JP2694185B2 - Refining and reforming method of crude wax - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for refining and modifying crude wax, and in particular, purifying crude wax obtained from the fruits of the Hazelaceae family by decolorizing and deodorizing the crude wax. The present invention relates to a method for reforming by increasing the hardness of wax and decreasing the peroxide value.

(Prior Art) There are wood wax and lacquer wax as waxes obtained from fruits of Hazelaceae plants, and each of them contains a large amount of fatty acid components. These waxes take advantage of their properties such as microcrystallinity, emulsification property, viscosity, etc. in various fields, such as sizing agents for pencils, crayons, food coatings, various lubricants, and release agents for polycarbonate. , Moisture proofing agents, luster polish for woodwork, refining candles, etc. From the viewpoint of price, wood wax is used for high-grade use, and lacquer wax is used for low-grade use.

In addition, crude wax is almost dark green brown, has a remarkable unpleasant odor, and contains a relatively large amount of impurities, so that it is required to be purified, decolorized and deodorized in order to be used in the above various applications. It Although various purifying methods have been conventionally studied for this purpose, the most commonly used methods are the sun exposure method, the oxidation treatment method with sodium chlorite and hydrogen peroxide (Japanese Patent Publication No. 40-16252). Yes Recently, the molecular distillation method may also be used.

(Problems to be Solved by the Invention and Objects of the Invention) However, the above-mentioned purification methods according to the prior art have various problems. That is, sun exposure method work to utilize the sunlight is affected by the weather, there is a problem in that it takes a long time required area becomes large, the exposure process, the oxidation treatment method ClO ₂ by chlorates It is not preferable as a working environment because toxic gases such as toxic gases are generated during the exposure process, and in order to decompose the remaining chemicals, for example, a pickling step with oxalic acid, sulfuric acid, citric acid, etc. is required, and therefore drainage treatment is performed. However, the molecular distillation method requires a large amount of equipment cost for its implementation.
This is a disadvantageous method because it is reflected in the product cost, and it is difficult to apply it as a refining method for lacquer wax, which is required to be particularly inexpensive.

Therefore, a main object of the present invention is to provide crude wood wax and crude lacquer wax, and to provide an inexpensive and easy method for purifying them by decolorizing and deodorizing them.

Another object of the present invention is to treat crude wood wax and crude lacquer wax to reduce the peroxide value thereof, and also to improve the hardness while maintaining the solvent solubility characteristic of wood wax and wetting wax. To provide a method for modifying these waxes.

A secondary but important object of the present invention is to purify and modify inexpensive lacquer wax to replace expensive wood wax (about twice the price).

(Means and Actions for Solving Problems and Achieving Purpose) In order to solve the above problems, the present inventors have paid attention to the fact that low-quality lacquer wax produced in China or the like can be obtained at a low price. ,
Various studies were conducted to open the way for that reason. That is, with respect to various known methods used for refining natural wax and combinations thereof, an attempt was made to apply them to refining of a rough lacquer tower. As a result, surprisingly, low-quality crude lacquer wax was targeted by combining the adsorption method used for refining various towers and the hydrogenation treatment method used for producing hardened oil from rice sugar wax. As a result of investigating the properties of the refined lacquer wax treated in this way, it was found that the peroxide value was lowered and the hardness was increased. .
In addition, lacquer wax is a wax obtained from the sumacaceae plant of the family Hazelaceae, and the above-mentioned purification method is also applicable to crude wax obtained from the fruits of other plants of the family Hazelaceae. When the above-mentioned refining method was applied to the crude wax which is the crude wax obtained from the above, the same result as in the lacquer wax was obtained.

The present invention is based on the above-mentioned findings, and after dissolving the crude wax obtained from the fruit of the Hazelaceae plant by hot water roasting, 2-5% (W / W) amount of activated carbon is added, 90-110
Activated carbon is recovered by stirring at ℃ for 1-3 hours or standing still, then filtering at a product temperature of about 95 ℃, and catalyst of 2% (W / W) or more of palladium based on the obtained pre-purified wax. Then, the temperature was set to 100-180 ° C, the hydrogen gas pressure was set to 10-25kg / cm ² , and hydrogenation treatment was performed.
It exists in a method for refining and modifying crude wax, which is characterized in that the wax is lowered to a certain degree and then filtered.

In the refining / reforming method according to the present invention, the treatment with activated carbon is first carried out. By this means, the adsorbable substances such as pigment contained in the crude wax are removed, and the hydrogenation treatment in the next step is effective. You can train them. On the contrary, if the hydrogenation treatment is first performed and then the treatment with activated carbon is performed, it is not possible to obtain a desired product that is sufficiently decolorized and deodorized. Even if decolorization is performed with a chemical after hydrogenation, decolorization is possible but the peroxide value increases. As the adsorbent substance, it is possible to use activated clay such as acid clay in addition to activated carbon, but if the raw wax to be treated is of good quality, it may be treated with activated clay if it is of poor quality. Sufficient decolorization is impossible, and therefore the desired product cannot be obtained even if hydrogenation treatment is performed in the next step.

