KR0163030B1 - Process for the preparation of internal olefin sulfonates - Google Patents

Abstract

None.

Description

Internal Olefin Sulfonate and Manufacturing Method Thereof

The present invention relates to a process for the preparation of internal olefin sulfonates and to internal olefin sulfonates as novel products.

It is generally known that internal olefins are more difficult to sulfonate than alpha-olefins (see Tensive detergent 22 (1985) 4, pp 193-195). In a paper titled Why Internal Olefins Are Difficult to Sulfonate, the authors use drop film reactors to sulfonate a variety of commercial internal olefins and laboratory prepared internal olefins, giving the internal olefins up to 90% conversion In addition, it was stated that in order to obtain a conversion of 95% or more, it is necessary to increase the molar ratio of SO ₃ : internal olefin to 1.6: 1 or more, and the resultant product is a very dark color and a high level of di- and polysulfur. It is described as having a fonned product.

US Pat. Nos. 4,183,867 and 4,248,793 disclose methods that are carried out in drop film reactors to produce light colored internal olefin sulfonates, although the amount of unreacted internal olefins is 10-20% and at least in the disclosed process, respectively. 20% was followed by special measures to remove unreacted internal olefins. Internal olefin sulfonates containing 10-20% and at least 20% unreacted internal olefins (also called free oils) must be purified prior to use. As a result, the preparation of internal olefin sulfonates with the desired bright color and the desired low preoil content presents significant difficulties.

It is an object of the present invention to produce internal olefin sulfonates having low free oil content, low inorganic sulfate content and light color.

Applicant cools the film reactor with cooling means having a temperature of 35 ° C. or lower, while the internal olefin and sulfonating agent having 8 to 26 carbon atoms and the sulfonating agent of 1: 1 to 1.25: 1 are molar of internal olefin in the film reactor. A process for the preparation of internal olefin sulfonates consisting of reacting at a rate and neutralizing and hydrolyzing the reaction product of the sulfonation step is disclosed.

The present invention also contains at least 10% by weight, preferably at least 25% by weight and more preferably at least 50% by weight of internal olefin sulfonates having 8 to 26 carbon atoms. It is about. Especially preferred are internal olefin sulfonates with 50-90% by weight of beta-hydroxy sulfonate, even more preferred are internal olefin sulfonates with 60-85% by weight of beta-hydroxy sulfonate.

In the preparation of sulfonates derived from internal olefins, the internal olefins react with sulfonating agents, preferably sulfur trioxide, to form beta-sultones and some alkenesulfonic acid.

The reaction product can be neutralized and hydrolyzed. Under certain circumstances, such as under aging, beta-sultone can be converted to gamma-sultone, which in turn can be converted to delta-sultone. After neutralization and hydrolysis gamma-hydroxy sulfonate and delta-hydroxy sulfonate are obtained respectively. A disadvantage of gamma- and delta-sultone is that it is more difficult to hydrolyze than beta-sultone.

The advantage of beta-sultone is that hydrolysis proceeds more easily than gamma- and delta-sultone.

After hydrolysis, beta-sultone gives beta-hydroxy sulfonate. Internal olefin sulfonates containing at least 10% by weight of beta-hydroxy sulfonate are new products.

Internal olefins used as starting materials in the present invention are those having 8-26 carbon atoms, preferably 13-22 carbon atoms. Examples of internal olefins have the following general formula:

Wherein each group of R ₁ , R ₂ , R ₃ and R ₄ is independently a linear or branched alkyl group or hydrogen, and the total number of carbon atoms of R ₁ , R ₂ , R ₃ and R ₄ is 6-24, provided that R ₁ And at least one of R ₂ and one of R ₃ and R ₄ is an alkyl group.

The sulfonation of the internal olefins is preferably carried out using sulfur trioxide in the film reactor. Falling film reactors are preferred.

The cooling means, preferably water, has a temperature not exceeding 35 ° C., in particular in the range of 0 ° C.-25 ° C. Lower temperatures may also be used depending on the environment.

