CN115677541A

CN115677541A - Continuous production process of long-chain alkenyl sulfonate

Info

Publication number: CN115677541A
Application number: CN202211456193.2A
Authority: CN
Inventors: 余水兵; 焦提留; 叶承忠; 陈伟鑫; 章勇锋; 杨广; 郑攀东
Original assignee: Sinolight Shaoxing Chemicals Co Ltd
Current assignee: Sinolight Shaoxing Chemicals Co Ltd
Priority date: 2022-11-21
Filing date: 2022-11-21
Publication date: 2023-02-03

Abstract

The invention discloses a continuous production method of long-chain alkenyl sulfonate, which comprises the steps of reacting sulfur trioxide gas with long-chain olefin in a tubular reactor to obtain a mixture of alkenyl sulfonic acid and sultone, reacting the mixture with liquid alkali and water in a neutralization mixing pump, and then feeding the mixture into a continuous hydrolyzer to hydrolyze to obtain a long-chain alkenyl sulfonate product. The method realizes the continuous production of the long-chain alkenyl sulfonate by developing a shell and tube sulfonation process and a continuous hydrolysis process suitable for the long-chain olefin, and the obtained product has the characteristics of few byproducts, light color, more excellent application performance and the like.

Description

Continuous production process of long-chain alkenyl sulfonate

Technical Field

The invention relates to the technical field of organic preparation of acyclic or carbocyclic compounds, in particular to a continuous preparation method of long-chain alkenyl sulfonate.

Background

The long-chain alkenyl sulfonate is an anionic surfactant obtained by sulfonating, neutralizing and hydrolyzing alpha-long-chain olefin, has the advantages of good surface activity, decontamination performance, biodegradability, foaming performance and the like, and is widely applied to the fields of tableware detergents, liquid detergents, feather cleaning agents, foam fire extinguishment, mineral check and the like.

The sulfur trioxide reacts with alpha-long chain olefin at a very fast speed to generate alkenyl sulfonic acid and sultone once contacting, and as sultone has no surface activity and certain skin sensitization, sultone needs to be removed.

Disclosure of Invention

In order to solve the technical problems in the background art, the present application provides a continuous production method of long-chain alkenyl sulfonate, comprising the following steps:

shell-and-tube sulfonation: continuously feeding long-chain olefin with the olefin carbon chain length of 16-18 and high-concentration SO 3/air mixed gas into a reaction tube of a tube type sulfonator according to a certain molar ratio for reaction to generate a mixture of alkenyl sulfonic acid and sultone, wherein the concentration of the SO 3/air mixed gas is more than or equal to 3.5%, the cooling temperature of the upper section of the reaction tube of the tube type sulfonator is 15-25 ℃, and the cooling temperature of the lower section of the reaction tube of the tube type sulfonator is 25-40 ℃;

pump-type neutralization: simultaneously feeding a mixture of alkenyl sulfonic acid and sultone, liquid caustic soda and water into a neutralization mixing pump for neutralization according to a certain proportion;

continuous hydrolysis: the neutralized materials enter a multi-tube heat exchanger to be heated to a certain temperature through steam, and then enter a multistage hydrolyzer to be hydrolyzed, so that the cyclic structure of sultone is opened. The multistage hydrolyzer is formed by connecting a plurality of hydrolyzers 1 in series, a partition plate 2 is arranged in each hydrolyzer 1, and through holes 3 are uniformly distributed on each partition plate 2. The material passes through hole 3 on the baffle 2 and forms the vortex in baffle both sides, increases the efficiency of hydrolysising. The retention time of the materials in the hydrolyzer is more than or equal to 1.5h, and the hydrolysis temperature is 130-160 ℃. The material after the completion of hydrolysis is through the material after the heat exchanger heating neutralization, reduces energy consumption.

Homogenizing a product: and (4) homogenizing the hydrolyzed material in a homogenizing tank until the product index is stable to obtain the long-chain alkenyl sulfonate product.

The application has the advantages that: the continuous production of the long-chain alkenyl sulfonate is realized, and the obtained product has few byproducts, light color and more excellent application performance.

