JPS59193863A - Sulfating device - Google Patents

Abstract

PURPOSE:The titled device capable of bringing a raw material such as a higher alcohol, etc. into contact with chlorosulfonic acid well, providing a high-quality sulfate in high yield, obtained by providing a reactor with both a circulating pipe connected to a continuous blender having an inlet pipe of chlorosulfonic acid and a cooler. CONSTITUTION:A higher alcohol, higher alcohol ethoxylate or alkylphenyl ethoxylate, a raw material, is fed to the reactor 1, passed into the circulating pipe 7 having the continuous blender 10 in a pipe by the circulating pump 8 and circulated. Chlorosulfonic acid is quantitatively passed through the inlet pipe 9 of chlorosulfonic acid, fed to the continuous blender 10, and the raw material is instantly blended and reacted with chlorosulfonic acid in the blender 10. Heat generated in the reaction is removed in the coolers 2, 11, and/or 15. Liquid-liquid contact is sufficiently attained by the device, the reaction is advanced without causing by-products, and a high-purity, and high quality highclass alcohol, etc. is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sulfation apparatus used for producing sulfates by reacting higher alcohols, higher alcohol ethoxylates, or alkylphenol ethoxylates with chlorosulfonate. In more detail, high purity and high quality higher alcohol sulfate, higher alcohol ethoxy sulfate, by reaction with higher alcohol, higher alcohol ethoxylate, or alkylphenol ethoxylate and tochlorosulfonic acid;
The present invention relates to a sulfation device for producing alkylphenol ethoxy sulfate.

Higher alcohol sulfates, higher alcohol ethoxy sulfates, and alkylphenol ethoxysulfates are usually obtained by sulfating higher alcohols, higher alcohol ethoxylates, or alkylphenol ethoxylates with sulfur trioxide, chlorosulfonic acid, sulfamino acid, and 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. Although the sulfur amino acid method provides high-purity and high-quality sulfate, it only yields sulfate am7nium salt, has poor workability because it involves handling powder, and has problems in terms of cost.

From the above two points, as a method to obtain sulfur-1 salt which is of high quality and is particularly suitable as a raw material for shampoos, cosmetics, etc.
Chlorsulfonic acid method is recommended.

Conventionally, the sulfation of higher alcohols, higher alcohol ethoxylates, and alkylphenol ethoxylates with chlorosulfonic acid involves charging the alcohol and/or alcohol ethoxylate to a reaction tank,
Usually, chlorosulfonic acid is stirred as it is, or is accompanied by an inert gas such as air, nitrogen, carbon dioxide, etc., and then supplied directly to the liquid level (= J or into the liquid) in the reaction tank for reaction. However, in the conventional method, the dispersion of -\ in the reaction solution of chlorosulfonic acid and the 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. This tendency is particularly remarkable when the raw stone is secondary alcohol ethoxylate or secondary alcohol ethoxylate, and when compared in terms of sulfation rate (mole ratio), it is found that according to the conventional method, it is The alcohol concentration is 96-97 for primary alcohol ethoxylates, 60-70 for secondary alcohols, and 90 for secondary alcohol ethoxylates. It is about 92 sections.

The object of the present invention is to improve the liquid-liquid contact between higher alcohol, higher alcohol ethoxylate, or alkylphenol ethoxylate, and chlorosulfonic acid, and to produce higher alcohol sulfate and higher alcohol ethoxylate in high yield and high quality. The object of the present invention is to provide a sulfation apparatus that can easily produce sulfate, mono- or alkylphenol ethoxy7 sulfate.

The present invention provides a higher alcohol characterized by comprising a reaction tank (II K % reaction tank (circulation pipe (7) for circulating the liquid II, continuous mixing device in the pipe provided in the circulation pipe (7) is 05), The present invention relates to a sulfation apparatus for producing sulfates by the reaction of higher alcohol ethoxylates or alkylphenol ethoxylates with chlorosulfonate.

The sulfation apparatus of the present invention will be explained in more detail with reference to the drawings. Figures 1 to 5 show examples of the sulfation apparatus according to the present invention. The rough higher alcohol, higher alcohol ethoxylate, or alkylphenol ethoxylate 1 is charged into the reaction tank N1 without being separated, and the circulation pipe (7 circulate through the tube.

