JPH0641578A - Production of fatty acid ester, and production of soap using the fatty acid ester - Google Patents

Abstract

PURPOSE:To obtain the fatty acid ester giving soaps extremely good in their smells by ester-exchanging palm oil, etc., with a lower alcohol, hydrogenating the product, and subsequently distilling to obtain the fraction. CONSTITUTION:For example, palm oil, palm nuclear oil or their mixture is ester-exchanged with a lover alcohol to produce a palm oil fatty acid lower alcohol ester, a palm oil nuclear fatty acid lower alcohol ester or their mixture. The ester or ester mixture is hydrogenated in the presence of a hydrogenation catalyst to reduce the linolic acid ester content of the ester in an amount of 10wt.% or more based on the linolic acid content of the non-hydrogenated ester, followed by distilling the hydrogenation product to provide a fraction for the objective ester.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a palm oil fatty acid lower alcohol ester, a palm kernel oil fatty acid lower alcohol ester or a mixture thereof, and a method for producing a soap having a good odor using these esters. .

[0002]

BACKGROUND OF THE INVENTION Soap is generally (a) beef tallow, lard, fish oil, palm oil, palm stearin or palm olein obtained by fractionating palm oil, soybean oil, olive oil, Cottonseed oil, a neutral oil saponification method of saponifying animal and vegetable oils and fats such as coconut oil or palm kernel oil with an alkali metal hydroxide, (b) a fatty acid neutralization method of neutralizing fatty acids obtained by hydrolyzing the animal and vegetable oils and fats, Alternatively, (c) an ester saponification method of saponifying a lower alcohol ester of a fatty acid obtained by using the animal or vegetable oil as a raw material. However, when palm oil or palm kernel oil is used as a raw material, no matter whether the soap is produced according to any of the methods (a), (b) or (c), the obtained soap is a peculiar one derived from palm oil or palm kernel oil. Had an offensive odor, which was a problem when used as soap for washing the human body. Therefore, an object of the present invention is to provide a method for producing a soap having a good odor even when palm oil or palm kernel oil is used as a raw material.

[0003]

Means for Solving the Problems The present inventor has conducted extensive studies for the purpose of improving the odor of soap obtained by using palm oil or palm kernel oil as a raw material, and as a result, palm oil produced by the method shown below. Lower alcohol esters of fatty acids or palm kernel oil Lower alcohol esters of fatty acids or lower alcohol esters of fatty acids or fatty acid esters containing at least a part of these esters as raw materials to produce soap by the ester saponification method. The inventors have found that the odor of soap obtained by using kernel oil as at least one raw fat and oil can be improved, and completed the present invention.

That is, the present invention includes the following steps (A) and (B)
And step (C) in this order, or the following step (A), step
Perform (C) and step (B) in this order, or
(D), step (A) and step (C) are carried out in this order to provide a method for producing a palm oil fatty acid lower alcohol ester, a palm kernel oil fatty acid lower alcohol ester or a mixed ester thereof. . Step (A) palm oil, palm kernel oil or a mixed oil thereof is transesterified with a lower alcohol, lower alcohol ester of palm oil fatty acid, lower alcohol ester of palm kernel oil fatty acid,
Or a step of obtaining the ester mixture. Step (B) lower alcohol ester of palm oil fatty acid obtained in the previous step, lower alcohol ester of palm kernel oil fatty acid or a mixture thereof is hydrogenated in the presence of a hydrogenation catalyst, and linole present in these esters is added. A step of reducing the acid ester content by 10% by weight or more with respect to the content before hydrogenation. Step (C) A step of distilling the lower alcohol ester of palm oil fatty acid, the lower alcohol ester of palm kernel oil fatty acid or the ester mixture obtained in the previous step to obtain a distillate. Step (D) Palm oil, palm kernel oil or a mixed oil thereof is completely transesterified with hydrogenated palm oil, hydrogenated palm kernel oil or a mixed oil thereof in the presence of a hydrogenation catalyst. The step of hydrogenating until the linoleic acid ester content in the obtained ester is reduced by 10% by weight or more with respect to the content before hydrogenation.

The palm oil in the present invention means crude palm oil, crude palm stearin or crude palm olein, or refined palm oil obtained by degumming, white clay treatment and distillation deoxidizing treatment (hereinafter, RBD palm oil). Say),
Purified palm stearin obtained by the same treatment (hereinafter, referred to as RBD palm stearin) or purified palm olein obtained by the same treatment (hereinafter, RBD)
It means Palm Olein). Further, the palm kernel oil in the present invention means a crude palm kernel oil or a refined palm kernel oil obtained by degumming it, treating it with clay and distilling and deoxidizing it (hereinafter referred to as RBD palm kernel oil). .