In the process according to the invention it is preferred that the reaction mixture from the film reactor is not aged for a long time. The reaction mixture may be aged for a short time, but it is preferred not to age at all since in this case the highest percentage of beta-hydroxy sulfonate can be obtained. For this purpose the reaction mixture is led to a neutral hydrolysis apparatus.

Neutralization / hydrolysis is carried out using a water soluble base such as sodium hydroxide or sodium carbonate. Corresponding bases derived from potassium or ammonium are also suitable. Neutralization of the reaction product from the drop film reactor is generally carried out using a base which is calculated to be in excess of the acid component. Neutralization is generally carried out at temperatures in the range of 0 ° C-80 ° C.

The hydrolysis may be carried out at a temperature in the range of 100 ° C.-250 ° C., preferably 130 ° C.-200 ° C. The hydrolysis time may generally be 5 minutes-4 hours. Alkaline hydrolysis can be carried out using bicarbonates, carbonates or hydroxides of alkali (earth) metals.

As mentioned above the beta-sultone of the internal olefin is converted to beta-hydroxy sulfonate according to the following formula in the process according to the invention.

Wherein R ₁ , R ₂ , R ₃ and R ₄ are as described above. The amount of beta-hydroxy sulfonate has been found to depend on the amount of beta-sultone. Beta-sultone is easily formed under a somewhat moderate reaction environment, and gamma- and delta-sultone are formed only in small amounts because slow ripening steps are generally avoided.

The process according to the invention can be carried out batchwise, semi-continuously or continuously. The reaction is generally carried out in a drop film reactor which is cooled by flowing cooling means to the outer wall of the reactor. At the inner wall of the reactor the internal olefins flow downwards. SO ₃ is diluted with a stream of nitrogen, air or other inert gas flowing into the reactor. The concentration of SO ₃ is generally 2-4% by volume relative to the volume of the carrier gas.

In the preparation of internal olefin sulfonates derived from olefins having 14 or more carbon atoms, the reactor product and the aqueous base must be mixed very uniformly during neutralization / hydrolysis. This can be done, for example, by the addition of efficient stirring, polar cosolvents (lower alcohols) or phase-transfer agents.

General analytical procedures are given in the table notes. Further details of the procedure used can be found in Technical Bulletin Shell Chemical Company SC-181-77, May 1976, entitled Alpha olefin sulfonate analysis method.

The following examples illustrate the invention.

Example 1-7

A mixture of C _{13-14 -internal} olefins was sulfonated in a stainless steel reactor 0.9 cm in diameter and 2 m in length.

Sulfur trioxide was prepared by reacting sulfur dioxide and oxygen (dry air) on a vanadium pentoxide catalyst at about 450 ° C. The reactor was cooled by flowing cold water along the outside of the stainless steel reactor tube.

The C _{13-14 -internal} olefin flowed along the inside of the reactor wall as a downward flowing film and reacted with sulfur trioxide. The reaction product was transferred to a stainless steel autoclave equipped with a magnetic stirrer, which was charged with aqueous sodium hydroxide solution. The mixture was stirred well in an autoclave and mixed. The autoclave was then closed and heated to the desired temperature and maintained at that temperature for the desired time. The autoclave was then cooled to ambient temperature and the contents analyzed by appropriate means.

The cooling water to cool the reactor had an inlet temperature of 8 ° C. and an outlet temperature of 13 ° C. and was countercurrent with the feed / SO ₃ stream.

The active material was obtained in near quantitative yield by hydrolysis at 160 ° C. for 1 hour with more than 20 mol% NaOH (calculated for the product from the reactor).

In Example 5 the cooling water had an inlet temperature of 10 ° C. and an outlet temperature of 15 ° C., while in Examples 6 and 7 the inlet temperature was 12 ° C. and the outlet temperature was 17 ° C.

In Example 5 hydrolysis occurred at 140 ° C. for 1 hour.

The free oil content, Na ₂ SO ₄ content and residual sultone content were calculated for the amount of active material. After sulfonation in Example 7, the product was aged at 30 ° C. for 30 minutes before neutralization / hydrolysis.

