JPH0420909B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sulfation apparatus used in producing sulfates by reaction of higher secondary alcohols or higher secondary alcohol ethoxylates with chlorosulfonic acid. More specifically, to produce high purity and high quality higher secondary alcohol sulfate or higher secondary alcohol ethoxysulfate by reacting higher secondary alcohol or higher secondary alcohol ethoxylate with chlorosulfonic acid. The present invention relates to a sulfation device. Higher alcohol sulfate or higher alcohol ethoxysulfate is usually obtained by sulfating with higher alcohol or higher alcohol ethoxylate, sulfur trioxide, chlorosulfonic acid, sulfamic acid, or the like. Among these methods, the method using sulfur trioxide causes the reaction to occur through gas-liquid contact, but sulfur trioxide has extremely high reactivity and is also a strong oxidizing agent, resulting in a decrease in yield and quality due to side reactions. , and even more likely to lead to the production of harmful substances such as sultones. In addition, the sulfamic acid method provides sulfate of high purity and high quality, but only sulfate ammonium salts are obtained, and since it involves handling powder, workability is poor, and there are also problems in terms of cost. From the above points, the chlorosulfonic acid method is recommended as a method for obtaining high-quality sulfate salts that are especially suitable as raw materials for shampoos, cosmetics, and the like. Conventionally, in the sulfation of higher alcohols or higher alcohol ethoxylates with chlorosulfonic acid, the raw materials alcohol and/or alcohol ethoxylate are charged into a reaction tank, and while stirring, the chlorosulfonic acid is directly mixed with air,
A commonly used method is to combine inert gases such as nitrogen and carbon dioxide gas and supply the mixture near the liquid level or directly into the liquid in a reaction tank to cause a reaction. However, in the conventional method, dispersion of chlorosulfonic acid into the reaction solution and removal of reaction heat are insufficient, resulting in a local increase in the concentration of chlorosulfonic acid and local heating, resulting in a decrease in yield and quality. bring about. This tendency is sometimes remarkable when the raw material is a secondary alcohol or secondary alcohol ethoxylate, and the sulfation rate (mol%) is 60 to 70% in the case of secondary alcohol, and In some cases, it is about 90-92%. The object of the present invention is to improve the liquid-liquid contact between higher secondary alcohols or higher secondary alcohol ethoxylates and chlorosulfonic acid, and to produce higher secondary alcohol sulfates or higher secondary alcohols with high yield and quality. An object of the present invention is to provide a sulfating apparatus that can easily produce alcohol ethoxy sulfate. The present invention includes a reaction tank 1, a circulation pipe 7 for circulating the liquid in the reaction tank 1, an internal continuous mixing device 10 provided in the circulation pipe 7, a chlorosulfonic acid introduction pipe 9 provided in the internal continuous mixing device 10, and a reaction tank, Cooling device 2, 1 installed in the circulation pipe and/or continuous mixing device in the pipe
The present invention relates to a sulfation apparatus for producing a sulfate by reacting a higher secondary alcohol characterized by comprising 1,15 or a higher secondary alcohol ethoxylate with chlorosulfonic acid. The sulfation apparatus of the present invention will be explained in more detail with reference to the drawings. Figures 1 to 5 show an example of the sulfation apparatus according to the present invention. First, a higher secondary alcohol or a higher secondary alcohol ethoxylate as a raw material is charged into the reaction tank 1 and circulated by a circulation pump 8 through a circulation pipe 7 equipped with an in-tube continuous mixing device 10 . Next, chlorsulfonic acid is quantitatively supplied through the chlorsulfonic acid inlet pipe 9 into the intra-tube continuous mixing device 10, and the raw material higher secondary alcohol or higher secondary alcohol ethoxy The chloride and chlorosulfonic acid are instantly mixed and reacted. The heat generated during the reaction is removed in cooling devices 2, 11 and/or 15. That is, Fig.