The present invention will be described in detail below. First,
Production of a lower alcohol ester of palm oil fatty acid, a lower alcohol ester of palm kernel fatty acid or a mixed ester thereof, which is a raw material for producing a soap having no offensive odor peculiar to palm oil or palm kernel oil, is the above-mentioned step (A ), Step (B) and step (C) in this order or the above step (A)
, Step (C) and step (B) are performed in this order, or step (D), step (A) and step (C) described above are performed in this order. Hereinafter, each method will be described.

Method: First, the step (A) is performed. Process (A)
Is a step of transesterifying palm oil, palm kernel oil or a mixed oil thereof with a lower alcohol to obtain a lower alcohol ester. Specifically, an alcohol having 1 to 6 carbon atoms,
Preferably, methanol is used in the presence of an alkali metal hydroxide or alcoholate catalyst at 40 to 80 ° C. and a reaction pressure of 1 to 5
After reaction with kg / cm ² G (G means gauge pressure), glycerin by-produced is separated into layers, and the ester layer is washed with water and dried. The step (B) following the step (A) is a step of hydrogenating in the presence of a hydrogenation catalyst, and N is used as a catalyst.
i, Cu, and a hydrogenation catalyst containing at least one metal selected from the group of platinum group metals such as Pt, Ru, and Pd as a metal species.
0.001-2% by weight (against ester) is used, room temperature to 230
℃ temperature, normal pressure ~ 20kg / cm ² G (G means gauge pressure)
The lower alcohol ester of palm oil fatty acid obtained in step (A), the lower alcohol ester of palm kernel oil fatty acid or a mixture of these esters under hydrogen pressure of linoleic acid ester present in the ester. The content is 10% by weight or more based on the content before hydrogenation, preferably
Reduce by 10 to 90% by weight. In this case, "10 wt% or more" has a critical meaning, even if the lower alcohol ester of palm oil fatty acid or the lower alcohol ester of palm kernel oil fatty acid obtained in step (A) is hydrogenated. , If the linoleic acid ester content present in these esters is reduced by less than 10% by weight relative to the content before hydrogenation, the effect desired by the present invention, namely, palm oil or palm kernel oil-specific A raw material ester for soap, which does not have an offensive odor and has a good odor, cannot be obtained. Process following process (B)
(C) is a step of distilling the ester obtained in step (B), which can be carried out by a commonly used vacuum distillation method at 270 ° C. or lower and 50 mmHg or lower. Also, the low boiling portion may be cut off at the initial distillation during this distillation.

Method: The method is a method in which the hydrogenation step and the distillation step of the method are performed in reverse, and each step (A), step
(B) and step (C) are the steps (A), (B) and
It can be done in the same way as (C).

Method: First, the step (D) is performed. Process (D)
Completely transesterify hydrogenated palm oil, hydrogenated palm kernel oil, or these hydrogenated mixed oils with palm oil, palm kernel oil or a mixed oil thereof in the presence of a hydrogenation catalyst. It is a step of hydrogenating until the content of the linoleic acid ester in the ester obtained under the assumption is decreased by 10% by weight or more, preferably 10 to 90% by weight with respect to the content before hydrogenation. In this case, the conditions for hydrogenation may be the same as the conditions described in step (B) in the above method. Also, the process
The condition of (10% by weight or more) in (D) has a critical significance, and even if palm oil, palm kernel oil, or a mixed oil thereof is hydrogenated, it is not hydrogenated palm oil or hydrogenated palm oil. The value of the linoleic acid ester content in the ester obtained by assuming complete transesterification of palm kernel oil or these hydrogenated mixed oils was less than 10% by weight with respect to the content before hydrogenation. When hydrogenated as described above, a lower alcohol ester of palm oil fatty acid obtained by the method, a lower alcohol ester of palm kernel oil fatty acid or a mixed ester thereof is used, and even if soap is produced, a good odor is obtained. I can't get good soap. Process
Steps (A) and (C) following (D) are the steps of the method.
It can be carried out in the same manner as in (A) and step (C).

