JP2003180388A - Method for producing clay-containing fatty acid metal salt composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a clay-containing fatty acid metal salt composition in high degree of freedom of the water content of the reaction system and in high hydrolysis rate by lipases. <P>SOLUTION: This method for producing the clay-containing fatty acid metal salt composition comprises homogeneously mixing a neutralizing agent into waste clay used for treating oil and fat, adding an aqueous solution or dispersion of lipases to the mixture to nearly simultaneously carry out hydrolysis of the oil and fat and neutralization of the resultant fatty acid; wherein as the lipases, two kinds whose hydrolytic activity peak temperatures differ from each other by ≥10°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a clay-containing fatty acid metal salt composition, and more specifically, to effectively utilize waste clay, to obtain a fatty acid metal salt (soap or metal soap).
Is to be manufactured.

[0002]

2. Description of the Related Art In the oil and fat industry and the like, for example, in order to bleach in the step of refining oil and fat, the oil and fat is treated with clay. After the filtration, about 25 to 40% by weight of oil and fat was adsorbed on the clay treated with oil and fat, but it was difficult to separate the oil and fat at an industrially appropriate cost. However, from the perspective of resource saving and waste reduction,
There is a demand for effective utilization of oils and fats adsorbed on white clay.

From this point of view, a method for obtaining a clay-containing fatty acid metal salt composition by mixing waste clay containing oil and fat with a neutralizing agent and an aqueous solution or dispersion of lipase, which has been used for treating oil and fat, is reacted. Are described in Japanese Patent Laid-Open No. 2000-139489.

[0004]

However, in the invention described in the above publication, it is necessary to limit the water content in the reaction system in order to suppress the inactivation of lipase, and therefore the hydrolysis rate itself by lipase is also high. It had the drawback of being low.

Therefore, the object of the present invention is to produce a clay-containing fatty acid metal salt composition which does not have the above-mentioned drawbacks, has a high degree of freedom of water content in the reaction system, and has a high hydrolysis rate by lipase. To provide a method.

[0006]

Means for Solving the Problems According to the present invention, after the neutralizing agent is uniformly mixed with the waste clay used in the treatment of fats and oils, an aqueous solution or dispersion of lipase is added to the fats and oils for hydrolysis reaction. In the method for producing a clay-containing fatty acid metal salt composition in which a neutralization reaction of a fatty acid is carried out substantially at the same time, at least two kinds of lipases having different hydrolysis activity peak temperatures of 10 ° C. or more are used as the lipase. The above object is achieved by providing a method for producing a clay-containing fatty acid metal salt composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The waste clay used in the present invention is the waste clay used for the treatment of fats and oils. For example, in the decolorizing step in the process of refining animal and vegetable fats and oils, activated clay is heated in addition to the fats and oils. , The pigments present in fats and oils are adsorbed and removed, and the clay adsorbed the pigments is filtered by a filter or the like to be separated from the fats and oils. It is generally called abandoned clay,
Such waste clay can be used.

The waste clay is not particularly limited by the fats and oils contained therein, but it is beef tallow, lard, fish oil, animal fats and oils such as whale oil, palm oil, palm kernel oil, soybean oil, rapeseed oil and corn. Oils, vegetable oils and fats such as rice bran, mixed oils and fats of these animal and vegetable oils, hydrogenated oils and fats (hardened oils) of these oils and fats, transesterified oils and fats of these oils and fats, and any oils or fats contained it can. In practical use, if necessary, oil,
Glycerin fatty acid ester, fatty acid, etc. can be added. Further, the waste white clay is not limited by the content of fats and oils contained therein, but the content of fats and oils in the waste white clay is 15 to
It is preferably 50% by weight, more preferably 20 to 45% by weight.

The neutralizing agent used in the present invention is one that is uniformly mixed with the above-mentioned waste white clay, and a known one can be used, and it is not particularly limited, and examples thereof include calcium hydroxide and magnesium hydroxide. Alkaline earth metal hydroxides, alkaline earth metal oxides such as calcium oxide and magnesium oxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and mixtures thereof, cements such as hydraulic cement, zinc oxide, etc. A known neutralizing agent can be added. Among these, calcium oxide, calcium hydroxide, cements, zinc oxide and magnesium oxide are preferable. Above all, calcium oxide and / or calcium hydroxide is particularly preferably used because of its high reactivity, and hydraulic cement is particularly preferably used because it is available as an inexpensive raw material.

