JPH0369516B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a method for processing fats and oils. In oil and fat processing, hydrogenation, fractionation, transesterification, etc. are the most basic conventional methods. Among these methods, a method using lipolytic enzymes has recently been newly suggested as a transesterification method. It is easy to introduce specific fatty acids into oils and fats, and in this respect, it has the potential to expand the flexibility of oil and fat processing technology. This selectivity of transesterification is particularly useful in the field of hard butter, cocoa butter-like oil production technology;
If the desired fatty acid is introduced from an external fatty acid source into an oil or fat whose fatty acid bound to the 2nd position is rich in oleic acid by the action of a lipolytic enzyme that is selective for the 1st and 3rd positions of glycerides, the overall fatty acid composition can be changed simply by introducing the desired fatty acid from an external fatty acid source. This makes it possible to better approximate the composition of cacao butter not only in the composition but also in the fatty acid composition of each part. For example, stearic acid is introduced into the 1st and 3rd positions of an oil fraction rich in POP (2-oleodipalmitin), and palmitic acid or stearic acid is introduced into the 1st and 3rd positions of an oil fraction rich in triolein. This is the mode of doing so. However, the essence of selective transesterification is
It is randomization (disordering) of fatty acid distribution between sites that acts selectively. Therefore, the greater the difference in the constituent fatty acids of the active site between the raw material oil to be processed and the target oil, the greater the need for a large amount of introduced fatty acid source, or the greater the difference between the target oil and fat after transesterification. This increases the drawback that the separated and recovered fatty acid or fatty acid ester has a composition significantly different from that of the introduced fatty acid source, making it difficult to use it again as an introduced fatty acid source in the same system. In addition, even if the difference in the constituent fatty acids between the raw material oil and fat to be processed and the target oil is not very large, when the fatty acid composition of the active site between the target oil and fat and the introduced fatty acid source is extremely similar. (For example, when trying to remove most of a certain type of fatty acid from a specific part of the target fat or oil), there is also the drawback that a large amount of introduced fatty acid source is required. Other difficulties in applying selective transesterification to hard butters where crystallinity is important, such as cocoa butter-like oils, are the reduction in yield due to hydrolysis accompanying transesterification, and the phase formation of the hydrolyzate and glycerides. Glyceride quality is inhibited due to solubility. This problem can be improved by conducting the reaction in a dry system, but as is the general trend in the fermentation industry, shortening the reaction time is still one of the issues to be improved. Under these circumstances, while conducting various studies on the application of selective transesterification to fat and oil processing technology for producing hard butter, the present inventors discovered that the transesterification reaction product was separated from fats and oils and recovered. Hydrogenating fatty acids or fatty acid esters,
By recycling this as part of the raw material, the amount of introduced fatty acid source used in the raw material fats and oils to be processed can be reduced, and the quality of hard butter products can be improved.
This invention was completed after discovering that it contributes to improving the yield and is also useful for shortening the reaction time. This invention is a reaction in which a mixture c consisting of glyceride a and triglyceride and a separable fatty acid ester or fatty acid b is selectively transesterified using an enzyme that transesterifies the 1st and 3rd positions of triglyceride but does not transesterify the 2nd position. From product d, fatty acid ester or fatty acid e that can be separated from triglyceride is separated from glyceride f and then hydrogenated, and this g is used as part of mixture c.Glyceride is separated from reactant d in the circulation system to obtain hard butter. This is a method of processing fats and oils that is based on this. This invention will be explained in detail below. As mentioned above, glyceride a is preferably an oil or fat in which the fatty acid bonded to the 2-position is rich in oleic acid. Olive oil, Oriental flower oil, Camellia oil, Palm oil, Rapeseed oil (Zero Erucic type), Shea butter, Sal fat, Mango fat, Corcum, Borneo tallow,
It is preferable to use raw or fractionated fats and oils such as Malabar fat and Malabar fat, which generally contain 70% or more of oleic acid among the fatty acids bonded to the 2-position. The fatty acid ester or fatty acid b that can be separated from triglyceride is a source of introduced fatty acids, and preferably contains palmitic acid or stearic acid. The fatty acid ester or fatty acid b may be in the form of a free fatty acid or an alcohol ester, but should be separable from triglycerides. For example, esters such as diglycerides form a eutectic mixture with triglycerides and can hardly be separated by normal industrial means, which has the disadvantage of remaining in the product and impairing the quality of hard butter. Alcohol esters include monohydric alcohols, dihydric alcohol esters such as propylene glycol esters, sorbitan esters, etc., but the most preferred are esters of monovalent lower alcohols having 1 to 4 carbon atoms. . In a production system including a step of fractionating and removing esters of fatty acids having different carbon numbers, which will be described later, ester b
Unless it is an ester of a monohydric alcohol, it will be difficult to separate esters based on the type of fatty acid. The mixture c consisting of glyceride a and triglyceride and the separable fatty acid ester or fatty acid b is preferably subjected to the transesterification reaction in as dry a state as possible. If the water content in mixture c is high, hydrolysis will proceed along with transesterification, increasing the production of diglyceride content that is difficult to separate from triglyceride, and will increase the hardness of the SFI curve, cooling curve, and tempering operations. It is a raw material that is difficult to use in the production of butter.
