JPS5911640B2 - Method for producing fats and oils with high trans isomer content - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for hydrogenating fats and oils.

More specifically, the present invention relates to a method of hydrogenating fats and oils to produce fats and oils with a high degree of selectivity and a high content of trans-isomer. Conventionally, a method of hydrogenating fats and oils using a sulfur-poisoned nickel catalyst has been used as a method for producing fats and oils with a high content of trans isomers.

This sulfur-poisoned nickel catalyst contains about 1 to 10% by weight of sulfur based on nickel, and has high isomerization performance, but the sulfur content in the catalyst tends to vary depending on the catalyst manufacturing conditions, resulting in poor isomerization performance, etc. It has the disadvantage that the catalytic activity varies, and it is difficult to control hydrogenation conditions and the like to obtain a specific oil or fat with a high trans isomer content. There is also a method of hydrogenating unpoisoned reduced nickel by adding hydrogen sulfide or the like while poisoning it, but this is not preferable from a food hygiene perspective and the reaction operation is complicated. Furthermore, there is a method in which sulfur-containing amino acids such as methionine are added to unpoisoned reduced nickel and hydrogenation is carried out while poisoning. ) is lower than 5, as is the conventional value, so even if hydrogenation is performed under selective conditions, it is not possible to avoid the formation of a large amount of high melting point part, and on the other hand, a large amount of methionine is added. As a result, hydrogenation does not proceed and the amount of trans isomer produced naturally decreases (see Comparative Example 6 of Comparison 20). The purpose of the present invention is to hydrogenate fats and oils without using catalysts that are poisoned by sulfur and hydrogen sulfide, which are undesirable from a food hygiene perspective, to achieve high selectivity with very simple operations, and to isomerize fats and oils. Adjust the degree arbitrarily with little variation 2
It is an object of the present invention to provide a method for isomerizing fats and oils that can be controlled in a highly controlled manner, that is, a method for hydrogenating fats and oils to produce fats and oils with a high degree of selectivity and a high content of trans isomer.

That is, the method of the present invention uses fats and oils with an iodine value of about 45 to 12,030 at a rate of 100 to 3,000 p! This is a method for producing a highly selective trans isomer-rich fat and oil, which is characterized by hydrogenation using a nickel catalyst in the presence of thiamine nitrate (1a).

As the raw material oils and fats of the present invention, natural animal and vegetable oils or fats 35 are:
Examples include processed fats and oils that have been subjected to treatments such as refining, bleaching, hydrogenation, fractionation, transesterification, acid rinsing, alcohol rinsing, and wintering. In addition, it is naturally necessary that the raw material fats and oils contain unsaturated fatty acids as bound fatty acids.
The iodine value is preferably about 45 to 120.
The amount of thiamine nitrate added to the raw material oil is usually within the range of 100 to 3000 VIfB relative to the raw material oil, and can be changed as appropriate within the above range depending on the amount of catalyst added, hydrogenation conditions, and the degree of isomerization desired for the product. is preferably 200-1
A range of 000 demons is desirable.

The hydrogenation of the present invention can be carried out using a nickel catalyst, for example, by bringing hydrogen into contact with the raw material oil and fat at a temperature of 180 to 220° C. under normal pressure or under pressure. According to the method of the present invention, if the type of raw material, type of catalyst, amount of catalyst added, and hydrogenation conditions are constant, by controlling the amount of thiamine nitrate added, The content can be controlled quantitatively, and when trying to obtain a hydrogenated oil or fat with a specific trans-isomer content, it has the effect that the desired product can be produced with very simple operations and with little variation. In addition, thiamine nitrate added and used in the present invention is a nutritional fortifier and poses almost no problem in terms of food hygiene.

Also, ΔTrans/ΔIV of a normal nickel catalyst is 1,
ΔTrans/JIV due to methionine poisoning is 4, whereas when using thiamine nitrate, ΔTrans/Δ
It has isomerization performance far superior to conventional poisoning compounds, such as an I value of 10 or more. Further, it is therefore possible to perform only isomerization without substantially lowering the iodine value, and it is possible to produce fats and oils with a high trans isomer content and having any iodine value. The hydrogenated fat (hardened fat) obtained by the method of the present invention has high selectivity and melts in the mouth.
This hydrogenated fat (hardened fat) can be used as it is, such as for example as a cacao substitute fat or an anthin substitute fat, and furthermore, this hydrogenated fat (hardened fat) can be subjected to a fractionation process such as solvent separation or a process such as transesterification to be used for various purposes other than the above-mentioned uses. It is used for various purposes.

