JPS58148876A - Separation process of sultone - Google Patents

Abstract

PURPOSE:To obtain high-quality sultone useful as a raw material for preparing a detergent, an antistatic agent, etc. simply and safely, and to use the remaining sulfonate effectively, by aging a reaction product obtained by sulfonating an olefin, adding a basic aqueous solution with a high concentration to it. CONSTITUTION:10-20C olefin is sulfonated, the reaction product is aged at 20- 150 deg.C (preferably at 40-80 deg.C), and a basic aqueous solution (e.g., >=40wt% aqueous solution of NaOH) with a high concentration is added to it, so that sultone is expelled from the micell of a sulfonate to the outside, separated as a continuous phase, and recovered by settled separation, centrifugation, filtration, etc. Since the remaining sulfonate can be recovered in a state nearly free from thermal decomposition, it is usable as an approximately pure anionic surface active agent with a high concentration. USE:A raw material for preparing a detergent, cosmetic, antistatic agent, auxiliary for fiber, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention, manufactured by company #i, relates to a method for separating sultone, and more particularly, to a method for separating and recovering sultone from a sulfonated product of an olefin having 10 to 20 carbon atoms.

+1#] class sultone can be used to produce a wide range of high value-added substances such as distinctive cleaning agents, cosmetics, antistatic agents, and textile auxiliaries by reacting with alcohol, ammonia, etc. It is an important raw material.

It is known that the sulfonation reaction product of olefins having carbon atoms of 0 to 20 usually contains higher sultones in addition to alkenyl sulfonic acids, hydroxyalkanesulfonic acids, unreacted olefins, etc. It is being

The method for separating nalton from the olefin sulfonation reaction product obtained by sulfonating a long chain olefin with sulfur trioxide is as follows: (1) After incubating the sulfonation reaction product at 100 t+ for an extended period of time, 1 wt. - A method of neutralizing with an aqueous NaOH solution, then extracting with 1-hexane, cooling and recrystallizing the extract (Japanese Patent Publication No. 4 of 1983), (2) 10% of the sulfonation reaction product by weight -NaO
Medium-
The sultone contained in the neutralized product is extracted with lighter hydrogen of pentane, □hequinane, and hezotannat, and the I! (3) A method for recovering sultone from a sulfonation reaction product by vacuum distillation (U.S. Patent No. 3,184,60)
No. 8 Specification 1lF) and the like are known.

However, the method of extraction with organic solvents is not a fool's errand as it requires a large amount of solvent, and since a considerable amount of these solvents are solubilized in the sulfonate solution after the sultone is separated, this sulfone There are some difficulties in using acid salt aqueous solutions as cleaning agents and raw materials for cosmetics. Additionally, multiple extractions are required to completely recover the saltone. Even if the solvent is recycled, losses are unavoidable because it is a low boiling point substance. In addition, light hydrocarbons are harmful to the human body when they vaporize, and since they have a low flash point, they are substances that should not be used from the viewpoint of fire prevention and disaster prevention. Furthermore, in order to facilitate extraction, the slurry obtained by neutralizing the sulfonation reaction product with a water-soluble base needs to have a low viscosity, and therefore the chain degree of the aqueous sulfonate solution produced by Salton Extraction should also be low. However, it becomes even more difficult to effectively utilize the sulfonate water, which is the extraction residue.

On the other hand, even if the sultone is separated in the distillation method, the remaining 9-sulfonate deteriorates severely due to heating, making its effective use virtually impossible.

As described above, the conventional method for separating O-sultone from the sulfonation reaction product has a complicated process and a problem in terms of practical use of the sulfonic acid in the sulfonation reaction product. ), which is impractical to implement on an industrial scale.

The present invention has been made to solve the above-mentioned drawbacks of the prior art. The purpose of the present invention is to provide a method for separating sultons.

That is, the method for separating sultones of the present invention
In the method for separating Delton from the sulfonation reaction product obtained by sulfonation of No. 40 olefin, after the completion of sulfonation of the olefin, the wrinkled sulfonation reaction product is aged at a temperature of 20 to 150°C, and then high concentration The sultone is separated by adding a basic aqueous solution of .

The present invention will be explained in more detail below.

