JPS6032759A - Production of inner olefinsulfonic acid salt - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an active component of detergent, etc., in high purity, by sulfonating an inner olefin, and adding a lower alcohol and optionally water to the reaction mixture to remove the unreacted olefin. CONSTITUTION:A 8-30C inner olefin is sulfonated with gaseous SO3, neutralized with an alkaline aqueous solution (e.g. sodium hydroxide solution), and hydrolyzed. At an arbitrary stage after the sulfonation process, a lower alcohol (e.g. methyl alcohol) or its mixture with water is added to the reaction mixture in an amount to give the concentration of the inner olefin sulfonic acid salt in the slurry of 2-30wt%, and the weight ratio of the lower alcohol to water of 2/8- 6/4. The unreacted olefin in the slurry is separated to the upper layer by the specific gravity difference. The layer containing the unreacted olefin is removed to obtain an inner olefinsulfonic acid salf free from unreacted olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an internal olefin sulfonate containing almost no unreacted oil. It relates to a method for removing unreacted olefin/olefin remaining at the time of completion by a simple means.

It is well known that sulfonation of olefins with gaseous SO3, neutralization and subsequent hydrolysis of the sulfonate yields olefin sulfonates which can be used as active ingredients in detergents and the like. However, when internal olefins are used as raw material olefins, they have lower reactivity toward SO than α-olefins, so a considerable amount of unreacted olefins remain in the sulfonation reaction product. Naturally, the reaction oil remains in the reaction product even after neutralization and hydrolysis. Therefore, in order to effectively utilize the internal olefin sulfonate produced by the above method using internal olefin as a raw material, it is necessary to remove unreacted oil.

By the way, conventional methods for removing unreacted oil can be found in Japanese Patent Application Laid-open No. 54-14918 and Japanese Patent Publication No. 54-14075. In the former method, after neutralizing the sulfonation reaction product of internal olefins, a halogenated hydrocarbon is added before hydrolysis to extract unreacted oil into the halogenated hydrocarbon. The latter is a method in which a polyhydric alcohol, polyoxyalkylene alkyl ether, $lioxyalkylene/alkylphenyl ether, etc. is added to the neutralized product of the sulfonation reaction product, and unreacted oil is removed by stripping. If these conventional methods are evaluated from the viewpoint of removal efficiency of unreacted oil, both methods can be given a passing score. However, in the former, the halogenated hydrocarbon that is the extractant is toxic, and there is a concern that this may be mixed into the internal olefin sulfonate solution that is the target product, and in the latter, IJ
This method is disadvantageous in that not only does it increase the cost of sulfonate solution, but also the polyhydric alcohol, polyoxyalkylene alkyl ether, etc. remain in the sulfonate solution, which limits the uses of the sulfonate solution. be.

The present invention provides a method for producing an internal olefin sulfonate that employs a completely different means from the above-mentioned conventional methods to remove unreacted oil, and the method uses carbon atoms of 8 to 3 carbon atoms.
0 internal olefin is sulfonated with gaseous SO8, then neutralized with an aqueous alkali solution, and further hydrolyzed to give an internal olefin sulfonate/1M! An aqueous slurry containing salt and unreacted oil, that is, unreacted olefin, is prepared, and a lower alcohol that is soluble in water in any proportion is added to this slurry.
If necessary, it is added together with water to form a slurry in which the concentration of internal olefin sulfonate is 2 to 30% by weight, and the weight ratio of lower alcohol to water is 278 to 6/4, and the unreacted oil in this slurry is removed. It is separated into the upper layer due to the difference in specific gravity,
The process is then characterized by removing this unreacted oil-containing 1-.

In the present invention, it is planned that the target product, internal olefin sulfonate, will be used as an active ingredient in detergents, etc., so the raw material olefin has a carbon number of B-30 represented by the following general formula, preferably 10 to 22 internal olefins are used.

(In the formula, R1 is a linear or branched alkyl group, "ls
FLS s ``4 is hydrogen or a linear or branched alkyl group.However, except when R+, , R, and R4 are all hydrogen) The internal olefin used as a raw material is of course an internal olefin with a different number of carbon atoms. A mixture of which has a supporting force <.

Furthermore, there is no particular restriction on the position of the double bond. By the way,
Table 1 shows an example of the composition of an internal olefin compound having 14 to 18 carbon atoms as viewed from the position of the double bond.

Table 1 In the present invention, internal olefins are diluted with an inert gas at a concentration of 1 to 15 volumes, preferably 1 to 10 volumes, for sulfonation. gas is used and the molar ratio SO1/internal olefin is from 0.5 to 3, preferably from 0.5 to 1,0
, sulfo/other conditions with a reaction temperature of 30 to 80°C are employed. In general, if the sulfonation conditions are made more severe, the amount of unreacted olefin decreases, but the coloring of the sulfonation reaction product becomes significant. It is preferable to employ conditions such as

As the sulfonation apparatus, either a continuous type thin film type sulfonation apparatus or a batch type seed type sulfonation apparatus can be used.