The amount of the neutralizing agent used is not particularly limited,
Assuming an acid value when fats and oils in the waste clay are converted into fatty acids by an enzymatic reaction, the acid value is preferably 0.7 to 1.5 equivalents, more preferably approximately equivalent. For example, the amount of the neutralizing agent used is preferably 3 to 10 parts by weight based on 100 parts by weight of the used white clay when the used white clay contains 30 to 40% by weight of oil and fat. If the amount of the neutralizing agent used is too small, the amount of the fatty acid metal salt produced may be too small, and if the amount used is too large, it can be carried out, but it is uneconomical.

The neutralizing agent can be used in the form of a solid (powder) or as an aqueous solution, but if the water content is too high, the aqueous solution of the neutralizing agent increases the possibility of deactivating lipase. When the neutralizing agent is used as an aqueous solution, the concentration of the neutralizing agent in the aqueous solution of the neutralizing agent is preferably 5 to 70% by weight, more preferably 10 to 50% by weight.

[0012] The aqueous solution or dispersion of lipase used in the present invention (hereinafter, referred to as "aqueous solution of lipase" including the dispersion of lipase in the present specification) is the above-mentioned waste clay and neutralizing agent. It is added to the mixture so that the hydrolysis reaction of fats and oils in the above-mentioned waste clay and the neutralization reaction of fatty acids are carried out substantially at the same time. The concentration of the lipase in the aqueous solution of the lipase is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight.

Incidentally, the aqueous solution of lipase may further contain salts and the like. Therefore, the aqueous solution of lipase may be a buffer solution or the like, and may further contain a chelating agent and a surfactant. In the case of the lipase dispersion, the dispersion medium may be water or the salt solution (for example, a buffer solution).

From the viewpoint of preventing deactivation of lipase, the total amount of water in the aqueous solution of these neutralizing agents and the aqueous solution of lipase is preferably 5 to 50 with respect to 100 parts by weight of the waste clay.
Parts by weight, more preferably 5 to 35 parts by weight, most preferably 10 to 20 parts by weight.

The lipase used in the present invention is not limited to its origin as long as it can hydrolyze fats and oils to produce fatty acids, and lipase derived from microorganisms, lipase derived from plants, lipase derived from animal pancreas (pancreatin lipase). ) Etc. can be used satisfactorily. Further, the substrate regiospecificity of lipase is not particularly limited, but a random type can be particularly preferably used. The lipase may be immobilized on a suitable carrier.

In the present invention, as the lipase, it is necessary to use at least two kinds of lipases having different hydrolysis activity peak temperatures of 10 ° C. or more. By using two types of lipases having different hydrolytic activity peak temperatures (hereinafter referred to as “P points”) of 10 ° C. or more, the hydrolysis rate of fats and oils in waste clay is dramatically improved. This is probably because the heat of reaction due to the initial hydrolysis reaction in the reaction system causes a non-uniform temperature distribution in the reaction system.

Further, in the present invention, the point P is 10
Of the two lipases that differ by ℃ or more, the P point of one lipase is 55 ℃ or less, preferably 35-55 ℃,
And the P point of the other lipase is 50 ° C or higher, preferably 5
It is preferably 0 to 70 ° C. from the viewpoint of improving the hydrolysis rate of fats and oils in the waste clay.

In the present invention, the point P is 10
P-point temperature difference between two types of lipases differing by ℃ or more is 10-45
C., preferably 10 to 30.degree. C. is also preferable from the viewpoint of improving the hydrolysis rate of fats and oils in the waste clay.

Further, in the present invention, the point P is 10
The amount of use of the two types of lipases that differ by ℃ or more does not exceed the weight of the amount of the other used by 4 times the amount of the other, and
It is also preferable that the total amount of the two kinds of lipases whose P points differ by 10 ° C. or more relative to the total weight of lipase is 70% by weight or more in order to improve the hydrolysis rate of oils and fats in the waste clay.

In the present invention, lipases other than two kinds of lipases having the above-mentioned P points differing by 10 ° C. or more can be used. In this case, as long as the above requirements are satisfied, any combination of lipases will be used. There is no problem even if it is set as two kinds of lipases that differ by ℃ or more.

