JP2006161002A - HIGH-CONCENTRATION alpha-SULFOFATTY ACID ALKYL ESTER SALT-CONTAINING PARTICLE AND METHOD FOR PRODUCING THE SAME AND DETERGENT - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide α-sulfofatty acid alkyl ester salt-containing particles containing an α-sulfofatty acid alkyl ester salt in a high concentration and capable of suppressing solidification even in storage at a high temperature for long period. <P>SOLUTION: The α-sulfofatty acid alkyl ester salt-containing particles comprise 50-95 mass% α-sulfofatty acid alkyl ester salt and a solidification-preventing agent. In the particles, the mass ratio of the α-sulfofatty acid alkyl ester salt to the solidification-preventing agent is 100.0:8.0 to 100.0:30.0. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing high-concentration α-sulfo fatty acid alkyl ester salt-containing particles that can be solidified even when stored at high temperatures.

  Many types of anionic surfactants used in laundry detergents have been developed and are incorporated into commercial detergents. As one of them, α-sulfo fatty acid alkyl ester salts are known. The α-sulfo fatty acid alkyl ester salt has excellent detergency and has high performance as a detergent material. Moreover, since biodegradability is favorable, it has the advantage that there is little influence with respect to an environment.

  There are two typical methods for producing high-concentration α-sulfo fatty acid alkyl ester salt-containing particles. One is a method in which α-sulfo fatty acid alkyl ester salt paste is dried to be concentrated to a high concentration, solidified, and then pulverized to obtain particles. The other is a dry neutralization method in which an α-sulfo fatty acid alkyl ester and an alkaline inorganic powder are directly mixed for neutralization. In the former method, there are various methods for drying the surfactant to a high concentration. As a method for continuously producing a large amount of product, a thin film type dryer for drying a paste in a thin film is generally used. This method is also frequently used for α-sulfo fatty acid alkyl ester salts (see Patent Document 1: Japanese Patent Laid-Open No. 06-184592, Patent Document 2: Japanese Patent Laid-Open No. 08-157895).

  In any method, it is possible to produce particles having a high concentration of α-sulfo fatty acid alkyl ester salt. In particular, in the former method, the α-sulfo fatty acid alkyl ester salt paste is more stable than the acid state. Since it manufactures, it can manufacture stably. However, the α-sulfo fatty acid alkyl ester salt has many merits as described above, but there is a problem that granules containing the α-sulfo fatty acid alkyl ester salt in a high concentration solidify during storage.

  Many proposals have been made on methods for improving the solidification of α-sulfo fatty acid alkyl ester salt-containing particles. For example, a method for improving fluidity immediately after production mainly by blending soap (see Patent Document 3: JP 09-302395 A, Patent Document 4: JP 09-302396 A), α-sulfo fatty acid It has been proposed to improve fluidity by coating an alkyl ester salt-containing particle with an inorganic powder (see Patent Document 5: Japanese Patent Application Laid-Open No. 08-157894). However, further improvement in solidification during long-term storage has been desired.

  On the other hand, for surfactant powder containing polycarboxylic acid, a method for producing α-sulfo fatty acid alkyl ester salt-containing particles containing water-soluble polycarboxylic acid has been proposed (Patent Document 6: Japanese Patent Laid-Open No. Hei 10-). 195497). This is for solving the solubility of the α-sulfo fatty acid alkyl ester salt-containing particles, and does not solve the solidification property of the present invention. Moreover, since there is little content of water-soluble polycarboxylic acid, it was inadequate to solve the solidification which generate | occur | produces at the time of the storage under high temperature of alpha-sulfo fatty-acid alkylester salt containing particle | grains.

  Particles containing a tripolyphosphate and an α-sulfo fatty acid alkyl ester salt are disclosed in Japanese Patent Publication No. 10-505631, but do not solve the problems peculiar to high-concentration α-sulfo fatty acid alkyl ester salts. .

Japanese Patent Application Laid-Open No. 06-184592 Japanese Patent Laid-Open No. 08-157895 JP 09-302395 A Japanese Patent Laid-Open No. 09-302396 Japanese Patent Laid-Open No. 08-157894 Japanese Patent Laid-Open No. 10-195497 Japanese National Patent Publication No. 10-505631

  The present invention has been made in view of the above circumstances, and contains α-sulfo fatty acid alkyl ester salt in a high concentration, can suppress solidification even during long-term storage at high temperatures, and is excellent in powder physical properties. An object is to provide particles containing a sulfo fatty acid alkyl ester salt.

  As a cause of solidification due to storage at high temperature, which is a problem of high concentration α-sulfo fatty acid alkyl ester salt-containing particles, the slow crystallization rate (crystal stabilization rate) peculiar to α-sulfo fatty acid alkyl ester salts Is mentioned. This is because, when stored in a state where the crystals are not stabilized, solidification easily occurs particularly under high temperature conditions. As a result of intensive studies to achieve the above object, the present inventor determined that the mass ratio of the α-sulfo fatty acid alkyl ester salt to the anti-caking agent in the α-sulfo fatty acid alkyl ester salt-containing particles was 100.0: 8.0. -100.0: 30.0, it has been found that solidification can be suppressed even during storage for a long period of time and at a high temperature without going through a process such as an aging process, and has led to the present invention. It is. In particular, it is preferable that the anti-caking agent is uniformly mixed in the α-sulfo fatty acid alkyl ester salt-containing particles.

Accordingly, the present invention provides (1) α-sulfo fatty acid alkyl ester salt-containing particles containing 50 to 95% by mass of an α-sulfo fatty acid alkyl ester salt and an anti-caking agent, Α-sulfo fatty acid alkyl ester salt-containing particles, wherein the mass ratio to the anti-caking agent is 100.0: 8.0 to 100.0: 30.0,
(2) The α-sulfo fatty acid alkyl ester salt-containing particles according to (1), wherein the anti-caking agent is uniformly mixed in the α-sulfo fatty acid alkyl ester salt-containing particles.
(3) α-sulfo fatty acid alkyl ester salt-containing particles according to (1) or (2), wherein the anti-caking agent is a water-soluble polycarboxylic acid and / or a salt thereof,
(4) The α-sulfo fatty acid alkyl ester salt-containing particles according to (1) or (2), wherein the anti-caking agent is a tripolyphosphate,
(5) The following steps [1] to [4]
[1]: a reaction of sulfonating a fatty acid alkyl ester with a sulfonation gas, a reaction of esterifying the product of the sulfonation step with a lower alcohol, and a reaction of neutralizing after the esterification step A step of obtaining an α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 15 to 40% by mass,
[2]: The α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 15 to 40% by mass obtained in the step [1] is dried to a dried product having a moisture content of 0.5 to 5% by mass using a thin film evaporator. The process of
[3]: A step of cooling and solidifying the dried product having a water content of 0.5 to 5% by mass obtained in step [2], and [4]: The solidified product obtained in step [3] Crushing into particles having a diameter of 200 to 700 μm,
A method for producing α-sulfo fatty acid alkyl ester salt-containing particles, which comprises blending an anti-caking agent in any of the steps [1] to [4],
(6) An anti-caking agent is blended in the α-sulfo fatty acid alkyl ester salt-containing paste obtained in step [1] or the dried product obtained in step [2] and mixed uniformly. 5. A method for producing particles containing α-sulfo fatty acid alkyl ester salt according to 5.
(7) A detergent containing the α-sulfo fatty acid alkyl ester salt-containing particles according to any one of (1) to (4) and a detergent component is provided.

  According to the present invention, it is possible to provide α-sulfo fatty acid alkyl ester salt-containing particles that contain α-sulfo fatty acid alkyl ester salt at a high concentration and can suppress solidification even when stored for a long period of time under high temperature. .

  The α-sulfo fatty acid alkyl ester salt-containing particles of the present invention contain 50 to 95% by mass of an α-sulfo fatty acid alkyl ester salt and an anti-caking agent, and include an α-sulfo fatty acid alkyl ester salt and an anti-caking agent. The mass ratio is 100.0: 8.0 to 100.0: 30.0.