Next, chlorsulfonic acid is quantitatively supplied through the chlornulfonic acid introduction pipe (9) into the continuous mixing device (00) in the pipe, and in the continuous mixing device (10), the raw higher alcohol, higher alcohol ethoxy Re-1: The separation is removed with alkylphenol ethoxylate, chloro.

Zunawaji, as shown in Figure 111C, a jacket or coil cooling device (2) is installed in the reaction tank (1), and a conduit (+
It can also be removed by flowing a refrigerant such as water strainer or ethylene glycol aqueous solution through 3) and (14),
Preferably, the circulation pipe (
7) A cooling device is provided inside the tube, and heat is efficiently removed by flowing a refrigerant such as water or ethylene glycol aqueous solution through the conduit (1), and as a result, a reduction in reaction time is also achieved. It is also possible to remove heat by using a double-pipe type continuous pipe mixing device 00) and flowing a refrigerant such as water or ethylene glycol aqueous solution through the jacket (ll'b).Agitator (5) of reaction tank (1) is not particularly necessary if mixing and heat removal in the circulation pipe (knife) are sufficient.

As the in-tube continuous mixing device used in the present invention, a rotary or 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 Non-stirring type in-tube mixers may be of any type as long as they produce turbulent flow in the tube, and may be of the orifice type, or those filled with a filler such as pole links, Berl saddles, Raschig links, wire mesh, etc., or those with elements. Can be used.

A non-stirring type in-tube mixer having elements that can reduce this internal pressure loss and allow efficient mixing is advantageous from an economic standpoint. 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, and suitable materials include, for example, ceramics, Hastelloy, 5US-316, and the like. The number of elements is 10 or more, preferably 15 to 2.
5 is suitable, and a static mixer manufactured by Noritake Company Limited or a high mixer manufactured 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 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 in the tube is less than 0.2++Z/sec, mixing of the circulating fluid and chlorsulfo/acid in the tube will be insufficient, resulting in a decrease in yield and quality.

Supplying chlorosulfonic acid into the in-tube continuous mixing device In order to avoid the generation of local high temperature spots due to the reaction between chlorosulfonic acid and alcohol or alcohol ethoxylate, the chlorsulfonic acid supply pipe is connected to the in-tube continuous mixing device. It is possible to provide a book or a plurality of pieces and supply them dividedly from one place or from a plurality of places.

The feeding rate of chlorosulfonic acid into the in-tube continuous mixing device is to ensure sufficient mixing in the in-tube continuous mixing device.
The volume ratio of chlorsulfonic acid supply amount to circulating fluid amount is 0.
．． 05 or less is preferable. 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 material alcohol or raw alcohol ethoxylate in the circulating reaction liquid 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 to gradually reduce the supply rate of chlorosulfonic acid as the reaction progresses. As a method for decreasing the amount of chlorsulfonic acid supplied, it may be continuously decreased in accordance with the supply rate of chlorosulfonic acid to the total supply #, or it may be lowered stepwise by -1. Especially after 90 cycles of chlorsulfic acid supply rate, circulating fluid 1j,
It is preferable that the volume ratio of the amount of chlorosulfonic acid supplied to the amount of chlorsulfonic acid is 0003F or less.

The reaction nW degree is not particularly limited, but varies depending on the type of alcohol or alcohol etoginate used as the raw material. For example, primary alcohol or primary alcohol ethoxylate is suitable at temperatures below 15°C, preferably above 25°C and below 35°C; There is. 40 in each case
At temperatures above ℃ or above 20℃, decomposition of the product tends to occur, resulting in a decrease in the yield and quality of sulfates.
do.

Hydrogen chloride, a by-product of reaction V, is present in the reaction solution by 70 cm.
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 entrained in the conduit (3).
It can be removed from 4). Removal of trenches under reduced pressure is also possible.