The sulfonation of olefins is carried out, for example, by sulfonating C1- to olefins, generally α-olefins, with ion trioxide diluted with an inert gas in a conventional manner, and this sulfonation product is In addition to high-grade sultones, these include alkenyl sulfonic acids,
Contains hydroxyalkanesulfonic acid, unreacted olefin, etc.

The molar ratio of SO1/olefin is not particularly limited, but considering the effective utilization of the sulfonate after separation of the saltone, 1
．． The range of o to 1.15 is preferable.

After the sulfonation is completed, the sulfonation product is heated at 20 to 150°C.
, preferably 30-100°C, more preferably &1:4
It is maintained at a temperature of 0 to 800° for ripening. At temperatures below 20° C., even if a high-therapeutic basic solution is added in the subsequent steps, almost no separation phenomenon line will be observed, and the sulfonation reaction product itself may be assimilated. on the other hand,
When ripened at high temperatures higher than 1B (1), a series of reactions occur (ζ), the recovery rate and purity of saltone decrease, and the color changes.
& cast a shadow. Furthermore, the sulfonic acid after sulton recovery also deteriorates and becomes discolored, making it difficult to use it as an anionic surfactant.

The aging time depends on the holding temperature, but for example, if the temperature is 3°C, F.
! It takes about 20 to 30 hours, and at 80° C., it takes about 1 hour to #iso minutes. If the aging time is too short, sufficient separation and recovery of the sultone will not be carried out, and if the aging time is too long, the recovery rate and purity of the sultone will decrease, and furthermore, the color of the sulfonate after recovering the sultone will deteriorate, which is undesirable. .

Ripe! lj, preferably the sulfonation reaction product after 20
The temperature is maintained at ~80°C, and 30 weight or more of a highly sickle basic aqueous solution is added thereto to separate the saltone. When the temperature falls below 20°C, solidification of naltone or sulfonic acid occurs, and no separation of sultone is observed, and when the temperature rises above SO°C, hydrolysis of sultone in the system is accelerated, resulting in a decrease in the sultone recovery rate. decreases. Therefore, in the next step of recovering the separated sultone, it is preferable to operate within the above temperature range, and first, it is desirable to separate the separated sultone from water as soon as possible.

When a basic water bath solution of 30% by weight or more is added, the sultone is expelled from the sulfonate micelles, and the sultone is separated with the sultone as a continuous phase and the sulfonate as a dispersed phase. Ru.

It is desirable that the basic water bath solution is as strong a base as possible and has a high concentration, and Na0i (aqueous solution, KOH aqueous solution) is generally convenient. When the sea level is 30 g/kg, the salton is deposited in the cell, and almost no separation phenomenon is observed.

In addition, the basic water #I solution is the pH value of the sulfonation reaction product.
It is preferable to add so that pH is 4 or more, and more preferably in the range of pHli to 1G. This is accomplished by adding a basic aqueous solution to the sulfonated product in an equivalent ratio of 0.4 to 0.8.

The sultone is separated as a continuous phase and the sulfonate as a dispersed phase, and the nine sultones are recovered by conventional mechanical separation operations such as static separation, centrifugation, and filtration. For example, if naltone is separated as a continuous phase and then subjected to centrifugation, it will separate into three layers from the bottom: +1) aqueous or basic aqueous solution phase, (2) sulfone salt phase, and (3) saltone phase. Bring out the phase.

The method of the present invention has fewer roots, does not use any low boiling point solvents, and is safe from both biological and disaster prevention perspectives. Furthermore, since the sulfonate salt remaining after saltone collection can be recovered with almost no thermal deterioration, it can be used as a nearly pure saponity anionic interfacial occupancy agent.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

implementation? lJ I CI4; 15 Nm% t Ctss 50) kkT
o e Csa: B 5mtts α-olefin (
The average molecular weight of 1 to 229) was subjected to film disulfonation using thin film iron sulfonation [11] by anhydrous sulfurization to obtain an olefin sulfonation reaction product. Note that the amount of unreacted olefin contained in this sulfonation reaction product was four times the amount of olefin introduced into the sulfonation apparatus.