  As the α-sulfo fatty acid alkyl ester salt (neutralized product), those represented by the following general formula (1) are preferable, and one kind can be used alone, or two or more kinds can be used in appropriate combination.

（式中、Ｒ¹は炭素数８〜２０の飽和又は不飽和の一価炭化水素基、Ｒ²はメチル基、エチル基又はプロピル基、Ｍはアルカリ金属を示す。）

(In the formula, R ¹ represents a saturated or unsaturated monovalent hydrocarbon group having 8 to 20 carbon atoms, R ² represents a methyl group, an ethyl group or a propyl group, and M represents an alkali metal.)

  The α-sulfo fatty acid alkyl ester salt is preferably produced by the production method described in JP-A-2001-64248. Specifically, a sulfonation step in which a fatty acid alkyl ester and a sulfonated gas are brought into contact with each other in the presence of a coloring inhibitor to sulfonate, an esterification step in which the product of the sulfonation step is esterified with a lower alcohol, It is a method for producing an α-sulfo fatty acid alkyl ester salt comprising a step of neutralizing after the esterification step to obtain a neutralized product and a bleaching step of bleaching the neutralized product to obtain a bleached product. By using this production method, an α-sulfo fatty acid alkyl ester having a low lower alcohol content can be obtained.

  The blending amount of the α-sulfo fatty acid alkyl ester salt is 50 to 95% by mass, preferably 55 to 90% by mass, in the α-sulfo fatty acid alkyl ester salt-containing particles. More preferably, it is 60-85 mass%. Although it can be produced even at less than 50% by mass, the merit unique to high-concentration granules cannot be obtained because of low concentration. Further, in order to produce the α-sulfo fatty acid alkyl ester salt-containing particles exceeding 95% by mass, a process such as purification is required, and the production may not be possible at low cost.

  Examples of the anti-caking agent of the present invention include water-soluble polycarboxylic acids, salts thereof and tripolyphosphates. These can be used individually by 1 type or in combination of 2 or more types. In particular, the anti-caking agent is uniformly mixed in the α-sulfo fatty acid alkyl ester salt-containing particles, and the anti-caking agent is uniformly present in the particles, so that the effect can be further exhibited.

  As the water-soluble polycarboxylic acid and a salt thereof, a homopolymer composed of any one of acrylic acid, methacrylic acid, maleic acid and itaconic acid, or a copolymer composed of two or more selected from these is preferably used. A copolymer of at least one selected from acrylic acid, methacrylic acid, maleic acid, and itaconic acid and maleic anhydride can also be used. As the counter ion of the water-soluble polycarboxylate, at least one selected from alkali metals, alkaline earth metals, and ammonium is preferably used. Among these, alkali metals such as sodium and potassium are preferable.

  The water-soluble polycarboxylic acid is preferably a copolymer of maleate and acrylate, which has a high chelating ability and is generally used as a detergent component. The molecular weight is preferably 40,000 to 80,000 from the viewpoint of chelating ability.

  In the present invention, the mass ratio of the α-sulfo fatty acid alkyl ester salt to the anti-caking agent is 100.0: 8.0 to 100.0: 30.0. When the solidification inhibitor is a water-soluble polycarboxylic acid or a salt thereof, α-sulfo fatty acid alkyl ester salt: water-soluble polycarboxylic acid and / or a salt thereof (mass ratio) = 100.0: 8.0 to 100.0: 20.0 is preferable, and more preferably 100.0: 8.0 to 100.0: 15.0. If the amount of the water-soluble polycarboxylic acid or its salt is less than 100.0: 8.0, solidification during storage cannot be prevented. On the other hand, when the ratio is more than 100.0: 30.0, the concentration of the α-sulfo fatty acid alkyl ester salt becomes low, and a merit specific to high concentration cannot be obtained.

  When the solidification inhibitor is a tripolyphosphate, the salt is preferably a sodium salt or potassium salt which is a water-soluble salt. The ratio is preferably α-sulfo fatty acid alkyl ester salt: tripolyphosphate (mass ratio) = 100.0: 10.0 to 100.0: 25.0, more preferably 100.0: 10.0 to 100.0. : 20.0. If the amount of tripolyphosphate is less than 100.0: 8.0, solidification during storage cannot be prevented. On the other hand, when the ratio is more than 100.0: 30.0, the concentration of the α-sulfo fatty acid alkyl ester salt becomes low, and a merit specific to high concentration cannot be obtained.

  In the α-sulfo fatty acid alkyl ester salt-containing particles of the present invention, components that are usually blended in detergents can be blended as long as the effects of the present invention are not impaired. Examples of such components include the following components, which can be used singly or in appropriate combination of two or more.

  Anionic surfactants other than α-sulfo fatty acid alkyl ester salts, nonionic surfactants, cationic surfactants, amphoteric surfactants, zeolites, alkali builders, neutral inorganic builders, anti-staining agents, viscosity modifiers, softening Agents, reducing agents, bleaching agents, bleach activators, fluorescent brighteners, fragrances, enzymes, dyes, surface modifiers, foam inhibitors, antioxidants, oil absorbing carriers and the like.

The bulk density of the α-sulfo fatty acid alkyl ester salt-containing particles is preferably 0.3 to 1.2 g / cm ³ , more preferably 0.4 to 1.1 g / cm ³ , and the angle of repose is 35 to 75 °. Preferably, it is 35 to 65 °. In the present invention, the average particle diameter, bulk density, and angle of repose are measured by the following methods.

Measurement of average particle size The particles were classified using a 9-stage sieve and a tray with openings of 1,680 μm, 1,410 μm, 1,190 μm, 1,000 μm, 710 μm, 500 μm, 350 μm, 250 μm and 149 μm. . The classification operation is performed by stacking the sieve with the small opening sieve in the order of the opening with the large opening, putting the base sample of 100 g / times from the top of the top of the 1,680 μm sieve, putting the lid on, and putting it on the low tap sieve shaker. Attaching to (made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), shaking for 10 minutes, and then collecting each sieve and the sample remaining on the tray for each sieve. Was done.

  By repeating this operation, 1,410 to 1,680 μm (1,410 μm.on), 1,190 to 1,410 μm (1,190 μm.on), 1,000 to 1,190 μm (1,000 μm.on) 710 to 1,000 μm (710 μm.on) 500 to 710 μm (500 μm.on), 350 to 500 μm (350 μm.on), 250 to 350 μm (250 μm.on), 149 to 250 μm (149 μm.on), dish to 149 μm A classified sample of each particle size (149 μm.pass) was obtained, and the weight frequency [%] was calculated.

  Next, the opening of the first sieve with a calculated weight frequency of 50% or more is set to a μm, the opening of the sieve one step larger than a μm is set to b μm, and the integration of the weight frequency from the tray to the sieve of a μm is c %, And the weight frequency on the a μm sieve was defined as d%, and the average particle size (weight 50%) was determined by the following formula.

Measurement of Bulk Density The bulk density of each particle and its mixture was measured according to JIS K3362.

Measurement of angle of repose θ In an atmosphere of 25 ° C., a sample is dropped from a height of about 20 cm through a funnel to form a conical deposited layer, and the angle θ is calculated from the radius and height of the bottom circle based on the following formula: Evaluation was performed according to the following evaluation criteria.
θ: Tanθ = height / radius of bottom circle

The α-sulfo fatty acid alkyl ester salt-containing particles of the present invention can be obtained by a method including the following steps [1] to [4] and a step of blending an anti-caking agent.
[1]: a reaction in which a fatty acid alkyl ester and a sulfonation gas are brought into contact with each other for sulfonation, a reaction in which the product of the sulfonation step is esterified with a lower alcohol, and a reaction in which the product is neutralized after the esterification step. A step of obtaining an α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 15 to 40% by mass,
[2]: The α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 15 to 40% by mass obtained in the step [1] is dried to a dried product having a moisture content of 0.5 to 5% by mass using a thin film evaporator. The process of
[3]: A step of cooling and solidifying the dried product having a water content of 0.5 to 5% by mass obtained in step [2], and [4]: The solidified product obtained in step [3] A step of grinding into particles having a diameter of 200 to 700 μm.