The water content in mixture c is preferably lower, for example, 0.18% by weight or less. Preferred enzyme agents that exhibit excellent activity in dry or non-hydrolyzed systems are those obtained by dispersing, adsorbing, or bonding the enzyme to a carrier in an aqueous system, and then drying this. Even those that have not been treated with microbial enzymes can still be used, although they have weak activity. However, in the present invention, there are no limitations on the type or preparation method of the enzyme, as long as it has transesterification activity in a low moisture system and exhibits the desired selectivity. The selectivity of transesterification is such that the 1st and 3rd positions of the triglyceride are transesterified, but the 2nd position is not transesterified. Examples of enzymes that exhibit such selectivity include those of animal and plant origin such as pancreatic lipase and rice bran lipase, and those of microbial origin such as Rhizopus deremer, Rhizopus japonicus, Rhizopus niveus, Aspergillus niger, and Mucor jabanicas. Ru. The reaction temperature is generally within the range of 20-75°C. The fatty acid ester that can be separated from the triglyceride or the fatty acid e and the glyceride f can be separated from the reactant d by a known method such as distillation or adsorption. Hard butter can be obtained from glyceride f as it is or by fractionating to remove the high melting point portion or the low melting point portion, and the technique of cutting off the high melting point portion or the low melting point portion is well known in the field of hard butter production. When hard butter is obtained from the same glyceride f, the quality and yield of hard butter are generally inversely proportional. In this invention, a circulating system is constructed in which fatty acid ester or fatty acid e is separated from glyceride f and then hydrogenated, and this g is used as a part of mixture c, and glyceride is separated from reactant d in the circulating system to make hard butter. One of the effects of obtaining this is that compared to the case where fatty acid ester or fatty acid e is simply recycled, the yield is increased without deteriorating the quality of hard butter obtained by separating glyceride from the reactant d in the circulation system. , or to improve the quality of hard butter without reducing the yield. Another effect of recycling the hydrogenated substance g as part of the mixture c is that in the above-mentioned production system, the amount of the introduced fatty acid source b can be significantly smaller than the amount of the raw material fat a. be. Hydrogenate g to mixture c
Another effect of recycling as part of mixture c is a reduction in the reaction time required for transesterification, and this effect can also be achieved by recycling all or the low melting point part of glyceride f as part of mixture c. By doing so, it will further increase. In other words, the circulation of the glyceride f component means that the transesterification performed on a certain raw material fat a is carried out in multiple stages, and in this multistage reaction, refreshed hydrogenated product g is supplied each time. In addition, when the low melting point part of glyceride f is supplied as part of mixture c, there is no loss due to the process of decomposition and synthesis by exposing the part of the glyceride that has the desired composition to the reaction again. In addition to being extremely efficient, the overall transesterification time is greatly reduced. This embodiment in which all or the low melting point part of glyceride f is recycled as part of mixture c,
An unsaturated fatty acid having 18 carbon atoms (oleic acid, linoleic acid, or linolenic acid) among the fatty acids bonded to the site where transesterification is selectively performed in mixture c.
is particularly useful when is greater than 10%. In other words, the higher the degree of unsaturation in mixture c, the higher the reaction rate in one transesterification reaction.
Even if the process is carried out up to 100%, good quality hard butter cannot be obtained from glyceride f unless the low melting point part is removed. This is because, in addition to shortening the reaction time, the effect of improving the yield by reusing the separated low melting point portion is achieved. Conventionally, when glycerides are separated into high, medium, and low melting point components, the low melting point portion contains few active ingredients as hard butter such as 2-unsaturated and 1,3-disaturated, or has a quality similar to diglyceride. It was never used again as a raw material for hard butter due to the presence of many inhibitory substances.
