in iodine value, it was carried out at the reaction temperature and other various conditions described in Table 2 without cooling to produce a hardened oil. The iodine value and the amount of trans acid of the obtained hardened oil are also shown in Table 2.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表２の結果からも明らかなように、冷却熱量および水素供給量の両方を調整することにより油脂温度上昇率を０．５に調整し、かつ反応の温度を７０～７４℃に調整して製造した実施例９の硬化油は、トランス酸含有量は２．５％で低く優れた硬化油となった。 As is apparent from the results in Table 2, the oil and fat temperature increase rate is adjusted to 0.5 by adjusting both the cooling heat amount and the hydrogen supply amount, and the reaction temperature is adjusted to 70 to 74 ° C. The cured oil of Example 9 was an excellent cured oil having a low trans acid content of 2.5%.
　一方、反応温度が所定範囲を超える１４０～１５６℃という高温であり、かつヨウ素価の１単位当りの油脂温度上昇率が１．７であって所定値の０．５より高い比較例３では、トランス酸含有量は１１．５％という高い硬化油であった。 On the other hand, in Comparative Example 3 where the reaction temperature is as high as 140 to 156 ° C. exceeding the predetermined range and the oil temperature rise rate per unit of iodine value is 1.7, which is higher than the predetermined value of 0.5, The trans acid content was as high as 11.5% hydrogenated oil.
１　油脂の供給路
２　触媒の供給路
２ａ　ホッパー
３　冷却コイル
４　チリングユニット
５　冷却器
６　水素の供給路
７　反応容器
８　攪拌装置
９　温度センサー
１０　圧力センサー
１１　電子コントローラ
１２　真空ポンプ
１３　水素流量計
１４　水素カウンター
１５　流量調整弁
１６　水素吹き込み管
１７　循環ポンプ DESCRIPTION OF SYMBOLS 1 Oil supply path 2 Catalyst supply path 2a Hopper 3 Cooling coil 4 Chilling unit 5 Cooler 6 Hydrogen supply path 7 Reaction vessel 8 Stirrer 9 Temperature sensor 10 Pressure sensor 11 Electronic controller 12 Vacuum pump 13 Hydrogen flow meter 14 Hydrogen Counter 15 Flow adjustment valve 16 Hydrogen blowing pipe 17 Circulation pump

Claims (3)

  1. 　全脂肪酸１００重量％に多価不飽和酸量を３０重量％以下含有する油脂に対し、ニッケル触媒の存在下で水素添加反応を行なう水素添加油脂の製造方法において、
    　前記水素添加反応の温度が６０～７５℃でありかつ前記水素添加反応で低下するヨウ素価の１単位当りの油脂温度上昇率が０．２２～０．５であるように、水素添加反応系に対する冷却熱量の調整および水素添加反応系に対する水素供給圧力を０．５Ｍｐ以下にする水素供給量の調整をすることを特徴とする水素添加油脂の製造方法。     In a method for producing hydrogenated fats and oils in which a hydrogenation reaction is performed in the presence of a nickel catalyst for fats and oils containing 30% by weight or less of polyunsaturated acids in 100% by weight of total fatty acids,
    The hydrogenation reaction system is adjusted so that the temperature of the hydrogenation reaction is 60 to 75 ° C. and the oil temperature increase rate per unit of iodine value that is decreased by the hydrogenation reaction is 0.22 to 0.5. A method for producing hydrogenated fats and oils, characterized by adjusting the amount of cooling heat and adjusting the amount of hydrogen supplied so that the hydrogen supply pressure to the hydrogenation reaction system is 0.5 Mp or less.
  2. 　全脂肪酸１００重量％に多価不飽和酸量を３０重量％以下含有する油脂が、牛脂、ラード、鶏脂、パーム油、分別パーム油、ハイオレイン菜種油およびハイオレインヒマワリ油から選ばれる１種以上の油脂である請求項１に記載の水素添加油脂の製造方法。 One or more types of fats and oils containing 30% by weight or less of polyunsaturated acid in 100% by weight of total fatty acids selected from beef tallow, lard, chicken fat, palm oil, fractionated palm oil, hyolein rapeseed oil and hyolein sunflower oil The method for producing a hydrogenated fat according to claim 1.
  3. 　請求項１または２に記載の水素添加油脂の製造方法において、
    　水素添加反応で増加するトランス酸の量が、前記水素添加反応で低下するヨウ素価の１単位当り０．２５重量％以下であるように冷却熱量の調整および水素添加反応系に対する水素供給圧力を０．５Ｍｐ以下にする水素供給量の調整をする水素添加油脂の製造方法。     In the manufacturing method of the hydrogenated fats and oils of Claim 1 or 2,
    Adjustment of the heat of cooling and the hydrogen supply pressure to the hydrogenation reaction system were set to 0 so that the amount of transacid increased by the hydrogenation reaction was 0.25% by weight or less per unit of iodine value decreased by the hydrogenation reaction. A method for producing hydrogenated fats and oils that adjusts the hydrogen supply amount to 5 Mp or less.
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