In the method of the present invention, filtration after the treatment with activated carbon is carried out at a product temperature of around 95 ° C. because it is preferable in order to sufficiently remove pigments and contaminants.

The reason why palladium is used as a catalyst in the hydrogenation treatment of the next step is that the desired effect was not obtained when nickel was used as a catalyst. The amount of palladium catalyst added was 2 with respect to the crude wax pretreated with activated carbon.
% (W / W) or more, but about 3% (W / W) is preferable,
As the carrier, activated carbon is preferable as obvious from the pretreatment. As the hydrogenation treatment condition, hydrogen gas pressure is 10-25 kg.
/ cm ² , preferably about 15 kg / cm ^2, and set the treatment temperature to 10
It is preferably set within the range of 0 to 180 ° C. If the product is left in a high temperature state after the completion of the hydrogenation reaction, coloring will occur, so it is necessary to cool the product as quickly as possible to lower the product temperature to about 100 ° C. After that, the catalyst is recovered by filtration, and the obtained liquid wax is poured into a mold and molded to obtain a product.

The wood wax and lacquer wax purified according to the present invention are the first described below.
As shown in the table, it was white and had no bad odor.

Further, by treating the crude wax with the method of the present invention, (1) the iodine value is lowered as shown in Table 1, and as a result, the hardness as a solid lipid is increased (according to the hardening effect due to the decrease in the degree of unsaturation, (2) The unprocessed product maintains the same solubility as crude wax as shown in Fig. 1 of the attached drawings, and (3) the peroxide value decreases as shown in Table 1. It is also modified.

When the refining / modifying method according to the present invention is applied to the refining of other natural waxes such as carnauba wax and candelilla wax, the intended effect cannot be obtained. It was found to be effective in the context of purification of.

(Examples) Next, the present invention will be described in more detail and specifically with reference to Examples and Reference Examples.

Example 1 Chinese crude lacquer wax having a deep green color and a strong unpleasant odor
Collect 100g in a 300ml beaker, melt in hot water and add 5% (W / W) of activated carbon to the molten crude lacquer wax.
Stirred for hours. Next, the funnel and the container were preheated, and 90 g of the preliminary decolorized lacquer wax was recovered by suction-filtering the molten lacquer wax using a filter paper.

50 g of this preliminary decolorizing lacquer wax was sampled, and using a hydrogenation device (capacity: 1000 ml) manufactured by Nitto Autoclave Co., Ltd., 1.5 g of palladium activated carbon, a treatment temperature of 160 ° C., a rotary stirring number of 1100 rpm, and a hydrogen gas pressure of 15 kg / cm. Hydrogenation treatment was performed for 30 minutes under the condition of ² . Immediately after completion of the hydrogenation treatment, the product temperature was lowered to about 100 ° C., and 43 g of purified lacquer wax was recovered by filtering as in the preliminary decolorization treatment. The yield of purified lacquer wax from 100 g of crude lacquer wax was 77.4%, the color of this purified lacquer wax was white as shown in Table 1 below, and the iodine value and the penetration were untreated. Compared to lacquer wax, it decreased (increased hardness), and the peroxide value also decreased as shown in Table 1.

The solvent solubility was the same as that of crude lacquer wax as shown in Fig. 1 and did not change. (In Fig. 1, the solvent solubility of each wax is shown by a temperature value. As for the value, toluene as a solvent and each wax as a test sample were sampled in a test tube, heated to completely dissolve the wax, and then visually observed while gradually cooling, and precipitation of wax was observed. The temperature value at the time, indicating that the lower the temperature, the higher the solvent solubility).

Example 2 Chinese crude lacquer wax 50 which has a deep green brown color and has a strong unpleasant odor
0 g was collected in a 1 liter beaker, and was roasted and melted, and 5% (W / W) of activated carbon of this molten crude lacquer wax was gradually added and stirred for 3 hours. Then, the funnel and the container were preheated, and 410 g of the preliminary decolorized lacquer wax was recovered by suction-filtering the molten lacquer wax using a filter paper.
300 g of this preliminary decolorizing lacquer wax was sampled and used with a hydrogenation device (capacity: 1000 ml) manufactured by Nitto Autoclave Co., Ltd.
Palladium activated carbon 9g, processing temperature 160 ℃, rotary stirring number 1200r
Hydrogenation treatment was performed for 60 minutes under conditions of pm and hydrogen gas pressure of 15 kg / cm ² .

Immediately after the completion of the hydrogenation treatment, the product was cooled to lower the product temperature to about 100 ° C., and filtered in the same manner as in the preliminary decolorization treatment to recover 280 g of purified lacquer wax. The yield of purified lacquer wax from 500 g of crude lacquer wax is 74.7%, the color of this purified lacquer wax is white as shown in Table 1 below, and the iodine value and the penetration are crude lacquer wax. (Hardness increased), and the peroxide value decreased as shown in Table 1.

The solvent solubility was equivalent to that of untreated crude lacquer wax as shown in FIG. 1, and did not change.

Example 3 100 g of Japanese wax having a deep green color and a strong unpleasant odor
Was collected in a 300 ml beaker and melted in hot water, 5% (W / W) of activated carbon was added to this molten crude wax, and the mixture was stirred for 2 hours. Next, the funnel and the container were preheated, and 90 g of preliminary decolorized wax was recovered by suction-filtering the molten wax of wood using a filter paper.

50 g of this preliminary decolorized wax was sampled, and using a hydrogenation device (capacity: 1000 ml) manufactured by Nitto Autoclave Co., Ltd., 1.5 g of palladium activated carbon, processing temperature of 160 ° C., rotation number of 1100 r
Hydrogenation was performed for 30 minutes under the conditions of pm and hydrogen gas pressure of 15 kg / cm ² . Immediately after the hydrogenation process is completed, the product is cooled and the product temperature is reduced to approximately
43 g of purified wood wax was recovered by dropping to 100 ° C. and filtering as in the pre-bleaching process. Crude wax 100g
The yield of the refined wax was 77.4%, the color of this refined wax was white as shown in Table 1, and the iodine value and the penetration were lower than those of crude lacquer wax (hardness Increased) and the peroxide number decreased as shown in Table 1 below.

The solvent solubility was the same as that of crude lacquer wax as shown in FIG. 1, and did not change.

Reference Example 1 When the bleached wood wax was subjected to a hydrogenation treatment by the same operation method as in Example 3, the color did not drop further and the physical properties did not change so much.

Reference Example 2 Chinese crude lacquer wax having a deep green brown color and a strong unpleasant odor
100 g was collected in a 300 ml beaker, melted in a hot water bath, added to this molten lacquer wax in an amount of 5% (W / W) of active seeds, stirred for 2 hours, and then preheated. 90 g of the preliminary decolorized lacquer wax was recovered by suction-filtering the above-mentioned molten lacquer wax with a filter paper using a filter funnel and a container.

Lacquer wax obtained only by treatment with activated carbon is slightly decolorized but insufficient, it is not decolorized like a hydrogenated product, it still has a color close to yellow and has a strong unpleasant odor. The physical properties were not so different from crude lacquer wax.

Reference Example 3 100 g of Brazilian crude carnauba wax (No. 2) was subjected to adsorption treatment and hydrogenation treatment with activated carbon under the same conditions as in Example 1, and as a result, 42 g of carnauba wax was recovered. However, the color tone of this treated wax was tan and did not become white like lacquer wax.

Reference Example 4 100 g of crude candelilla wax produced in Mexico was subjected to adsorption treatment with activated carbon and hydrogenation treatment under the same conditions as in Example 1, and as a result, 43 g of candelilla wax was recovered. However, the color tone of this treated wax was a little more decolorized than crude wax, but it was yellow and did not become white like lacquer wax.

(Effects of the Invention) By carrying out the refining method according to the present invention, crude lacquer wax can be almost completely decolorized and deodorized. In particular, although low-quality crude lacquer wax is inexpensive to obtain, it is difficult to sufficiently decolorize and deodorize with the conventional method, resulting in a high price for purified products. In fact, lacquer wax was originally good in solubility in a solvent, but its use was limited such that it was soft and sticky and could not be used in foods due to its high peroxide value. However, if crude lacquer wax is refined by the method of the present invention, decolorization /
Modification is performed without being deodorized, and as a result, the peroxide value is lowered and the hardness is increased, so that it can be used as an alternative to expensive wood wax.

As for crude wood wax, the method of the present invention is easier than the conventional method for obtaining bleached wood wax, so that the refining cost is lower.

Further, the method of the present invention which brings about such an effect is that the crude wax is treated with activated carbon, and then hydrogenation treatment is carried out using palladium as a catalyst, the treatment operation is easy, and particularly expensive equipment is required. Not so, its practical value is great.

[Brief description of the drawings]

FIG. 1 shows the solvent solubility of crude wood wax and crude lacquer wax as raw materials and purified products (activated carbon and hydrogenated wood wax and lacquer wax) obtained by the method of the present invention. It is a graph shown together with solvent solubility such as.

Continuation of the front page (56) Reference JP-A-57-125297 (JP, A) JP-A-50-5405 (JP, A) JP-B-40-16252 (JP, B1) JP-B-30-2987 (JP , B1) Patent 100020 (JP, C2) Megumi Yo, Kusano, Industrial Chemistry 32 "Fat and fat, wax", September 30, 1960, published by Nikkan Kogyo Shimbun, Ltd. p64-65

Claims (1)

(57) [Claims] 1. A crude wax obtained from a fruit of a Hazelnutaceae plant is melted by hot water roasting, and then 2-5% (W / W) amount of activated carbon is added, and the product temperature is 90-110 ° C. for 1-3 hours. Stir or let stand,
Then, the activated carbon is recovered by filtering at a product temperature of about 95 ° C, and palladium is used in an amount of 2% (W / W) or more with respect to the obtained pre-purified wax, and the temperature is 100-180 ° C and the hydrogen gas pressure is Is set at 10-25 kg / cm ² and hydrogenated, and then the product temperature is quickly lowered to about 100 ° C. and filtered, and the crude wax is purified and reformed.