1, a jacket or coil cooling device 2 is installed in the reaction tank 1, and the water or ethylene glycol aqueous solution can be removed by flowing a coolant such as water or an aqueous solution of ethylene glycol through the conduits 13 and 14. As shown in -3, a cooling device 11 is provided in the circulation pipe 7, and a refrigerant such as water or an aqueous ethylene glycol solution is allowed to flow through the conduit 12, thereby efficiently removing heat, and as a result, shortening the reaction time. . Alternatively, as shown in FIGS. 4 and 5, the in-tube continuous mixing device 10 may be of a double-pipe type, and heat may be removed by flowing a refrigerant such as water or an aqueous ethylene glycol solution through the jacket 15. The stirring plate 5 in the reaction tank 1 is not particularly necessary if mixing and heat removal in the circulation pipe 7 are sufficient. As the in-tube continuous mixing device used in the present invention, a rotationally driven line-type homomixer or a non-stirring in-tube mixer can be used, but preferably a non-stirring in-tube mixer without a driving part is preferable in terms of heat generation and power costs. It is more suitable from The non-stirring type in-pipe mixer can be any type as long as it produces turbulent flow in the pipe, and can be an orifice type, or one filled with a material such as a pole ring, a Berl saddle, a Raschig ring, or a wire mesh, or one with an element. . A non-stirring type in-tube mixer having an element that can reduce internal pressure loss and achieve efficient mixing is advantageous from an economical point of view. The material of the element in this case is not particularly limited, but may be any material as long as it is not corroded by chlorosulfonic acid and the sulfation reaction solution, such as ceramics,
Hastelloy, SUS-316, etc. are suitable. The number of elements is suitably 10 or more, preferably 15 to 25, and Static Mixer manufactured by Noritake Company Limited or Hi Mixer manufactured by Toray Industries, Inc. can be suitably used. In order to efficiently perform mixing in the non-stirring tube mixer, the linear velocity of the circulating liquid in the tube is preferably 0.2 m/sec or more, preferably 0.5 m/sec or more.
If the number of elements is less than 10 or if the linear velocity inside the tube is less than 0.2 m/sec, the circulating fluid and chlorosulfonic acid will not be sufficiently mixed within the tube, resulting in a decrease in yield and quality. Chlorsulfonic acid is supplied into the in-pipe continuous mixing device in order to avoid the generation of localized high-temperature spots due to the reaction between chlorsulfonic acid and secondary alcohol or secondary alcohol ethoxylate. One or more chlorosulfonic acid supply pipes are provided inside the container, and the supply can be divided into one or a plurality of locations. The rate of supply of chlorosulfonic acid into the continuous pipe mixing device is preferably 0.05 or less in terms of volume ratio of the amount of chlorsulfonic acid supplied to the circulating fluid in order to ensure sufficient mixing within the continuous mixing device. If chlorosulfonic acid is supplied at a ratio of 0.05 or more, the yield and quality will decrease due to insufficient mixing. In particular, as the reaction progresses, the viscosity of the circulating reaction liquid increases, and the concentration of the raw alcohol or raw alcohol ethoxylate in the circulating reaction liquid decreases, so the yield and quality decrease due to decomposition of sulfates. It tends to occur in the latter half of the reaction. Therefore, it is preferable that the supply rate of chlorosulfonic acid be gradually reduced as the reaction progresses. As a method for reducing the amount of chlorsulfonic acid supplied, it may be continuously reduced depending on the supply rate to the total amount of chlorosulfonic acid supplied, or it may be reduced stepwise. In particular, after the chlorsulfonic acid supply rate is 90% or higher, it is preferable that the volume ratio of the amount of chlorsulfonic acid supplied to the amount of circulating fluid is 0.03 or less. The reaction temperature is not particularly limited, but in the case of higher secondary alcohols or higher secondary alcohol ethoxylates, a temperature of 20°C or lower, preferably 15°C or lower is suitable. Above 20°C, decomposition of the product is likely to occur, resulting in a decrease in the yield and quality of the sulfate. Hydrogen chloride produced by the reaction may remain as it is in the reaction solution, or during or after the reaction, air or an inert gas such as nitrogen or carbon dioxide is supplied into the stirring tank through the conduit 3. It is removed from the conduit 4 by entrainment. Removal under reduced pressure is also possible. High-grade second grade raw material used in the present invention
As alcohols or higher secondary alcohol ethoxylates, synthetic higher secondary alcohols synthesized by paraffin oxidation method etc. can be used as they are,
Alternatively, higher secondary alcohol ethoxylates obtained by adding these ethylene oxides by known methods can be used. Synthetic higher secondary alcohol or synthetic higher secondary alcohol
