JP2002526602A - Continuous method for producing detergent compositions - Google Patents

Abstract

A continuous process for preparing granular detergent composition including a first step of dry neutralizing an acid precursor of an anionic surfactant with a particulate water-soluble alkaline material in a high speed mixer for a mean residence time of about 0.2 to about 50 seconds, thereby partly or totally neutralizing the acid precursor and producing a dry neutralized material containing the anionic surfactant, in the form of a free-flowing powder; and a second step of agglomerating the free-flowing powder into a detergent agglomerate using an agglomeration binder. The agglomeration binder is preferably a viscous sufactant paste binder. The resulting agglomerates are dry, free-flowing, and have a substantially more narrow particle size distribution, compared to the free-flowing powder, with reduced fine particles and over-sized particles that generally are recycled.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] Technical Field The present invention generally relates a continuous process without using a tower for the production of granular detergent compositions. More particularly, the present invention is directed to a continuous method of agglomerating dry neutralized free flowing detergent powder with a liquid or viscous paste binder to form an agglomerate. I have. By this method, detergent agglomerates with small amounts of fines and extra-large particles that need to be recycled are obtained.

[0002] Recently, in the detergent industry, is a "compact", Therefore, has been considerably increased interest in small laundry detergent of the volume to be used at a time. In order to facilitate the production of these so-called low usage detergents, high bulk density detergents, e.g.
Many attempts have been made to produce detergents of / l or more. Low usage detergents are currently in great demand because they conserve resources and can be sold in smaller packaging containers that are more convenient for consumers. However, it remains unclear to what extent modern detergent products must actually be "compact". In fact, many consumers, particularly those in developing countries, still prefer higher levels of use in each washing operation.

In general, there are two main types of methods by which detergent granules or powders can be made. The first type of method involves spray drying an aqueous detergent slurry in a spray drying tower to produce highly porous detergent granules (eg, using a tower for low density detergent compositions). . In a second type of process, the various detergent components are dry mixed and then agglomerated with a binder such as a nonionic or anionic surfactant to create a high density detergent composition (eg, a high density detergent composition). Aggregation method for products). In the above two methods, the key factors that determine the density of the resulting detergent granules are the shape, porosity, and particle size distribution of the granules, the density of the various starting materials, the shapes of the various starting materials, and The chemical composition of the starting material.

Many attempts have been made in the art to obtain a method for increasing the density of detergent granules or powders. Particular attention has been given to the densification of spray-dried granules by processing after the column. The following documents relate to densification of spray-dried granules. U.S. Pat. No. 5,133,924 to Appel et al. (Leaver); U.S. Pat. No. 5,164,108 to Appel et al. (Leaver); U.S. Pat.
160,657 (Lever), British Patent No. 1,517,713 to Johnson et al. (Unilever), and European Patent Application 451,894 to Curtis. As an example, one attempt is to use a batch method in which a spray-dried or granulated detergent powder containing sodium tripolyphosphate and sodium sulfate is densified and spheroidized in a marmalizer ^R. Including. The apparatus comprises a rough, rotatable, substantially horizontal table inside and at the base of a substantially vertical cylinder having smooth walls. However, this method is essentially a batch method and is therefore less suitable for large-scale production of detergent powders. More recently, other attempts have been made to obtain a continuous method of increasing the density of detergent granules "after the tower" or spray dried. Typically, such a method requires a first device for milling or grinding the granules and a second device for increasing the density of the milled granules by agglomeration. The stochastic nature of most pulverization-agglomeration methods often leads to undesired broadening of the particle size distribution, resulting in both dusty and coarse oversized particles. This method requires additional conditioning steps such as sieving, suspension separation, milling, and recirculation to meet the desired product specifications for particle size. For this reason, "after-the-tower" processing or densification is undesirable in view of economics (high invested capital costs) and the complexity of the operation. Moreover, all of the above methods essentially densify spray dried granules,
Otherwise it is for processing. In addition, products made by treating or densifying granules “after the tower” or spray-dried without other post-treatment steps such as spray coating can be spray-dried. Intrinsic limitations typically limit the ability to have high surfactant levels. At present, there are limitations on the relative amounts and types of materials that are subjected to spray drying in the manufacture of detergent granules. For example, high levels of surfactant in the resulting detergent composition are properties that facilitate the production of detergents in a more efficient manner,
It was difficult to achieve. Accordingly, it is desirable to provide a method that can produce a detergent composition without the limitations imposed by conventional spray drying techniques.

[0005] A number of methods involving the aggregation of detergent compositions to achieve that end have also been disclosed in the art. For example, attempts have been made to mix zeolites and / or layered silicates in a mixer to agglomerate the detergent builders to produce free flowing agglomerates. The method of using a mixer / coagulation device can increase the production of a product. However, these products typically have a broad particle size distribution (ie, they contain powdery and coarse extra-large particles) or are effectively classified to maintain the desired particle size distribution. A recirculation loop (for example, a production ratio of 20
Weight percent). For example, US Pat. No. 5,516,4
See No. 48.

The following documents relate to the production of detergents by coagulation. International Patent Application Publication No. WO 93 / 23,523 (Henkel) to Beujean et al., US Pat.
No. 992,079 (FMCC Corporation); U.S. Pat. No. 4,427,417 to Porasik et al. (Corex); U.S. Pat. No. 5,108 to Beerse et al.
U.S. Patent No. 5,3,646, Procter and Gamble, Capeci et al.
No. 66,652 (Procter & Gamble), European Patent Application No. 351,937 (Unilever) by Hollingsworth et al., U.S. Pat. No. 5,205,958 to Swatling et al., International Patent Application Publication No. WO 96/95 to Dhalewadikar et al. 04
No. 359 (Unilever). For example, International Patent Application Publication No. WO 93/2
No. 3,523 (Henkel) discloses a high-density detergent composition comprising less than 25% by weight of granules having a diameter of more than 2 mm, comprising a pre-coagulation by a low-speed mixer and a further coagulation step by a high-speed mixer. The method of obtaining is described. U.S. Patent No. 4,
No. 427,417 (Corex) describes a continuous agglomeration method which reduces caking and oversize agglomerates.

