JPS59175463A - Preparation of sulfate - Google Patents

Abstract

PURPOSE:To obtain the titled compound in high purity, by using a sulfating device equipped with an outer circulating pipe having a line mixer, recycling a higher alcohol through the circulating pipe, feeding chlorosulfonic acid into the line mixer, reacting them. CONSTITUTION:In sulfating a higher alcohol shown by the formula RO(CH2 CH2O)nH (R is 8-20C alkyl; n is 0-20) and/or higher alcohol ethoxylate with chlorosulfonic acid, a sulfating device equipped with the outer circulating pipe 4 having the line mixer (6) is used, the higher alcohol and/or higher alcohol ethoxylate is recycled through the outer circulating pipe 4, chlorosulfonic acid is fed to the line mixer 6 by the pump 8, and a sulfate after the reaction is recovered from the pipe 10. In the operation, a volume ratio of chlorosulfonic acid fed to the recycling solution passing through the circulating pipe 4 is <=0.05.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the sulfation of higher alcohols and/or higher alcohol ethoxylates with chlorosulfonic acid. More specifically, using a sulfating apparatus equipped with an external circulation pipe equipped with a line mixer, higher alcohol and/or higher alcohol ethoxylate are circulated through the external circulation pipe equipped with a line mixer, and chlorosulfonic acid is introduced into the line mixer. The present invention relates to a method for producing higher alcohol sulfate and/or higher alcohol ethoxy sulfate with high purity and high quality by reacting while feeding.

Higher alcohol sulfate and/or higher alcohol ethoxy sulfate are usually obtained by sulfating higher alcohol and/or higher alcohol ethoxylate with 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. Furthermore, although the sulfamic acid method provides sulfate of high purity and quality, it only yields sulfate ammonium salt, has poor workability because it handles powder, and has problems in terms of cost.

From the above points, the chlorosulfonic acid method is recommended as a method for obtaining high-quality female sulfate salts that are particularly suitable as raw materials for shampoos, cosmetics, and the like.

Conventionally, chlorosulfonic acid was used to produce higher alcohols and
Alternatively, for sulfation of higher alcohol ethoxylates, the raw materials alcohol and/or alcohol ethoxylate are charged into a reaction tank, and the chlorosulfonic acid is extracted from the reactor as it is or with air, an inert gas, etc.
A commonly used method is to supply the substance near the liquid level in a reaction tank or directly into the liquid and cause the reaction to occur. 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 particularly remarkable when the raw material is a secondary alcohol or a secondary alcohol ethoxylate, and when comparing the sulfation rate (mol%), according to the conventional method, primary alcohol t H primary alcohol ethoxylate In the case of alcohols, it is 96 to 97 degrees, whereas in the case of secondary alcohols, it is about 60 to 70 degrees, and in the case of secondary alcohol ethoxylates, it is about 90 to 92 degrees.

Therefore, the present inventors have conducted extensive research in order to improve the liquid-liquid contact between alcohol and chlorosulfonic acid, which are raw materials, and to obtain higher alcohol sulfate and/or higher alcohol ethoxy sulfate with high yield and high quality. As a result, we have arrived at the present invention.

In other words, the present invention has the general formula % (%) [wherein R is an alkyl group having 8 to 20 carbon atoms, and R is a difference number of 0 to 20 on average. ] In the method of sulfating the higher alcohol and/or higher alcohol ethoxylate with chlorosulfonic acid, a sulfating apparatus equipped with an external circulation pipe with a line mixer is used to sulfate the higher alcohol and/or higher alcohol ethoxylate. The present invention relates to a method for producing sulfates, characterized in that ethoxylate is circulated through an external circulation pipe equipped with a line mixer, and all of the chlorosulfonic acid is supplied into the line mixer for reaction.

The manufacturing method of the present invention will be explained in more detail using the drawings. FIG. 1 shows an example of the manufacturing method according to the present invention. First, the raw materials higher alcohol and/or higher alcohol ethoxylate are charged into the stirring tank (1), and the external circulation pipe (4) equipped with a line mixer (6)
circulate through. Next, chlorosulfonic acid is quantitatively supplied into the line mixer (6) by the metering pump (8), and in the line mixer (6), it is mixed with the raw material higher alcohol and/or higher alcohol ethoxylate. Instantly mix and react chlorosulfonic acid. During the reaction, the heat generated is transferred to the jacket (2) of the stirring tank (1).
It is also possible to remove the heat exchanger (
7), and by passing a coolant such as water or an aqueous ethylene glycol solution through the conduit α5), heat is efficiently removed, and as a result, the reaction time can be shortened. The stirrer (II) of the stirring tank (1) is not necessary if the stirring action of the external circulation pipe is sufficient.

As the line mixer, a rotary drive type line type homomixer or a non-stirring type in-tube mixer can be used, but preferably a non-stirring type in-tube mixer without a driving part is more suitable in terms of heat generation and power cost. Non-stirring type in-tube mixers are those filled with pipe links, wire mesh, etc.
Those with elements can be used. A non-stirring type in-tube mixer having an element that can reduce internal pressure loss and achieve efficient mixing is advantageous from an economic standpoint. In this case, the material of the element is not particularly limited, but it is recommended that the number of elements is 10 or more, preferably 15 to 25, since it is corroded by the chlorosulfonic acid and sulfation reaction liquid. A mixer or a high mixer made by Toshi ■ can be suitably used.

In order to efficiently perform mixing in the non-stirring type in-tube mixer, the linear velocity of the circulating liquid in the tube is preferably at least 0.2 ml seconds, preferably at least 0.5 ml seconds.

If the number of elements is less than 10, or if the linear velocity in the tube is less than 0, zm/sec, the mixing of the circulating fluid and chlorosulfonic acid in the tube will be insufficient, resulting in a decrease in yield and quality.

In order to supply chlorsulfonic acid into the line mixer, a chlorsulfonic acid supply pipe is connected to the line mixer to avoid generating localized high temperature spots due to the reaction between chlorsulfonic acid and higher alcohols and/or higher alcohol ethoxylates. It is possible to provide one or more of them and to divide and supply them to one or more locations.

The rate of supply of chlorsulfonic acid into the line mixer is determined by the volume ratio of the amount of chlorsulfonic acid supplied to the amount of circulating liquid to ensure sufficient mixing within the line mixer.
The following are preferred.

If chlorosulfonic acid is supplied at a ratio of 0.005 or more, insufficient mixing will result, resulting in a decrease in yield and quality. In particular, as the reaction progresses, the viscosity of the circulating reaction liquid increases, and the concentration of raw material higher alcohol and/or raw material higher alcohol ethoxylate in the circulating reaction liquid decreases, so that the yield due to the decomposition of sulfates decreases. Deterioration in quality tends to occur in the latter half of the reaction. therefore,
It is preferable that the feed rate of chlorosulfonic acid is gradually reduced as the reaction progresses. As a method for reducing the supply amount of chlorsulfonic acid, it may be continuously reduced according to the supply rate with respect to the total supply amount of chlorosulfonic acid,
It can also be lowered in stages. In particular, when the chlorsulfonic acid supply rate is 90 cm or higher, the volume ratio of the amount of chlorsulfonic acid supplied to the amount of circulating fluid is preferably 0.03 or less. An example of a suitable change in the amount of chlorsulfonic acid supplied (capacity ratio) to the amount of circulating fluid accompanying the supply of chlorsulfonic acid is shown in FIG.

The reaction temperature is not particularly limited, but varies depending on the type of higher alcohol and/or higher alcohol ethoxylate used as the raw material. For example, 40°C in the case of primary alcohols and/or primary alcohol ethoxylates.
In the case of secondary alcohols and/or secondary alcohol ethoxylates, the temperature is preferably 25°C or higher and 35°C or lower, preferably 20°C or lower, preferably 15°C
The following are suitable. Above 40° C. or above 20° C., in each case, decomposition of the product is likely to occur, resulting in a reduction in the yield and quality of the sulfate.

During or after the reaction, hydrogen chloride gas produced as a by-product of the reaction can be removed by supplying air or an inert gas such as nitrogen or carbon dioxide into the stirring tank through the conduit (3) and entraining it. 121. Removal under reduced pressure is also possible.

The higher alcohols and/or higher alcohol ethoxylates used as raw materials in the present invention include:
Higher alcohols derived from natural animal and vegetable oils and fats such as coconut oil, palm oil, beef tallow, and whale oil, or synthetic higher alcohols synthesized by the oxo method, Ziegler method, paraffin oxidation method, etc., and/-! Higher alcohol ethoxylates obtained by adding ethylene oxide to bamboo shoots by a known method can be used.

Examples of synthetic higher alcohols and synthetic higher alcohol ethoxylates include the following. Namely, random secondary alcohols obtained by liquid phase oxidation of linear paraffins are produced by Nippon Shokubai Chemical Co., Ltd. The commercially available product name is ``Softanol'', or ``Targitol'' is sold by Union Carbide Corporation. It is a primary alcohol produced by the oxo process and contains about 20 alpha-branched substances, and is a shell chemical limited. "Dopanol" and "Neodol" sold by Shell Oil Corporation and Shell Oil Corporation, respectively, are oxo alcohols containing about 25% alpha methyl branched materials and about 10% ethyl branched materials manufactured by Uzingman et c. ``Acropol'', sold by Imperial Chemicals Industries Limited, containing 45-55 alkyl branched components (mostly methyl branches); ``Ryalls'' is a primary oxo alcohol containing a branched component of
, "Rutennurse" sold by BASF, etc. can be suitably used.

The raw material molar ratio of chlorosulfonic acid to higher alcohol and/or higher alcohol ethoxylate is not particularly limited, but according to the method of the present invention, mixing is sufficient;
Since almost no side reactions occur, it may be substantially 1.0, and preferably 1.05 or less. When 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 with hydroxyl groups or reagents to accelerate the reaction, such as paraffin, chlorinated alkanes, xylene, ethers, dioxane, dimethylformamide, etc. It is also possible to contain inert organic solvents, inorganic salts, etc.

According to the method of the present invention, sufficient liquid-liquid contact between the higher alcohol and/or higher alcohol ethoxylate and chlorosulfonic acid is achieved, and the sulfation reaction proceeds with almost no by-products produced, so that the reaction is completed. The higher alcohol sulfate salt and/or higher alcohol ethoxy sulfate salt obtained by subsequent neutralization with an aqueous basic substance by a known method has high purity and high quality without requiring processes such as deodorization and bleaching. It can be used in a wide variety of applications as a cleaning agent base material.

Examples will be described below to specifically explain the present invention.
These do not limit the invention.

Example 1 10 moles of dodecyl alcohol was placed in a 51NftW tank (1), the stirrer (11) was activated, and the circulating fluid feed pump (5)
The mixture was circulated through an external circulation pipe (4) equipped with a line mixer (6) at a flow rate of 1.517 minutes. As the line mixer (6), a static mixer (manufactured by Noritake Kannoku Knee Limited) having 15 elements and an inner diameter of 8 wl was used. The linear velocity of the circulating liquid in the line mixer (6) was o, s m 7 seconds. 10 mol of chlorosulfonic acid was passed through the jacket (2) of the stirring tank (1) and through the conduits α3) and 04) as a refrigerant of 50% ethylene glycol aqueous solution while maintaining the temperature of the reaction solution in the stirring tank at 30 to 35°C. was fed into the line mixer (6). The feed rate of chlorosulfonic acid was gradually decreased according to the changes shown in FIG. That is, the chlorsulfonic acid supply rate is 30 rnl/min up to 50, and the chlorsulfonic acid supply rate is 50 to 8.
12Tnl/min between 0 and chlorsulfonic acid supply rate 8
After 0%, it was set as 3m1Z. At this time, the amount of chlorsulfonic acid supplied (capacity ratio) to the amount of circulating fluid is 0.0.
2, 0.008 and 0.002.

After the supply of chlorosulfonic acid is completed, nitrogen gas is supplied into the stirring tank (1) through the conduit (3), by-product hydrogen chloride gas is removed through the conduit (121), and then the reaction liquid is heated while maintaining the temperature at 40°C or less. The reaction solution was extracted through a sulfate extraction pipe aO) and neutralized by supplying the reaction solution into an aqueous solution of caustic soda (not shown) to obtain an aqueous solution of about 25% by weight of sulfate sodium salt. The results were as shown in Table-1.

Example 2 In Example 1, the raw material alcohol has 1 carbon number.
The procedure was the same as in Example 1, except that an average 3 mole ethylene oxide adduct of primary oxo alcohols Nos. 2 and 13 (average molecular weight: 326) was used. The results are in Table-1
It was as shown in .

Example 3 In Example 1, the raw alcohol has 12 or more carbon atoms.
Random secondary alcohol of 14 (produced in the same manner as in Example 1 except that 10.3 mol of chlorosulfonic acid was supplied while maintaining the temperature between normal and 15°C. The results are shown in Table 1.
It was as shown in .

Example 4 In Example 3, the raw alcohol has 12 to 12 carbon atoms.
14 unreacted alcohols (non-ethylene oxide adducts)
An average 3 mole ethylene oxide adduct (average molecular weight 333, trade name 80
The same procedure as in Example 3 was carried out except that FTANOL-30 (manufactured by Nippon Shokubai Chemical Industry Co., Ltd.) was used. The results are in the table-
It was the case as shown in 1.