  Step [1] includes a reaction in which a fatty acid alkyl ester and a sulfonation gas are brought into contact with each other, a reaction in which the product of the sulfonation step is esterified with a lower alcohol, and a reaction in which the product is neutralized after the esterification step. Is a step of obtaining an α-sulfo fatty acid alkyl ester salt-containing paste having a water content of 15 to 40% by mass, preferably 20 to 35% by mass. A reaction for bleaching the neutralized product may be included, and the bleaching may be performed before the reaction for neutralization.

FIG. 1 is a flowchart showing an example of a production process of an α-sulfo fatty acid alkyl ester salt-containing paste of the present invention, FIG. 2 is a schematic configuration diagram showing an example of a production apparatus, and FIG. 3 shows an example of a sulfonation reactor. FIG. In FIG. 2, fatty acid methyl ester as a raw material fatty acid alkyl ester, SO ₃ gas diluted with dehumidified air or nitrogen gas as a sulfonated gas, Na ₂ SO ₄ (sodium nitrate) as a coloring inhibitor, and methanol as a lower alcohol An example of conditions when an aqueous NaOH solution is used as the alkaline aqueous solution and H ₂ O ₂ (hydrogen peroxide) is used as the bleaching agent is shown. The% described in FIG. 2 is mass%, Na ₂ SO ₄ is 5 mass% with respect to the raw material, methanol is 4 mass% with respect to the sulfonic acid, and hydrogen peroxide is AI (active ingredient: α-sulfo). It means that 1.0% by mass is used in a pure content with respect to (fatty acid alkyl ester salt).
Hereinafter, with reference to FIG.2, 3, it demonstrates according to the manufacturing process of (alpha) -sulfo fatty-acid alkylester salt containing paste.

  First, a fatty acid alkyl ester and a coloring inhibitor as raw materials are charged into a batch-type stirring / mixing reaction tank 1 equipped with a stirring device. Examples of the raw material fatty acid alkyl ester include animal fats derived from beef tallow, fish oil, lanolin, etc .; vegetable fats derived from palm oil, palm oil, soybean oil, etc .; synthetic fatty acids derived from the oxo method of α-olefins Any of alkyl ester etc. may be sufficient and it does not specifically limit. Specifically, methyl laurate, ethyl laurate or propyl laurate; methyl myristate, ethyl myristate or propyl myristate; methyl palmitate, ethyl palmitate or propyl palmitate; methyl stearate, ethyl stearate or stearin Hardened beef tallow fatty acid methyl, hardened beef tallow fatty acid ethyl or hardened beef tallow fatty acid propyl; Hardened fish oil fatty acid methyl, ethyl or propyl; Palm oil fatty acid methyl, ethyl or propyl; Palm oil fatty acid methyl, ethyl or propyl; Palm kernel oil fatty acid methyl , Ethyl or propyl and the like. These can be used individually by 1 type or in mixture of 2 or more types.

A lower iodine value of the raw material fatty acid alkyl ester is preferable from the viewpoint of both color tone and odor. In the present invention, 1 or less is preferable, and 0.5 or less is more preferable. Those having an iodine value of 1 or less have a greater effect of improving the color tone than those having an iodine value of more than 1.
In the present invention, fatty acid alkyl esters represented by the following general formula (2) are particularly preferred.
R ³ CH ₂ COOR ⁴ (2)
(In the formula, R ³ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms.)

  In order to obtain a lighter α-sulfo fatty acid alkyl ester, it is preferable to perform a sulfonation reaction in the presence of a coloring inhibitor. As the coloring inhibitor, organic acid salts and inorganic sulfates which are monovalent metal salts are used, and inorganic sulfates are preferably used. Examples of the organic acid salt include sodium formate, potassium formate, and sodium acetate. The inorganic sulfate is not particularly limited as long as it is a powdered anhydrous salt that is a monovalent metal salt, and examples thereof include sodium sulfate, potassium sulfate, and lithium sulfate. Inorganic sulfates are highly effective in inhibiting coloration, are often inexpensive, and are further incorporated into detergents. Therefore, when producing α-sulfo fatty acid alkyl ester salts for use in detergents, inorganic sulfates can be converted into α-sulfo fatty acids. This is preferred because it does not need to be removed from the alkyl ester salt.

  The average particle size of the coloring inhibitor is preferably 250 μm or less, and particularly preferably 100 μm or less. The reason for the particle size is that, for example, the inorganic sulfate is hardly dissolved in the raw material liquid phase during the reaction to the extent that its surface is slightly dissolved, and is dispersed in the raw material liquid phase. Therefore, by using the inorganic sulfate having a small particle diameter as described above, the contact area with the raw material liquid phase is increased, the dispersibility is improved, and the effect can be further enhanced. 0-30 mass% is preferable with respect to raw material fatty acid alkyl ester, and, as for the addition amount of a coloring inhibitor, More preferably, it is 0.5-20 mass%, More preferably, it is 3-20 mass%. If the amount added exceeds 30% by mass, the effect may be saturated.

  Moreover, although the tank reactor (reaction tank 1) is used in the example of the figure, the reaction method is not particularly limited, and other methods such as a film reaction and a tube-type gas-liquid mixed phase reaction are applied. . Further, the sulfonation method is not particularly limited, and thin film type sulfonation method, batch type sulfonation method and the like are applied. In addition, when using a color inhibitor during the sulfonation reaction, it is preferable to contact the sulfonated gas in a state where it is dispersed as uniformly as possible in the raw material. Is preferred.

  In this example, while stirring with the stirrer 3, the internal temperature of the reaction vessel 1 is raised to a predetermined reaction temperature to obtain a raw material liquid phase 2 in which coloring inhibitor particles are dispersed in a liquid raw material. The reaction temperature is a temperature at which the fatty acid alkyl ester has fluidity. Generally, it is above the melting point of the fatty acid alkyl ester, preferably from the melting point to a temperature 70 ° C higher.

  Next, a sulfonated gas is introduced into the raw material liquid phase 2 from the sulfonated gas inlet 4. The sulfonated gas is introduced from the gas sparger 5 a of the gas introduction pipe 5 and dispersed in the raw material liquid phase 2 by the stirrer 3. At the same time, the coloring inhibitor particles are uniformly dispersed in the raw material liquid phase 2.

  The introduction of the sulfonated gas from the gas sparger 5a is preferably at a speed of 10 m / sec or more, more preferably from 50 to 200 m / sec. If the introduction speed is less than 10 m / sec, the bubbles may become large.

  The peripheral speed at the tip of the stirring blade 3b of the stirrer 3 is preferably 0.5 to 6.0 m / sec, and more preferably 2.0 to 5.0 m / sec. When the peripheral speed is less than 0.5 m / sec, the effect of dispersing bubbles is insufficient, and the reaction rate may decrease. Moreover, since dispersion | distribution of a coloring inhibitor becomes inadequate, the coloring suppression effect may fall. On the other hand, when the peripheral speed exceeds 6.0 m / sec, the coloring suppression effect is saturated, but the power consumption may increase.

  In this step, the introduction time of the sulfonated gas is usually about 10 to 180 minutes from the viewpoint of production efficiency. When emphasizing the suppression of coloring rather than the production efficiency, it is 180 minutes or more. In this way, by increasing the introduction time and gradually bringing the sulfonated gas into contact with the raw material liquid phase 2, coloring of the α-sulfo fatty acid alkyl ester can be further suppressed.

Examples of the sulfonated gas include SO ₃ gas and fuming sulfuric acid, but SO ₃ gas is preferred. More preferably, a sulfonated gas diluted with an inert gas such as dehumidified air or nitrogen so that the SO ₃ concentration becomes 1 to 40% by volume is used. When the SO ₃ concentration is less than 1% by volume, the volume of the sulfonated gas becomes large, and the capacity of the reactor increases due to gas hold-up, which may be inconvenient. On the other hand, if it exceeds 40% by volume, the reaction becomes excessive and by-products are likely to be generated, and the color tone of a sulfonated product such as α-sulfo fatty acid alkyl ester may deteriorate. In particular, when the sulfonated product is an α-sulfo fatty acid alkyl ester, it is preferable to dilute the sulfonated gas to 1 to 30% by volume in order to suppress color tone deterioration.