The results are shown in the table below.

1) Free oil is a substance that can be extracted with petroleum ether in an aqueous-alcohol solution of internal olefin sulfonates.

2) Determined according to SMS 1721-76.

3) Measured with Klett-Summerson photoelectron colorimeter equipped with KSNo42 color filter and 2x4 cm glass cell on 5% active material solution.

4) Beta-hydroxy sulfonate determined by C NMR spectroscopy.

5) Gas chromatography of preoil using C-terminal delta-sultone as internal standard.

6) Bleached with 1% by weight of hydrogen peroxide calculated on the weight of the active substance.

Example 8

The sulfonation of C-internal olefins was carried out in a glass reactor 0.5 cm in diameter and 1 mm in length.

The sulfonation reaction was carried out in the same manner as described in the above examples under the following conditions:

Coolant temperature: 15 ℃

SO / feed ratio, moles / moles: 1.2

SO in N,% by volume: 3

Feed rate, moles / hour: 1.5

Neutralization, NaOH for acidic products, moles / moles: 1.4

Hydrolysis time, h: 1

Hydrolysis temperature, ℃: 160

Neutralization and hydrolysis were performed with NaOH in a water / ethanol solution (volume / volume, 75:25). The product contained 1.6 wt% preoil and 2.4 wt% NaSO (calculated for the amount of active material). 80 mol% of the product was identified as beta-hydroxy sulfonate.

Example 9

Sulfonation of the C-internal olefins was carried out under the same conditions as described in Example 8. Neutralization and hydrolysis (1 hour at 160 ° C.) were carried out using aqueous sodium hydroxide solution in the presence of C-internal olefin sulfonate (10 wt% relative to acid usage).

The product contained 7.9 wt% preoil and 3.9 wt% NaSO. The product had a color index of 200 (according to cleats).

Example 10

Sulfonation of the C-internal olefins was carried out under the same conditions as described in Example 8. The resulting mixture was vigorously stirred and neutralized and hydrolyzed (1 hour at 160 ° C.) using an aqueous sodium hydroxide solution.

The product contained 7.4 wt% preoil and 5.4 wt% NaSO. The product had a color index of 140 (according to cleat).

Example 11

Sulfonation of the C-internal olefins was carried out under the same conditions as described in Example 8. Neutralization and hydrolysis (1 hour at 160 ° C.) were carried out with aqueous sodium hydroxide solution in the presence of a certain amount of DOBANOL 91-10 (5% by weight relative to acid usage). DOBANOL 91-10 is an alcohol mixture of primary, linear C, C and C alcohols (weight ratio 18/50/32) ethoxylated to an average number of ethylene oxide of 10. The product contained 5.5 wt% preoil and 4.8 wt% NaSO.

Example 12

Sulfonation of the C-internal olefins was carried out under the same conditions as described in Example 8. While stirring vigorously, neutralization and hydrolysis (1 hour at 160 ° C.) were carried out with an aqueous sodium hydroxide solution in the presence of DOBANOL 91-10 (5% by weight relative to acid usage).

The product contained 3.1 wt% preoil and 4.6 wt% NaSO.

Example 13

Sulfonation of C-internal olefins was carried out in a reactor as described in Example 8. The sulfonation reaction was carried out under the following conditions:

Coolant temperature, ℃: 15

SO / feed ratio, moles / moles: 1.1

SO in N,% by volume: 2.8

Feed rate, moles / hour: 1.5

Neutralization, NaOH for acid product, mol / mol: 1.2

Hydrolysis time, h: 1

Hydrolysis temperature, t: 160

The product contained 2.1 wt% free oil and 2.4 wt% NaSO. The product (unbleached) had a color index of 90 (according to cleat).

Example 14

[Sulfonation]

C range (≤ C2 wt%; C25 wt%; C26 wt%; C24 wt%; C18 wt%; ≥ C5 wt%; Purity: 98% calculated; 2% residues under sulfonation conditions as disclosed in Example 8 Sulfonation of the mixture of internal olefins containing internal olefins: paraffin).