The higher alcohols or higher alcohol ethoxylates used as raw materials in the present invention include higher alcohols derived from natural animal and vegetable fats and oils such as coconut oil, palm oil, beef tallow, and whale oil, or the Okin method, Cheekler method, and paraffin oxidation method. Synthetic higher alcohol or synthetic higher alcohol ethoxylate obtained by adding ethylene oxide to these by a known method can be used. Synthetic higher alcohol or synthetic higher alcohol ethoxylate-1. For example, the following items can be opened: In other words, it is a random secondary alcohol obtained by liquid-phase oxidation of linear paraffins [trade name ``Softanol■'' sold by Yomoto Shokubai Kagaku Kogyo■, or Union Car), sold by Kuito Corporation. "Tajitor", produced by the Ogin method and approximately 2
"Dopanol" is a primary alcohol containing alpha-branched substances of 0 modulus and is sold by Shell Chemicals Limited and Shell Oil Corporation respectively.
``Acrobol'' is manufactured by Nisinkman et c., an ogisoalcohol containing about 25% alf-methyl branched substance and about 10% ethyl branched fK. ``Ryalls'', which is a 1st and ogisoalcohol containing a branched component of about 601 (approximately 601), manufactured by Imperial Chemicals Industries, which contains an alkyl branched component of 45 to 55 (mostly methyl branched); The Ziegler process primary alcohol derived from ethylene and produced by Kononi Konotia [
-Alfort J, "-Lutenosol" sold by BASF, etc. can be suitably used.

Further, as the alkylphenol ethogibrate, those prepared by adding ethylene oxide to alkylphenol such as octylphenol, nonylphenol, tesylphenol, and dotesylphenol by a known method can be suitably used.

The raw material molar ratio of chlorosulfonic acid to higher alcohol, higher alcohol ethoxylate I, or alkylphenol ethoxylate I is not particularly limited, but according to the method of the present invention, mixing is sufficient and side reactions hardly occur. It may be substantially 1.0, 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.

Additives to the reaction solution are usually not required, but small amounts of active organic compounds with hydroxyl groups or reagents to accelerate the reaction, such as halafine, chlorinated alkanes, xylene, ethers, dioxane, dinotylformamide, etc. It is also possible to contain inert organic solvents and inorganic salts such as.

By using the sulfation equipment of the present invention, sufficient liquid-liquid contact between higher alcohols, higher alcohol ethoxylates, alkylphenol ethoxylates, and chlorosulfonic acid can be achieved, resulting in sulfation without producing nearly any side reaction products. The reaction is allowed to proceed, and after the reaction process is completed, the aqueous basic substance is prepared using a known method. It has high purity and high quality without requiring processes such as deodorization, bleaching, etc., and can be used in a wide range of applications as a cleaning agent.

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 (molar ratio) Petroleum ether soluble content determined by the nib method (methylene blue method) (wt%) Sal 7-x ~ Tosoda salt 25 weight - Petroleum ether in aqueous solution - R3J soluble concentration color Phase (APHA) Value of sulfate soda salt 25 weight ratio aqueous solution APHAN
Represented by o.

Example 1 A sulfation apparatus as shown in Figure 1, that is, a jacket (
2), gas inlet pipe (3), gas discharge pipe (4), stirrer (
5) and a reaction tank (1) composed of a reaction liquid extraction pipe (6), an in-pipe continuous mixing device (10) installed in a circulation pipe (7) that circulates the liquid in the reaction tank (1), and an in-pipe continuous mixing device (10) The chlorosulfonic acid inlet pipe (
9) Unreacted alcohol (
12 or more carbon atoms removed (non-added product with ethylene oxide)
14. Random secondary alcohol with an average of 3 moles of ethyleneoxy l-additive (average molecular weight: 333, trade name: 5OFT)
ANOLe-30 (manufactured by Nippon Shokubai Chemical Co., Ltd.)) 10 mol of 5 was placed in a full reaction tank, the stirrer (5) was activated, and the circulating liquid was circulated using the circulating liquid feed pump (8), which was equipped with an in-pipe continuous mixing device (10). Pass the tube (7) through 1. , sl was circulated at a flow rate of 1 minute. An in-tube continuous mixing device (+01 was a static mixer with an inner diameter of 8 embrittlement and 15 elements (manufactured by Noritake Company Limited) was used.

The linear velocity of the circulating fluid in the pipe continuous mixing device (10) is 0.5 m.
/second. 1. on the jacket (2) of the reaction tank (1).
A refrigerant of 50% by weight ethylene glycol aqueous solution is passed through the conduit (+31o,, i: hiQ41f), and the reaction tank (
While maintaining 1 m4 of the reaction solution in 1) at 10 to 15°C, 10 mmol of chlorosulfonic acid was fed into the tube continuous mixing device (1o).