Drawings

FIG. 1 is a process flow diagram of example 1 of the present invention;

FIG. 2 is a schematic structural diagram of the multistage hydrolyzer of the present invention;

FIG. 3 is a cross-sectional view AA of FIG. 2 of the present invention.

Detailed Description

In order to make the technical solutions of the present application better understood, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention. The experimental procedures, in which specific conditions are not specified in the examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.

Example 1

Shell and tube sulfonation: the method comprises the steps of continuously feeding long-chain olefin with the olefin carbon chain length of 18 and high-concentration SO 3/air mixed gas into a reaction tube of a tube type sulfonator according to different molar ratios to react to generate a mixture of alkenyl sulfonic acid and sultone, wherein the concentration of the SO 3/air mixed gas is 4.0%, the cooling temperature of the upper section of the reaction tube of the tube type sulfonator is 15 ℃, and the cooling temperature of the lower section of the reaction tube of the tube type sulfonator is 30 ℃.

Pump-type neutralization: and simultaneously feeding the mixture of the alkenyl sulfonic acid and the sultone, the liquid caustic soda and the water into a neutralization mixing pump for neutralization according to a certain proportion.

Continuous hydrolysis: and the neutralized material enters a multi-tube heat exchanger to heat the material to a certain temperature through steam, and then enters a multistage hydrolyzer to be hydrolyzed, so that the annular structure of sultone is opened. The multistage hydrolyzer is formed by connecting a plurality of hydrolyzers 1 in series, a partition plate 2 is arranged in each hydrolyzer 1, and through holes 3 are uniformly distributed on each partition plate 2. The material passes through the through-hole 3 on the baffle 2 and forms the vortex in baffle both sides, increases the efficiency of hydrolysising. The retention time of the materials in the hydrolyzer is more than or equal to 1.5h, and the hydrolysis temperature is 130-160 ℃. The materials after hydrolysis are heated and neutralized by the heat exchanger, so that energy consumption is reduced.

TABLE 1 influence of sulfonation of C18 olefins and SO3 at different molar ratios on the product index

It can be seen from table 1 that when the C18 olefin to SO3 molar ratio is 1: at 0.85, the active matter in the product is 28.01%, the conversion rate of olefin is 83.6%, and the product contains nearly 4% of raw material residues, which not only affects the product quality, but also increases the production cost; when the molar ratio of the C18 olefin to the SO3 is 1: at 1.05, the conversion rate of the olefin is 97.2 percent, and all indexes of the product meet the requirements of national standard on alkenyl sulfonate products; when the molar ratio of the C18 olefin to the SO3 is 1: at 1.25, the color and inorganic salt of the product are obviously increased, which indicates that the sulfonation state is destroyed in the reaction process and the over-sulfonation phenomenon occurs.

Example 2

Shell and tube sulfonation: mixing long-chain olefin with olefin carbon chain length of 16 with high-concentration SO 3/air mixed gas according to the proportion of 1:1.05 continuously feeding the mixture into a reaction tube of a tubular sulfonator for reaction to generate a mixture of alkenyl sulfonic acid and sultone, wherein the concentration of the mixed gas of SO 3/air is 4.0 percent, the cooling temperature of the upper section of the reaction tube of the tubular sulfonator is 20 ℃, and the cooling temperature of the lower section of the reaction tube of the tubular sulfonator is 30 ℃.

Continuous hydrolysis: and the neutralized material enters a multi-tube heat exchanger to heat the material to a certain temperature through steam, and then enters a multistage hydrolyzer to be hydrolyzed, so that the annular structure of sultone is opened. The multistage hydrolyzer is formed by connecting a plurality of hydrolyzers 1 in series, a partition plate 2 is arranged in each hydrolyzer 1, and through holes 3 are uniformly distributed on each partition plate 2. The material passes through the through-hole 3 on the baffle 2 and forms the vortex in baffle both sides, increases the efficiency of hydrolysising. The retention time of the materials in the hydrolyzer is more than or equal to 1.5h, and the hydrolysis temperature adopts 110 ℃, 130 ℃ and 150 ℃ respectively. The material after the completion of hydrolysis is through the material after the heat exchanger heating neutralization, reduces energy consumption.