On the other hand, there is also known an example of a method for producing a detergent product having a narrow particle size distribution by an extrusion / spheroidization method. However, the particle size of these products is typically limited to about 1000 μm or greater, and typically does not increase the processing speed as much as using a mixer / coagulator. While such attempts have shown that the methods can be used to produce detergent agglomerates, the starting detergent material in the form of pastes, liquids, and dry matter is free-flowing and free flowing. It does not provide a method that can effectively aggregate the detergent aggregates. Here, the detergent product is i)
High effective levels of chemical surfactant (ie, generally greater than 15% by weight)
Ii) the aggregate has a geometric average particle size of 250 to 1200 μm, a geometric standard deviation of 2.5
And iii) high bulk density (ie 500 g / l)
Higher) and produced by a continuous, high-volume (ie, more than 1 metric ton / hour) detergent manufacturing process. Here, this method has a too fine particle size (for example, 250 μm).
m or less than coarse (eg, greater than 1400 μm) is efficient because the rate of recirculation of the product is minimal (ie, less than 20% by weight of the production ratio).

[0008] Therefore, there remains a need in the art to provide a column-free method for the continuous and continuous production of detergent compositions from starting detergent components. Here, the density of the obtained detergent composition can be controlled by adjusting the processing conditions.
In addition, (1) in order to give flexibility to the final density and particle size of the final composition, (2)
Large scale production of detergents is required to incorporate high levels of detergent surfactants in the final composition and (3) to provide flexibility for incorporating several different detergent components (especially liquid components) into the process. There remains a need for a more efficient, flexible and economical method that can be easily performed.

DISCLOSURE OF THE INVENTION The present invention relates to: (a) a high-speed mixer comprising a liquid acid precursor of an anionic surfactant and a solid and granular water-soluble alkali substance with an average residence time of about 0.2 to about 50 seconds; In the form of a free-flowing powder comprising a salt of the anionic surfactant precursor, partially or totally neutralizing the acid precursor by dispersion and mixing in the A first step of forming a dry neutralized substance; and (b) dispersing and mixing the agglomerated binder and the above-mentioned free-flowing powder in a medium-speed mixer, whereby the powder is agglomerated to obtain a granular detergent. It provides a continuous process for preparing a granular detergent aggregate having a density of about 500 g / l or more, comprising a second step of forming an aggregate.

According to the present invention, detergent surfactant levels are high and the particle size distribution is relatively narrow,
A high-density detergent agglomerate for a granular detergent composition is obtained. Also, the method is inherently efficient because it significantly reduces the amount of agglomerates that exceed the acceptable particle range.
The present invention also satisfies the above-mentioned needs in the art by providing a method of making a granular detergent composition that allows flexibility in the final density of the final composition in an agglomerated (eg, non-tower) manner. is there. In this method, the bulk density is high (500 gm /
l), it is not necessary to use a conventional spray-drying tower with limited ability to produce a composition with a high surfactant content (concentration).

Accordingly, an object of the present invention is to control the residence time in a mixer, the tip speed of a mixing element, and the dispersion conditions of a binder to control the bulk density, particle size, particle size distribution, chemical composition, and chemical composition of a final product. It is an object of the present invention to provide a method for continuously producing a detergent composition which is flexible with respect to the effective level of surfactant. The object of the present invention is also
It is to provide a more efficient, flexible and economical way to facilitate large-scale production.

According to the method described herein, having a high density of about 500 g / l or more,
A relatively narrow granular detergent agglomerate with a particle size distribution of less than about 2.5 as evaluated by the geometric standard deviation is produced with high throughput, higher production efficiency, and only by recycling a small amount of unacceptable particle size material be able to. While other methods involving a classification-recirculation loop have been found to allow for a narrower particle size distribution upon completion of the final product, the advantage of the present invention is that the particle size distribution is narrower prior to any classification. is there.

[0013] Best Mode definitions for carrying out the invention: The term "aggregate" as used herein, the granular detergent material, surfactant and /
Alternatively, it refers to particles formed by agglomerating with a binder such as a solution (so that the agglomerated particles are larger in size than the particulate detergent material contained therein).

The term “average residence time” as used herein is defined as follows. Average residence time (h) = mass (kg) / flow throughput (kg / h). The residence time can be conveniently determined by measuring the steady state weight (in kg) of the agglomerated powder and components in the mixer and dividing it by the mass throughput of the mixer (in kg / min).

As used herein, the term “particle size distribution” refers to the mass-based distribution of the particle size of the agglomerate. This distribution is shown as a geometric mean and a geometric standard deviation. The geometric mean and standard deviation on a mass basis are those most commonly measured using standard sieving tests.

[0016] All percentages used herein are "percent by weight" unless otherwise specified. All ratios are by weight unless otherwise specified. As used herein, “comprising” means that other steps and other ingredients which do not affect the result can be added. The term "consisting of" or "consisting essent
ially of) ".

[0017] The present invention relates to a continuous process resulting granular detergent agglomerates with a free flowing. According to this method, a product having a density of about 500 g / l or more and having a narrow particle size distribution at the end of the agglomeration step can be produced, and a low recirculation rate can improve the process efficiency.

First Step (Dry Neutralization) In the first step of the process, a dry neutralized substance in the form of a free flowing powder is prepared. The dry neutralized material is dry neutralized in a high-speed mixer between the acid precursor of the anionic detergent surfactant and the water-soluble alkali inorganic particulate material, whereby the acid precursor is partially partially anionic surfactant. Or by completely neutralizing it.
In order to ensure sufficient neutralization of the acid precursor under high speed mixing conditions, it is preferred to use an excess of alkali inorganic particulate material. Substantially dry, small particle size, free flowing from excess alkali inorganic particulate matter present in the high speed mixer in the dry neutralization step and other particulate inorganic or organic detergent components that are preferably present Powdered materials tend to be produced. Such powdered materials are generally too powdery and dense to be incorporated directly into detergent products.

The particulate water-soluble alkali inorganic material is continuously introduced into the high-speed mixer in the form of fine particles. At the same time, the liquid acid precursor of the anionic surfactant is introduced into the mixer to be sufficiently dispersed and adsorbed on the surface of the fine particles of the alkali inorganic substance. Neutralization of the acid precursor to the corresponding salt occurs immediately. As the alkaline inorganic material is milled to a smaller particle size with a larger reactive surface area, the rate and capacity of the acid precursor to be neutralized to salts increases. The inherent binding capacity of the acid precursor liquid typically results in some intermediate aggregation in the first step to form a dry neutralized material.
The degree of the intermediate aggregation is controlled mainly by the amount of the liquid to be added and the shear rate of the mixer. The average particle size of the dry neutralized material is generally about 50-5
00 μm, preferably about 100-250 μm. Generally, the bulk density of the dry neutralized material of the first mixer is at least 500 g / l, more typically at least 600 g / l, preferably about 650-800 g / l.

