SU891651A1 - Method of preparing sulphoethoxylates or alkylsulphates - Google Patents

Description

The invention relates to the improvement of methods for producing sulfoethoxylates or alkyl sulfates of the formulas.

RO (CgH ₄ O) _h SO, M. (I) or ROSO, M (II) *, where R is alkyl with 8-18 carbon atoms; ⁵ p = 2-5;

M - Na or (C ^ NdON) ^ NH-, which are used as surface-active substances (surfactants) used for foaming compositions. ¹⁰ There is a known method for producing sulfoethoxylates or alkyl sulfates of the formula I or II, for example, a method for producing the triethanolamine salt of lauryl sulfate, wherein the lauryl technical alcohol is subjected to sulfation with chlorosulfonic acid in a molar ratio of 1: 1.12 and 25–40 ° C s subsequent neutralization of the obtained sulfonic acids with a 16-26% aqueous solution of triethanolamine, the yield of the target product 89%, the content of unsulfurized compounds 6% of the active substance, sulfates and chlorides of triethanolamine 23% of the active substance of [1].

The disadvantages of this method include the use of expensive chlorosulfonic acid, as well as the relatively low yield and quality of the target product.

There is also known a method for producing sodium sulfoethoxylates or alkyl sulfates of the formula 1 or II, which is the closest to the proposed method, namely, that the primary aliphatic alcohols fraction C ^ _o -C ^ g with a molecular weight of 190-220, a hydroxyl number of 250-290 mgKOH / g and iodine number less than equal 1 g 9/100 g or fraction alcohols; ethoxylated with three moles of elite oxide, with a molecular weight of 295 “350” hydroxyl number

160-190 mg / KOH / g and an iodine value of 0.3 g

9/100 g is subjected to sulfation with chlorosulfonic acid at molar

8'91651 in a ratio of 1: 1.05 * 1> 1 "at? -5 * 35 ° C, followed by neutralization of the resulting sulfonic acids with sodium hydroxide. Sodium alkyl sulfates,%: yield 87 * 92, non-sulfonated compounds 7 * 11 from the active substance, inorganic salts (sodium sulfates and chlorides) 10 * 14 from the active substance, sodium sulfoethoxylates, '% ·. yield 93.8, the content of non-sulfonated compounds 5 and inorganic compounds 25. The viscosity of a 20% solution of sulfoethoxylates at 20 ° C 460 cP G2].

The disadvantages of the known method are low yields and quality of the target products, as well as the use of expensive chlorosulfonic acid as a sulfonating agent, which entails the disposal of waste hydrogen chloride gas, which in general leads to an increase in the cost of the whole process.

The purpose of the invention is to increase the yield and quality of the target products and the cost of the process.

This goal is achieved in that according to the method for producing sulfoethoxylates or alkyl sulfates of the formula I or II, which consists in the fact that the corresponding alcohols are subjected to sulfonation with a mixture of liquid sulfuric anhydride in sulfur dioxide in an upward flow of reactants while bubbling vapor of sulfur dioxide through the reaction mass into

In the case of sulfonation of ethoxylated alcohols, the process is carried out at -4 - -10 C, in a molar ratio of sulfuric anhydride-alcohol equal to 1.25-1.4: 1, respectively, and the concentration of sulfonating agent for sulfuric anhydride is 5 ~ 10 wt%. .

Yield,%: alkyl sulphates 97 ~ 98, the content of non-sulfonated compounds of 1.7 - 1.8, inorganic. connections up to 4.

% Yield: 95 ^_ 98 sulfoetoksilatov content nonsulfated compounds 1 * 3, 15 March inorganic compounds "4. viscosity of 30% aqueous solutions of sulfoethoxylates at 20 ° C 240 *

330 cP, 20% solutions at 20 ° C 150-250 cP.