The supply rate of chlorsulfonic acid is 7° 5me 7 minutes when the supply rate is 80% relative to the total supply amount of chlorsulfonic acid, and 32ne 7 minutes after the chlorsulfonic acid supply rate is 80%.
It was a minute. At this time, the amount of chlorsulfonic acid supplied to the amount of circulating fluid (volume ratio) is 0゜()o5 and 0゜0, respectively.
02, and the supply time of chlorsulfic acid was approximately 120 minutes. After the supply of chlorsulfonic acid is finished, the reaction tank (
1) Supply nitrogen gas into the inside from the gas introduction pipe (3) K,
The by-product hydrogen chloride gas in the reaction tank flll is removed from the gas release pipe (
4). Next, the reaction solution was extracted through the reaction solution extraction tube (6) and poured into a caustic soda aqueous solution (1 yen not shown) at a temperature of 35 to 7 Io C. VC yarn f/: 4
';'+' 1 ~ was neutralized by feeding to obtain an aqueous solution of about 25% by weight of sulfate noda salt. The results were as shown in Table-1.

In Example J, a sulfation device as shown in Figure 2, that is, an in-tube continuous mixing device (10) was used instead of the jacket (2) provided in the reaction tank (1) as a cooling device.
and a cooler 01) provided between the reaction tank (1) and the reaction tank (1),
The reaction was carried out in the same manner as in Example 1, except that a sulfation apparatus without a stirrer (5) was used and a refrigerant of a 50 weight width ethylene glycol aqueous solution was caused to flow through the conduit (12).The results are shown in Table 1. It was as follows.

Example 3 In Example 3, a sulfation device as shown in Figure 3, namely, a cooling device provided in the reaction tank (1) and an in-tube continuous mixing device (10) were used. A sulfating apparatus is used with a condenser (01) installed between the conduits (12, 03 and 0(1))
A refrigerant of 50% by weight aqueous ethylene glycol solution was passed through the reactor to cause a reaction. The supply rate of chlorsulfonic acid is a supply rate of 50 multiplied by 1 with respect to the total supply amount of chlorsulfonic acid.
Then, 3 omp/min, chlorosulfonic acid supply rate 50-80
% is 12 ml 11 minutes, chlorosulfonic acid supply rate 80%
From then on, the distance was 3 m and 17 minutes. At this time, the amount of chlorosulfonic acid supplied to the circulating fluid H74 (volume tB, ratio) is 0°02.0.0 (+8) and 0°0 (12
The supply time of chlorosulfonic acid was approximately 75 minutes. The rest was carried out in the same manner as in Example 1. Result (d
, as shown in Table-1.

Example 4 In Example 3, the raw material 7' alcohol was an unreacted alcohol having 12 to 14 carbon atoms (without ethylene oxide).
-1 additive) removed random secondary alcohol ΔI
Z %) 0 mole ethylene oginte compound (flat) molecule jji5!l 7, trade name 5OFTANOL[F]-・
] 0]
1 was prepared in the same manner as in Example 3, except that 5.15 mol of colsulfonic acid was fed over a period of about -10 minutes. Result d Table-1 and one liteatsu/ko.

Example 5 Example: + In VC, the number of carbon atoms is 12 and 1 as the raw material alcohol;
Mol ethylene oxide l-1 additive (average molecular weight 326
)] using 0 mol, the temperature of the reaction solution in the reaction tank (1) was set to 3.
The procedure was carried out in the same manner as in Example 3, except that 10 moles of chlorosulfonic acid was divided into approximately 75 fractions and fed into the in-tube continuous mixing device (10) while maintaining the temperature at 0 to 35°C/Co results are shown in Table 1. It was as follows.

Example 6 In Example 3, an average of 7 moles of nonylphenol (6 moles of ethylene ogyne (t) with an average molecular weight of 527) was used as the raw alcohol, and the reaction density of the reaction liquid in the reaction tank (1) was While maintaining the temperature at 20-25°C, 6 moles of chlorosulfonic acid was added to the in-tube continuous mixing device (for about 15 minutes).
10) The same method as in Example 3 was carried out except that the solution was supplied into the container. The results were as shown in Table-1.