The SO ₃ reaction molar ratio is suitably 1.0 to 2.0 times mol, preferably 1.0 to 1.7 times mol, more preferably 1.05 to 1.5 times mol of the raw material. If the amount is less than 1.0 times mol, the sulfonation reaction does not proceed sufficiently. If the amount exceeds 2.0 times mol, the sulfonation reaction becomes more radical, which may cause by-products or coloring.

  After introducing the sulfonated gas into the raw material liquid phase 2 as described above, it is preferable to perform aging after introducing the sulfonated gas while keeping the inside of the reaction tank 1 at a predetermined temperature. The aging temperature is preferably 70 to 100 ° C. If it is lower than 70 ° C., the reaction does not proceed rapidly, and if it exceeds 100 ° C., coloring may be remarkable.

  The aging time is preferably 1 to 120 minutes. At this time, by rotating the stirring blade 3b while maintaining the above-mentioned preferable peripheral speed range, it is possible to react while sufficiently dispersing the coloring inhibitor even in aging. In the example of FIG. 2, the sulfonation process is set at 80 ° C. for 1 hour, and the aging process is set at 80 ° C. for 30 minutes.

Next, esterification with a lower alcohol is performed by supplying a lower alcohol. Esterification is a process for suppressing by-products and improving the purity of the α-sulfo fatty acid alkyl ester salt. If an α-sulfo fatty acid alkyl ester salt of sufficient purity can be obtained by sulfonation and aging if necessary (reaction) If the SO ₃ bimolecular adduct in the liquid is sufficiently small), this esterification step does not need to be carried out, but usually esterification is carried out.

The lower alcohol used for esterification has the same carbon number as that of the alcohol residue of the starting fatty acid alkyl ester and is preferably 1 to 6, but is not particularly limited. The lower alcohol is suitably used in an amount of 0.5 to 10 times mol, preferably 0.8 to 5.0 times mol for the SO ₃ bimolecular adduct in the reaction solution. When the amount is less than 0.5 times mol, esterification is insufficient, and when the amount exceeds 10 times mol, the effect is saturated, and a step for recovering excess lower alcohol may be required. The reaction temperature is suitably 50 to 100 ° C., preferably 50 to 90 ° C., and the reaction time is 5 to 120 minutes. In the example of FIG. 2, it is set to 80 ° C. and 30 minutes.

  After esterification, the sulfonated product extracted from the esterification reaction tank 10 is supplied to the neutralization line 17 by the action of the esterification acid supply pump 12 and neutralized with an aqueous alkaline solution. At this time, the AI concentration (effective concentration of the α-sulfo fatty acid alkyl ester salt) in the neutralized product is preferably 10 to 80% by mass, more preferably 60 to 80% by mass, and still more preferably 62 to 75% by mass. . In the condition example shown in FIG. 2, the AI concentration is 70% by mass. When the AI concentration is in the range of 10 to 60% by mass, the production efficiency is low in the low concentration range, but the viscosity of the neutralized product is low. In the high concentration range, the viscosity of the neutralized product tends to be high. In the range of 60 to 80% by mass, the viscosity is moderately low, which is preferable from the viewpoints of handling and production efficiency.

  As the aqueous alkali solution, for example, an aqueous solution of an alkali metal, an alkaline earth metal, ammonia, or ethanolamine is used. The concentration of the aqueous alkaline solution is preferably 50% by mass or less, and more preferably about 15 to 50% by mass. If it is less than 15% by mass, it may be difficult to adjust the AI concentration of the neutralized product to a range of 60 to 80% by mass. In the example of FIG. 2, the concentration of the alkaline aqueous solution is 34% by mass. In the present invention, the sulfonated product and the neutralized product (preliminarily neutralized product) may be mixed using the neutralized premixer 14. The total amount of the neutralized product (preliminarily neutralized product) of the sulfonated product and the aqueous alkali solution added thereto is suitably 5 to 25 times, preferably 10 to 20 times the mass. When the amount is less than 5 times the mass, the effect of suppressing by-products is small, and when it exceeds 25 times the mass, the production efficiency may be lowered. In this example, the mass is set to 20 times.

  As described above, in the neutralization step, the viscosity of the neutralized product is further lowered by the remaining lower alcohol. Thereby, the by-production of the α-sulfo fatty acid dialkali salt due to a part of the sulfonated product being in contact with a high-concentration alkaline aqueous solution at the initial stage of the reaction can be suppressed. Moreover, by-product formation can be suppressed by the presence of the lower alcohol. The neutralization temperature is preferably 30 to 140 ° C, preferably 50 to 120 ° C, more preferably 50 to 100 ° C, and the neutralization time is preferably 10 to 60 minutes. Further, the neutralization step is preferably carried out when the pH of the mixture of the sulfonated product, the neutralized product and the alkaline aqueous solution is in the acidic or weak alkaline range (pH 4 to 9). In the case of strong alkalinity, the ester bond may be easily cleaved. The neutralization step of the present invention can be carried out by reacting sulfonic acid with a solid metal carbonate or hydrogen carbonate in addition to using an alkaline aqueous solution. In particular, neutralization with solid metal carbonate (concentrated soda ash) is preferable because it is cheaper than other bases. In addition, when neutralization is performed with a solid metal carbonate, water in the reaction mixture is reduced, and a strong alkali is not obtained. Moreover, since the heat of neutralization at the time of neutralization is lower than the case of a metal hydroxide, it is advantageous. Examples of the metal carbonate or hydrogen carbonate include sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, and the like, including anhydrous salts, hydrated salts or mixtures thereof. 1 type can be used individually or in combination of 2 or more types as appropriate. The neutralization step is set at 70 ° C. for 20 minutes in the example of FIG.

  Moreover, it is preferable to perform the process for improving the color tone of (alpha) -sulfo fatty-acid alkylester salt to the color close | similar to white before or after a neutralization process. Examples of the treatment for improving the color tone include a bleaching treatment using a bleaching agent, and preferably performed after the neutralization step.

  As the bleaching agent, for example, an aqueous solution of hydrogen peroxide, hypochlorite or the like is used. These are used in a pure amount of AI (active ingredient: α-sulfo fatty acid alkyl ester salt), preferably 0.1 to 10% by mass, preferably 0.1 to 5% by mass. The hydrogen peroxide concentration or hypochlorite concentration of the aqueous solution is not particularly limited. In the example of FIG. 2, the pure content is set to 1.0 mass% with respect to AI. In the example of FIG. 2, the neutralized product is bleached. As a result, compared to the conventional esterification of the sulfonated product, the neutralized product is more stable and does not interact with the esterification reaction. Moreover, since the consumption of a bleaching agent is small, the usage-amount of a bleaching agent can be decreased conventionally. Moreover, it is preferable to mix the neutralized product (preliminary bleached product) mixed with the bleaching agent 5 to 30 times by mass with respect to the unbleached neutralized product. When the amount is less than 5 times the mass, the effect of suppressing by-products is small, and when it exceeds 30 times the mass, the production efficiency may be lowered.

  The bleaching temperature is preferably 50 to 140 ° C., preferably 60 to 120 ° C. when hydrogen peroxide is used, and 30 to 80 ° C. when hypochlorous acid is used. The total reaction time in the bleaching agent mixing line 21 and the bleaching line 23 is about 30 to 360 minutes. In the example of FIG. 2, it is set to 80 ° C. and 3 hours. The pH in the bleaching step is preferably 4-9.

  Although not shown in the apparatus diagram of FIG. 2, when heat treatment is performed between the neutralization step and the bleaching step with the bleach, the color tone of the powder and the like can be further improved. That is, the neutralized product is suitably heated to 80 ° C. or higher, preferably 80 to 170 ° C., suitably 0.5 hours to 7 days, preferably 1 hour to 5 days, more preferably 2 to 24 hours. Hold.