In order to achieve the desired tight dispersion and adsorption, the mixer must have a high shear rate and be balanced with the viscosity of the liquid component. In a preferred embodiment, the mixer is a device having a mixer moving at a tip speed of 10 m / s or more, and a narrow gap of less than 2 cm between the tip of the mixer and the wall or other fixed element of the mixer. It consists of Preferably, the average residence time in the first mixer is from about 0.2 to about 50 seconds, more preferably, from about 1 to about 30 seconds. Examples of high-speed mixers for the first step are the Ladyge CB mixer from Ladyge (Germany), the turbulator from Bepex Company (USA) and the Shougy (
Shogi Flexomatic (eg, Model FX-160) manufactured by The Netherlands.

The particulate water-soluble alkaline substance is preferably sodium carbonate alone or in combination with other substances such as sodium bicarbonate or silicate. Alkaline substances with other salts, such as lithium and potassium salts, can also be used. Aqueous alkaline materials such as sodium hydroxide can also be used in combination with the granular alkaline material, but their use is to prevent the resulting intermediate agglomerates from becoming sticky or becoming less fluid. Should be kept to a minimum. The carbonate has an average diameter of 0.1 to 100 μm, preferably 2 to 25 μm, more preferably 5 to 15 μm.
m is preferably a fine powder. Typically, the water content of the carbonate is less than about 2%, more preferably less than 1%. The carbonate is present in about 25 to about 8 of the resulting aggregates.
It can be 0% by weight, preferably about 30 to about 60% by weight.

A preferred method for finely grinding carbonate is described in International Patent Application No. WO 98/20104, published May 14, 1998, which is hereby incorporated by reference. As in the process, using a suitable mill that can make such finely divided carbonates from commercially available carbonate raw materials. Commercially available carbonates typically have a median particle size of about 50-150 μm and contain less than 2% water, preferably less than 1%. A crusher preferably used for this purpose is Hosokawa Micron Powder, Summit, New Jersey.
An air classifier pulverizer such as the Micro-ACM CX300 available from Systems.

The particle size distribution of the milled carbonate is measured with any instrument that approximates the particle size, such as the diameter of a spherical particle occupying the same volume as the particle under measurement. The median particle size is the size at which 50% by volume of the particles are smaller and 50% by volume of the particles are larger. A suitable instrument for measuring the particle size of the milled carbonate is the Moulburn Series 2600 Optical Laser, available from Moulburn Instruments Company, Moulburn, PA.

Preferably, the amount of alkali inorganic material is such that at least 80% of the acid precursor is neutralized before the alkali inorganic material leaves the first mixer. Typically, the stoichiometric amount of the alkaline inorganic material is at least twice that required to completely neutralize the acid precursor. It is well known in the art to neutralize an acid precursor with an alkaline powder by dispersion / adsorption. AS Davidsohn and B. Midlewsky
See, Synthetic Detergents, 7th Edition, pp. 202-209. The amount of liquid acid precursor that can be added in this step is up to about 30% by weight. It should be noted that higher levels of acid precursors can be added by using micronized powders such as sodium carbonate milled in an air classifier mill as described above. In the case of detergent surfactant acid precursors that are more crystalline than the alkyl benzene sulphonates, for example alkyl sulphate, generally a larger amount of the acid precursor can be charged into the mixer.

The liquid acid precursor is an ordinary C₁₁~ C₁₈Alkylbenzenesulfonic acid ("H
LAS "), first branch and random C₁₀~ C₂₀Alkylsulfuric acid ("HAS
)), Formula CH₃(CH₂)_x(CHOSO₃ ⁻H⁺) CH₃, And CH₃(CH ₂ )_y(CHOSO₃ ⁻H⁺) CH₂CH₃(X and (y + 1) are better than about 7
Preferably an integer greater than or equal to about 9)₁₀~ C₁₈Secondary (2,3) alkyl sulfate
Unsaturated alkenyl sulfates such as oleyl sulfate, and C₁₀~ C₁₈Alkyl
Alkoxy sulfate ("HAE_XS "; especially EO1-7 ethoxysulfate)
preferable. Most preferred are HLAS and HAS. Produce the above acid precursor
Methods for doing so are well known in the art. Acid precursors reduce HLAS
It is preferred that both are contained at 50%. Less detergent surfactant in the final detergent product
At least 50% by weight was produced by neutralization of the acid precursor in the first step
Preferably it is.

In addition to the alkaline inorganic material, other particulate inorganic and organic detergent components can be added to the first stage mixer. Such other granular detergent components will be described later. The addition of other particulate detergent components to the process can improve the properties of the dry neutralized material. However, in the first step, no other particulate inorganic materials, specifically particulate detergent builder materials such as phosphates, polyphosphates, and aluminosilicates, are present or present to a minimum. It may be preferable to use only the granular water-soluble alkali substance, rather than using only the amount. in this case,
The dry neutralized material will contain less than about 5% by weight of such particulate builder material.

In order to initiate and maintain the neutralization reaction between the acid precursor and the alkali inorganic substance,
Preferably, some free water is present in the high speed mixer. Typically, this is some amount, eg, about 1%, of free water present in the acid precursor liquid. If the alkali inorganic material (carbonate) is finely divided as described above, any additional free water is generally added to the mixture to initiate and sustain the neutralization reaction. No need. The water of the reaction mixture, which is defined as non-water that is hydrated to the inorganic salt at a temperature of 135 ° C. or that is firmly bound as water of crystallization, must not be so high as to substantially agglomerate the powder. Generally, the moisture of the powdered material in the first mixer is less than about 5%, more preferably less than about 2%.

[0028] The dry neutralization in the first stage results in a detergent material containing a salt of an anionic surfactant. At this time, preferably 80% or more, more preferably 90% or more, and most preferably all of the acid precursor of the anionic surfactant is neutralized.

The detergent material emerging from the first mixer may optionally be processed in any intermediate steps before being transferred as a free-flowing powder to the second step flocculation mixer.
Such an intermediate step may be a mixing step, in which any liquid or particulate matter may be added. Such optional liquid materials are generally added at a level of less than 10% by weight of the free-flowing powder and may include a nonionic surfactant or other binder as described herein. A liquid can be included. The optional particulate material may be a free-flowing auxiliary such as zeolite or carbonate. The mixer may be a static mixer, such as a box mixer with baffles, or a mechanical mixer, such as a shougi drum or cage mixer. Such an optional step may involve liquid material that may interfere with the actual dry neutralization of the acid precursor in the first step, or the actual aggregation in the second step (as in the case of nonionic surfactants). ) Can be conveniently used for the addition.

Second Step (Aggregation) In the second step, a granular detergent aggregate is made from a free-flowing powder and a flocculable binder. The free-flowing powder obtained from the first step is fed to a second mixer. The second mixer is preferably a completely separate mixer, but may be in a zone downstream of the first mixer, provided that it meets the mixing conditions. The second step comprises dispersing an agglomerated binder in the free-flowing powder obtained in the first step to form a detergent agglomerate. The amount of agglomerated binder used is about 1 to about 50% by weight of the detergent agglomerates (based on effective levels), preferably about 5 to about 3%.
It may be 5% by weight (based on the effective level). The present invention can accept a wide range of surfactant paste levels based on rheological properties, and can vary paste levels during processing. The average particle size of the resulting detergent agglomerates is from about 250 μm to about 1200 μm, more preferably from about 400 μm to about 10 μm.
The particle size distribution at the end of the second step of agglomeration is relatively narrow such that the geometric standard deviation is less than about 2.5, preferably less than about 2.0.

The second step of the method is preferably carried out at an operating temperature high enough to effectively agglomerate the free-flowing powder and the agglomerated binder, the temperature being excessively agglomerated or Not so high that "boring" occurs and the powder is in large chunks. Typically, the working temperature of the mixture of the second step in the second mixer is about 30-70.
° C. The temperature of the agglomerated binder, typically in the range of about 20-70 ° C., is such that the agglomerated binder can be sprayed or dripped into the mixing zone of the second mixer, or a mechanical fluid within the mixing zone. It can be adjusted independently to form a thick viscous paste that must be dispersed into particles. In one method, the flowable liquid agglomerated binder is agglomerated in a second mixer using a single liquid spray nozzle or an air atomized spray nozzle, which can be easily selected depending on the work required. Can be sprayed. Fluid liquid is
It may be dripped or introduced into the mixer as a liquid stream from a tube. However, in order to efficiently and effectively adhere the powder particles to the outer surface of the agglomerated binder and cover the outer surface, it is important to sufficiently disperse and distribute the fluid liquid in the powder.

Another approach, in the case of a thick viscous paste binder, is to inject the binder into a series of narrow paste streams. Where these paste streams are
Inject directly at one or more high-speed chopper blades deployed in the mixer. Typical tip velocities of the chopper blade are about 3 m / sec or more, preferably greater than about 15 m / sec, more preferably greater than about 20 m / sec. A typical design of a chopper blade includes at least four radial blades. This is very suitable for the plowshare design of mixers with internal choppers, for example the Ladyge KM mixer from Ladyge (Germany). The mixer may be provided with a lance tube capable of injecting the binder liquid into the chopper. In the present invention, the lance tube can be further divided into smaller tubing flows. Where each (
The cross-sectional area of the flow port (divided further) is less than about 80 mm ² , most preferably less than about 1 mm ² . In this preferred embodiment, each stream is cut into fine units of binder by a combination of the paste injection rate divided by the number of streams and the chopper cutting rate. Here, the volume of each flow of the paste per one cut calculated by calculation is less than about 1 ml, more preferably less than about 0.01 ml,
Most preferably from about 0.00005 to about 0.01 ml, or about 13 m
m, more preferably an average equivalent diameter of about 4 mm. Binder particles of this size are placed in the second mixer until the size of the agglomerates falls in a range where the strength of the agglomerate particles resists further grinding as a result of the fines covering the binder particles and being embedded in the binder particles. Torn apart into smaller sizes. This size range for the agglomerates is generally from about 50 to about 2000 μm, exceeding the range of acceptable average detergent particle sizes (about 250 to 1200 μm) and fines (aggregates and particles less than 250 μm). And oversized particles (aggregates exceeding 1400 μm).

Most preferably, the agglomerated binder is dispersed in droplets or particles having an equivalent diameter of about 0.5 to about 1 mm. This particle size is comparable to the size of the desired detergent agglomerate. Binder particles in this size range do not tend to tear to smaller sizes. When the agglomerate binder is dispersed in this size range, the resulting detergent agglomerates have a very narrow particle size range and minimize the amount of oversized particles and fines.

The volume of the binder per one cut can be calculated from the cutting speed and the volume flow rate of the binder. The cutting speed in units of the number of cuts / second is “the number of rotations of the chopper per second × the number of chopper blades per rotation”. Here, it is assumed that the cutting is performed once by one chopper blade. The volumetric flow rate of the binder in ml / sec is "mass of binder / density of binder" (the unit of mass of binder is kg / sec and the unit of density of binder is kg / ml). . Therefore, the volume of the binder per one cut is “volume flow rate of binder / cutting speed”.

The tubes used to inject the (further divided) binder stream are positioned so that their outlets are slightly upstream of the chopper. In this way, the plow share in the mixer causes the binder stream and intermediate particles to be swept into the chopper, where the binder is pulverized and covered with powder.

Another embodiment is an additional mode for dispersing the binder, such as by adding compressed air to the binder line at or before the opening of the binder tube in the mixer. The mechanical device is supplemented by the device for injecting the further divided binder described above. The air may be pulsed to further split the binder stream into uniform pieces. Also, the use of a vibrating element such as a reed at the injection point can further improve the uniformity of binder dispersion.

To reduce viscosity and improve dispersibility and pumpability, it is convenient to increase the supply temperature of the flowable liquid binder to or above the working temperature. is there. It is within the skill of one in the art to optimize the processing conditions and to select a liquid binder supply temperature that can avoid problems such as unstable binders or thermal decomposition.

In a most preferred embodiment, a viscous surfactant paste binder is used, characterized by shear rate thinning exhibiting an apparent yield stress. This shear rate thinning is advantageous for transferring the paste binder, typically from a storage tank to a mixer / coagulator. The apparent yield stress properties are important for mechanically cutting the paste and for maintaining the structural integrity of the as formed agglomerates, especially when the effective level of binder is high.

The shear rate thinning and apparent yield stress properties are measured according to the techniques adopted in the art of rheological characterization, such as using a parallel plate viscometer or a cone-plate viscometer. can do. Viscosity is typically determined using a stress gradient program. Here, the stress (τ) is increased from about 10 Pa to about 1000 Pa during a ramp time of about 10 minutes, and the resulting strain rate (γ) is measured. The apparent viscosity (η) is determined from the data of the stress range and the strain rate by calculating as follows. η = τ / γ

Thereafter, the logarithm of the calculated viscosity is plotted against the logarithm of the shear rate. For a shear-thinning paste with yield stress, log (η) vs. log (γ)
Is typically approximately linear over a strain rate range of about 0.1 to about 10 sec- ¹ . More specifically, the correlation coefficient ^{r 2} of the regression are typically greater than 0.99. l
The downward (negative) slope of the og-log plot indicates shear thinning, i.e., the viscosity decreases as the shear rate increases. The viscosity of a yield stress fluid is typically governed by yield stress effects at shear rates in this range. This is characteristically indicated by the regression slope value approaching -1, generally a value between -0.7 and -1.0. For the purposes of the present invention, the apparent yield stress (τ _y ) is defined as the product of the viscosity and the shear rate at a shear rate value of 1 sec- ¹ . For good dispersion of the paste binder by mechanical cutting, the value of the apparent yield stress τ _y must be greater than about 20 Pa, preferably greater than about 50 Pa, more preferably greater than about 100 Pa. In general, the apparent yield stress of the paste binder increases with decreasing temperature, so that the agglomerates can have improved physical integrity and the resistance to soiling increases as the product cools.

In addition, a preferred paste binder is a viscoelastic rheology characterized by a complex shear modulus (G ^* ) which is the vector sum of its elastic storage (G ′) and viscous loss (G ″) parts. Have The ratio of the loss shear modulus to the storage shear modulus is the tangent of the phase angle (δ), tan (δ) = G ″ / G
'. In a preferred embodiment, t at a frequency of about 2 to about 20 Hz
A paste binder having an (δ) value of less than 1.0, more preferably less than about 0.5 is used. Decreasing the value of tan (δ) to 1.0 or less means that the accumulated shear modulus becomes dominant over the loss shear modulus. The predominant accumulated shear modulus helps to mechanically cut the paste and to disperse the paste as a discrete unit of binder. Dispersing the high viscoelastic binder as discrete mass units is convenient for embedding the powder in the discrete mass unit binder to form an aggregate. In addition, the low value of tan (δ) helps to reduce the tendency of the binder to foul the agglomerate surface and the mechanical elements inside the medium shear mixer. Reduced fouling is advantageous for improving the operating efficiency of the process by reducing the tendency of the product to build up and adhere to the interior of the mixer. The above viscoelastic rheology data can be measured by those skilled in the art of rheology using a vibrating parallel plate viscometer.

The high viscosity, apparent yield stress, and viscoelastic properties of a viscous agglomerated binder are well suited for the mechanism of agglomeration where solid particles cover, adhere to, and become embedded in the binder. . In this case, the mixed shear stress of the method is:
It need only be sufficient to cover the particles and to embed the particles into finely divided droplets or particles of the binder. Thus, the mixing shear stress of the second mixer is intentionally maintained below the point at which the binder spreads extensively over the particle surface.

As in the case of a liquid binder having more fluidity, it is possible to efficiently and effectively disperse and distribute a viscous binder in a powder having a free flow so that powder particles can be efficiently and effectively aggregated. It is important to adhere to and cover the outer surface of the device. Also,
As in the case of liquid binders, the feed temperature of the viscous binder is above the working temperature (i.e., about 7
(0.degree. C. or more). For viscous binders that do not allow the binder to be pumped into the mixer and / or raise the temperature of the binder to a temperature where it can be sprayed, generally, such as cutting and / or shredding equipment, It is necessary to provide a means for mechanically dispersing the binder. Another particularly preferred embodiment for very hard binders is to use a pelletizing extruder to send uniform pellets of small binder to a coagulation mixer. In this embodiment, both a single screw extruder and a twin screw extruder are used. in this case,
An extruder is used to conveniently solidify the binder prior to injection into a mixer, as disclosed in US Pat. No. 5,451,354, which is incorporated herein by reference. Can be used. In this embodiment, the binder is dispersed by extruding the binder through a die plate having a large number of small openings into a noodle shape, which is then fed to an agglomeration mixer. If desired, the noodle-like binder can be cut into pellets using various cutting equipment configurations well known in the extrusion / pelletization art prior to feeding to the mixer. In a more preferred embodiment, using a fine noodle size of less than about 10 mm ² cross-sectional area, also using the configured chopper as carve into short lengths of less than about 4mm noodles. In a most preferred embodiment, a thinner noodle size with a cross-sectional area of less than about 1 mm ² is used, and a chopper configured to cut the noodles into shorter lengths of less than about 1 mm.

In general, the more uniform the aggregate binder is dispersed as particles or droplets, the more uniform the size of the detergent aggregate obtained from the second mixer.
Stated another way, the narrower the particle size distribution or droplet size distribution of the agglomerated binder, the narrower the size distribution of the detergent agglomerates.

The agglomerated binder can be selected from the group consisting of an anionic surfactant paste (most preferred), liquid silicates, cationic surfactants, aqueous or non-aqueous polymer solutions, water, and mixtures thereof. Examples of preferred anionic surfactant solutions as agglomerated binders include effective levels of about 30-95%, about 12-18 carbon atoms.
NaLAS having an alkyl chain of about 12 to about 12 carbon atoms with an effective level of about 30 to 95%.
NaAS with an alkyl chain of １８18; effective levels of about 30-95%; NaAS with a branched alkyl chain of about 10-20 carbon atoms; and an effective level of about 20-95%
NaAExS solution having an alkyl chain having about 10 to 18 carbon atoms (x is about 1 to 10
); And mixtures of the above surfactant solutions with a net effective level of 30-95%. More preferred is an effective level of about 70-80% with about 14-15 carbon atoms.
NaAS and NaLAS surfactants having an alkyl chain of AExS surfactant having an alkyl chain of about 12 to 14 carbon atoms having an effective level of about 70 to 80% (
x is about 3). Other minor components such as polyethylene glycols, organic polymers, silicates, and alkali salts may be present in the paste composition.

The cationic surfactant is a mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactant (the remaining N-position is a methyl group, a hydroxyethyl group, or a hydroxypropyl group. Quaternary ammonium surfactant selected from (substituted). Other binders are disclosed in US Pat.
No., 108,646 (Beerse et al.) And may be incorporated herein by reference.

[0047] Additional particulate detergent components of the type used in the first step can be added to the mixer of the second step, if necessary, with the free-flowing powder, to agglomerate with the binder. Typically, about 0-10%, more preferably about 2-5%, by weight of the detergent agglomerates, of the particulate detergent component is added to the second mixer.

[0048] The second mixer for agglomeration may be any type of mixer known to those skilled in the art, as long as the above conditions for the second step can be maintained. Preferred are (i) an average residence time of about 10 seconds to about 15 minutes, more preferably about 1 to about 2 minutes, and (ii) a tip speed of about 0 for a mixing tool mounted in the mixing zone.
. 5 to about 5 m / sec, and (iii) specific energy conditions of about 0.15 to about 7 kj / k
g is a second mixer capable of performing the second step under the condition of g. A preferred example of the second mixer is a Ladyge KM mixer manufactured by Ladyge (Germany).

[0049] The free-flowing powder of the first step is generally introduced directly into the second mixer, but, if necessary, is first processed using another mixing or transfer device as described above. Or can be processed.

As a result of the above two steps, a product having a bulk density of 500 g / l or more is obtained. The resulting product can be further subjected to drying, coating, fluid bed coagulation, and / or cooling, if desired. Surprisingly, the product emerging from the second stage mixer has a narrow particle size distribution, especially compared to a free flowing powder. A narrow particle size distribution means that a product with a high weight fraction of particles in the acceptable size range comes out of the second mixer. Thus, a lower rate of recycle of fines (very small particles) and extra-large particles (larger particles) to run the entire process results in higher production and more efficient operations. In addition, the surfactant precursor added in the first step, and the surfactant paste binder added in the second step, compared with the one-step aggregation using only one type of binder, the surfactant Agglomerates can be made with significantly higher effective levels of.

Detergent surfactant in detergent agglomerates made according to the present invention (acid precursor in the first step, surfactant paste agglomerated binder in the second step, and detergent incorporated by auxiliary detergent components) Surfactant) is generally from about 5 to about 80% by weight
More preferably from about 10 to about 60% by weight, more preferably from about 15 to about 5% by weight.
0% by weight. The amount of surfactant formed by dry neutralization of the acid precursor in the present method may be from about 5 to about 40% by weight of the agglomerated product, more preferably from about 10 to about 30% by weight. , Most preferably from about 15 to about 25% by weight.

Non-limiting examples of preferred anionic surfactants formed by dry neutralization of the acid precursor in the first step of the present invention include the usual C ₁₁ -C ₁₈ alkylbenzene sulfonates (“LAS "), the first branched and Randanmu _C 10 _{-C 20} alkyl sulfates (" AS "), the formula _{CH 3 (CH 2) x (} CHOSO 3 - M +) CH 3,
And _{CH 3 (CH 2) y (} CHOSO 3 - M +) CH 2 CH 3 (x and (y + 1)
Is an integer greater than or equal to about 7, preferably greater than or equal to about 9, and M is a water solubilizing cation, especially sodium) C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfate, oleyl sulfate unsaturated sulfates such as and _C 10 _{-C 18} alkyl alkoxy sulfates ( "AE _X S"; especially EO1~7 ethoxy sulfates) include.

The method of the present invention comprises: (1) a CB and / or a shougi mixer capable of injecting one or more liquid components per mixer, and (2) a chopper capable of injecting one or more paste binder components. KM mixer with blade, (3)
When carried out using any extruder and / or pelletizing device capable of injecting one or more additional paste binder components into the KM, at least four with a wide range of viscosities and other rheological properties. Different types of liquid components can be used in the method. Thus, the proposed method is convenient for those skilled in the art to incorporate into granulation processes starting from liquid, rather expensive detergent materials, which can be more difficult to handle and / or store than solid materials. It is.

Other optional detergent surfactants : Other anionic surfactants, nonionic surfactants, zwitterionic surfactants,
Other optional detergent surfactants, such as amphoteric and cationic surfactants, and compatible mixtures thereof, can also be included in the detergent product.
Such other detergent surfactants may be added as a liquid or powder in small amounts (typically 10% or less) in the first or second step, or any optional intermediate or finishing steps. it can. Detergent surfactants useful in the present invention include Norris U.S. Pat. No. 3,664,961 issued May 23, 1972, and Laughlin et al. U.S. Pat. 3,929
, 678, each specification. Both of these patents are described herein by reference. Useful cationic surfactants include Cockrell U.S. Patent No. 4,222,905 issued September 16, 1980, and 1980.
And US Pat. No. 4,239,659 to Murphy, issued Dec. 16, 2016. Both of these patents are described herein by reference. Cationic surfactants also can be used as a detergent surfactant in the present invention, quaternary ammonium surfactants suitable are mono C ₆ -C _16, preferably C ₆ -C 10 _N-alkyl or alkenyl ammonium Surfactant (the remaining N-position is substituted with a methyl group, a hydroxyethyl group, or a hydroxypropyl group).

Granular Inorganic or Organic Detergent Ingredients Particulate inorganic or organic detergent components which can be introduced into one or more of the first step, the second step, and any other step are: , Preferably a finely divided free flowing powder, ground soda ash or carbonate (
Including excess of inorganic inorganic particulate matter added in the first step), powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground or powdered sodium sulfate, aluminosilicate, crystals Functional layered silicate, nitrilotriacetate (NTA), pyrophosphate, orthophosphate, precipitated silicate, polymer, other carbonates, citrates, powders such as alkanesulfonic acid in powder form It is preferred to select from the group consisting of surfactants in the form of powder and an internal recycle stream of the powder produced by the process of the invention. Here, the average diameter of the powder is 0.1 to 500 μm, preferably 1 to 500 μm.
It is 300 μm, more preferably 5 to 100 μm. When hydrated STPP is used as the fine powder of the present invention, STPP hydrated to a level of 50% or more is preferred.
The aluminosilicate ion exchange material used as a detergent builder in the present invention preferably has both a high calcium ion exchange capacity and a high exchange rate. Without wishing to be bound by theory, it is believed that such high calcium ion exchange rates and capacities are a function of several interrelated factors derived from the process for producing the aluminosilicate ion exchange material. In that regard, the aluminosilicate ion exchange material used in the present invention is preferably prepared according to U.S. Patent No. 4,605,509 to Corkill et al. (Procter & Gamble). This patent is disclosed herein by reference.

The particulate inorganic or organic detergent component can also serve as a coating when added to the second mixer. Preferred as coatings are phosphates, carbonates, and aluminosilicates. The coating enhances the free-flowing properties of the resulting agglomerates and also prevents or minimizes excessive agglomeration in the second mixer. It may be convenient to include only carbonates or other particulate matter that is not a builder material. Thereby, detergent agglomerates can be made that contain little (less than 10% by weight, preferably less than 5% by weight) or no detergent builder. This allows the producer to make a single detergent agglomerate for detergents with or without phosphate.

The aluminosilicate is in the “sodium” form, since the potassium and hydrogen forms of the aluminosilicate ion exchange material do not exhibit as high an exchange rate and capacity as the sodium form. preferable. In addition, the aluminosilicate ion exchange material is preferably in an over-dried state to facilitate the production of free-flowing detergent agglomerates as described herein. The aluminosilicate ion exchange materials used in the present invention preferably have a particle size diameter that optimizes their effect as detergent builders. As used herein, the term "particle size diameter" refers to the average particle size diameter of a particular aluminosilicate ion exchange material as measured by conventional analytical techniques such as microscopy or scanning electron microscopy (SEM). . The preferred particle size diameter of the aluminosilicate is from about 0.1 to about 10 μm, more preferably from about 0.5 to about 9 μm. The particle size diameter is about 1 to about 8 μm,
Most preferred.

Preferably, the aluminosilicate ion exchange material has the formula Na _z [(AlO ₂ ) _z · (SiO ₂ ) _y ] x H ₂ O. Wherein z and y are integers of 6 or greater, the molar ratio of z to y is about 1 to about 5, and x is about 10 to about 264. More preferably, the aluminosilicate are those having the formula _{Na 12 [(AlO 2) 12} · (SiO 2) 12] xH 2 O. Wherein x is from about 20 to about 30, preferably about 27. These preferred aluminosilicates include, for example, zeolite A, zeolite B
, And Zeolite X. Alternatively, naturally occurring or synthetically obtained aluminosilicate ion exchange materials suitable for use in the present invention may be as described in U.S. Pat. No. 3,985,669 to Krummel et al. Can be made. This patent is disclosed herein by reference.

The aluminosilicates used in the present invention are further characterized in that their ion exchange capacity, calculated on an anhydride basis, is at least about 200 mg CaCO ₃ hardness equivalent per gram. Ion exchange capacity is about 300-35 per gram
Preferably it is 2 mg CaCO ₃ hardness equivalent. In addition, the aluminosilicate ion exchange material has a calcium ion exchange rate of at least about 2 Glen C
a ⁺⁺ / gallon / min / -gram / gallon, more preferably about 2 to about 6 GlenCa ⁺⁺ / gallon / min / -gram / gallon.

The amount of particulate inorganic or organic detergent component that can be present in the first step is about 30-94% by weight of the detergent agglomerates coming from the second step, preferably 50-94%.
90% by weight. An additional amount of the particulate inorganic or organic detergent component can be added to any optional intermediate steps or to the second step to obtain a powdery or free flowing substance.

Auxiliary Detergent Components In a subsequent step of the method, additional detergent components can be incorporated into the detergent composition. These auxiliary ingredients include other detergency builders, bleaches, bleach activators, foam enhancers or defoamers, rust inhibitors and corrosion inhibitors, soil suspending agents, soil release agents, germicides,
Includes pH adjusters, non-builder alkali sources, chelating agents, smectite clays, enzymes, enzyme stabilizers, and fragrances. Baskerville, J., February 3, 1976
See U.S. Patent No. 3,936,537 issued to R. et al.
This patent is incorporated herein by reference.

Optional Processing Steps The method of the present invention can be used to make a detergent agglomerate suitable for use as is as a detergent product after any additional detergent components have been added. However, it may be preferable to further adjust or treat this detergent agglomerate through an optional treatment step. Such optional processing steps may include any oversized detergent in a sieving apparatus that can take a variety of forms, but is not limited to conventional sieves, selected to produce a finished detergent product of the desired particle size. Sieving the agglomerates is included. Another optional step, especially when the loading level of the anionic paste in the agglomeration step is high, is to add the agglomerate to the additional drying, as can be performed using an airlift or fluidized bed dryer, detergent. Aggregate conditioning is included.

An internal recycle stream of fine agglomerates having an average diameter of about 75 to 400 μm generated by suspension separation from an apparatus such as a fluidized bed dryer, a fluidized bed cooler, or another classifying apparatus is used as one of fine powders. If necessary, it can be supplied to the mixer of the first step or the mixer of the second step. The amount of such internal recycle stream can be from 0 to about 60% by weight of the final product stream on an instantaneous basis and less than about 20% by weight of the final product stream based on average production rates. Is preferred.

The process generally requires that the resulting detergent agglomerates be finished by various methods, including spraying and / or mixing with other conventional detergent components. For example, the finishing step includes spraying the finished agglomerates with fragrances, brighteners, and enzymes to create a more complete detergent composition. Such techniques and components are well known in the art.

[0065] Examples Example 1: [Step 1] a liquid acid precursor HLAS (valid level 97%) 222kg / a hour, soda ash (average particle size 15μm) 297kg / time grinding, the powder zeolite (average particle size of about 5 [mu] m) 295 kg / H, ground sodium sulfate (average particle size 15 μm
) Continuously disperse and mix with the pins of the Loedige CB-30 mixer, with an internal recycle stream of the powder from step 2 at 10 kg / h and less than 20% by weight (of the CB mixer throughput). The acid precursor is supplied at about 40 ° C. and the powders are supplied at room temperature. The conditions of the CB-30 mixer are as follows. Average residence time: about 5 seconds Tip speed: about 20 m / s Dry neutralization of the acid precursor with carbonate in the presence of other particulate matter gives a free flowing powder. This free flowing powder has an average particle size of about 290 μm, a geometric standard deviation of about 2.1 and a bulk density of about 730 g / l.

[Step 2] Four free-flowing powders obtained from the CB-30 mixer are provided in the lengthwise direction of the internal chopper assembler (each chopper assembler has three stages of choppers, and each stage has Are continuously fed to a Redige KM-600 mixer (each time the chopper makes one revolution, four cuts are made at each stage of the chopper assembly). NaAS paste (C14.5 sulfate, sodium salt;
About 48% of an effective level 75%) and NaAES paste (C14.5 ethoxy-1)
Prepare a surfactant paste mixture with about 52% (sulfate, sodium salt; effective level 75%). Calimed CSL- of such a surfactant paste mixture
The apparent yield stress measured using a 100 Controlled Stress Rheometer has been found to be 78 Pa at a shear rate of 1 sec- ¹ and a temperature of 60C.
This paste binder is continuously injected at a temperature of about 60 ° C. into the first three chopper assemblies at a total rate of 175 kg of paste per hour. Each paste stream for each chopper assembler is further split into three smaller streams, each directed to a respective stage of the chopper. Here, the discharge diameter of each of the smaller flows is 2 mm. Each chopper rotates at about 3500 RPM.
The calculated mass of the paste in discrete chunks is about 0.023 grams. This corresponds to an equivalent sphere diameter of about 3.4 mm. The conditions of the KM-600 mixer are as follows. Average residence time: about 60 seconds Tip speed of plow shear: about 2 m / s The bulk density of the granular detergent aggregate obtained from Step 2 is about 630 g / l, and the average particle size is 51.
0 μm, the geometric standard deviation is 1.9, and the level of anionic surfactant is about 37% by weight. This agglomerate is treated in an optional processing step of drying and cooling in a fluidized bed and an optional processing step of sizing using a particle separating means. The acceptable rate of agglomerates obtained after sizing ("pass" rate) is about 90% (10% by weight recycle rate). Here, the allowable size range is a particle size of about 150 to 1180 μm. The resulting acceptable agglomerates have an average particle size of about 550 μm, a geometric standard deviation of the particle size distribution of about 1.7, and a bulk density of about 680 g / l. The unacceptable large particles are milled in a pulverizer before being recycled with the unacceptable particles back to step 1.