Examples of alcohol ethoxylates include the following. Namely, it is a random secondary alcohol obtained by liquid-phase oxidation of linear paraffin, and is sold under the trade name "Softanol" by Nippon Shokubai Chemical Co., Ltd., or by Union Carbide Corporation. "Tajitor" can be suitably used. The raw material molar ratio of chlorosulfonic acid to higher secondary alcohol or higher secondary alcohol ethoxylate is not particularly limited, but according to the method of the present invention, mixing is sufficient and side reactions hardly occur, so it is substantially 1.0. , preferably 1.05 or less. If it is 1.05 or more, excess chlorosulfonic acid becomes a factor that promotes the decomposition of generated sulfates. Although additives are not normally required in the reaction solution, small amounts of active organic compounds having hydroxyl groups or reagents for promoting the reaction, such as paraffin, chlorinated alkanes, xylene, ethers, dioxane, dimethylformamide, etc. It is also possible to contain inert organic solvents, inorganic salts, etc. By using the sulfation apparatus of the present invention, sufficient liquid-liquid contact between higher secondary alcohol or higher secondary alcohol ethoxylate and chlorosulfonic acid can be achieved, and the sulfation reaction can be carried out without producing almost any side reaction products. In order to advance the reaction, higher secondary alcohol sulfate salts or higher secondary alcohol ethoxysulfate salts obtained by neutralizing with an aqueous basic substance by a known method after the completion of the reaction are subjected to processes such as deodorization and bleaching. It is highly pure and of high quality without the need for it, and can be widely applied as a base material for cleaning agents. Hereinafter, the present invention will be explained in more detail with reference to Examples. However, this example is one embodiment of the invention and does not limit the invention. The test method was as follows. Sulfation rate (mol%) Petroleum ether soluble content determined by Epton method (methylene blue method) (wt%) Concentration of petroleum ether soluble content in 25% by weight aqueous solution of sulfate sodium salt Hue (APHA) Sulfate sodium salt 25 Weight% aqueous solution value
Represented by APHA NO. Example 1 A sulfation apparatus as shown in Fig. 1, namely, a reaction tank 1 and a reaction tank 1, each consisting of a jacket 2, a gas inlet pipe 3, a gas discharge pipe 4, a stirrer 5, and a reaction liquid withdrawal pipe 6, is used. An intra-pipe continuous mixing device 10 provided in the circulation pipe 7 that circulates the liquid, and a chlorosulfonic acid introduction pipe 9 provided in the intra-pipe continuous mixing device 10
Unreacted alcohol (non-ethylene oxide adduct) was removed using a sulfation device consisting of an average of 3 moles of ethylene oxide adduct (average molecular weight 333, trade name: SOFTAnol ^R -) of a random secondary alcohol with 12 to 14 carbon atoms. 30 Nippon Shokubai Chemical Industry Co., Ltd.) 10
5 mol was placed in the reaction tank 11, the stirring plate 5 was operated, and the circulating liquid was circulated at a flow rate of 1.5/min through the circulation pipe 7 equipped with an in-tube continuous mixing device 10 using the circulating liquid sending pump 8. As the in-tube continuous mixing device 10, a static mixer (manufactured by Noritake Company Limited) having 15 elements and an inner diameter of 8 mm was used. The linear velocity of the circulating fluid in the pipe continuous mixing device 10 is
It was 0.5m/sec. A refrigerant of 50% by weight ethylene glycol aqueous solution was passed through the jacket 2 of the reaction tank 1 through conduits 13 and 14, and 10.3 moles of chlorosulfonic acid was added into the pipe while maintaining the temperature of the reaction liquid in the reaction tank 1 at 10 to 15°C. It was fed into a continuous mixing device 10. The supply rate of chlorsulfonic acid is up to 80% of the total supply of chlorsulfonic acid.
The rate was 7.5 ml/min, and after 80% chlorsulfonic acid supply rate, the rate was 3 ml/min. At this time, the amount of chlorsulfonic acid supplied (weight ratio) to the amount of circulating fluid is 0.005, respectively.
and 0.002, and the feeding time of chlorosulfonic acid was about 120 minutes. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the reaction tank 1 through the gas introduction pipe 3, and by-product hydrogen chloride gas inside the reaction tank 1 was removed through the gas discharge pipe 4. Next, the reaction solution is extracted through the reaction solution extraction tube 6, and neutralized by supplying it into a caustic soda aqueous solution (not shown) while maintaining the temperature at 35 to 40°C, to form an approximately 25% by weight aqueous solution of sulfate sodium salt. Obtained. The results were as shown in Table-1. Example 2 In Example 1, an in-pipe continuous mixing device 1 was used instead of the sulfation device as shown in Figure 2, that is, the jacket 2 provided in the reaction tank 1 as a cooling device.