  In this invention, it is preferable to include the process of aging the paste obtained at the 1st process. In this case, the α-sulfo fatty acid alkyl ester salt-containing paste is transferred to the bleach tank 25, and a paste having a good color tone can be obtained through an aging step. Aging means holding at a predetermined temperature for a predetermined time. The aging temperature is suitably 60 to 90 ° C., preferably 70 to 80 ° C., and the aging time is suitably 1 to 48 hours, preferably 2 to 24 hours, more preferably 2 to 12 hours. If the aging temperature is less than 60 ° C. or the aging time is less than 1 hour, the color tone of the paste may not be improved. If the aging temperature is 90 ° C. and the aging time exceeds 48 hours, the α-sulfo fatty acid alkyl ester salt May hydrolyze.

  Step [2] is a step of drying the α-sulfo fatty acid alkyl ester salt-containing paste having a water content of 15 to 40% by mass into a dried product having a water content of 0.5 to 5% by mass using a thin film evaporator. The moisture is preferably 0.5 to 4% by mass. The apparatus is preferably a thin film evaporator that forcibly makes the paste into a thin film to promote drying. In addition, more efficient drying can be performed by reducing the pressure in the apparatus, and the jacket temperature of the apparatus can be kept low, so that thermal degradation of the surfactant can be suppressed. As such a thin film evaporator, an evaporator (manufactured by Sakai Seisakusho Co., Ltd.), Exeva (manufactured by Shinko Environmental Solution Co., Ltd.), a control dryer (manufactured by Hitachi Ltd.) and the like are preferably used.

  The jacket temperature of the thin film evaporator is preferably 100 to 150 ° C. If the temperature exceeds 150 ° C., the α-sulfo fatty acid alkyl ester salt may be thermally deteriorated. If the temperature is lower than 100 ° C., the productivity is not preferable because the flow rate must be remarkably reduced and the residence time in the apparatus must be increased in order to reduce the drying capacity to 5% by mass or less. The pressure in the thin film evaporator is preferably reduced from the viewpoint of drying efficiency. In drying the α-sulfo fatty acid alkyl ester salt paste, the dry moisture can be 5% by mass or less at any pressure, but is preferably 0.0399 MPa or less, more preferably 0.0266 MPa or less, and still more preferably 0.0133 MPa or less. It is.

  The clearance between the tip of the wing and the wall surface of the thin film evaporator is preferably 1.5 to 3 mm. It may be difficult to reduce the clearance to less than 1.5 mm in an actual production apparatus. If the clearance is larger than 3 mm, the thinning becomes insufficient and the drying efficiency may be significantly deteriorated.

  Step [3] is a step of cooling and solidifying the dried product having a water content of 0.5 to 5% by mass obtained in step [2]. Cooling may be performed until the dried product is solidified, and specifically, it may be cooled to the melting point or lower of the dried product. The cooling rate is not particularly limited, but it is preferable to cool to the melting point or less in a short time for effective production. The apparatus and method for cooling the dried product having a water content of 0.5 to 5% by mass are not particularly limited. As an example, it can be carried out by using an air cooling method of a bell max (manufactured by Okawara Manufacturing Co., Ltd.), a steel belt type cooling device (manufactured by Sandvik) or a belt type vacuum cooler. In addition, since it can be directly flaked after the cooling step, a drum type cooler (drum flaker; manufactured by Kashiwagi Machinery Co., Ltd., double drum dryer; manufactured by Kansoh Co., Ltd.) is more efficient and preferable.

  Step [4] is a step of pulverizing the solidified product obtained in step [3] into particles having an average particle size of 200 to 700 μm. As the pulverizer, a feather mill (manufactured by Hosokawa Micron Corporation), a speed mill (manufactured by Okada Seiko Co., Ltd.) or the like is preferably used.

  At this time, the use of a pulverization aid increases the capacity and suppresses adhesion to the apparatus. As the pulverization aid, inorganic particles having an average particle size of 20 μm or less are preferable. In addition to zeolite, white carbon, etc., inorganic particles such as sodium carbonate and sodium sulfate are pulverized to have an average particle size of 20 μm or less. Can also be used. The amount is preferably 1 to 20% by mass and more preferably 2 to 15% by mass with respect to 100% by mass of the solidified product.

  Further, by introducing cold air during pulverization, the same effect as described above can be expected. The temperature of the cold air at this time is preferably 20 ° C. or less. It is also preferable to use air having a low relative humidity as the air introduced during pulverization. By preventing moisture absorption of the α-sulfo fatty acid alkyl ester salt-containing particles, adhesion to the pulverizing apparatus can be suppressed. The relative humidity is preferably 40% or less, and more preferably 30% or less.

  The average particle size of the pulverized α-sulfo fatty acid alkyl ester salt-containing particles is preferably 200 to 700 μm, more preferably 300 to 600 μm. If it is less than 200 μm, the fluidity may be remarkably deteriorated. If it exceeds 700 μm, the solubility may be a problem when used as a detergent.

  The anti-caking agent can be blended in any of the steps [1] to [4]. However, in order to uniformly mix the anti-caking agent inside the α-sulfo fatty acid alkyl ester salt-containing particles, the α-sulfo fatty acid alkyl ester salt-containing paste obtained in step [1] or obtained in step [2]. It is preferable to mix an α-sulfo fatty acid alkyl ester salt-containing dried product with an anti-caking agent and uniformly mix it. In particular, when mixing with the dried product in step [2], it is preferable to mix with the dried product in a high-temperature molten state immediately after drying.

  As a method of blending the anti-caking agent into the α-sulfo fatty acid alkyl ester salt-containing paste obtained in the step [1], an anti-caking agent is added to the α-sulfo fatty acid alkyl ester salt-containing paste stored in the tank. You may stir and you may add and mix | blend an anti-caking agent from the middle of the piping which transfers (alpha) -sulfo fatty-acid alkylester salt containing paste, and may mix with a static mixer etc. after that.

  As a method of blending the anti-caking agent into the dried product containing the α-sulfo fatty acid alkyl ester salt in the high-temperature molten state immediately after drying in the step [2], the dried product and the anti-caking agent are introduced into a kneading apparatus and kneaded. A method is mentioned. Preferable examples of the kneader include a KRC kneader (manufactured by Kurimoto Steel Works) and a universal mixer (manufactured by Dalton Co.). In this case, it is preferable to use an anti-caking agent having a low water content. When the anti-caking agent containing a large amount of water is used, the water content of the α-sulfo fatty acid alkyl ester salt-containing particles increases, which may cause problems such as a decrease in pure content and deterioration in powder physical properties. In particular, when a water-soluble polycarboxylic acid is used as the anti-caking agent, it is preferable to mix it before drying because many water-containing materials are used from the viewpoint of handling. Moreover, it is preferable to use an anhydride for tripolyphosphate for the same reason.

  The α-sulfo fatty acid alkyl ester salt-containing particles of the present invention can be made into a detergent containing these by mixing with detergent components.

  The detergent component is not particularly limited as long as it is generally used in detergents, such as a cleaning component, a bleaching component, a manufacturability and a component that improves powder physical properties. Detergent components that can be used in the granular detergent of the present invention include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, chelating agents (zeolites, organic builders, etc.), neutral inorganic builders, Alkali inorganic builder, anti-staining agent, viscosity modifier, softening agent, reducing agent, bleach, bleach activator, fluorescent brightener, fragrance, enzyme, dye, surface modifier, foam suppressor, antioxidant Agents, water and the like. These can be used individually by 1 type or in combination of 2 or more types.

  The form of the detergent component contained in the detergent is not particularly limited, and raw materials such as the detergent component may be used as they are, or may be used as detergent particles. The detergent particle is not particularly limited as long as it contains a component that contributes to cleaning in the detergent component, and those containing any of surfactants, alkali builders, and chelating agents are particularly preferable. The blending mass ratio of the α-sulfo fatty acid alkyl ester salt-containing particles and the detergent component in the detergent is preferably 96: 4 to 4:96, preferably 60:40 to 5:95, and particularly preferably 30:70 to 10:90. .