In the present invention, point P is the temperature at which the hydrolysis activity of lipase for olive oil is highest,
That is, the amount of free fatty acid measured at various temperatures (predetermined temperature) is measured by the following method, and the temperature showing the highest value is defined as P point.

[Method for measuring amount of free fatty acid] (1) Lipase aqueous solution: 0.01 g / liter (2) 2% by weight polyvinyl alcohol aqueous solution: 200 ml of distilled water, 4.5 g of polyvinyl alcohol having a weight average molecular weight of 87,000, and Weight average molecular weight 30
5,000 polyvinyl alcohol (0.5 g) is added and suspended, and the temperature is raised to 80 ° C. with stirring, and the temperature is maintained and stirring is continued until it becomes transparent. When it becomes transparent and completely dissolved, it is left to cool to room temperature, and distilled water is added to make 250 ml. (3) Olive oil emulsion: 75 ml of pharmacopoeial olive oil and 2% by weight aqueous solution of polyvinyl alcohol 2 of (2)
25 ml is placed in a homogenizer container and emulsified in an ice bath for 10 minutes at 14500 ± 300 rpm. (4) Hydrolysis reaction: 5 ml of the olive oil emulsion of (3) and 4 ml of Mcllvain buffer were placed in a test tube and placed in a constant temperature bath for 5 minutes, and then (1).
1 ml of the aqueous lipase solution was added, shaken to thoroughly mix, and then allowed to stand in a constant temperature bath for 30 minutes.
Then, acetone-ethanol mixed solution (volume ratio 1: 1)
Add 10 ml and shake to mix well to stop the reaction. (5) Next, 10 ml of 0.05N sodium hydroxide aqueous solution and an acetone-ethanol mixed solution (volume ratio 1:
1) Add 10 milliliters to neutralize free fatty acids,
The residual amount of sodium hydroxide is titrated with a 0.05N hydrogen chloride aqueous solution while blowing nitrogen gas and stirring. (6) Separately, as a blind test value, olive oil emulsion 5 of (3)
After taking 4 ml of McClvain buffer and 4 ml of McClvain buffer into a test tube, 10 ml of acetone-ethanol mixed solution (volume ratio 1: 1) was added thereto, and then (1)
1 ml of the aqueous lipase solution was added, shaken to mix well, and then titrated in the same manner. (7) The amount of free fatty acid due to the hydrolysis reaction is calculated from the difference between the titration values.

In the present invention, the total amount of lipase used is
The activity and presence or absence of immobilization, should be appropriately set depending on the amount of fats and oils contained in the waste clay, but it is possible to use the usual amount used in the conventional enzyme treatment of fats and oils, For example, there is no problem as long as it is about 0.01 to 0.5% by weight with respect to the oil and fat in the waste clay.

Needless to say, when adding the aqueous solution or dispersion of the lipase to the mixture of the above-mentioned waste clay and the neutralizing agent, it is preferable to sufficiently mix them, but the subsequent hydrolysis reaction with the lipase is It can be carried out by leaving the mixture as it is, kneading the mixture with a kneader or the like, or temporarily kneading (single or multiple times without any problem).

The time of the hydrolysis reaction treatment with lipase is not particularly limited, and the desired decomposition rate of fats and oils (the total amount of fats and oils and fatty acids remaining in the reaction system such as waste clay after being affected by lipases by lipase is determined by lipase). It suffices to process until the value obtained by dividing by the value before being affected reaches the value obtained by subtracting 1).

The clay-containing fatty acid metal salt composition obtained according to the present invention can be used, for example, as a water repellent, and especially as a water repellent that can be internally added for a ceramic siding material and a pulp cement board, and particularly a ceramic siding. It is preferable to use it as a water-repellent agent that can be added internally for a material, because an extremely excellent water-repellent effect can be obtained. When the clay-containing fatty acid metal salt composition obtained by the present invention is added as a water repellent to a ceramic siding material, a pulp cement board or the like, the ceramic siding material, the base material of the pulp cement board or the like is particularly limited. Not done.

When the clay-containing fatty acid metal salt composition obtained by the present invention is used as a water repellent, the content of the fatty acid metal salt as an active ingredient is preferably in the clay-containing fatty acid metal salt composition (water repellent). Is 10 to 50% by weight, more preferably 25 to 50% by weight. Further, in this case, when the water repellent is used for a ceramic siding material, a pulp cement board, etc., the amount of the water repellent added is such that the fatty acid metal salt (active ingredient) is added to the hydraulic substance in the slurry. , Preferably 0.05 to 3% by weight, more preferably 0.1 to 3% by weight.
The amount is 2% by weight.