Example 7 In Example 3, the raw alcohol had 12 carbon atoms.
~14 random secondary alcohols (average molecular weight 20)
) was used in the same manner as in Example 3.

The results were as shown in Table IK.

Example 8 The same method as in Example 5 was carried out except that totenyl alcohol (molecular weight 186) was used as the raw alcohol. The results were as shown in Table-].

Comparative Example 1 Sulfation equipment as shown in Figure 6, i.e. reaction tank (1)
, jacket (2), gas inlet pipe (3), gas discharge pipe (
4) Using a sulfating device consisting of a stirrer (5), a reaction liquid extraction tube (6), and a chlorosulfonic acid introduction brass (9), unreacted alcohol (added with ethylene oxide) is used.
An average of 3 moles of ethylene oxytoibide additive (average molecular weight 3.33, trade name 5OFTA, NOL'B'-3 (l
t1 (manufactured by Hon Shokubai Kagaku Kogyo ■) was added to a 1 t reaction tank (1
), and 7 Yakenote (2) to the conduit (13 and (I4
), a refrigerant of ethylene glycol aqueous solution of 50% by weight is flowed through the tube to adjust the temperature of the reaction liquid in reaction tank +11 to 1() to 15%.
℃, and while stirring the reaction solution vigorously using a stirrer (5), 1.05 mol of chlorosulfonic acid was split into about 90 pieces and dropped into the reaction tank (1) for reaction. The results were as shown in Table-1.

Comparative Example 2 In Comparative Example 1, an average of 3 moles of ethylene oxide compound (carbon number) of 2 and 1:
While maintaining the temperature of the reaction solution in reaction tank (1) at 30 to 35°C, 1 mol of chlorosulfonic acid was divided into approximately 60 portions and dropped into the reaction tank ill for reaction. The same method as in Comparative Example 1 was used except that the method was different.

The results were as shown in Table-1.

Comparative Example 3 In Comparative Example 1, 1 mol of an average 7 mol ethylene oxide adduct of nonylphenol (average molecular weight s 27 ) was used, and the temperature of the reaction solution in the reaction tank (1) was set at 20 to 25°C.
Comparative Example 1 except that about 60 moles of chlorsulfonoic acid were added dropwise into the reaction tank (1) and allowed to react while maintaining the
It was done in the same way.

The results were as shown in Table-1.

Comparative Example 4 Comparative Example 1 was carried out in the same manner as in Comparative Example 1, except that a secondary alcohol having 12 to 14 carbon atoms (average molecule -4H2o+) was used. The Itoyoshi fruits are listed in Table 1.

Comparative Example 5 Comparative Example 2 was carried out in the same manner as in Comparative Example 2, except that dodecyl alcohol was used. The results were as shown in Table 11.

[Brief explanation of drawings]

Figures 1 to 5 are diagrams showing the sulfation apparatus according to the present invention. FIG. 6 is a diagram showing a known sulfation apparatus related to the present invention. (1) Reaction tank (2) Jacket (3) Gas inlet pipe (4) Gas discharge pipe (5) Stirrer
(6) Reaction liquid withdrawal pipe (7) Circulation pipe (8) Pump (9) Chlorosulfonic acid inlet pipe flo) In-pipe continuous mixing device 0]) Cooler (12 refrigerant pipes (14) Refrigerant 4 tubes (1G cooler
11Q refrigerant conduit θ1) Refrigerant conduit patent applicant Nippon Shokubai Chemical Co., Ltd. 425-

Claims (1)

[Claims] l. In the reaction tank (1), there is a circulation pipe (7) for circulating the liquid in the reaction tank (1), an in-tube continuous mixing device θ0) provided in the circulation pipe (7), and an in-tube continuous mixing device (θ0) provided in the in-tube continuous mixing device (10). High alcohol, higher alcohol ethoxylate 4fcld, alkylphenol ethoxylate with tochlorosulfonic acid, characterized by comprising a chlorine sulfonic acid inlet pipe (9), and a cooling device (2) and /-1'. A sulfation device that produces sulfates through a reaction.