These differences make it possible to increase the yields of the target products: alkyl sulfates from 87-92% to 97-98%, sulfoethoxylates * from 93-94% to 95-98%; improve the quality of the target products, reduce the content of non-sulfonated and inorganic compounds for alkyl sulfates from 7-11¾ to 1.7 “1.8% and from 10-14% to 4%, for sulfoethoxylates from 5 to 1-3% and from 25¾ to 3 “4%, reduce the viscosity of 20%. Solutions of sulfoethoxy ₃₀ pats at 20 ° C - from 460 cP to 150,250 cP; reduce the cost of the process, since the cost of the sulfonating agent used in the described method is 2.6 times cheaper than the chlorosulfonic acid used in the known method ³⁵ .

The technology of the method consists in several zones with a separate zone-by-zone introduction of a sulfonating agent into the stream in the first several zones by spraying it over a mirror of the boiling reaction mass of the corresponding zone with subsequent exposure of the reaction mass in the following zones at -10 °, -. + 30 ° C, the molar ratio of sulfuric anhydride is the corresponding alcohol, equal to 1.11.4: 1, respectively, and the concentration of sulfonating agent for sulfuric anhydride is 5 * 25 wt.%, Followed by neutralization of the obtained sulfonic acids with sodium hydroxide or triethanolamine.

In the case of sulfonation of alcohols, the process is carried out at 10-30 C, the molar ratio of sulfuric anhydride to alcohol is 1.11.2: 1, respectively, and the concentration of sulfonating agent for sulfuric anhydride is 20-25 wt.%.

next.

The drawing shows a continuous sulfation scheme.

The starting alcohols are fed to the bottom of reactor 1 via line 2. Below, through line 3, a portion of gaseous 50 ^ enters the reactor through a bubbler. The mixture of alcohols and gaseous sulfur dioxide through the distribution cap plate enters the first zone of the reactor. The liquid sulfonating mixture SO ^ —SOg enters the lower reaction zones of reactor 1 along lines 4 and 5 and is introduced into these zones by spraying it over. a mirror of the reaction mass. When mixing alcohols with a sulfonating mixture, sulfuric anhydride boils, providing intensive mixing (boiling) of the liquid.

The reaction ends in the upper zones, sulfonic acid is discharged from the upper part of the reactor via line 6 to neutralization, SO ^ vapors are discharged from the top of the reactor via line 7 to condenser 8, from where liquid SO ^ flows down line 9 to mixer 10, where it is mixed with SOj supplied via line 11. From mixer 10, a sulfonating mixture of liquid SO ^ —SO — j is sent to line sulfonation through line 12. Part of the gaseous SO-z, bypassing the capacitor 8, enters through line 3 directly to the bottom of the reactor 1.

Example 1. At the bottom of the reactor, which is a five-stage column, partitioned in height by cap plates, with a volume of 110 ml, d 30 mm, Η 1 \ 80 mm, equipped with a jacket for thermostating with a cooling mixture, molten alcohols of the fraction C ^ _o -C ^ g are fed at a rate of 200 ml / h. Sulfonating mixture 0 ^ -0 at -10 ° C and a concentration of SO ^ 20 wt.% Sprayed over a mirror of boiling liquid in the first and second sections in the amount of

350 ml / h, and in the first section -. give 80% of the total. The excess SO3 in relation to alcohol is 20 mol.%, Which corresponds to a ratio of SO ^ to alcohol of 1.2: 1. Reaction temperature 25 ° C, average residence time 15 minutes The resulting product is continuously taken from the top of the reactor, SO ^ is removed by heating to 50 ° C, and then under vacuum (residual pressure of 100 mm Hg), the sulfonic acid is neutralized with a 10% NaOH solution.

With

Analysis of the obtained product,%: Н ₂ 0 59, 7, Na ^ SO ^ 1.6 (4.2 from the active substance) "unsulfurized soy. length 0.7 (1.84 of the active substance), active substance 38.

The yield of Na-alkyl sulfates is 97.6%. The color of the solution is 4 units. on the iodine scale.