A sulfation apparatus equipped with a cooler 11 provided between the 0 outlet and the reaction tank 1 and without a stirrer 5 was used, and a refrigerant of 50% by weight ethylene glycol aqueous solution was flowed through the conduit 12 to cause the reaction. It was carried out in the same manner as in Example 1. The results were as shown in Table-1. Example 3 In Example 1, a sulfating apparatus as shown in Figure 3, that is, a jacket 2 provided in the reaction tank 1 as a cooling device and a cooling device provided between the outlet of the in-tube continuous mixing device 10 and the reaction tank 1 was used. Using a sulphating apparatus equipped with vessel 10, conduits 12, 13 and 1
A refrigerant of 50% by weight aqueous ethylene glycol solution was passed through the tube to cause a reaction. The supply rate of chlorsulfonic acid is 30ml/min up to 50% of the total supply of chlorsulfonic acid, 12ml/min between 50% and 80% of the chlorsulfonic acid supply rate, and 12ml/min after the chlorsulfonic acid supply rate is 80%. was set at 3 ml/min. At this time, the amount of chlorsulfonic acid supplied (volume ratio) to the amount of circulating fluid is 0.02, 0.008, and 0.002, respectively.
The chlorsulfonic acid feed time was about 75 minutes.
The rest was carried out in the same manner as in Example 1. The results were as shown in Table-1. Example 4 In Example 3, a random secondary alcohol with an average of 9 moles of ethylene oxide adduct (average molecular weight 597, trade name SOFTANOL- 90 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) was used, and chlorosulfonic acid
Example 3 except that 5.15 mol was fed over about 40 minutes.
It was done in the same way. The results were as shown in Table-1. Example 5 The same method as in Example 3 was carried out except that a random secondary alcohol having 12 to 14 carbon atoms (average molecular weight: 201) was used as the raw alcohol. The results were as shown in Table-1. Comparative Example 1 In Example 3, in the sulfation apparatus as shown in FIG. 7, that is, in FIG. The same method as in Example 3 was carried out except that a sulfation apparatus was used. The results were as shown in Table-1. Comparative Example 2 Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that a random secondary alcohol having 12 to 14 carbon atoms (average molecular weight: 201) was used. The results are in the table-
It was as described in 1. Comparative Example 3 A sulfation apparatus as shown in Figure 6, that is, a reaction tank 1, a jacket 2, a gas feed pipe 3, a gas discharge pipe 4, a stirrer 5, a reaction liquid withdrawal pipe 6, and a chlorosulfonic acid introduction pipe 9, was used. Using the configured sulfation equipment, unreacted alcohol (non-ethylene oxide adduct) was removed to produce an average 3 mole ethylene oxide adduct (average molecular weight 333, product name: SOFTANOL ^R ) of a random secondary alcohol with 12 to 14 carbon atoms. -30 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) was placed in reaction tank 1 of 1, and was transferred to jacket 2 through pipes 13 and 14.
% by weight of ethylene glycol aqueous solution was flowed, the temperature of the reaction liquid in the reaction tank 1 was maintained at 10 to 15°C, and 1.05 mol of chlorosulfonic acid was added for about 90 minutes while stirring the reaction liquid vigorously using the stirrer 5. The mixture was dropped into the reaction tank 1 to cause a reaction. The results were as shown in Table-1. Comparative Example 4 The same method as in Comparative Example 1 was used except that a random secondary alcohol having 12 to 14 carbon atoms (average molecular weight: 201) was used. The results were as shown in Table-1. 【table】

[Brief explanation of drawings]

Figures 1 to 5 are schematic diagrams showing the sulfation apparatus according to the present invention. FIG. 6 and FIG. 7 are schematic diagrams showing a known sulfation apparatus related to the present invention. 1... Reaction tank, 2... Cooling device, 3... Gas feed pipe, 4... Gas discharge pipe, 5... Stirrer, 6...
Reaction liquid extraction pipe, 7... Circulation pipe, 8... Pump, 9
... Chlorsulfonic acid introduction pipe, 10 ... Continuous mixing device in the pipe, 11 ... Cooling device, 12 ... Refrigerant pipe, 13 ... Refrigerant pipe, 14 ... Refrigerant pipe, 15
...Cooling device, 16... Refrigerant conduit, 17... Refrigerant conduit.

Claims (1)

[Claims] 1 a reaction tank 1, a circulation pipe 7 for circulating the liquid in the reaction tank 1, an in-pipe continuous mixing device 10 provided in the circulation pipe 7,
Chlorosulfonic acid introduction pipe 9 provided in the intra-pipe continuous mixing device 10 and cooling devices 2, 11, 15 provided in the reaction tank, circulation pipe and/or in-pipe continuous mixing device
A sulfation device for producing a sulfate by reacting a higher secondary alcohol or a higher secondary alcohol ethoxylate with chlorosulfonic acid, characterized by comprising: