JPS59227856A - Preparation of sulfate compound - Google Patents

Abstract

PURPOSE:To sulfate the titled compound useful as a base meterial for detergents in high purity in high yield, by circulating an alkyl phenol ethoxylate through a device having an external circulating pipe with a line mixer, feeding chlorosulfonic acid to the mixer. CONSTITUTION:An alkylphenol ethoxylate shown by the formula (R is 4-16C alkyl; n is average 1-20) (A for short) is sulfated with chlorosulfonic acid. In the operation, the stirring tank 1 is charged with A, A is circulated through the external circulating pipe 4 with the line mixer 6, chlorosulfonic acid is quantitatively fed from the storage tank 9 of it to the line mixer 6 by the constant delivery pump 8, they are instantly mixed and reacted. The feeding rate is preferably a volume ratio of feed amount of chlorosulfonic acid to amount of circulating chlorosulfonic acid of<=0.05. This process improves the liquid-liquid contact between A and chlorosulfonic acid, and hardly forms by-products, and is advantageous.

Description

DETAILED DESCRIPTION OF THE INVENTION Kine IJ'J tJ: , relates to a method for sulfating argylphenol ethoxylate with chlorosulfonic acid. More specifically, a sulfation apparatus equipped with an external circulation pipe equipped with a line mixer is used, and the alkylphenol ethquinate is circulated through the external circulation pipe equipped with a line mixer, and the reaction is carried out while supplying chlorosulfonic acid into the line mixer. By doing so, we can produce highly pure and high quality alkylphenol ethoxy sulfate.
Regarding how to

Alkylphenol ethoxy sulfate is obtained by sulfating WJ common alkylphenol ethoxylate with sulfur trioxide, chlorosulfonic acid, sulfamic acid, etc. Among these, the method using sulfur trioxide is
The reaction is caused by contact with liquid, but sulfur trioxide has extremely high reactivity and is also a strong oxidizing agent, which can lead to a decrease in yield and quality due to side reactions, as well as the formation of harmful substances such as sultones. . Although the sulfamic acid method provides high purity and high quality sulfate, it only yields sulfate ammonium salt, has poor workability because it involves handling powder, and has problems in terms of cost.

From the above points, how to obtain high quality sulfate salt and [
7, the chlorsulfonic acid method is recommended.

Conventionally, sulfation of alkylphenol ethoxylates with chlorosulfonic acid has been carried out by charging the raw material argylphenol xylate into a reaction tank, and then adding chlorosulfonic acid as it is or entraining air, inert gas, etc. while stirring. A commonly used method is to supply the substance near the liquid level in the liquid or directly into the liquid and cause the reaction to occur. However, in the conventional method, the dispersion of chlorosulfonic acid into the reaction solution and the removal of the 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.

The present inventors improved the liquid-liquid contact between alcohol and chlorosulfonic acid as raw materials, and produced alkylphenol ethoxy sulfate with high yield and high quality! As a result of extensive research in order to achieve this goal, we have arrived at the present invention.

That is, the present invention is based on the general formula [wherein RN is an alkyl group having 4 to 16 carbon atoms, n
is an integer from 1 to 20 on average. ] In the method of converting alkylphenol ethoxylate represented by chlorosulfonic acid into Hm, using a sulfation apparatus equipped with an external circulation pipe equipped with a line mixer, circulating the alkylphenol ethoxylate through the external circulation pipe equipped with a line mixer, The present invention relates to a method for producing a sulfate, characterized by supplying chlorosulfonic acid into the line mixer and allowing it to react.

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 material alkylphenol ethoxylate is charged into the stirring tank (1), and the line mixer (6
) through an external circulation pipe (4). Next, chlorosulfonic acid is quantitatively supplied into the line mixer (6) by the metering pump (8), and the line mixer (
6) The raw materials alkylphenol ethoxylate and chlorosulfonic acid are instantaneously mixed and reacted.

The heat generated during the reaction is connected to the jacket (2) of the stirring tank (1) through conduits o1 and 11. Although it is also possible to remove water by flowing a refrigerant such as an ethylene glycol aqueous solution with fi): J, external circulation pipe (
4) Install a heat exchanger (7) inside, and supply water to the conduit (19)!!
Heat is efficiently removed by passing a refrigerant such as bamboo ethylene glycol aqueous solution, and as a result, the reaction time can be shortened. The stirrer 0D in the stirring tank (1) is not necessary if the stirring action of the circulation pipe is sufficient.

As a line mixer, a rotary drive type line type homomixer or a non-stirring type in-tube mixer can be used.
Preferably, a non-stirring type in-tube mixer without a driving part is more suitable in terms of heat generation and power cost. A non-stirring type in-pipe mixer may be used as long as it produces turbulent flow in the pipe, such as an orifice, a gill ring, a Berrusad product, etc.
Those filled with a filler such as a Raschig ring or wire mesh, or those with elements can be used. A fingerless stirring type in-tube mixer having an element that can reduce internal pressure loss and achieve efficient mixing is advantageous from an economic standpoint.

The material of the element in this case is not particularly limited, but any material may be used as long as it is not corroded by chlorsulfonic acid and the sulfation reaction solution; for example, ceramics, Nosteroy, 5US-316, etc. are preferable. 5ru. In addition, the number of elements is 10 or more, preferably 5 to 25, and the static
A high mixer manufactured by Michiley or Toshiki Co., Ltd. can be suitably used.

In order to efficiently perform mixing in the non-sweep type in-tube mixer, the linear velocity of the circulating liquid in the tube is preferably 2 m/sec, preferably 110057)+7 seconds or more.

If the number of elements is less than 10 or the linear velocity inside the tube is 0°2 y? If the time is longer than +7 seconds, the circulating fluid and chlorosulfonic acid will not be sufficiently mixed in the tube, resulting in a decrease in yield and quality.

Supplying chlorsulfonic acid into the line mixer: In order to avoid the generation of localized high-temperature areas due to the reaction with chlorsulfonic acid toalkylphenol etoginate, one or more chlorsulfonic acid supply pipes are installed into the line mixer. The supply speed of chlorosulfonic acid into the line mixer must be set at a rate of chlorosulfonic acid relative to the amount of circulating fluid in order to ensure sufficient mixing within the line mixer. Volume ratio of sulfonic acid supply amount is 0.0
It is preferably 5 or less.

If chlorosulfonic acid is supplied at a ratio of 0.05 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 solution increases and the concentration of alkylphenol ethoxylate, which is the raw material 1, in the circulating reaction solution decreases, resulting in lower yield and quality due to the decomposition of sulfates. The decrease tends to occur in the latter half of the reaction. Therefore, it is preferable that the supply rate of chlorosulfonic acid is gradually reduced as the reaction progresses. As a method for reducing the amount of chlorosulfonic acid supplied, it may be continuously reduced in accordance with the supply rate to the total amount of chlorosulfonic acid supplied, or it may be reduced stepwise. Especially chlorsulfonic acid supply rate 90
%, the volume ratio of the amount of chlorosulfonic acid supplied to the amount of circulating fluid is preferably 0103 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 40°C or less is suitable. Above 40°C, decomposition of the product tends to occur, resulting in a decrease in the yield and quality of the sulfate.

Hydrogen chloride gas, which is a by-product of the reaction, may be left as is in the reaction solution, or during or after the reaction is completed.
Air or an inert gas such as nitrogen or carbon dioxide gas is supplied into the stirring tank through the conduit (3) and removed from the conduit (1) by being entrained. Removal under reduced pressure is also possible.

As the alkylphenol ethoxylate which is a raw material used in the present invention, for example, those prepared by adding diethylene oxide to alkylphenols such as octylphenol, nonylphenol, tecylphenol, and dodecylphenol by a known method can be suitably used.

The raw material molar ratio of chlorosulfonic acid to alkylphenol ethoxylate cannot be particularly limited, but according to the method of the present invention, mixing is sufficient and side reactions hardly occur, so it may be substantially 1.0, and 1.05 or less. is preferred. When it is 1°05 or more, excess chlorosulfonic acid
This becomes a factor that inhibits the decomposition of generated sulfates.

In addition, although additives are not normally required in the solution, a few active organic compounds having a hydroxyl group or other reagents to promote the reaction, such as thihalafine,
! It can also contain inert organic solvents and inorganic salts such as hydrogenated alkanes, xylene, ethers, dioxane, and dimethylformamide.

According to the method of the present invention, sufficient liquid-liquid contact between the alkylphenol ethoxylate and chlorosulfonic acid can be achieved, and other oxidation reactions can proceed without producing nearly any side reaction products. The alkylphenol ethoxy sulfate salt u obtained by neutralizing it with an aqueous basic substance is of high purity and high quality without requiring processes such as deaeration and bleaching, and can be used as a cleaning agent base material for various slag applications. Can be widely applied to

Examples will be described below to specifically explain the present invention.
These forces are limitations on the present invention and are limited to Ir, ru.

Example J An average of 3 moles of nonylphenol 10 moles of ethylene oxide compound (average molecule N 352 ) was added to a stirred tank (1
), operate the stirrer 0]) and turn on the circulating fluid feed pump (5).
) with an external circulation pipe (4) with a line mixer (6)
] JfiL, was circulated at a flow rate of 1°5 t/min. As the line mixer (6), a static mixer (manufactured by Noritake Company Limited) having 15 elements and an inner diameter of 8 sieves was used. The linear velocity of the circulating liquid in the line mixer (6) was O, S m 7 seconds. A refrigerant of 50% by weight ethylene glycol aqueous solution was flowed through the conduits (1, ÷, ・j◇ and (ld) to the jacket (2) of the stirring tank (1) and the body side of the external heat exchanger (7). , Chlorosulfonic acid 1 was added while maintaining the temperature of the reaction solution in the stirring tank at 20 to 25°C.
0 mol was fed into the line mixer ((5)).

The feed rate of chlorsulfonic acid was adjusted to IF according to the changes shown in FIG. That is, the chlorsulfonic acid supply rate is 307/min up to 50 liters, and the chlorsulfonic acid supply rate is 50/min.
Between 80 and 80, it was 12 rap, 7 minutes, and chlorsulfonic acid (1 was also used for 3 me 1 minute after delivery at 80.

At this time, the amount of chlorsulfonic acid supplied relative to the amount of circulating fluid (volume 11.+) was 0.02, 0.008, and 0.002, respectively.

After the supply of chlorosulfonic acid is completed, nitrogen gas is supplied into the tank (1) through the conduit (3), by-product hydrogen chloride gas is removed along the conduit CI2, and then the temperature is maintained at 40°C or less. , +fI,, y, -, the reaction solution was extracted through the sulfate extraction pipe 00, and neutralized by supplying the reaction solution into a caustic soda aqueous solution (not shown). The solution was (4+).The results were as shown in Table-1.

Example] The same method as in Example 1 was used except that 6 moles of an average 7 mole ethylene oxytoi qadduct (average molecular weight 527) of nonylphenol was used as the alcoholic alcohol, and 6 moles of chlorosulfonic acid was supplied. The results were as shown in Table-1.

Comparative Example j In Example], 1 mol of an average 3 mol ethylene oxide adduct of nonylphenol (average molecule i 3s 2 ) was placed in a stirring tank of 14, and 1 mol of chlorosulfonic acid was added to about 1 mol while stirring vigorously without external circulation. The same method as in Example 1 was carried out except that the mixture was added dropwise into a stirred sodium sulfur solution for 1 hour to react. The results were as shown in Table-1.

Comparative Example 2 In Comparative Example I, an average 7 mole ethylene oxide adduct of nonylphenol (average molecule t 527 ) was used.
It was carried out in the same manner as in Comparative Example 1 except for . The results were as shown in Table-1.

[Brief explanation of the drawing]

Figure 281 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 liquid) (
FIG. (1)...Orange Stirring tank (1)...Silicate extraction pipe (2)...Jacket Ou...(■ Stirrer (31...Entrained gas inlet pipe (1)...Hydrogen chloride gas release Pipe (4)... Circulation pipe (place... Refrigerant (5)... Bomb 1 (a)... Refrigerant (6)... Line mixer fld... To cold Ii (
7)--Heat exchanger (8) Chlorsulfonic acid feeding bonder (9) Chlorsulfonic acid storage tank

Claims (5)

[Claims] (1) General formula [In the formula, R is an alkyl group having 4 to 16 carbon atoms. It is an integer from 1 to 20 on average. ] In the method of sulfating the alkylphenol ethoxylate represented by A method for producing sulfates by circulating chlorosulfonic acid through an external circulation pipe equipped with a line mixer, supplying chlorosulfonic acid into the line mixer, and reducing the amount of chlorsulfonic acid without causing a reaction. (2) The method according to claim 1, wherein the volume ratio of the amount of chlorosulfonic acid supplied to the amount of circulating bath passing through the line mixer external circulation pipe is 0.05 or less. (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 the chlorsulfonic acid supply increases, and the circulating liquid 3. The method according to claim 1, wherein the volume ratio of the amount of chlorosulfonic acid supplied to the amount of chlorosulfonic acid supplied is 0.03 or less. (4) The method according to any one of claims 1 to 3, wherein the line mixer is a non-stirring type in-tube mixer. (5) The linear velocity of the circulating fluid in the line mixer is 0.2 m/
5. The method according to any one of claims 1 to 4, wherein the time is longer than seconds.