  Examples of the mixing method of the α-sulfo fatty acid alkyl ester salt-containing particles and the detergent component include a method selected from powder mixing, kneading and crushing, and stirring granulation. In the case of powder mixing, α-sulfo fatty acid alkyl ester salt-containing particles are introduced into a solid-mixable device, and detergent components, particularly granular detergent components, are added, and the mixing temperature is 5 to 60 ° C., preferably 10 to 50 ° C. Mix for 5 seconds or longer, preferably 5 seconds or longer, particularly preferably 30 seconds or longer. The upper limit of the mixing time is not particularly limited. The apparatus used for the powder mixing is not particularly limited, but a horizontal cylindrical mixer, a V-type mixer, and a stirring granulator are preferable.

  In the case of kneading and crushing, α-sulfo fatty acid alkyl ester salt-containing particles and detergent components are mixed into a continuous kneader (KRC kneader; manufactured by Kurimoto Iron Works) or a batch kneader (vertical kneader; manufactured by Dalton). Into a lump, etc., and then crushed with a grinder such as a feather mill (manufactured by Hosokawa Micron Corporation) or a speed mill (manufactured by Okada Seiko Co., Ltd.) to obtain detergent particles. In the pulverization, adhesion of the pulverizer can be prevented by adding fine inorganic particles such as zeolite, sodium carbonate, and white carbon.

  In the case of stirring granulation, α-sulfo fatty acid alkyl ester salt-containing particles and a detergent component are combined with a Laedige mixer (manufactured by Matsubo Co., Ltd.), a Shugy mixer (manufactured by Paulek Co., Ltd.), a high speed mixer (Fukae). Industrial detergents), Pro-shear mixers (Daihei Kiko Co., Ltd.) and other agitation granulators can be used to obtain detergent particles by pulverization and sieving as necessary. it can.

  The present invention also provides a granular detergent in which α-sulfo fatty acid alkyl ester salt-containing particles produced by the above production method are mixed with a detergent component to prepare a slurry having a water content of 20 to 50% by mass, and this slurry is spray-dried. It is good also as a manufacturing method. In this case, the blending mass ratio of the α-sulfo fatty acid alkyl ester salt-containing particles and the detergent component in the granular detergent is preferably 96: 4 to 4:96, more preferably 60:40 to 5:95, and still more preferably 30. : 70 to 10:90. The obtained spray-dried particles containing the α-sulfo fatty acid alkyl ester salt may be granulated with other detergent components by a kneading / crushing method, a stirring granulation method or the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition represents mass%, and the ratio represents mass ratio.

[Examples 1 to 15 and Comparative Examples 1 to 4]
The α-sulfo fatty acid alkyl ester salt-containing particles were prepared by the method described below, and the solidification property during storage was evaluated by the following evaluation method. Tables 2 to 5 show the compositions and evaluation results of the α-sulfo fatty acid alkyl ester salt-containing particles.
<Evaluation of solidification during storage>
The obtained α-sulfo fatty acid alkyl ester salt-containing particles were charged with 118 cm ^{3 in} a cell having a diameter of 50 mm and a length of 100 mm immediately after preparation so that no aging time was provided. A load of 2.5 kg was applied to the upper part. In this state, it was stored in a constant temperature bath at 40 ° C. for 1 week to form a cake. The formed cake was put into a sieve having an opening of 4.75 mm and dropped 20 times from a height of 10 mm. Residual rate (%) on the sieve was calculated by the following formula, where A was the mass of the cake that was broken by the impact and passed through the sieve with an opening of 4.78 mm, and B was the mass of the cake before dropping. From the obtained residual rate (%) on the sieve, the solidification property during storage was evaluated based on the following evaluation criteria.
Residual rate on sieve (%) = (B−A) / B × 100

<Evaluation criteria>
◎: Residual rate on sieve is less than 15% ○: 15-30%
X: 30 to 60%
XX: 60% or more In the present invention, ◯ or more was regarded as a good value for the solidification property during storage.

Step [1] Preparation of α-sulfo fatty acid alkyl ester salt-containing paste (sulfonation step)
Sulfonation was performed in the reactor shown in FIG.
The apparatus was made of SUS316L with a capacity of 200 L, jacket cooling, and a stirrer 3 and the reaction temperature was controlled by a circulation line 7. First, 80 kg of raw fatty acid methyl ester was charged into the reaction vessel 1, and 5% of finely powdered sodium sulfate was added to the fatty acid methyl ester as a coloring inhibitor while stirring well. While continuing stirring, the reaction temperature was 80 ° C., the circulation amount in the circulation line 7 was 80 L / min, and SO ₃ gas (sulfonated gas) diluted to 8% by volume with nitrogen gas was 102 m ³ (1 relative to the raw material methyl ester). .2 moles) was blown at a constant speed with a ring sparger over 1 hour. Further, aging was performed for 30 minutes while maintaining at 80 ° C.

(Esterification process)
As the esterification reaction tank 10, a jacketed three-stage stirring tank type was used. In addition, methanol was supplied as a lower alcohol at 4.5 kg / hr, and esterification was performed while controlling the sulfonated product to be 4%. The esterification reaction rate was 80 ° C., and the aging time was 30 minutes.

(Neutralization process)
Subsequently, the sulfonated product extracted from the esterification reaction tank 10 was continuously supplied to the neutralization line 17 at 117 kg / hr. The neutralization method employs the neutralization method described in JP-A No. 2001-64248. Between the neutralization premixer 14 and the neutralization mixer 15, a 34% by mass sodium hydroxide aqueous solution is 46.6 kg / hr. The feed was quantitatively fed at a rate of 5 to ensure continuous neutralization. The sulfonated product was previously mixed with the pre-neutralized product with the neutralizing premixer 14 in advance, and then mixed with an aqueous sodium hydroxide solution to obtain a neutralized product. The amount of the pre-neutralized product circulating through the loop was 20 times the total amount of the sulfonated product and the alkaline aqueous solution to be added. The neutralization temperature was controlled at 70 ° C. by adjusting the water temperature in the heat exchanger 16 of the loop circuit. The residence time of the neutralized product was 20 minutes. Although not shown in FIG. 2, a sodium hydroxide aqueous solution supply rate (amount of supply) is provided by a Ford back controller that adjusts the supply rate of the sodium hydroxide aqueous solution by installing a pH control system in the circulation loop. Controlled. The pressure inside the circulation loop was 4 kg / cm ² . The pH of the obtained neutralized product was 6.5.

(Bleaching process)
Subsequently, this neutralized product was fed to the bleaching agent mixing line 21 at a feed rate of 164 kg / hr. The bleaching agent mixing line 21 was a circulation loop system including a circulation line 22 having a heat exchanger 20. Then, 35% hydrogen peroxide water is supplied at 6.6 kg / hr (1.0% pure with respect to AI (active ingredient: α-sulfo fatty acid alkyl ester salt)), and bleaching and mixing from the circulation line 22 is performed. Thoroughly mix with used neutralized product (pre-bleached product). The amount of loop circulation was 15 times the amount of neutralized product newly added to the preliminary bleached product, and the pressure in the circulation loop pipe was 4 kg / cm ² . The temperature of the circulation loop was adjusted to 80 ° C. by the heat exchanger 20, and the residence time of the circulation loop was 10 minutes. Subsequently, it was introduced into a distribution pipe type bleaching line 23 to proceed with bleaching. The bleaching line 23 is a jacketed double tube, and the temperature and pressure can be adjusted. The flow of the bleaching agent mixture was a piston flow, the pressure was adjusted to 4 kg / cm ² , the temperature was adjusted to 80 ° C., and the residence time was 180 minutes.

(Aging process)
Next, the α-sulfo fatty acid alkyl ester salt-containing paste thus obtained is transferred to the bleach tank 25 and aged at 80 ° C. for about 10 hours to obtain α-sulfo fatty acid alkyl ester salt-containing particles. A salt paste was obtained. Table 1 shows the composition of the α-sulfo fatty acid alkyl ester salt paste. In the table, α-sulfo fatty acid alkyl ester salt is abbreviated as MES.