The sulfonation reaction product is then neutralized and further hydrolyzed. By mixing the sulfonation reaction product with an aqueous alkali solution and stirring at high speed at a temperature of 40 to 80°C, the internal olefin sulfonic acid in the sulfonation reaction product is neutralized to an alkali salt, and then this mixture is heated to a temperature of Zoo to 18
By aging at 0° C. for 5 minutes to 7 hours, the sultone in the sulfonation reaction product is hydrolyzed. In this neutralization-hydrolysis step, the alkaline aqueous solution has a concentration of 30 to 45 fi.
It is common to use an aqueous sodium hydroxide solution of
The amount used is selected so that the pH of the aqueous slurry obtained after neutralization-hydrolysis is in the range 7-14.

The aqueous slurry obtained from the neutralization-hydrolysis step contains unreacted oil (same as unreacted olefin) solubilized in the aqueous solution of internal olefin sulfonate, and if left as is, unreacted oil will be separated and removed. Can not do it. However, by mixing this aqueous slurry with water and a soluble lower alcohol in any proportion, and further adding water as necessary, the internal olefin sulfonate concentration in the slurry can be adjusted to 2 to 30% by weight. In addition, if the weight ratio of lower alcohol to water is adjusted to 2/8 to 6/4K14, the slurry in which unreacted oil is in a solubilized state will be eliminated, and the difference in specific gravity will cause unreacted oil to be transferred to the upper layer of the internal olefin sulfonate aqueous solution. Can be separated. In this case, if the concentration of internal olefin sulfonate in the slurry is less than 2 parts by weight, not only will the amount of throughput when separating unreacted oil increase, but also the amount of internal olefin sulfonate after separating unreacted oil will increase. There is also the disadvantage that the acid salt solution has a low concentration;
If it exceeds this, it becomes difficult to separate unreacted oil due to the difference in specific gravity. Therefore, in the unreacted oil separation step of the present invention, the concentration of internal olefin sulfonate in the slurry should generally be maintained in the range of 2 to 30% by weight, preferably in the range of 5 to 15% by weight. Chiru. Regarding the weight ratio of lower alcohol to water in the slurry, if this ratio is less than 278, it becomes virtually impossible to separate unreacted oil due to the difference in specific gravity, while if it exceeds 6/4, Since the lower alcohol is observed to be distributed to the unreacted oil layer, this is inconvenient when attempting to subject the unreacted oil to the sulfonation reaction again. Therefore, considering the separation of unreacted oil and the reuse of recovered unreacted oil, the weight ratio of lower alcohol to water should be 377 to 5.
It is preferable to set it in the range of 15.

In the unreacted oil separation step of the present invention, it is essential to adjust the concentration of internal olefin sulfonate in the slurry and the weight ratio of lower alcohol to water, but this adjustment operation does not necessarily affect the sulfonation reaction product. It is not required to carry out after neutralization and hydrolysis. If necessary, a lower alcohol, along with water if necessary, can be added to the sulfonation reaction product prior to or simultaneously with mixing the aqueous alkaline solution to determine the concentration of internal olefin sulfonate in the slurry and the weight of lower alcohol to water. There is no problem even if the ratio is adjusted within the above range. but,
Generally, it is preferable to carry out the above concentration adjustment and weight ratio adjustment after neutralization and hydrolysis.

Examples of lower alcohols that can be used in the present invention and which can be used in any ratio with zeta-filtered water include methyl-, ethyl-, propyl-, isozolopyl-1t-rt-butyl, and other aliphatic saturated alcohols and allyl alcohols. ; -Al can be exemplified, but among H, it is practical to use aliphatic saturated alcohols having 1 to 3 carbon atoms.

Separation of unreacted oil based on the difference in specific gravity is achieved by allowing the slurry to stand or by applying it to a centrifuge.
An internal olefin sulfonate aqueous solution containing lower alpol is formed in the lower layer, and an unreacted oil layer is formed in the upper layer. Therefore, by removing the unreacted oil layer by a suitable means, the internal olefin sulfonic acid has an unreacted oil content of about 6 weight* (based on the olefin sulfonate) or less! solution can be obtained. The resulting sulfonic acid solution contains almost all of the lower alcohol used in the unreacted oil separation step, but from this solution the alcohol can be easily recovered and the sulfonate concentrated, preferably using a thin film evaporator. can be achieved.

Although a trace amount of alcohol inevitably remains in the internal olefin sulfonate aqueous solution concentrated in this way,
For the purpose of imparting antibacterial properties to the cleaning agent, about 2 to 5 parts by weight of lower alcohol is blended, so there is no problem with the mixing of the above-mentioned alcohols. Further, the unreacted oil and lower allols recovered in the present invention can be recycled to the sulfonation step and the unreacted oil separation step, respectively.

As is clear from what has been explained above, according to the method of the present invention, removal of unreacted oil, which is essential when producing internal olefin sulfonate, can be achieved using a very simple method using lower alcohol. In addition, after separation and removal of unreacted oil, an internal olefin sulfonate which can be fully used as an active ingredient in detergents etc. can be obtained by heating and straining under relatively mild conditions. It's self-explanatory.

Example 1 Internal olefin mixture with 18N14 carbon atoms (C,,55
wt%, C, 4Bwt%HdO%, Δ327%, Δmillet 2
1%, Δ420%, ΔIN? 32%) was sulfonated in a conventional thin film continuous sulfonation apparatus, neutralized with an aqueous sodium hydroxide solution, and further hydrolyzed to obtain an aqueous slurry. The amount of internal olefin sulfonate (hereinafter abbreviated as MU) in this slurry was 4 e wt, and the amount of unreacted oil was 515 wt $ (vs. MU).

Next, ethanol and water were added and mixed to the above slurry to prepare a slurry having an AI concentration and an ethanol/water weight ratio as shown in Table 2, and each slurry was kept in an apparatus overnight to separate it into two layers, upper and lower. Ta. Thereafter, collect each layer and quantify the unreacted oil content in the lower layer (human I phase) and the ethanol content in the upper layer (unreacted oil phase). The results are shown in Table-2.

(1) By fl-hexane extraction method.

(2) Based on the Gask four Madograph internal standard method.

Force 9mm: Porapak-Q (5 (1w8G mesh), 2m injection temperature: 180℃, Force 2mm temperature 140℃
Detection part temperature: 180°C, detector: FID carrier gas: nitrogen, internal standard substance: n-propatool A; amount of unreacted oil in the slurry before addition and mixing of alcohol and water (
B: Amount of unreacted oil in the lower layer (relative to Iwt%) As is clear from the above table, by adjusting the AI concentration and alcohol to water weight ratio in the slurry to a predetermined range according to the method of the present invention. , it is possible to obtain internal olefin sulfonate with an unreacted oil amount of 8.6 wt % or less (see slurry floor 2.3).

Example 2 An internal olefin mixture consisting of 25 wt% Cso and 76 wt% C1t was sulfonated in the same manner as in Example 1, followed by neutralization and hydrolysis to obtain an aqueous slurry of sodium internal olefin sulfonate. The I concentration of this slurry was 40 wt-14-1, and the amount of unreacted oil in the three layers was 2 wt-1 (vs. AI).

Add and mix 429 g of insolonol and 17.1 g of water to 100 g of this slurry to bring the AI concentration to 25 wt.
%, and the weight ratio of isoprono-9ol to water was adjusted to 476, and the mixture was then kept in an apparatus overnight to separate into upper and lower layers. Then, similar to Example 1, these two layers were collected separately,
When the amount of unreacted oil in the lower layer was measured, the amount was 3.1
It was wt96 (vs. AI). Therefore, when the recovery rate of unreacted oil separated into the upper layer is calculated according to footnote (3) of Shishi-2, the value is found to be 90 wt%.

Example 3 C1,I Wi % %C,. 49 vrt% %C@
@ 18 vt %bC,, 15wt%, C, 611w
191, an internal olefin mixture consisting of Cm@s wt% and C1°1 wt% was sulfonated in a conventional sulfonation apparatus, and the sulfonation reaction product was neutralized with an aqueous sodium hydroxide solution and then hydrolyzed. An aqueous slurry having a concentration of B 5 vt was obtained. The amount of unreacted oil contained in this slurry was 55 wt% (relative to AI).

100g of this slurry, 264g of methanol and 219g of water
Add and mix the AI concentration to 6 wt%, the weight ratio of methanol to water to 5 s, and after adjusting the K11ii, 50
Centrifugation was performed at 00 rpm for 15 minutes, and the AI phase separated into the lower layer was collected. When the amount of unreacted oil contained in this AI phase was measured, the amount was 5.9wt q6
(vs. 1), and the recovery rate of unreacted oil separated into the upper layer was 89 cm.

Claims (1)

[Claims] 1. An internal olefin having 8 to 30 carbon atoms in gaseous SO3
After sulfonation with aqueous alkaline solution, it is further hydrolyzed to obtain an aqueous slurry containing an internal olefin sulfonate and an unreacted olefin, and the unreacted olefin in the slurry is removed to form an internal olefin sulfonic acid. In producing a salt, a lower alcohol that is soluble in water in any proportion or a mixture of the lower alcohol and water is added to any of the steps after sulfonation, so that the concentration of the internal olefin sulfonate in the slurry is Add so that the weight ratio of alcohol to water is 278 to 6/4,
A method for producing an internal olefin sulfonate, which comprises separating unreacted olefin in this slurry into an upper layer based on a difference in specific gravity, and then removing this unreacted olefin-containing layer. 2. The method according to claim 1, wherein the lower alcohol is one or more aliphatic saturated alcohols having 1 to 3 carbon atoms.