In this invention, the property of being unsaturated at the 2nd position is actively utilized in hard butter, and since a product with a low glyceride content can be obtained, cyclic use is less likely to be hindered. Prior to hydrogenating the fatty acid ester or the fatty acid e, the hydrogenation catalyst may be purified to remove catalyst poisons, if necessary. The degree of hydrogenation is most preferably carried out to a so-called extremely hard state; however, the unsaturated portion of the fatty acid at the site where the transesterification of the recovered fatty acid ester or fatty acid e is carried out (the degree of unsaturation is It is preferable that at least 40% of the iodine value (expressed in terms of iodine value) be saturated by hydrogenation. The greater the degree of hydrogenation here, the greater are the effects of improving quality, increasing yield, reducing the amount of fatty acid ester or fatty acid b used relative to glyceride a, and shortening the transesterification reaction time. Another preferred embodiment of the present invention is to separate an ester of a fatty acid having 16 or less carbon atoms or a fraction of a fatty acid having 16 or less carbon atoms that can be separated from triglycerides from the reactant d, fatty acid ester or fatty acid e, or hydrogenated product g. However, a step of removing this from the system is also carried out, but this embodiment can be carried out in one step with separating the fatty acid ester or fatty acid e and the glyceride f from the reactant d (rectification). In this embodiment, the fatty acids bonded to the site of interesterification in mixture c are mainly composed of C ₁₈ fatty acids and C ₁₆ fatty acids, and moreover, considering the fatty acid composition that should be in the target hard butter, C ₁₆ fatty acids are When trying to lower the content, the effects of curing the fatty acid ester or fatty acid e component, i.e., increasing the absorption rate, reducing the amount of fatty acid ester or fatty acid b used relative to glyceride a, and shortening the transesterification reaction time. It has the effect of increasing the effect. In today's world SOS
(2-oleodystearin)-rich resources.
Resources rich in POPs are more abundant and cheaper, so in order to obtain hard butter rich in POPs (2-oleo-1,3-palmitostearin), it is better to use resources rich in POPs than to use resources rich in SOS. In the production of highly pure SOS or POP, which can be used as a physical property improver such as adjusting the melting point of cocoa butter or hard butter, it is more advantageous to produce expensive SOS. d, fatty acid ester or fatty acid e, or hydrogenated product g, it is often useful to utilize this embodiment of removing C ₁₆ or less fractions. In this invention, the ratio of fatty acid ester or fatty acid to glyceride in mixture c is usually 1:
One of the effects of the present invention is that the amount of fatty acid source consumed relative to the consumed glyceride can be used in an extremely small amount when viewed in the entire repeated production system. This invention will be explained below with reference to Examples. Example 1 Commercially available Rhizopus japonicus lipase
Disperse and dissolve 1.5 parts in 5 parts of cold water, add 2.5 parts of diatomaceous earth, mix, and dry under reduced pressure at 20°C to obtain a moisture content of 1.8%.
diatomaceous earth enzyme was obtained. On the other hand, 100 parts of medium melting point part of palm (IV35) and 100 parts of methyl stearate (purity 90%, IV0.5) were mixed and dried under reduced pressure to obtain a reaction substrate with a water content of 0.01%.
For 200 parts of this reaction substrate, add 10 parts of the diatomaceous earth enzyme mentioned above.
After stirring at 45℃ for 4 days to prevent moisture absorption, the enzyme agent was removed, and further rectification was performed to divide the triglyceride classification (hereinafter referred to as TG classification), C ₁₆ classification (C ₁₆ 90% purity), and C ₁₈ Classification ( _C18 90% purity)
The _C18 fraction is cured (hydrogenated).
After bringing it below IV1, another fresh methyl stearate was added to make up the same amount as the first, and again mixed 1:1 with fresh palm mid-melting part, and the above production system was repeated. The triglyceride fraction obtained each time was subjected to solvent fractionation to remove the high melting point portion to obtain hard butter. As a comparison, an identical production system was also repeated without curing the recovered C ₁₈ section. The IV of the recovered methyl ester is shown below.

[Table] The hard butter of this example obtained every time had a fat similar to cocoa butter, and good results were obtained in the thiokolate test, but the hard butter of the comparative example had a high melting point at the fifth time. The melting point is low (30.7℃, 33.5℃ in this example)
°C), the low melting point portion was removed (ie, the yield was reduced), and the result was an oil that closely resembled cocoa butter. In addition, in order to carry out the reaction at once, the same amount of palm medium melting point part (500 parts) used for 5 repetitions is 500 parts.
of methyl stearate, whereas in this example, in which the C ₁₈ methyl ester fraction after the reaction was recovered, cured, and recycled, about 260 parts was sufficient even including operational losses. The properties of the hard butter of this example after 5 repetitions were as follows: melting point: 33.5°C, IV: 35; fatty acid composition:

[Table] Example 2 Using commercially available Rhizopus niveus lipase and pearlite as a carrier to make pearlite enzyme, using stearic acid instead of methyl stearate, reacting at 69°C for 4 days, and The same production system as in Example 1 was repeated, except that a silica gel column was used to separate the fatty acid fractions, and oils and fats similar to cocoa butter were stably obtained each time. Example 3 Commercially available lipase from Rhizopus japonicus (intracellular enzyme) was dried under reduced pressure to a moisture content of 1.5%. On the other hand, 35 parts of palm medium melting point part (IV34), 65 parts of sal fat liquid side fractionated oil (IV67) and fatty acid methyl ester (stearic acid 60%, palmitic acid 40%)
200 parts of the reaction substrate were mixed, and 9 parts of the above-mentioned enzyme were added to 300 parts of this reaction substrate, and the mixture was stirred at 45°C for 7 days under airtight conditions. After the reaction product was collected, the methyl ester was separated by distillation, and after being cured, it was mixed with the separated and collected triglyceride fraction, and the enzymatic reaction was repeated again.
