JP3134203B2 - Sorbitan stable against heat and / or alkali and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Industrial applications]

[0002] The present invention relates to sorbitan which is stable against heat and / or alkali and a method for producing the same. That is,
The present invention relates to sorbitan that is stable to heat and / or alkali and a method for producing the same.

[0003]

[Prior art]

[0004] Conventional sorbitan is obtained by concentrating sorbitol, causing an intramolecular dehydration reaction of one molecule in the presence of an acid catalyst such as sulfuric acid, diluting the mixture with water, neutralizing the resultant, and activating activated carbon or the like. It is manufactured through purification operations such as decolorization, deionization, and crystallization using an ion exchange resin.

The sorbitan thus obtained is esterified with, for example, a fatty acid such as oleic acid or stearic acid to produce a nonionic surfactant, sorbitan fatty acid ester, as a detergent for kitchen use or ice cream. Widely used for various applications such as emulsifiers.

However, with the recent improvement in quality of various raw materials and high quality of products, many fields in which sorbitan cannot be satisfied with conventional quality have appeared.

Among the quality of sorbitan, the industry has been most requested to improve the stability of the sorbitan against heat and alkali, that is, storage, pre-treatment, use, for example, storage at room temperature. Coloring during heating, such as during the heat dissolution of sorbitan crystals, or during the esterification reaction between sorbitan and a fatty acid or the like.

Several methods for improving these properties have been proposed. Typical examples are (1) JP-B-61-59311 and JP-B-61-59312.
And (2) JP-A-6
There is a method as introduced in JP-A-3-79844.

The two methods mentioned in the above (1) are intended to improve the stability of sorbitan against heat and alkali.
Based on the idea that it is effective to reduce or remove coloring cause substances mixed with sorbitan,
The purpose is to produce sorbitan of high purity.

The former method is characterized in that an ion exchange fiber is used as an acid catalyst used in the intramolecular dehydration reaction of sorbitol, instead of a commonly used aqueous acid solution.

In the latter method, sorbitan produced by the intramolecular dehydration reaction of sorbitol is diluted, and an aqueous solution of sorbitan obtained by neutralization is passed through an ion exchanger column. It is characterized by obtaining.

On the other hand, the method introduced in the above (2) requires that the stability of sorbitol, which is a raw material of sorbitan, to heat and alkali must be increased in order to obtain sorbitan having high heat and alkali stability. It is based on the technical idea.

[0013] As a means thereof, there is a method of obtaining a heat- and alkali-stable sugar alcohol such as sorbitol by reducing glucose, subjecting the resulting aqueous solution of sorbitol to heat treatment with an alkali, and then purifying the solution.

[0014]

[Problems to be solved by the invention]

However, the conventional sorbitan and the method for producing the same had serious problems despite various improvement efforts.

The problem is that sorbitan produced by a conventional method is (a) markedly colored with time when an aqueous sorbitan solution or sorbitan crystal is stored or concentrated at room temperature.

(B) Despite various conventional efforts for improvement, there has been a phenomenon that, when subjected to a subsequent use, in particular, an esterification reaction with a fatty acid or the like, a significant coloration occurs.

Further, even when sorbitan is produced using sorbitol produced as described in (2) above, the problems (a) and (b) are pointed out, although to a lesser extent. Was not fully resolved.

Accordingly, there has been a strong demand for solutions to the above-mentioned problems (a) and (b) in accordance with high quality of various raw materials and high quality of products.

[0020]

[Means for Solving the Problems]

The present inventors have conducted various studies on the method for producing sorbitan and the quality of sorbitan in order to solve the above-mentioned problems, and have obtained various findings.

For example, it has been found that simply increasing the purity of sorbitan by a conventional method cannot reduce the color-causing substance to a level that satisfies the current demands of the industry.

Further, even if an operation of removing the coloring agent at the stage of sorbitol as a raw material is performed, a newly generated coloring agent remains in the product when producing sorbitan,
Phenomena that could not be completely removed by ordinary purification means and that a new colored substance seems to be generated during dilution or concentration of sorbitan were confirmed.

Further, when storing the sorbitan obtained by the conventional method, it was confirmed that the coloring phenomenon progressed with time regardless of whether the storage state was liquid or crystalline.

Based on the various findings described above, the present inventors have found that in order to obtain sorbitan that is stable against heat and / or alkali, a purification operation after producing sorbitan is indispensable.
It has been concluded that the coloring substances mixed in sorbitan cannot be completely removed by a conventional purification operation.