Example 5 In Example 3, the raw alcohol has 12 to 12 carbon atoms.
14 unreacted alcohols (non-ethylene oxide adducts)
removed random secondary alcohol average 9 mole ethylene oxide adduct (average molecular weight 597, trade name 80F
The procedure was carried out in the same manner as in Example 3, except that 5 moles of TANOL-90 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) were used and 5.15 moles of chlorosulfonic acid were supplied. The results were as shown in Table-1.

Comparative Example 1 In Example 1, 1 mol of dodecyl alcohol was placed in the stirring tank No. 11, stirred vigorously without external circulation, and 1 mol of chlorosulfonic acid was dropped into the stirring tank over about 1 hour.
The same method as in Example 1 was carried out except that the reaction was carried out.

The results were as shown in Table 1.

Comparative Example 2 In Example 2, 1 mole of primary alcohol having 12 and 13 carbon atoms was placed in a stirring tank, and 1 mole of chlorosulfonic acid was stirred for about 1 hour while stirring vigorously without external circulation. The same method as in Example 2 was carried out except that the mixture was dropped into the tank and reacted. The results are shown in Table 1.

Comparative Example 3 Example 3 In the beak, carbon number 12-140 random second
1 mol of alcohol (average molecular weight 201) was added to a stirring tank of iz9, and 105 mol of chlorosulfonic acid was dropped into the stirring tank over about 1.5 hours with no external circulation and with vigorous stirring, and the reaction was allowed to occur. The process was continued in the same manner as in Example 3.

The results were as shown in Table 1.

Comparative Example 4 In Example 4, an average 3 mole ethylene oxide adduct (average molecular weight 333, trade name 5OFTANOL-30) of a random secondary alcohol from which unreacted alcohol having 12 to 14 carbon atoms (ethylene oxide non-adduct) was removed was used.
1 mol of Nippon Shokubai Kagaku Kogyo Co., Ltd. was placed in a stirring tank No. 11, and 1.05 mol of chlorosulfonic acid was dropped into the stirring tank over about 1.5 hours while stirring vigorously without external circulation and allowed to react. The same method as in Example 4 was carried out except for the above.

The results were as shown in Table-1.

[Brief explanation of the drawing]

FIG. 1 is a diagram of an apparatus showing an embodiment of the sulfation method according to the present invention. Figure 2 shows the amount of chlorsulfonic acid supplied/the amount of circulating liquid (the amount of chlorsulfonic acid supplied/the amount of circulating fluid) that accompanies the chlorsulfonic acid supply rate in the sulfation method according to the present invention.
FIG. 3 is a diagram illustrating an example of a change in capacitance ratio. (1) Stirring tank 00)...Sulfide extraction pipe (2) Jacket (11). stirring
Stirrer (3) - Entraining force 2 A x ”71 (12
)・Hydrogen chloride gas Nagibiao total liquid transfer pump (9)・Chlorsulfonic acid storage tank

Claims (1)

[Claims] (1) General formula % Formula % [In the formula, R is an alkyl group having 8 to 20 carbon atoms, and R is an integer of 0 to 20 on average. ] In the method of sulfating higher alcohol and/or higher alcohol ethoxylate represented by chlorosulfonic acid, a sulfating apparatus equipped with an external circulation pipe with a line mixer is used, and the higher alcohol and/or A method for producing a sulfate, which comprises circulating higher alcohol ethoxylate through an external circulation pipe equipped with a line mixer, and supplying chlorosulfonic acid into the line mixer for reaction. (2) The volume ratio of the amount of chlorosulfonic acid supplied to the amount of circulating liquid passing through the external circulation pipe with line mixer is 0.05 or less. A method according to claim 1. (3) The volume ratio of the amount of chlorsulfonic acid supplied to the amount of circulating liquid passing through the external circulation pipe with a line mixer is gradually lowered as chlorsulfonic acid is supplied, and the supply rate to the total amount of chlorsulfonic acid supplied is 90 or more. The method according to any one of claims 1 to 3, wherein the volume ratio of the amount of chlorosulfonic acid supplied to the amount of circulating fluid is 0.03 or less. (5) The linear velocity of the circulating fluid in the line mixer is 0.2
5. The method according to any one of claims 1 to 4, wherein the speed is at least m/sec. (6) Higher alcohol and/or higher alcohol ethoxylate has the general formula (R+, R2 each have 1 to 18 carbon atoms, the total number of carbon atoms of R1 and R2 is 7 to 19, and n is 0 to 20 on average. is an integer.] The method according to any one of claims 1 to 5, which is a higher secondary alcohol and/or a higher secondary alcohol ethoxylate represented by the following.