Next, the soap manufacturing process will be described. In this step, the lower alcohol ester of palm oil fatty acid, the lower alcohol ester of palm kernel oil fatty acid or a mixed ester thereof obtained by the above method is mixed alone or with another fatty acid ester (mixing ratio may be any). According to a known method, a soap base material is produced by saponification with at least one selected from the group consisting of alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates, and various additives are added and mixed therewith. It can be produced by kneading, extruding, and stamping. That is, for example, lower alcohol ester of palm kernel oil fatty acid obtained by the above method, lower alcohol ester of palm oil fatty acid or a mixed ester thereof alone or beef tallow, lard, fish oil, palm oil, palm stearin, palm olein. , Soybean oil, olive oil, cottonseed oil, coconut oil, palm kernel oil, etc., after mixing with a lower alcohol ester of a fatty acid, alkali metal hydroxides such as caustic soda and caustic potash,
A soap base material is produced by saponifying with an alkali metal carbonate such as sodium carbonate and potassium carbonate, an alkali metal bicarbonate such as sodium bicarbonate and potassium bicarbonate, and a moisturizing agent such as propylene glycol and glycerin, and a fragrance. , Dyes, UV absorbers, bactericides, preservatives, fatty acids, higher alcohols,
Ester, other surfactants, etc. are added and mixed, kneading,
It can be extruded and stamped.

In this case, various conventionally known auxiliary components can be added to the soap base material. Examples of such components include stabilizers such as fragrance, EDTA, ethane-1-hydroxy-1,1-diphosphonic acid or alkali metal salts thereof. Further, a surfactant other than the soap base material can be added to the soap base material of the present invention in order to further enhance the detergency. Examples of such a surfactant include α-sulfo fatty acid ester, isethionate ester, alkylaryl sulfonic acid, alcohol sulfuric acid ester, sulfuric acid ester of alcohol ethoxylate, olefin sulfonic acid, paraffin sulfonic acid, N
-Acyl glutamic acid and esters and salts thereof, as well as alkylbetaine, alkylsulfobetaine and the like can be mentioned.

Further, in order to adjust the effect of residual oil on the skin, generally known superfat agents and various skin protective agents can be added. Specific examples thereof include hydrocarbons such as squalene, squalane, olefin oligomer, wax, petrolatum and mineral oil; fatty acids such as stearic acid, isostearic acid, oleic acid, ricinoleic acid, palmitic acid, myristic acid and behenic acid; various glycerides. Fatty acid esters such as sugar ester, lanolin, isopropyl myristate, isopropyl palmitate and isobutyl stearate; aliphatic alcohols such as cetyl alcohol, stearyl alcohol, oleyl alcohol; polyols such as glycerin, polyethylene glycol, polypropylene glycol; alcohols Ethoxylates of fatty acids; silicones such as dimethyl silicone; other various proteins and protein derivatives; vitamins and the like. Furthermore, in addition to pigments and fragrances, anti-inflammatory agents such as allantoin and dipotassium glycyrrhizinate may be added to the soap base material depending on the purpose of use.
4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'-trichlorocarbanilide (TC
C), a bactericide such as benzoic acid can be added.

Further, in the case of obtaining a mixed fatty acid soap of palm oil fatty acid or palm kernel oil fatty acid and another fatty acid, palm oil fatty acid lower alcohol ester or palm kernel oil fatty acid lower alcohol ester obtained by the above method Other than the method of mixing with other fatty acid ester,
(A) A method in which palm oil or palm kernel oil in (D) is mixed with palm oil or palm kernel oil and other animal or vegetable oils or fats, or step (B) or (C)
In, in the palm oil fatty acid lower alcohol ester or palm kernel oil fatty acid lower alcohol ester, a method of using a mixture of palm oil fatty acid lower alcohol ester or palm kernel oil fatty acid lower alcohol ester and other fatty acid ester can also be used. it can.

[0014]

The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1 RBD palm kernel oil was transesterified with methanol in the presence of a caustic soda catalyst (0.2% by weight relative to oil) at 50 ° C. and normal pressure to separate by-produced glycerin and to remove it, followed by washing with water and drying. Then, a methyl ester of palm kernel oil fatty acid was obtained. The content of linoleic acid methyl ester in the methyl ester is
The result of GLC analysis was 2.4% by weight. 0.04 wt% (Ni wt% of ester) of Ni catalyst was added to the methyl ester of RBD palm kernel oil fatty acid, and hydrogenation was performed at a hydrogen pressure of 0.5 to ² kg / cm ² G and a temperature of 170 to 190 ° C. A methyl ester of palm kernel oil fatty acid having an acid methyl ester content of 1.0% by weight was obtained. The methyl ester was distilled under a reduced pressure of bottom temperature max of 240 ° C. and 3 mmHg to obtain palm kernel oil fatty acid methyl ester. The initial distillate was cut by 6% by weight during the distillation.

Example 2 RBD palm kernel oil was transesterified with methanol at 50 ° C. and normal pressure in the presence of a caustic soda catalyst (0.2% by weight of oil) to separate and remove by-product glycerin, followed by washing with water and drying. Then, a methyl ester of palm kernel oil fatty acid was obtained. The content of linoleic acid methyl ester in the methyl ester is
The result of GLC analysis was 2.4% by weight. This methyl ester was distilled at a bottom temperature of max. 240 ° C. under a reduced pressure of 3 mmHg (the initial distillate was cut by 6% by weight), the distillate was hydrogenated under the same conditions as in Example 1, and the result of GLC analysis showed that linole A palm kernel oil fatty acid methyl ester having an acid methyl ester content of 0.8% by weight was obtained.

Example 3 Crude palm kernel oil was transesterified with methanol in the presence of a caustic soda catalyst (0.2% by weight oil) at 50 ° C. and normal pressure,
After the by-product glycerin was separated and removed, it was washed with water and dried to obtain a crude palm kernel oil fatty acid methyl ester. The content of linoleic acid methyl ester in the methyl ester was GL
The result of C analysis was 2.3% by weight. The methyl ester was hydrogenated in the same manner as in Example 1 to obtain a crude palm kernel oil fatty acid methyl ester having a linoleic acid methyl ester content of 1.3% by weight. The methyl ester was distilled under the same conditions as in Example 1 to obtain a palm kernel oil fatty acid methyl ester.

Example 4 RBD palm kernel oil was added with 0.04 wt% (Ni wt% relative to RBD
(Palm kernel oil) Ni catalyst was added, and hydrogenation was performed at a hydrogen pressure of 0.5 to ² kg / cm ² G and a temperature of 170 to 190 ° C. to obtain hydrogenated RBD palm kernel oil. 50% of the hydrogenated RBD palm kernel oil in the presence of caustic soda catalyst (0.2% by weight oil).
After transesterification with methanol at ℃ and atmospheric pressure to separate and remove the by-product glycerin, the product was washed with water and dried to obtain methyl ester. The content of linoleic acid methyl ester in the methyl ester was 1.3% by weight as a result of GLC analysis. Then, it distilled similarly to Example 1 and obtained the methyl ester of palm kernel oil fatty acid.

Example 5 RBD palm stearin was transesterified in the same manner as in Example 1 to obtain palm stearin fatty acid methyl ester.
The content of linoleic acid methyl ester in the methyl ester was 5.9% by weight as a result of GLC analysis. The methyl ester was hydrogenated in the same manner as in Example 1 to obtain palm stearin fatty acid methyl ester having a linoleic acid methyl ester content of 1.5%. The methyl ester was distilled under a reduced pressure of bottom temperature max240 ° C. and 3 mmHg to obtain palm stearin fatty acid methyl ester.

Example 6 Hydrogen esterification and transesterification were carried out in the same manner as in Example 4 except that RBD palm stearin was used as a raw material instead of RBD palm kernel oil to obtain a methyl ester. As a result of GLC analysis, the content of linoleic acid methyl ester in the methyl ester was 2.5% by weight. Then, it distilled similarly to Example 4 and obtained palm stearin fatty acid methyl ester.

Example 7 RBD palm kernel oil and RBD palm stearin were transesterified in the same manner as in Example 1 to obtain RBD palm kernel oil fatty acid methyl ester and RBD palm stearin fatty acid methyl ester. The content of linoleic acid methyl ester in the RBD palm kernel oil fatty acid methyl ester and the RBD palm stearin fatty acid methyl ester is
They were 2.4% by weight and 5.9% by weight, respectively. afterwards,
After mixing both at 1: 1, hydrogenation was carried out in the same manner as in Example 1 to obtain a methyl ester having a linoleic acid methyl ester content of 1.5% by weight. Then, it distilled similarly to Example 1 and obtained the mixed ester of palm kernel oil fatty acid methyl ester and palm stearic fatty acid methyl ester.

Comparative Example 1 The methyl ester of RBD palm kernel oil fatty acid obtained by transesterification in Example 1 was distilled as in Example 1 without hydrogenation to obtain a methyl ester.

Comparative Example 2 0.04 wt% (Ni wt% relative to ester) of Ni catalyst was added to the methyl ester of RBD palm kernel oil fatty acid obtained by transesterification in Example 1 to give 0.5 kg / cm ² G or less. Hydrogen pressure,
Hydrogenation was carried out at a temperature of 140 to 170 ° C. to obtain a methyl ester of palm kernel oil fatty acid having a linoleic acid methyl ester content of 2.2% by weight. The methyl ester was distilled in the same manner as in Example 1 to obtain a methyl ester.