Based on this consideration, as a result of various investigations on the method of removing the coloring agent of sorbitan, the inventors succeeded in removing the coloring agent by adding an alkali to the sorbitan aqueous solution and subjecting it to heat treatment. Then, by performing a deionization operation of an ordinary ion exchange resin or the like, or a purification operation such as decolorization or deodorization with activated carbon, it is stable against heat and / or alkali and hardly undergoes a coloring phenomenon during storage. Sorbitan was successfully obtained, and the present invention was completed.

That is, the present invention firstly adjusts the pH of the aqueous sorbitan solution to 8 to 14 with an alkali,
It is a sorbitan that is heat and / or alkali stable, obtained by heat treatment at ° C. and then purified.

Further, the present invention relates to a method for producing a sorbitan,
(1) the sorbitan purity in the solid is 60% or more;
(2) The heat resistance test was performed by adding 5 g of a 10% aqueous solution of potassium hydroxide to 60 g of a 50% aqueous solution of a sample.
When carried out under conditions of heating for 30 minutes above boiling water over 30 ° C., the degree of coloration of the sample is determined by APHA [American Public Healthy Association].
ealthy Association) to determine the color
(3) temperature 0 to 40 ° C., pH 2 to 10.
Is a heat and / or alkali stable sorbitan, characterized in that when stored under the conditions described above, the color tone measured on the 30th day of storage has a property of being in the range of 0 to 20 in APHA.

Thirdly, the present invention provides a method of adjusting the pH of an aqueous sorbitan solution to 8 to 14 with an alkali,
A method for producing sorbitan that is stable against heat and / or alkali, which is characterized by purifying after heating at ℃.

Further, the present invention fourthly adjusts the pH of the aqueous sorbitan solution to 9 to 13 with an alkali,
This is a method for producing sorbitan, which is stable against heat and / or alkali, after subjecting to heat treatment at 0 ° C. for 5 minutes to 2 hours, followed by purification.

Sorbitan, which can be used as a raw material in carrying out the present invention, does not require any special restrictions on its production method, purity, type of mixed substances, etc., but it means that the effects of the present invention can be advantageously exerted. The sorbitan content in the solid matter is preferably about 60% by weight or more due to restrictions in later uses and the like.

For the same reason as described above, it is preferable that sorbitol or a similar sugar alcohol is mainly contained in the sorbitan aqueous solution as a raw material, and it is more preferable that unreduced sugar such as glucose is small.

The concentration of the aqueous sorbitan solution is preferably about 30 to 80% by weight, in addition to the above-mentioned reasons, from the viewpoint of preventing decay and the like during storage before application of the present invention. Alternatively, the concentration adjustment and the pH adjustment in the next step can be simultaneously performed using a dilute alkaline aqueous solution.

The alkali usable in the present invention has no particular restrictions on its form, type, quality, etc.
Various ion exchangers other than alkali metals such as sodium and calcium, hydroxides and carbonates of alkaline earths, etc.
It may be a mold or a solid alkali.

The alkali may be added during heating, but in that case, in order to accurately adjust the pH, it is necessary to adjust the amount of the alkali based on a strict calculation. Addition before heating is easier in terms of pH control and the like.

In practicing the present invention, the amount of alkali added varies depending on the amounts of acid components and alkali components contained in the aqueous sorbitan solution used as a raw material. , Sorbitan aqueous solution at pH 8
It is sufficient that the amount is about 14 to about,
On the other hand, when using a normal alkali aqueous solution, the concentration of the alkali used is not a critical constraint,
The range of 1 to 50% by weight is preferable for operational reasons such as easy preparation.

When the present invention is carried out, the preferable pH is 8 to 14, more preferably about 9 to 13 in order to sufficiently exhibit the effects of the present invention. The progress of the reaction is insufficient, the coloring-causing substance may not be in a form that can be sufficiently removed, and the properties of the finally obtained sorbitan may not be sufficiently improved. When subjected to a heat treatment in a state, the amount of alkali tends to be increased more than necessary, and it is economically meaningless because it requires more cost than necessary to remove the alkali in the subsequent purification operation. Further, if the pH is extremely increased, an unnecessary reaction may be induced during heating, which is not preferable.

Further, a preferred heat treatment temperature for practicing the present invention is 90 to 220 ° C., more preferably 110 to 220 ° C.
Although it is 140 ° C., it is necessary to select an appropriate range for the heat treatment temperature in combination with other conditions such as the heat treatment time and pH.

If the heat treatment temperature is lower than 90 ° C., the coloring substance may not be sufficiently removed in some cases, and the properties of the obtained sorbitan may be insufficiently improved. When the heat treatment is carried out at a temperature exceeding 220 ° C., it is not preferable because the raw material sorbitan may be scorched or the yield may be reduced due to excessive reaction.

In carrying out the present invention, the heating reaction time is as follows:
It is necessary to set in accordance with an appropriate combination with the above various heat treatment conditions, but a preferable range is about 5 minutes to 2 hours.

In the present invention, not only a batch system but also a continuous heating system can be employed, and a device used for the system can be a long reactor in addition to a normal reaction vessel.

Further, the material of the apparatus to be used does not need to be particularly expensive such as glass lining, and general-purpose materials such as stainless steel used for ordinary apparatuses are sufficient.

As a purification method employed in carrying out the present invention, a known method used for the purification of ordinary sugars and sugar alcohols is sufficient. For example, a dilution or concentration operation, if necessary, After neutralization operation, decolorization / deodorization operation with various adsorbents such as activated carbon and adsorption resin, deionization operation with various ion exchangers such as ion exchange resin, ion exchange membrane, ion exchange fiber, zeolite, etc. Is mentioned.

[0044]

【Example】

Hereinafter, the content of the present invention will be described more specifically with reference to examples, but the content of the present invention is not limited to the following examples. In the following examples,% represents% by weight unless otherwise specified.

[0046]

Embodiment 1

7.1 kg of a sorbitol solution [Sorbit D-70, manufactured by Towa Kasei Kogyo Co., Ltd.] is placed in a 10 liter container, concentrated under reduced pressure at 100 ° C., and 1% sulfuric acid is added to the weight of sorbitol. After that, a dehydration reaction was performed at 120 ° C. for 90 minutes while maintaining a weak reduced pressure state with an aspirator to obtain a reactant-1.

Next, after cooling to about 60 ° C., 200 g of the reactant-1 was placed in another container, diluted with hot water at 50 ° C. to a concentration of 50%, and diluted with sodium hydroxide 2
A 0% aqueous solution was added to adjust the pH of the reaction solution to 10.6, and the mixture was heated at 130 ° C. for 30 minutes to obtain a treatment liquid-1.

Then, after allowing to cool to 80 ° C., activated carbon having a solid content of 2% with respect to the treatment liquid was added, the mixture was stirred for 15 minutes, filtered to remove the activated carbon, and passed through a 300 ml mixed bed type ion exchange resin. The solution was subjected to a deionization operation to obtain a product-1 of the present invention.

The product-1 of the present invention is in the form of an aqueous solution or a crystal, and when stored at room temperature, coloring with time is hardly observed.
As a result of the heat resistance test in the presence of an alkali, the sorbitan had a low degree of coloring, was less colored even during an esterification reaction with a fatty acid, and was stable to heat and / or alkali.

The saccharide composition in the solid content of the obtained product-1 of the present invention was measured by gas chromatography. As a result, sorbitan 75.2%, isosorbide 5.4%, sorbitol 12.1%, and other saccharides were determined. The alcohol was 7.3%.

[0052]

Embodiment 2

From the reaction product-1 obtained in Example 1, 200
g in a container, and hot water at 60 ° C.
The pH was adjusted to 5%, a slurry-like liquid containing 5% of calcium hydroxide was added to adjust the pH to 9.0, and the mixture was heated at 120 ° C. for 40 minutes to obtain a treatment liquid-2.

Next, the same purification treatment as in Example 1 was performed to obtain the product-2 of the present invention, which is sorbitan stable to heat and / or alkali of the present invention.

As a result of measuring the purity by the same method as in Example 1, the sorbitan content was 75.3%.

[0056]

Embodiment 3

Of the reactants-1 obtained in Example 1, 200
g in a container and hot water at 80 ° C.
Adjust to 2%, add 25% aqueous solution of potassium hydroxide and add p
H was adjusted to 11.0, and the onerator in which the coil having an inner diameter of 3 mm was immersed in an oil bath was heated to 140 ° C. in advance and adjusted to have a residence time of 20 minutes. And heated to obtain a treatment liquid-3.

Next, the same purification treatment as in Example 1 was performed to obtain the product-3 of the present invention which is a sorbitan which is stable against heat and / or alkali of the present invention.

As a result of measuring the purity by the same method as in Example 1, the sorbitan content was 74.9%.

[0060]

Embodiment 4

From the reactants-1 obtained in Example 1, 200
g in a container, and hot water at 60 ° C. is added to reduce the solid content to 5 g.
The pH was adjusted to 0%, the pH was adjusted to 10.6 by adding a 20% aqueous sodium hydroxide solution, and the mixture was heated at 135 ° C. for 20 minutes to obtain a treatment liquid-4.

Next, the same purification treatment as in Example 1 was carried out to obtain a product-4 of the present invention which is a sorbitan which is stable against heat and / or alkali of the present invention.

As a result of measuring the purity by the same method as in Example 1, the sorbitan content was 74.7%.

[0064]

[Comparative test 1]

The sorbitan of the present invention obtained in each of the above Examples and the sorbitan obtained by the conventional method were as follows:
The following comparative tests were performed to compare the stability to heat and alkali.

For comparison, Japanese Patent Publication No. 61-5931
Sorbitan prepared by the method of Example 1 described in Japanese Patent Publication No. 2 was used as Control Product-1.

When the purity of the control product-1 was measured by gas chromatography, sorbitan was 99.5% and other sugar alcohols were 0.5%.

Also, 200 g was taken out of the reactant-1 obtained in Example 1, adjusted to a concentration of 50%, activated carbon having a solid content of 3% relative to the reactant was added, and the mixture was treated at 60 ° C. for 20 minutes. The activated carbon was removed by filtration, and 500 ml of a strongly acidic ion exchange resin column, a strongly basic anion exchange resin column, and 300 ml each.
Sorbitan purified by passing through a mixed bed type ion exchange resin in the order of ml was used as a control product-2.

Each of the sorbitans of the present invention products-1 to 4 obtained in Examples 1 to 4 and each of the sorbitans of the control products 1 and 2 were adjusted to a concentration of 50%, and 60 g of each was placed in a glass container. 5 g of a 10% aqueous potassium hydroxide solution was added to each, and a reflux tube was mounted on the glass container.

Next, each container was heated on a boiling water bath for 30 minutes, cooled to 20 ° C., and then measured for color tone, amount of reducing sugar, absorbance and the like.

Incidentally, the Somogyi method was employed as a method for measuring the amount of reducing sugar, but the analytical value is obtained by expressing the amount of reducing sugar contained in an aqueous solution having a sample concentration of 70% in accordance with the practice of the industry. .

Table 1 shows the obtained measurement results. In addition,
The coloring degree of the control product-2 was 50% of the maximum coloring index of APHA.
Since the measured value exceeded 0 and could not be measured by the usual method, the result of preparing and comparing a diluted solution of the control product-2,
The 80-fold diluted solution of Control-2 had a color tone equivalent to APHA30.

[0073]

[Table 1]

[0074]

[Comparative test 2]

The following comparative tests were conducted to compare the change over time in color between the sorbitan of the present invention obtained in each of the above Examples and the sorbitan obtained by the conventional method.

The sorbitan of each of the products of the present invention-1 to 4 obtained in Examples 1 to 4 and the sorbitan of each of the control products 1 and 2 obtained in the above comparative test 1 were adjusted to a concentration of 50%.
0 g, and put each in a Nessler tube at a temperature of 40
The sample was stored in a constant temperature room at a temperature of ° C., and changes in color tone were periodically observed by the APHA method.

Table 2 shows the observation results. The numerical values in Table 2 represent the color tone by the APHA method.

[0078]

[Table 2]

From the results of the above comparative tests 1 and 2, the heat and / or alkali stable sorbitan of the present invention obtained through a relatively simple process is compared with the sorbitan produced by the conventional method. The results of the heat test also reveal that the degree of coloring is extremely low, the degree of coloring over time is extremely low, and the stability to heat and alkali is significantly improved.

[0080]

【The invention's effect】

According to the present invention, when the sorbitan aqueous solution or the sorbitan crystal is stored or concentrated at room temperature,
It does not color significantly over time and does not significantly color even when subjected to an esterification reaction with a fatty acid or the like, and can cope with high quality of various raw materials and high quality of products.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 307/20 C07D 309/10 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. The pH of an aqueous sorbitan solution is adjusted to 8 with an alkali.
A sorbitan that is heat- and / or alkali-stable obtained by adjusting to ~ 14, heating at 90 to 220 ° C, and then purifying. 2. A sorbitan comprising: (1) a sorbitan purity of 60% or more in a solid substance; and (2) a heat resistance test was conducted by adding 5 g of a 10% aqueous potassium hydroxide solution to 60 g of a 50% aqueous sample solution. Add 95
The degree of coloring of the sample is in the range of 0 to 40 by APHA when it is carried out under the condition of heating on boiling water for 30 minutes or more at (3) temperature of 0 to 40 ° C. and pH 2 to 10 for storage. When the color tone measured on the 30th day of storage is 0 to
A sorbitan that is stable against heat and / or alkali, having a property falling within the range of 20. 3. The pH of an aqueous sorbitan solution is adjusted to 8 with an alkali.
A method for producing sorbitan that is stable against heat and / or alkali, wherein the method is adjusted to ~ 14, heat-treated at 90 to 220 ° C, and then purified. 4. The pH of an aqueous sorbitan solution is adjusted to 9 with an alkali.
A method for producing sorbitan, which is stable to heat and / or alkali, comprising adjusting the temperature to 110 to 13, heating at 110 to 140 ° C. for 5 minutes to 2 hours, and then purifying.