Example '2. The reaction is carried out under the conditions of example 1. Decyl is fed to the bottom of the reactor at a rate of 200 ml / h. alcohol. A sulfonating mixture of SO ^ -SO-} at -10 ° C and a concentration of SO-j of 25 wt.% Is sprayed over a mirror of boiling liquid in the first and second sections in an amount of 243 ml / h. The excess SOj in relation to the alcohol is 10 mol% (SOj: alcohol = 1.1: 1). The reaction temperature is 12-14 ° C, the average residence time is 15 minutes. . Received of pro-Na-decyl sulfates 98%. Color measures 3. The reaction is carried out in example 1. At the bottom of the reactor, the duct was isolated by the same method as in example 1.

Product analysis,%: Н ^ О 60, Na ^ SO ^ 1,5 (4 from the active substance) "unsulfonated compounds 0,65 (1,7 from the active substance), active substance 37,85.

The output of the solution is 4 units. on the iodine scale.

Under conditions at a rate of 200 ml / h, the alcohols of the ethoxylated mole fraction of ethylene oxide are fed. Sulfonating mixture 15 SO ^ -SO at a liquid temperature in the first and second sections in an amount of 760 ml / h, an excess of 0 ^ relative to alcohol is 30 mol.% (50 ^: alcohol = 1.3: 1), the reaction temperature is 10 ° C, average residence time 15 min. The resulting product is isolated by the same method as in example 1.

Product analysis,%: H ^ O 68.76, Na ₂ S04 0.86 (2.87 from the active substance), non-sulfonated compounds 0.38 (1.27 from the active substance), active substance 30.

The yield of Na sulfoethoxylates is 98.3%; the color of the solution is 5 units. on the iodine scale. The viscosity of a 30% aqueous solution at 20 ° -240 cP.

Example 4. In the reactor described in example 1, the alcohols of the fraction Cg-C ^ d ethoxylated with 2 mol of ethylene oxide are continuously fed at a rate of 250 ml / h. The process is carried out under the conditions of example 1 at -4 ° C, the ratio of S0} to alcohol = 1.4: 1 and the concentration of the sulfonating mixture is 10 wt.% By S0}.

After neutralization, a product is obtained containing,%: H ₂ 0 67.9,

Na ^ SO ^ 1.1 (3.7 of the active substance) "unsulfurized compounds 1 (3.3 of the active substance)" of the active substance 30.

The yield of sulfoethoxylates of Na- 95.1%, the color of the solution is 8 units. 30% viscosity at 20 ° -330 cP.

Example 5 · obtained under the conditions of example 1, was neutralized with a 26% aqueous solution of triethanolamine.

Product analysis,%: HjO 61, triethanolamine sulfate 1.4 (3.8 of the active substance), non-sulfonated on an iodine scale, aqueous solution

Sulfonic acid

Ί 89 compounds 0.6 (1.6 of the active substance), active substance 37.

The yield of triethanolamine alkyl sulfates is 97.5%. Solution color 3 units. on the iodine scale.

Example 6. The sulfonic acid obtained in the conditions of example 3 / was neutralized with a 16% solution of triethanolamine. .

Product analysis,%: Н ^ О 68.3, triethanolamine sulfate 1.57 (5.4 from the active substance), non-sulfonated compounds 0.93 (3.2 from the active substance), active substance 29.2.

The yield of triethanolamine sulfoethoxylates is 95.2%. The color of the solution is 7 units. on the iodine scale. The viscosity of a 20% aqueous solution at 20 ° C is 200 cP.