Comparative Example 3 The methyl ester of crude palm kernel oil fatty acid obtained by transesterification in Example 3 was distilled in the same manner as in Example 1 without hydrogenation to obtain a methyl ester.

Comparative Example 4 The RBD palm stearin fatty acid methyl ester obtained by transesterification in Example 5 was distilled as it was in the same manner as in Example 5 without hydrogenation to obtain a methyl ester.

Example 8 The palm kernel oil fatty acid methyl ester obtained in Example 1 and the palm stearin fatty acid methyl ester obtained in Example 5 were mixed at a weight ratio of 1: 1 and saponified with caustic soda by a conventional method. , Manufactured soap chips. The smell of the soap chips was evaluated by the following method. The results are shown in Table 1. <Method of Evaluating Odor of Soap Chip> A sample was placed in an odorless bottle, and the odor was evaluated by 10 panelists as it was according to the following criteria. Rank 1: Almost no odor characteristic of palm oil or palm kernel oil Rank 2: Weak odor characteristic of palm oil or palm kernel oil Rank 3: Clear odor characteristic of palm oil or palm kernel oil Rank 4: Strong Offensive odor peculiar to palm oil or palm kernel oil Rank 5: Very strong offensive odor peculiar to palm oil or palm kernel oil Examples 9 to 11 Methyl esters were mixed as shown in Table 1 and similar to Example 8. Manufactured soap chips. The odor was evaluated by the above method. The results are shown in Table 1.

Example 12 Using the methyl ester obtained in Example 7, soap chips were produced in the same manner as in Example 8. The odor was evaluated by the above method. The results are shown in Table 1.

Examples 13 and 14, Comparative Examples 5 to 7 Methyl esters were mixed as shown in Table 1 to prepare soap chips in the same manner as in Example 8. The odor was evaluated by the above method. The results are shown in Table 1.

[0029]

[Table 1]

Example 15 Palm oil was transesterified in the same manner as in Example 1 to obtain coconut oil fatty acid methyl ester. The methyl ester was distilled in the same manner as in Example 1 to obtain coconut oil fatty acid methyl ester. Then, this coconut oil fatty acid methyl ester and the palm stearin fatty acid methyl ester obtained in Example 5 were mixed at a weight ratio of 1: 1 to obtain soap chips in the same manner as in Example 8. The smell of the chip was rank 1.

[0031]

EFFECTS OF THE INVENTION According to the present invention, a soap having an extremely good odor can be obtained from palm oil or palm kernel oil.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display C11D 13/00

Claims (3)

[Claims] 1. The following step (A), step (B) and step (C)
Or perform the following steps (A), (C) and
(B) in this order, or the following step (D), step (A)
And the step (C) are performed in this order, a method for producing a palm oil fatty acid lower alcohol ester, a palm kernel oil fatty acid lower alcohol ester, or a mixed ester thereof. Step (A) palm oil, palm kernel oil or a mixed oil thereof is transesterified with a lower alcohol, lower alcohol ester of palm oil fatty acid, lower alcohol ester of palm kernel oil fatty acid,
Or a step of obtaining the ester mixture. Step (B) lower alcohol ester of palm oil fatty acid obtained in the previous step, lower alcohol ester of palm kernel oil fatty acid or a mixture thereof is hydrogenated in the presence of a hydrogenation catalyst, and linole present in these esters is added. A step of reducing the acid ester content by 10% by weight or more with respect to the content before hydrogenation. Step (C) A step of distilling the lower alcohol ester of palm oil fatty acid, the lower alcohol ester of palm kernel oil fatty acid or the ester mixture obtained in the previous step to obtain a distillate. Step (D) Palm oil, palm kernel oil or a mixed oil thereof is completely transesterified with hydrogenated palm oil, hydrogenated palm kernel oil or a mixed oil thereof in the presence of a hydrogenation catalyst. The step of hydrogenating until the linoleic acid ester content in the obtained ester is reduced by 10% by weight or more with respect to the content before hydrogenation. 2. A lower alcohol ester of palm oil fatty acid, a lower alcohol ester of palm kernel oil fatty acid, or a mixture of the esters obtained by the production method according to claim 1, is treated with an alkali metal hydroxide, an alkali metal carbonate and an alkali metal heavy salt. A method for producing a soap, comprising saponifying with at least one selected from the group consisting of carbonates. 3. A lower fatty acid ester of a palm oil fatty acid or a lower fatty acid ester of a palm kernel oil fatty acid obtained by the production method according to claim 1, at least a part of which is an alkali metal hydroxide,
A method for producing a soap, comprising saponifying with at least one selected from the group consisting of alkali metal carbonates and alkali metal bicarbonates.