[Continuous neutralization]

The continuously stirred tank reactor (CSTR) is continuously stirred with the acid product mixture from the drop film sulfonation reactor continuously and at or near the 6- (flat-) bladed impeller (diameter: 35 m). Pumped directly into). At the same time aqueous caustic soda (1.2 equiv when calculated for acid usage) was also pumped continuously into the CSTR near and at the level of the impeller. The volume of CSTR was maintained at 500 ml by siphoning the product at the top of the reactor. Operated in this manner, the average residence time in the CSTR reached 20 minutes (calculated). While maintaining the CSTR at 30 ° C. by external cooling / heating, the impeller speeds were 750 revolutions / minute, 1000 revolutions / minute and 1500 revolutions / minute, respectively; The power input due to the agitation in the device is 1.2-9.7 kw / m (Calculation). The analytical data of the product obtained in this range was independent of the input power.

Continuous neutralization was performed on CSTR filled with C internal olefin sulfonate containing the following analytical data (obtained from experiments without a maturation step between sulfonation and neutralization steps) and containing 70-90% of beta-hydroxysulfonate. Started using.

Active material, AM (wt%): 26-31

Free oil (% by weight relative to AM): 6-10

Inorganic sulfate (% by weight relative to AM): 3-8

By continuously starting and operating the neutralization reactor in this way, the product formed itself acts as an instant emulsifier produced.

[Hydrolysis]

Samples were taken from the product stream only after waiting for at least 1 hour (ie after 3 residual times) after starting the continuous neutralization, and these samples were batch hydrolyzed at 160 ° C. for 1 hour.

The product is 4.9 wt% NaSO and 6.7 wt% free oil (calculated 2% of 6.7% paraffin, calculated on the basis of the active substance as above, so the actual preoil content calculated for 100% olefin is 4.7 wt% %). The product (unbleached) had a color index of 500 (according to cleats). About 85 mole% of the product was identified as beta-hydroxysulfonate.

Claims (15)

Internal olefins having 8 to 26 carbon atoms in the film reactor with a molar ratio of sulfonating agent to internal olefin of 1: 1 to 1.25: 1, cooling the film reactor with cooling means at a temperature not exceeding 35 ° C. Reacting, neutralizing the reaction product obtained in the sulfonation step, and hydrolyzing the neutralized reaction product without extracting the unreacted internal olefin. A process according to claim 1, wherein said cooling means is water having a temperature in the range of 0 ° C-25 ° C. The method for producing an internal olefin sulfonate according to claim 1 or 2, wherein the sulfonating agent is sulfur trioxide. 3. The method of claim 1, wherein the internal olefin comprises 13-22 carbon atoms. The process according to claim 1 or 2, wherein the aging step is substantially not carried out. 3. The process according to claim 1, wherein the reaction is carried out in a drop film reactor. The process of claim 1 or 2, wherein the reaction product of the sulfonation step during neutralization / hydrolysis is homogeneously mixed with the aqueous base solution. 8. A process according to claim 7, wherein said mixing is by stirring, addition of co-solvent or addition of phase-transfer agent. Internal olefin sulfonates having 8 to 26 carbon atoms, characterized in that they consist of at least 10% by weight of beta-hydroxy sulfonate, based on the total sulfonate weight. 10. The internal olefin sulfonate of claim 9 wherein the beta-hydroxy sulfonate is at least 25% by weight. The internal olefin sulfonate of claim 10, wherein the beta-hydroxy sulfonate is at least 50% by weight. The internal olefin sulfonate of claim 11, wherein the beta-hydroxy sulfonate is 50-90 weight percent. 13. The internal olefin sulfonate of claim 12 wherein the beta-hydroxy sulfonate is 60-85 weight percent. The internal olefin sulfonate of claim 9 or 10, wherein the sulfonate is an alkali (earth) metal sulfonate or an ammonium sulfonate. The internal olefin sulfonate of claim 14, wherein said sulfonate is sodium sulfonate or potassium sulfonate.