After recovering the substrate liquid and removing methyl ethyl, the hard butter obtained by removing the high melting point portion by solvent fractionation was an oil similar to cocoa butter in fatty acid composition and melting point. The recovered methyl ester could be cured and subjected to repetition of the production system. Example 4 5gr of commercially available watermelon lipase was mixed with 2gr of polyvinyl alcohol cyanated with bromcyanite and
After being refrigerated overnight with 50 ml of 0.1M phosphate buffer (PH7.5), it was recovered and dried under reduced pressure to obtain a polyvinyl alcohol-immobilized enzyme (water content 1.7%). On the other hand, 100 parts of olive oil and 100 parts of ethyl stearate were dried under reduced pressure to obtain a reaction substrate (water content: 0.015%). After adding 7.5 parts of polyvinyl alcohol-immobilized enzyme to this reaction substrate and stirring at 45°C for 3 days, the substrate was recovered and separated into an ethyl ester fraction and a triglyceride fraction by distillation. After the recovered ethyl ester fraction was cured, it was mixed again with the separated triglyceride fraction and the enzymatic reaction was repeated. After the reaction, the substrate was recovered and the ethyl ester was recovered by distillation. Furthermore, the same curing, mixing, enzymatic reaction, and recovery are repeated,
The obtained triglyceride fraction is further separated into a solid side and a liquid side by solvent fractionation, and the solid side has a melting point of 36.5℃.
The fatty acid composition of IV36 was as shown below, and it was an excellent cocoa butter substitute when mixed with palm mid-melting point part at a ratio of 1:1. C ₁₆ C ₁₈ C ₁₈ : ₁ C ₁₈ : ₂ C ₂₀ 10.5 49.2 38.1 1.2 0.3 Example 5 1 part of commercially available Rhizopus delemer lipase and 2 parts of diatomaceous earth were mixed, and an appropriate amount of cold water was further sprayed with stirring. This was granulated and dried under reduced pressure at 15°C to obtain diatomaceous earth enzyme with a water content of 1.5%. Separately, 100 parts of purified safflower oil (high oleic acid) and 100 parts of methyl stearate (93% purity) were heated and dried under reduced pressure to create a reaction substrate (moisture 0.01%), and to this was added 10 parts of the diatomaceous earth enzyme. After stirring for 5 days at 45° C. under closed conditions, the substrate oil was recovered. After removing the methyl ester by distillation, the triglyceride fraction was separated into solid and liquid sides using a solvent. 60 parts of this liquid side is made up to 100 parts by adding the same purified safflower oil, and then the separated methyl ester is extremely hardened and the missing amount of methyl ester (93% purity) is added to make 100 parts, and these are mixed. Then, the reaction, distillation, and fractionation were repeated in the same manner as above as a reaction substrate.

[Table] The high melting point part of this 5th triglyceride classification can be used as is, but in order to further improve the quality, the high melting point part and the middle melting point part obtained by removing the liquid side are used as hard butter as shown below. It had excellent properties (melting point 38.0℃, IV33). This hard butter was further mixed with the mid-melting point portion of palm in an equal amount, and the mixture was also a good thiokolate-like hard butter.

[Table] Example 6 The same operation as in Example 5 was repeated except that 0.3% by weight of water was further added to the reaction substrate each time, and the diglyceride content in the reaction product was
10.3%, and 14.5% the second time.

Claims (1)

[Scope of Claims] 1. A mixture c consisting of glyceride a and triglyceride and a separable fatty acid ester or fatty acid b is selectively esterified using an enzyme that transesterifies the 1st and 3rd positions of the triglyceride but does not transesterify the 2nd position. From the exchanged reactant d, fatty acid ester or fatty acid e that can be separated from triglyceride is separated from glyceride f and then hydrogenated, and this g is used as part of mixture c.
A method of processing fats and oils, which is characterized by separating glycerides from the oil to obtain hard butter. 2. The processing method according to claim 1, wherein hard butter is obtained by separating glyceride from reactant d in a circulating system in which all or a low melting point part of glyceride f is also used as part of mixture c. 3 Separate the ester of fatty acids with 16 or less carbon atoms or the fraction of fatty acids with 16 or less carbon atoms that can be separated from triglycerides from the reactant d, fatty acid ester or fatty acid e, or fatty acid ester or fatty acid g, and remove this from the system. The processing method according to claim 1, which removes.