Claims (2)

The invention relates to the improvement of methods for the preparation of sulfoethoxylates or alkyl sulfates of the formulas. RO (, .Ct) or ROSO, M Cu / where R is alkyl with 8-18 carbon atoms M — Na or {C2. HdON) 5YH-, which are used as surface-active substances (surfactants) used for washing compositions. A known method for preparing sudofotoxylates or alkyl sulfates of the formula I or II is, for example, a method for preparing the triethanolamine salt of lauryl sulfate, which consists in subjecting lauryl technical alcohol to sulfation with chlorosulfonic acid at a molar ratio of 1: 1.12, followed by neutralization of the resulting sulfonic acid and 1 2b with an aqueous solution of triethanolamine. The yield of the target product, the content of non-sulfated compounds 6% of the active substance, sulfates and chlorides of triethanolamine 23% of the active substance tl 1. The disadvantages of this method include the use of expensive chlorosulfonic acid, as well as the relatively low yield and quality of the target product. A method is also known for preparing sodium sulfoethoxylates or alkyl sulphates of formula II, which is closest to the proposed method, consisting in that the primary aliphatic alcohols of the fraction with a molecular weight of 190-220, a hydroxyl number of 250290 mgKbN / g and an iodine number less than 1 g V / 100 g or alcohols of the fraction.-C /) 4 ethoxylated with three moles of elite oxide, with a molecular weight of 295-350, a hydroxyl number of 160-190 mg / KOH / g and an iodine number of 0.3 g 100 g is subjected to sulfation with chlorosulfonic acid at molar ratio 38 and, equal to 1: 1, at -5-35 ° C, followed by neutralization of the resulting sulfonic acids with sodium hydroxide. Sodium alkyl sulfates D: yield 87-92, content of non-sulfated compounds 7-11 from the active substance, inorganic salts (sulfates and sodium chlorides) 10-14 from the active substance, sodium sulfatoxylates,,: yield 93 | 8, content of non-sulfonated compounds 5 and inorganic compounds 25, the viscosity of a 20% solution of sulfoethoxylates at 20 k6Q cp 2. The disadvantages of this method are the low yields and quality of target products, as well as the use of expensive chlorosulfonic acid as a sulphating agent, which entails ization exhaust gaseous hydrogen chloride, which generally increases the cost of the process. The purpose of the invention is to increase the yield and quality of target products and reduce the cost of the process. The goal is achieved in that according to the method for producing sulfoethoxylates or alkyl sulfates of formula I or II, the corresponding alcohols are sulfated with a mixture of liquid sulfuric anhydride in sulfuric anhydride in the ascending stream of reagents during sparging of sulfuric anhydride through the reaction mass of sulfuric anhydride. several zones with a separate post-nylon introduction of the sulfating agent into the flow in the first few zones by spraying it over the mirror of the boiling reaction mass of the corresponding zone with the next exposure of the reaction mass in the following zones at -10 °, -. + 30 ° C, the sulfuric anhydride molar ratio is the corresponding alcohol, respectively, 1.11, 4: 1, and the concentration of the sulfating β-agent for sulfuric anhydride is 5-25 followed by neutralization of the resulting sulfonic acids with sodium hydroxide or triethanolamine. In the case of sulfonation of alcohols, the process is carried out at 10–30 ° C, the molar ratios are sulfuric anhydride alcohol equal to 1.11, 2: 1, respectively, and the concentration of sulfonating agent for sulfuric anhydride is 20–25 wt. In the case of sulfonation of ethoxylated alcohols, the process is carried out at -k -10 ° C, the sulfuric anhydride – alcohol molar ratio is 1.25-1.4: 1, respectively, and the concentration of the sulfonating agent in sulfur anhydride is 5-10 weight D. The yield, Z: alkyl sulfates 97-98, content of non-sulfated compounds 1.7-1.8, inorganic compounds up to 4. Yield,%: sulfoethoxylates 95-98, content of non-sulfated