TABLE 2 Effect of hydrolysis temperature on by-product sultone in the product

It can be seen from table 2 that the sultone content in the hexadecenyl sulfonate product is 950ppm when the hydrolysis temperature is 110 ℃, because the hydrolysis rate of sultone is in positive correlation with the temperature, the sultone in the product cannot be completely hydrolyzed by the hydrolysis rate at 110 ℃, and when the hydrolysis temperature is 130 ℃ and 150 ℃, sultone is not detected in the product, and all indexes of the product also meet the requirements.

Any embodiment of the present application may be used as an independent technical solution, or may be combined with other embodiments. All patents and publications mentioned in the specification of the present application are indicative of the state of the art to which this application pertains and are intended to be applicable. All patents and publications cited herein are hereby incorporated by reference to the same extent as if each individual publication were specifically and individually indicated to be incorporated by reference. The present application herein may be practiced in the absence of any element or elements, limitation or limitations, which are not specifically disclosed herein. The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described, but it is recognized that various modifications and changes may be made within the scope of the claims and the application. It is understood that the embodiments described herein are examples and features of some embodiments and that modifications and variations may be made by one of ordinary skill in the art in light of the teachings of this disclosure, and are to be considered within the purview of this application and the scope of the appended claims and their equivalents.

Claims

1. A continuous production method of long-chain alkenyl sulfonate is characterized by comprising the following steps:

1) Shell-and-tube sulfonation: continuously feeding the mixed gas of long-chain olefin and SO3 into a reaction tube of a tube type sulfonator according to a certain molar ratio for reaction to generate a mixture of alkenyl sulfonic acid and sultone;

2) Pump-type neutralization: simultaneously feeding a mixture of alkenyl sulfonic acid and sultone, liquid caustic soda and water into a neutralization mixing pump for neutralization according to a certain proportion;

3) Continuous hydrolysis: the neutralized material enters a multi-tube heat exchanger to be heated to a certain temperature through steam, then enters a multistage hydrolyzer to be hydrolyzed, the annular structure of sultone is opened, and the hydrolyzed material heats the neutralized material through the heat exchanger;

4) Homogenizing a product: and (4) homogenizing the hydrolyzed material in a homogenizing tank until the product index is stable to obtain the long-chain alkenyl sulfonate product.

2. A continuous process for the production of a long chain alkenyl sulfonate as claimed in claim 1, wherein: the molar ratio of the long-chain olefin to the SO3 in the step 1 is 1.9-1.1.

3. A process for the production of a long chain alkenyl sulfonate according to claim 1, wherein: the molar ratio of the long-chain olefin to the SO3 in the step 1 is 1.05.

4. A process for the production of a long chain alkenyl sulfonate according to claim 1 wherein: the molar ratio of the alkenyl sulfonic acid to the liquid alkali in the step 2 is 1:1-1.05.

5. A process for the production of a long chain alkenyl sulfonate according to claim 1 wherein: the length of the long-chain olefin carbon chain is 16-18; the SO3 mixed gas is formed by mixing high-concentration SO3 with air, and the concentration of the SO3 in the SO3 mixed gas is more than or equal to 3.5 percent; the cooling temperature of the upper section of the shell and tube sulfonator is 15-25 ℃, and the cooling temperature of the lower section is 25-40 ℃.

6. A process for the production of a long chain alkenyl sulfonate according to claim 1 wherein: the multi-tube heater for the continuous hydrolysis process is used for heating materials to 130-160 ℃ by passing the materials through a tube pass and passing steam through a shell pass.

7. A process for the production of a long chain alkenyl sulfonate according to claim 1, wherein: in the step 3, the retention time of the materials in the hydrolyzer is more than or equal to 1.5h, and the hydrolysis temperature is 130-160 ℃.

8. The continuous production method of long-chain alkenyl sulfonate according to claim 1, wherein: the multistage hydrolyzer comprises a plurality of hydrolyzers (1) which are connected in series, wherein a partition plate (2) is arranged in each hydrolyzer (1), and through holes (3) are uniformly distributed on each partition plate (2).