This sulfonation reaction product was heated and kept warm at the temperature shown in Table 1, and then I9 was aged for a certain period of time, then allowed to cool in air. After lowering the liquid temperature to room temperature 41i4 degrees 1, add 48ffit9 to this sulfonation reaction product while stirring.
A constant volume of FElr aqueous NaOH solution of No. 6 was gradually added while maintaining the neutralization temperature in the sulfonation reaction product at about 70°0. As a result, the sulfonic acid is neutralized and the sulfone & salt is dispersed with the sultone as the continuous phase. Then,
Immediately transfer the entire amount to a centrifuge tube and spin at 4000 rpm for 2 hours.
When the 0-minute relative concentration was performed, from the bottom: (1) aqueous phase or NaOH aqueous solution phase, (2) sulfonate phase, (3)
The sultone phase was separated into three layers, and the sultone in the upper layer was immediately recovered. The recovery rate of the sultone recovered in this way is shown in the first box. When measured, it was 32 to 33°C. When I9, infrared spectrum analysis was performed, it was mainly 1.s-1.
! , a mixture of 4-sultones.

(Blank below) A: The recovered sultone was dissolved in CHCl, and the trace amount of sulfone #salt was adsorbed and removed by silica gel, and then hydrolyzed and the sultone was quantified as a sulfonate (pure sultone fraction ('r) B N-hexane extract in the sulfonation reaction product of niolefin (gr) Unreacted olefin content (gr) in the sulfonation reaction product of C niolefin Comparative Example 1 Sulfonation reaction product of the same olefin as in Example 1 10
When 0gr was kept at 10℃ for 14 hours, it partially solidified, but while stirring, 411111ONaOH
Although 12 gF of an aqueous solution was added, no separation of saltone was observed. Furthermore, when 6 gr of Okaji NaOH water solution was added, it was still slurry-like. Furthermore, N
After adding 13 gr of the same aqueous solution, no separation was observed.

Comparative Example 2 Same olefin sulfonation reaction product 10 as Example 1
After heating 0 gF at 180°C for 15 minutes and keeping it warm, it was allowed to cool to room temperature. Then, while stirring, 4g of NaOH aqueous solution 181r was gradually added, and separation of saltone was observed, so the entire amount of the neutralized solution was immediately transferred to a centrifuge tube, and centrifuged in the same manner as in Example 1. I did this.

The recovery rate of Salto/ was determined in the same manner as in Table 1 and was found to be as low as 35% by weight. Furthermore, the color tone of the sulfone saline solution (slurry) after recovering the sultone had deteriorated significantly and turned brown, making it no longer possible to use it as a surfactant.

Example 2 An olefin (average molecular weight 196) of Cs*: "Cs*" (average molecular weight: 196) was sulfonated in the same manner as in Example 1 to obtain an olefin sulfonation reaction product. The conversion of olefin in this reaction was 96 wt.

Next, 100 gr of this sulfonation reaction product was heated at 2s°C.
Heated and kept warm for SO hours to produce a high saponity Na of 48 wt.
1@gr of OH aqueous solution was gradually added with stirring. Separation of the saltone was observed, so the entire amount of the neutralized solution was immediately transferred to a seven-layer sedimentation tube and centrifuged in the same manner as in Example 1. The saltone recovery rate was measured using the same method as in Table 1.
It was 91 times 1.

Comparative Example 3 Same olefin sulfonation reaction product 10 as Example 2
After heating and keeping warm at zs℃ for 50 hours, 87 gr of a 20 wt. low yielding NaOH aqueous solution was gradually added and mixed, but the neutralized product was in the form of a slurry and no separation of cisaltone occurred. Ta. Therefore, 20 weight-low backing N
Although aOH water II solution B II gr was gradually added, no saltone separation occurred.

Comparative Example 4 The same olefin as in Example 2 was sulfonated in the same manner as in Example 1 to obtain a sulfonation reaction product with an olefin conversion of 96.

Immediately, 100 gr of this sulfonation reaction product was collected, and 13 gr of a highly concentrated NaOH aqueous solution in a 48-layer lid was immediately added thereto, followed by stirring. However, the neutralized product was in the form of a homogeneous slurry, and no separation of sultone was observed. Therefore, an additional 4811 liters of 18 gr of aqueous NaOH solution was gradually added, but no sintering or separation of salton was obtained.

Claims (1)

[Claims] 1. In a method for separating sultone from a sulfonation reaction product obtained by sulfonating a carbon 910-200 olefin, the sulfonation reaction product is aged at a temperature of 20-150°C,
A method for separating sultones, which comprises then adding a basic aqueous solution having an Aw of 1 degree to separate the sultones.