compounds 1-3, inorganic compounds 3-4 ,. viscosity of 30% aqueous solutions of sulfoethoxylates at 20 ° С 240– 330 сП, solutions at 20 ° С 150-250 сП. These differences allow to increase the yields of the target products: alkyl sulfates from 87-32% to 97-98, sulfoethoxylates - from 93-94 to 95-98; improve the quality of target products, reduce the content of non-sulfated and inorganic (x compounds for alkyl sulfates from 7-11 to 1.7-1, and from 10-14 to k%, for sulfoethoxylates from 5 to 1-3% and from 25 to 3- 4, reduce the viscosity of 20. solutions of sulfoethoxylates at - from 460 cP to 150,250 cP; reduce the cost of the process, since the cost of the sulphating agent used in the described method is 2.6 times cheaper than the chlorosulfonic acid used in the known method. is as follows. The drawing shows a continuous sulphate scheme 1 1. Alcohols are fed to the bottom of reactor 1 through line 2. Below, through line 3, a portion of gaseous 50 enters the reactor through a sparger. A mixture of alcohols and gaseous sulfuric anhydride enters the first zone of the reactor through the distribution cap plate. Liquid sulphate mixture enters the lower reaction zones of reactor 1 through lines 4 and 5 and introduced into these zones by spraying it over the reaction mass mirror. When mixing alcohols with a sulphating mixture, sulfur dioxide boils, providing intensive mixing (boiling) Liquids. The reaction ends in the upper zones, the sulfonic acid is withdrawn from the upper part of the reactor via line 6 to neutralization, the SO vapor is withdrawn from the top of the reactor through line 7 to condenser 8, from which liquid SO flows down through line 9 to mixer 10, where it mixes with incoming through line 11 From the mixer 10, the liquid sulfide mixture is fed via line 12 to sulfonation. Part of the SO gas, gaseous condenser 8, flows through line 3 non-directly to the bottom of reactor 1. Example 1. Into the bottom of the reactor, which is a five-turn column, sectioned in height by cap plates with a volume of 110 ml, d 30 mm, N mm, equipped with a jacket for thermostating with a cooling mixture, the molten alcohols of the C o-Qyo fraction are fed at a rate of 200 ml / h Sulfur mixture at and concentrations of 50 to 20 weight. 350 ml / h is sprayed over the mirror of the boiling liquid in the first and second sections, with 80% of the total amount being supplied to the first section. An excess of SOj with respect to alcohol is 20 mol, which corresponds to a ratio of 50 to alcohol 1.2: 1. Reaction temperature 2S °, average residence time 15 min. The resulting product is continuously taken from the top of the reactor, SO, removed by heating to 50 ° C, and then under vacuum (residual pressure of 100 mm Hg) the sulfonic acid is neutralized with a solution of NaOH. Analysis of the obtained product,% 59.7, Na2.SO1.6 (i, 2 from the active substance) I non-sulfated from the dinene 0.7 (1.8 from the active substance), the active substance 38. The yield of Na-alkyl sulfates is 97 , 6%. Color solution on iodine scale. Example 2. The reaction is carried out under the conditions of Example 1. Decyl alcohol is fed to the bottom of the reactor at a rate of 200 ml / h. Sulfonate 1 SO SO SO mixture at -10 ° C and SO-j25Bec concentration. sprayed over a mirror of boiling liquid in the first and second sections in the amount of ml / h. An excess of SOa with respect to alcohol is 10 mol. -5; (50: alcohol 1, 1: 1). Reaction temperature, average residence time 15 minutes. The product obtained was isolated by the same method as in Example 1. Analysis of the product,%: NO 60,. 1.5 (4 from active substance), non-sulfated compounds 0.65 (1.7 from active substance), active substance 37.85 Output Ma-decyl sulfate 58. Color of solution k units. on iodine scale. Example 3. The reaction is carried out under the conditions of Example 1. Alcohols of the fraction ethoxylated with 3 mol of ethylene oxide are fed to the bottom of the reactor at a rate of 200 ml / h. The sulphating mixture, at the temperature of the liquid in the first and in the second sections in the amount of 760 ml / h, the excess of O with respect to alcohol is 30 mol. (50z: alcohol 1.3: 1). The reaction temperature is -10 ° C, the average residence time is 15 minutes. The resulting product was isolated by the same method as in Example 1. Analysis of the product,%: 68.76, 0.86 (2.87 from the active substance), non-sulfated compounds 0.38 (1.27 from the active substance), active substance 30 Output of Na sulfoethoxylates - 98.3 color of solution 5 units. on iodine scale. The viscosity of a 30% aqueous solution at 20 ° -2kQ cP. Example 4. In the reactor described in example 1, continuously fed with a speed of 23U ml / h alcohols fraction) d, ethoxylated 2 mol of ethylene oxide. The process is carried out under conditions of example 1 at -k ° C, a ratio of 50 to alcohol 1, +: 1 and a concentration of a sulphating mixture of 10 wt. Gyu $ 0e | “After neutralization, a product is obtained containing, in%: B7.9, Na, SO 1.1 (3.7 active substances), non-sulfated compounds 1 (3.3 from the active substance) 30. The output of Na sulfoethoxylates - 95.1%, color of solution 8 units. on iodine scale. The viscosity of a 30% aqueous solution at cp. Example 5- The sulfonic acid obtained under the conditions of Example 1 was neutralized with a 2b% aqueous solution of triethanolamine. Analysis of the product,%: 61, triethanolamine I sulfate, (3.8 from the active substance), non-sulfated compounds 0.6 (1.6 from the active substance) g active substance 37. The yield of triethanolamine alkyl sulfates is 97.5%. Color solution 3 units. p iodine scale. Example 6. Sulfonic acid obtained under the conditions of the example of Zu neutralized by a solution of triethanolamine. . Analysis of the product,%: 68.3, triethanolamine sulfate 1.57 (5, from the active substance), non-sulfated compounds 0.93 (3.2 from the active substance) active substance 29.2. The output of sulfoethoxylate triethanol amine - 95 ,. Color solution 7 units. p iodine scale. The viscosity of a 20% aqueous solution at 20 ° C is 200 cP. Claim 1. Investigation method of sulfoethoxylates or alkyl sulphates of formula I or RO () SOjMd) or (II), where R is alkyl with 8-18 carbon atoms, M - Na or () NH - by sulfonation of the corresponding alcohols, followed by neutralization of the resulting sulfonic acids sodium hydroxide or triethanolamine, characterized in that, in order to increase the yield and quality of target products and reduce the cost of the process, a mixture of liquid sulfuric anhydride in sulfuric anhydride is used as a sulphating agent when bubbling sulfuric anhydride vapors over the reaction mass in several zones with separate post-injection of sulfating agent into the stream in the first few zones by spraying it over the mirror of the boiling reaction mass of the corresponding zone with subsequent aging of the reaction mass in the following 8 zones at -10 ° C , the molar ratio of sulfuric anhydride is the corresponding alcohol, equal to 1.1 - I, respectively: 1, and the concentration of sulfating agent on sulfuric anhydride 5-25 weight D. 2. Method according to claim 1, characterized in that in the case of sulfonic Ani alcohols, the process is carried out pri10-30 C, a molar ratio of sulfur trioxide - alcohol equal respectively 1.1-1.2: 1, and the concentration of the sulfonating agent is sulfuric anhydride vesD 20-25. 3. Method pop. 1, distinguished by the fact that, in the case of sulfonation of ethoxylate alcohols, the process is carried out at - C - 10 ° C, the sulfuric acid alcohol has a molar ratio of 1.251, 4: 1, respectively, and the concentration of sulfating agent according to sulfuric anhydride on weight. %. Sources of information taken into consideration during the examination 1. Technological regulations No. of production of triethanolamine salt of lurylsulfate and foam former. 1975, State Union Ivanovo Chemical Plant named. Batur ina. 2. Temporary technological regulations No. 311-77 produced by pilot batches of oxanol L-3 TV. 1977, State Union Ivanovo Chemical Plant named after Baturin (prototype).