Examples of the present invention are shown below, but the present invention is not limited to these Examples.

Example 1 Palm soft part oil (iodine value 56.6) 250f11 commercially available nickel catalyst (Sakai Chemical SO-110, nickel content 23
%) 0.75g, Thiamine Nitrate 69Tf9 1.51
placed in an autoclave at a temperature of 210°C and a hydrogen pressure of 3.
k9/Cd (gauge pressure), stirring speed 450r. p. m.
Hydrogenation was performed using

The obtained hydrogenated fat had an iodine value of 47.6 and a trans isomer content (referring to the content of trielaidin based on the total glycerade; the same shall apply hereinafter) of 38.7%. Example 2 Thiamine nitrate 250 instead of thiamine nitrate 69m9
Palm soft part oil was hydrogenated in exactly the same manner as in Example 1 except that m9 was used, and a hydrogenated fat and oil with an iodine value of 51.1 and a trans isomer content of 41.9% was obtained.

The isomerization ability ΔTrans/ΔI at this time was about 11.5. Example 3 High oleic safflower oil (iodine value 98.8) 2
509, the same commercially available nickel catalyst as Example 1, 0.759,
Thiamine nitrate 69Tr19 was placed in a 1.51 autoclave at a temperature of 210°C and a hydrogen pressure of 3kg/C7Fi (
gauge pressure), stirring speed 450r. p. m. Hydrogenation was performed using

The obtained hydrogenated fat had an iodine value of 78.2 and a trans isomer content of 67.8%. Example 4 Cottonseed salad oil (iodine value 115.5) 2509, commercially available nickel catalyst (N-122 manufactured by JGC Chemical) 0.759, and thiamine nitrate 62η were placed in a 1.51 autoclave.
Hydrogenation was carried out at a temperature of 210° C., a hydrogen pressure of 3 kg/(11 Ff (gauge pressure)), and a stirring speed of 450 rpm.

The obtained hydrogenated oil had an iodine value of 78.4 and a trans isomer content of 64.8%.

Comparative Example 1 Hydrogenation was carried out in the same manner as in Example 1 except that thiamine nitrate was not added at all, and the iodine value was 4.
A hydrogenated oil and fat having a 7.01 trans isomer content of 12.4% was obtained.

Comparative Example 2 The same procedure as in Example 1 was carried out except that sulfur-poisoned nickel catalyst (sulfur content 4%) 0.759 was used instead of commercially available nickel catalyst (nickel content 23%) 0.759 and thiamine nitrate 697V. When palm soft part oil was hydrogenated, the iodine value was 49.8 and the trans isomer content was 18.
A 3% hydrogenated fat was obtained.

Comparative Example 3 Hydrogenation was carried out in exactly the same manner as in Example 1 except that methionine 25 ~ was used in place of thiamine nitrate 69, and a hydrogenated fat and oil with an iodine value of 50.8 and a trans isomer content of 13% was obtained. .

Comparative Example 4 Hydrogenation was carried out in the same manner as in Example 3, except that no thiamine nitrate was added, and a hydrogenated fat and oil with an iodine value of 78 and a trans isomer content of 39.8% was obtained.

Comparative Example 5 Hydrogenation was carried out in the same manner as in Example 4, except that thiamine nitrate was not added at all, and the iodine value was 79.
2. Hydrogenated fat and oil with a trans isomer content of 32.7% was obtained.

Comparative Example 6 After adding commercially available nickel catalyst 59 and 2.54 g of methionine to 1.05 kg of palm soft part oil (iodine value 57.5), the reaction tank was replaced with hydrogen, and 560 m7! The reaction was carried out under a reduced pressure of LHg, and then the pressure was increased to 3k9/~ (gauge pressure) to carry out a hydrogenation reaction.

Claims (1)

[Claims] 1 Add an oil or fat with an iodine value of 45 to 120 to
1. A method for producing a highly selective trans-containing oil and fat, which comprises hydrogenating using a nickel catalyst in the presence of 0 to 3,000 ppm of thiamine nitrate.