＊ｄｉ−Ｎａ：α−スルホ脂肪酸ジナトリウム

* Di-Na: α-sulfo fatty acid disodium

Step [2]: Drying step of α-sulfo fatty acid alkyl ester salt-containing paste The α-sulfo fatty acid alkyl ester salt-containing paste obtained in the above step [1] is rotated at 1,060 rpm and blade tip speed is about 11 m / sec. 50 to 90 kg in vacuum thin film evaporator EXEVA rotating at a heat transfer surface (0.5 m ² , inner diameter: 205 mm, clearance between heat transfer surface and blade tip: 2 to 4 mm, manufactured by Shinko Pantech Co., Ltd.) / Hr, and drying and concentration were performed at an inner wall heating temperature of 110 to 130 ° C. and a degree of vacuum of 0.0133 MPa. The temperature of the dried product after drying and concentration was 80 to 110 ° C.

Step [3]: Cooling / solidification step The dried and concentrated dried product obtained in Step [2] is cooled to 20 to 30 ° C. using a drum flaker (manufactured by Kashiwagi Machinery Co., Ltd.). α-Sulfo fatty acid alkyl ester salt-containing flakes were obtained.

Step [4]: Grinding step Feather mill (DKA-3, manufactured by Hosokawa Micron Corporation) in which the α-sulfo fatty acid alkyl ester salt-containing flakes obtained in Step [4] were arranged in two stages in series. Type, 1st stage screen diameter 8mmφ, 2nd stage screen diameter: 3.5mmφ, blade rotation speed 1st stage: 4,700rpm, 2nd stage: 1,410-3,760rpm), relative humidity at 15 ° C It was introduced together with cold air of 40% or less (wind speed: 16 m / s) and crushed into particles at a treatment speed of 100 kg / hr. At that time, those with the mark of auxiliary zeolite in Tables 2 to 5 were pulverized by adding a pulverizing auxiliary. All of the obtained α-sulfo fatty acid alkyl ester salt-containing particles had an average particle diameter of 400 to 600 μm, a bulk density of 0.6 to 0.75 g / cm ³ , and an angle of repose of 45 to 60 °.

Formulation of anti-caking agent In Examples 1 to 8, an anti-caking agent was added in the middle of the transfer pipe when transferring the α-sulfo fatty acid alkyl ester salt-containing paste before the step [2] drying step. As the blending device, when water-soluble polycarboxylic acid was blended as an anti-caking agent, a MONO pump (manufactured by Hyojin Equipment Co., Ltd.) was used. Moreover, when mix | blending sodium tripolyphosphate, it added from piping using the in-line powder dissolution apparatus (made by Noritake Co., Ltd.). The anti-caking agent was uniformly dispersed by passing through a static mixer after the addition. A mixture of this α-sulfo fatty acid alkyl ester salt-containing paste and a solidification inhibitor was used in the above step [2]: drying step.

  In Examples 9 to 15, a predetermined amount of the dried product after the step [2] drying step and sodium tripolyphosphate was added to a predetermined KRC continuous kneader (S-4, manufactured by Kurimoto Steel Works) at a capacity of 100 kg / hr). And kneaded. The resulting mixture of dried product and anti-caking agent was used in the above step [3]: cooling / solidification step.

[Examples 16 to 21]
The α-sulfo fatty acid alkyl ester salt-containing particles of Examples 5 and 14 were powder-mixed with other detergent component particles to obtain granular detergents having the compositions shown in Table 6. For mixing, α-sulfo fatty acid alkyl ester salt-containing particles and other detergent components were put into a horizontal cylindrical mixing drum having a diameter of 0.6 m and a length of 1.2 m, and mixed at 30 rpm for 5 minutes. In addition, the preparation method and composition of detergent component particles are shown below.

The composition and preparation method of the detergent component particles 1 to 5 are shown below.
[Detergent component particles 1]
Product name NABION15, manufactured by Rhodia. The composition is shown in Table 7 (see Rhodia catalog Nab / HC 07.2000).

[Detergent component particles 2]
Among the compositions shown in Table 8, raw materials excluding A-type zeolite and fragrance were blended at a predetermined ratio to prepare a slurry having a water content of 40% and a temperature of 70 ° C. Note that LAS-Na was charged with LAS-H and NaOH to generate LAS-Na in the slurry. The slurry was transferred to the top of the drying tower (diameter 2 m, effective length 5 m) by a plunger pump, and then sprayed into the tower from a pressure nozzle at a pressure of 30 kg / cm ² and dried. The temperature in the drying tower was 260 ° C. at the hot air inlet, and the exhaust air temperature during operation was 100 ° C. The powder obtained from the bottom of the tower and A-type zeolite were mixed and a fragrance was sprayed to obtain mixed particles 2. The temperature of the obtained mixed particles 2 was 40 ° C., and the bulk density was 0.40 g / cm ³ . Table 8 shows the composition of the detergent component particles 2.

[Detergent component particles 3]
Among the compositions shown in Table 9 (dry particle composition), raw materials excluding coating type A zeolite were blended at a predetermined ratio to prepare a slurry having a water content of 40% and a temperature of 70 ° C. LAS-K was charged with LAS-H and KOH to produce LAS-K in the slurry.
The slurry was transferred to the top of the drying tower (diameter 2 m, effective length 5 m) by a plunger pump, and then sprayed into the tower from a pressure nozzle at a pressure of 30 kg / cm ² and dried. The temperature in the drying tower was 260 ° C. at the hot air inlet, and the exhaust air temperature during operation was 100 ° C. The powder obtained from the bottom of the tower was coated with A-type zeolite as a coating agent to obtain dry powder having the composition shown in Table 9.

The obtained dried particles, nonionic surfactant, and water were mixed at a ratio of 88.44: 3.33: 0.89 (mass ratio of appearance) by a kneader (Kazuwa machine, manufactured by Kurimoto Seiko Co., Ltd.). , KRC kneader, model S-4) to obtain a kneaded mixture having a temperature of 60 ° C. The capacity was 150 kg / hr as a kneaded mixture. The kneaded mixture was put into a pelleter (Fuji Paudal Co., Ltd., die hole diameter 10 mmφ) to obtain a pellet-shaped solid having a diameter of about 10 mm and an average length of 10 to 30 mm. Fitzmill (manufactured by Hosokawa Micron Corporation, DKA) in which the obtained pellet-like solid and A-type zeolite were arranged in three stages in series with cold air of 15 ° C. at a ratio of 92.67: 4.00 (mass ratio) -3 type, 1st stage: screen diameter 12 mmφ, 2nd stage: screen diameter 6 mmφ, 3rd stage: screen diameter 2.3 mmφ, total number of rotations 4,700 rpm), and pulverized at a processing speed of 190 kg / hr. The obtained pulverized particles had an average particle size of 550 μm, an angle of repose of 50 °, and a bulk density of 0.75 g / cm ³ .

The obtained pulverized particles are placed on a horizontal cylindrical rolling drum (with a baffle plate of diameter 0.70 m, length 1.40 m, inclination angle 3 °, thickness 1 mm × height 50 mm × length 350 mm), type A It was continuously added together with zeolite, and a nonionic surfactant and a fragrance were sprayed inside to obtain detergent component particles 3. The mass ratio of the ground product, A-type zeolite, sprayed nonionic surfactant: fragrance added to the horizontal cylindrical rolling drum was 96.67: 2.90: 0.33: 0.10. The obtained mixed particles had an average particle diameter of 550 μm, an angle of repose of 40 °, and a bulk density of 0.82 g / cm ³ . Table 10 shows the composition of the finally obtained detergent component particles 3.

[Detergent component particles 4]
In Table 11 below, the main blend of A-type zeolite, white carbon, sodium carbonate (1), equipped with a bladed shovel, and a shovel-wall clearance of 5 mm is a Ladige mixer (manufactured by Matsubo Co., Ltd.) M-20 type) was charged in an amount of 50% capacity (powder temperature: about 30 ° C.). Thereafter, the main shaft and the chopper were rotated at 200 rpm and 6,000 rpm, respectively, for 30 seconds to mix the powder.
A nonionic surfactant and 12 hydroxystearic acid are melted and mixed at 85 ° C. in advance, and after mixing of the powder, the melt and mixture of the nonionic surfactant and 12 hydroxystearic acid are maintained with the spindle and chopper rotated. Added in about 60 seconds.
After completion of the addition of the melt and the mixture, the divided A-type zeolite was added and stirred for 90 seconds while the rotation of the spindle and chopper was continued. Thereafter, the zeolite A of the coating was added and stirred for 30 seconds, and then taken out from the Leedige mixer.
The obtained particles were passed through a sieve having an opening of 2,000 μm to obtain detergent component particles 4.