To produce a ceramic siding material, a pulp cement board or the like by using the clay containing fatty acid metal salt (preferably calcium salt) composition obtained by the present invention as a water repellent, the above clay containing fatty acid metal salt is used. After the composition is uniformly mixed with powder of a hydraulic substance such as cement or added to a material slurry in which an additive and an additive material are blended with the hydraulic substance as necessary, the mixture is molded, cured, Let it harden.

When the white clay-containing fatty acid metal salt composition obtained by the present invention is used as a water repellent, the water repellent may be:
Other components such as a curing retarder, a curing accelerator, an AE agent, a water reducing agent, a defoaming agent, an emulsion or a surfactant for stabilizing the suspension may be added within a range that does not impair the performance.

The clay-containing fatty acid metal salt composition obtained by the present invention can be preferably used as it is as a detergent, especially as a cleanser.

[0031]

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

[Example 1] 1 kg of waste white clay treated with beef tallow (oil content 37.7% by weight) was placed in a small kneader, and at room temperature, 70 g of sodium hydroxide was dissolved in 250 g of water and an aqueous solution was added with stirring. , A uniform paste-like mixture.

Next, 0.2 g of lipase having a P point of 50 ° C. (manufactured by Amano Enzyme Inc .: trade name Amano 30G),
An aqueous solution prepared by dissolving 0.3 g of lipase having a P point of 65 ° C. (manufactured by Novozymes Japan KK: trade name Lipozyme TL) in 50 g of water was added dropwise to the kneader over 30 minutes. Immediately after the start of dropping, the hydrolysis reaction and the neutralization reaction proceeded with heat generation, and the mixture changed from brown to pale yellow while thickening. At the end of the dropping, the temperature was 40 ° C.

Transfer to a beaker to complete the reaction,
Aged at room temperature. The heat generation continued, and one hour after the start of aging, the temperature of the center of the mixture reached 70 ° C., and the mixture was left as it was.

Twenty-four hours after the start of aging, the paste-like mixture was spread on an aluminum tray, air-dried at 60 ° C., crushed with a table crusher, and a yellowish white clay-containing fatty acid metal salt composition (containing white clay). Sodium soap) powder 11
70 g were obtained. Despite the large amount of water at the time of hydrolysis, the oil and fat content in the obtained powder was 4.8% by weight,
About 85% of the oil and fat contained in the waste clay was converted into fatty acid sodium.

1 g of the obtained powdery white clay-containing fatty acid metal salt composition (white clay-containing sodium soap) was weighed in a glass bottle with a lid, 50 g of water was added, and the mixture was shaken 50 times to foam very well for 30 minutes. The foam afterwards was also good.

Further, when the white clay-containing fatty acid metal salt composition is attached to a sponge moistened with water and the surface of a glass beaker coated with an oil-based ink is polished, the same polishing and cleaning effects as those of a commercially available cleanser can be obtained. there were. Further, when the clay-containing fatty acid metal salt composition was sprinkled on a concrete floor with machine oil and brushed with a deck brush moistened with water to wash, the machine oil was removed, and a clean floor was obtained.

Comparative Example 1 Amano 30G as lipase
A powder of a clay-containing fatty acid metal salt composition was obtained in the same manner as in Example 1 except that only 0.5 g of the above was used. The oil and fat content in the obtained powder was 13.0% by weight, and 59% of the oil and fat content in the waste clay was converted to fatty acid sodium.

[Comparative Example 2] Lipozyme T as lipase
A white clay-containing fatty acid metal salt composition powder was obtained in the same manner as in Example 1 except that only 0.5 g of L was used. The oil and fat content in the obtained powder was 12.2% by weight, and only 62% of the oil and fat content in the waste clay was converted to fatty acid sodium.

Example 2 1 kg of waste white clay treated with palm oil (oil-containing fat content 39.1% by weight) was placed in a small kneader, 70 g of Portland cement powder was added, and the mixture was stirred and mixed until uniform.

Next, 0.2 g of lipase having a P point of 45 ° C. (manufactured by Meito Sangyo Co., Ltd .: trade name Lipase OF) and 0.1 g of lipozyme TL dissolved in 140 g of water were placed in a kneader. The mixture was added dropwise over 30 minutes and mixed uniformly.

The obtained mixture has a wet powder of several mm to
It became a granular material granulated to about 1 cm. The temperature at the end of dropping was about 35 ° C., and the mixture was transferred to a beaker to complete the reaction and aged at room temperature. The heat generation continued, and one hour after the start of aging, the temperature of the center of the mixture reached 66 ° C, and the mixture was left as it was.

After 48 hours from the start of aging, the completely solidified granules were crushed by a table crusher and dried by ventilation at 60 ° C.,
Powdery clay containing palm oil fatty acid calcium 1135g
Got The oil and fat content in this powder was 2.4% by weight,
About 93% of the oil and fat contained in the waste clay was converted into fatty acid calcium. Also, this powder contains clay.
It was extremely water repellent and had excellent powder flowability.

[Comparative Example 3] Lipase OF as lipase
A powder of clay-containing fatty acid metal salt composition was obtained in the same manner as in Example 2 except that only 0.3 g of the above was used. The oil and fat content in the obtained powder was 8.2% by weight, and only 78% of the oil and fat content in the waste clay was converted to fatty acid calcium.

[Comparative Example 4] Lipozyme T as lipase
A white clay-containing fatty acid metal salt composition powder was obtained in the same manner as in Example 2 except that only 0.3 g of L was used. The oil and fat content in the obtained powder was 13.2% by weight, and 62% of the oil and fat content in the waste clay was converted into fatty acid calcium.

[Example 3] 87.5 g of powdered calcium carbonate as a neutralizing agent and 0.2 of lipase OF as a lipase
Powder of a clay-containing fatty acid metal salt composition was obtained in the same manner as in Example 1 except that 5 g and 0.25 g of lipase having a P point of 55 ° C. (manufactured by Meito Sangyo Co., Ltd .: trade name Lipase QL) were used. .

The oil and fat content in the obtained powder was 1.7% by weight, and about 84% of the oil and fat contained in the waste clay was converted into fatty acid calcium. In addition, this powder contained white clay, had extremely high water repellency, and had excellent powder fluidity.

[0048]

The effect of the present invention is that the hydrolysis rate by lipase is high, the degree of freedom of water content in the reaction system is high, the raw materials can be uniformly mixed, and the product has a wide range of applications. It is to provide a method for producing a fatty acid metal salt composition containing fatty acid.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasushi Adachi             7-23 Higashiohisa, Arakawa-ku, Tokyo Sunshine             Industry Development Laboratory (72) Inventor Daisuke Kurita             7-23 Higashiohisa, Arakawa-ku, Tokyo Sunshine             Industry Development Laboratory F-term (reference) 4B064 AD87 CA21 CB03 CC04 CD23                       DA16 DA20

Claims (4)

[Claims] 1. A method in which the neutralizing agent is uniformly mixed with the waste clay used in the treatment of fats and oils, and then an aqueous solution or dispersion of lipase is added to omit the hydrolysis reaction of fats and oils and the neutralization reaction of fatty acids. In the method for producing a clay-containing fatty acid metal salt composition to be carried out at the same time, as the above-mentioned lipase, at least two kinds of lipases having different hydrolysis activity peak temperatures of 10 ° C. or more are used. Production method. 2. One of the two lipases having different hydrolytic activity peak temperatures of 10 ° C. or more has a hydrolytic activity peak temperature of 55 ° C. or less, and the other lipase has a hydrolytic activity peak temperature of 50 ° C or higher,
A method for producing the clay-containing fatty acid metal salt composition according to claim 1. 3. The clay-containing fatty acid metal salt composition according to claim 1 or 2, wherein the difference in hydrolytic activity peak temperature between the two types of lipases having different hydrolytic activity peak temperatures of 10 ° C. or more is 10 to 45 ° C. Manufacturing method. 4. The amount of the two kinds of lipases whose hydrolytic activity peak temperatures differ by 10 ° C. or more does not exceed four times the weight of the other one, and the total amount of lipase is the same. In contrast, the above hydrolysis activity peak temperature is 1
The method for producing a clay-containing fatty acid metal salt composition according to any one of claims 1 to 3, wherein the total amount of two kinds of lipases differing by 0 ° C or more is 70% by weight or more.