The raw materials used are shown below.
(1) Fatty acid methyl ester The fatty acid methyl ester used as a raw material reduces the iodine value by hydrogenating a fatty acid methyl ester obtained by esterification of palm oil (trade name: Edenor ME PA MY (manufactured by Cognis)). The purified product was used. The hydrogenation treatment was carried out under the conditions of 170 ° C. and 8 hours by adding 0.15% of the trade name SO-850 (manufactured by Sakai Chemical Co., Ltd.) as a hydrogenation catalyst to the fatty acid methyl ester. . Table 12 shows the carbon distribution and properties of the raw fatty acid methyl ester.

(2) Sulfonation gas: A gas produced by catalytic oxidation of SO ₂ using air (dew point −55 ° C.) was used.
(3) LAS-H: Raipon LH-200 (manufactured by Lion Corporation), linear alkylbenzene sulfonic acid having an alkyl group having 10 to 14 carbon atoms (AI = 96%, the balance being unreacted alkylbenzene, sodium sulfate, water Etc.), used as LAS-Na, LAS-K.
(4) AOS-K: C ₁₄ : C ₁₆ : C ₁₈ = 15: 50: 35 α-olefin potassium sulfonate and hydroxyalkyl sulfonate potassium mixture (70% pure, α-olefin sulfonate potassium: hydroxy (The ratio of potassium alkylsulfonate is 7: 3, the remainder is unreacted α-olefin, sodium sulfate, sultone, sodium hydroxide, water, etc.)
(5) Soap: C ₁₆ : C ₁₈ : TMD (ester mixture of C _{10 to 20} ) = 1: 3: 1 fatty acid sodium (AI = 67%)
(6) Nonionic surfactant: alcohol ethoxylate obtained by adding an average of 15 moles of ethylene oxide to an alcohol having 12 to 13 carbon atoms (purity = 90%, the balance being unreacted alcohol, PEG (polyethylene glycol), water, etc.)
(7) Methanol: Pure Chemical Co., Ltd., reagent grade 1 methanol (8) Sodium hydroxide: Asahi Glass Co., Ltd., Caustic soda food flakes (9) Potassium hydroxide: Asahi Glass Co., Ltd., caustic potash food additive Flakes (10) Hydrogen peroxide: manufactured by Junsei Chemical Co., Ltd., first grade reagent, aqueous solution containing 35% hydrogen peroxide (11) Sodium carbonate (1): Light ash (manufactured by Asahi Glass Co., Ltd.), pure content 99%, bulk Density 0.55g / cm ³
(12) Sodium carbonate (2): granular ash (manufactured by Asahi Glass Co., Ltd.), pure content 99%, bulk density 1.07 g / cm ³
(13) Potassium carbonate: manufactured by Asahi Glass Co., Ltd., food grade, pulverized product, pure content 99%, bulk density 0.77 g / cm ³
(14) Sodium tripolyphosphate: manufactured by Taihei Chemical Industry Co., Ltd., food grade, pure content 85%, bulk density 0.97 g / cm ³
(15) Zeolite: manufactured by Mizusawa Chemical Co., Ltd., trade name: Shilton B, bulk density 0.30 g / cm ³
(16) Sodium sulfate: fine powder mirabilite (manufactured by Shikoku Kasei Co., Ltd.), industrial grade, average particle size of 40-50 μm
(17) Potassium sulfate: manufactured by Ueno Pharmaceutical Co., Ltd., diluted with potassium sulfate 20 to 30 μm (18) Calcium carbonate: Pure Chemical Co., reagent grade calcium carbonate (19) Sodium sulfite: Jinzu Chemical ( Co., Ltd., anhydrous sulfite (20) maleic acid / acrylic acid copolymer: manufactured by Nippon Shokubai Co., Ltd., trade name Aqualic TL-400 (pure 40% aqueous solution)
(21) Sodium polyacrylate-1: manufactured by Nippon Shokubai Co., Ltd., trade name Aqualic DL-40 (40% pure aqueous solution)
(22) Sodium polyacrylate-2: manufactured by Nippon Shokubai Co., Ltd., trade name Aqualic DL-100 (solid)
(23) White carbon: Tokuyama N, manufactured by Tokuyama Corporation
(24) 12-hydroxystearic acid: manufactured by KE Trading Co., Ltd.

It is the flowchart which showed an example of the manufacturing process of the alpha-sulfo fatty-acid alkylester salt containing paste of this invention. It is the schematic block diagram which showed an example of the apparatus used for the manufacturing method of this invention. It is the schematic block diagram which showed an example of the sulfonation reactor.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Raw material liquid phase 3 Stirrer 3a Rotating shaft 3b Stirring blade 4 Sulfonation gas introduction port 5 Gas introduction pipe 5a Gas sparger 6 Exhaust gas port 7 Sulfonation external circulation line 8 Feed pump 9 Sulfonation external circulation heat exchanger DESCRIPTION OF SYMBOLS 10 Esterification reaction tank 11 Esterification buffer tank 12 Esterification acid supply pump 13 Neutralization recycle pump 14 Neutralization premixer 15 Neutralization mixer 16 Neutralization heat exchanger 17 Neutralization line 18 Bleaching mixer 19 Bleaching recycling pump 20 Bleaching heat Exchanger 21 Bleach Mixing Line 22 Bleaching Circulation Line 23 Bleaching Line 24 Vacuum Defoamer 25 Bleaching Tank

Claims (7)

  α-sulfo fatty acid alkyl ester salt-containing particles containing 50-95% by mass of an α-sulfo fatty acid alkyl ester salt and an anti-caking agent, wherein the mass ratio of the α-sulfo fatty acid alkyl ester salt to the anti-caking agent is Α-sulfo fatty acid alkyl ester salt-containing particles, characterized in that the ratio is 100.0: 8.0 to 100.0: 30.0.   The α-sulfo fatty acid alkyl ester salt-containing particles according to claim 1, wherein the anti-caking agent is uniformly mixed in the α-sulfo fatty acid alkyl ester salt-containing particles.   The α-sulfo fatty acid alkyl ester salt-containing particles according to claim 1 or 2, wherein the anti-caking agent is a water-soluble polycarboxylic acid and / or a salt thereof.   The α-sulfo fatty acid alkyl ester salt-containing particles according to claim 1 or 2, wherein the anti-caking agent is a tripolyphosphate. The following steps [1] to [4]
[1]: a reaction of sulfonating a fatty acid alkyl ester with a sulfonation gas, a reaction of esterifying the product of the sulfonation step with a lower alcohol, and a reaction of neutralizing after the esterification step A step of obtaining an α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 15 to 40% by mass,
[2]: The α-sulfo fatty acid alkyl ester salt-containing paste having a moisture content of 15 to 40% by mass obtained in the step [1] is dried to a dried product having a moisture content of 0.5 to 5% by mass using a thin film evaporator. The process of
[3]: A step of cooling and solidifying the dried product having a water content of 0.5 to 5% by mass obtained in step [2], and [4]: The solidified product obtained in step [3] Crushing into particles having a diameter of 200 to 700 μm,
And a method for producing α-sulfo fatty acid alkyl ester salt-containing particles in which a solidification inhibitor is blended in any one of the steps [1] to [4].   6. The anti-caking agent is blended and uniformly mixed with the α-sulfo fatty acid alkyl ester salt-containing paste obtained in step [1] or the dried product obtained in step [2]. A process for producing α-sulfo fatty acid alkyl ester salt-containing particles. The detergent containing the alpha-sulfo fatty-acid alkylester salt containing particle | grains of any one of Claims 1-4, and a detergent component.

Images