Example 2: [Step 1] 231 kg / h of the liquid acid precursor HLAS (97% effective level) was added to 586 kg / h of ground soda ash (average particle size 15 μm) and 20 (of the CB mixer throughput). Continuously disperse and mix by means of pins of a Redige CB-30 mixer with an internal recycle stream of the powder from step 2 of less than% by weight. The acid precursor is supplied at about 40 ° C. and the powders are supplied at room temperature. The conditions of the CB-30 mixer are as follows:
It is as follows. Average residence time: about 5 seconds Tip speed: about 20 m / s Dry-neutralizing the acid precursor with a carbonate gives a free-flowing powder. This free flowing powder has an average particle size of about 290 μm, a geometric standard deviation of about 2.4 and a bulk density of about 700 g / l.

[Step 2] Four free-flowing powders obtained from the CB-30 mixer are provided in the longitudinal direction with four internal chopper assemblies (each chopper assembly has three stages of choppers, and each stage has (There are four blades). The feeder is continuously supplied to a Redige KM-600 mixer (each time the chopper makes one rotation, four cuts are made at each stage of the chopper assembly). NaAS paste (C14.5 sulfate, sodium salt;
About 48% of an effective level 75%) and NaAES paste (C14.5 ethoxy-1)
Prepare a surfactant paste mixture with about 52% (sulfate, sodium salt; effective level 75%). The apparent yield stress of this mixture, measured using a Carimed CSL-100 Controlled Stress Rheometer, is 78 Pa at a shear rate of 1 sec- ¹ and a temperature of 60C. The paste binder is continuously injected at a temperature of about 60 ° C. into the first three chopper assemblies at a total rate of about 182 kg of paste per hour. Each paste stream for each chopper is further split into three smaller streams, each directed to a respective stage of the chopper. here,
The outlet diameter of each of the smaller flows is 2 mm. Each chopper is about 3
Rotate at 500 RPM. The calculated mass of the paste in discrete chunks is about 0.024 grams. This corresponds to an equivalent sphere diameter of about 3.5 mm.
The conditions of the KM-600 mixer are as follows. Average residence time: about 60 seconds Plowshare tip speed: about 2 m / s The bulk density of the granular detergent agglomerate obtained from step 2 is about 550 g / l, and the average particle size is 72
0 μm, the geometric standard deviation is 1.9, and the level of anionic surfactant is about 35% by weight. This agglomerate is treated using an optional treatment step of drying and cooling in a fluidized bed and an optional treatment step of sizing using a particle separation means. The acceptable rate of agglomerates obtained after sizing ("pass" rate) is about 90% (10% by weight recycle rate). Here, the allowable size range is a particle size of about 300 to 1700 μm. The resulting acceptable agglomerates have an average particle size of about 720 μm, a geometric standard deviation of the particle size distribution of about 1.7, and a bulk density of about 610 g / l. The unacceptable large particles are milled in a pulverizer before being recycled with the unacceptable particles back to step 1.

Example 3 [Step 1] Liquid acid precursor HLAS (effective level 97%) 5400 kg / h was finely ground soda ash (average particle size about 15 μm) 12,040 kg / h, powdered STPP 7200 kg / h 3885 kg / hr of sodium sulphate in powder form and less than 20% by weight (of the throughput of the CB mixer), continuously with the internal recirculation flow of the powder from step 2, by means of the pins of a Littleford CB-100 mixer. dispersion·
Mixed. The acid precursor was supplied at about 40 ° C. and the powders were supplied at room temperature. CB-
The conditions of the 100 mixer were as follows. Average residence time: about 5 seconds Tip speed: about 12 m / s Dry neutralization of the acid precursor with carbonate in the presence of other particulate matter gave a free-flowing powder. The average particle size of this free flowing powder is about 25
0 μm, the geometric standard deviation was about 2.2, and the bulk density was about 680 g / l.

[Step 2] Six free-flowing powders obtained from the CB-100 mixer are provided in the longitudinal direction of the internal chopper assembler (each chopper assembler has three stages of choppers, and each stage has Has four blades) and is continuously fed to a Redige KM-15000 mixer with a forward facing half plow (i.e., Becker blade). (Each revolution of the chopper cuts at each stage of the chopper assembly. Done four times). NaAES surfactant paste was used as the cohesive binder. The NaAES paste has a C14.5 ethoxy-3 sulphate having an apparent yield stress measured using a Carimed CSL-100 Controlled Stress Rheometer, a shear rate of 1 sec ^-1 and 135 Pa at a temperature of 25 ° C. The salt was the sodium salt (effective level 70%). The paste binder was continuously injected at a temperature of about 30 ° C. into the first four chopper assemblies at a total rate of 1224 kg of paste per hour. Each paste stream for each chopper assembly was further split into three smaller streams, each directed to a respective stage of the chopper. Here, the outlet diameter of each of the smaller flows was 2 mm. Each chopper was rotated at about 3500 RPM. The calculated mass of the paste in discrete chunks was about 0.12 grams. This corresponds to an equivalent spherical diameter of about 6 mm. The conditions of the KM-15000 mixer are as follows. Average residence time: about 16 seconds Tip speed of Becker blade: about 4 m / s The bulk density of the granular detergent agglomerate obtained from Step 2 is about 710 g / l, and the average particle size is 310 μm
m, the geometric standard deviation is 2.3, and the level of anionic surfactant is about 24% by weight. At this stage of the process, the fraction of fines smaller than 150 μm was about 15% by weight, and the fraction of oversized particles larger than 1180 μm was about 7% by weight. This agglomerate was further processed using an optional processing step of cooling in a fluidized bed and an optional processing step of sizing using a particle separation means. The rate of acceptable agglomerates obtained after sizing ("pass" rate) was about 85% (15% by weight recycle rate). here,
An acceptable size range is a particle size of about 150-1180 μm. The resulting acceptable agglomerates have an average particle size of about 410 μm and a geometric standard deviation of the particle size distribution of about 2.0
And the bulk density was about 750 g / l. The unacceptable large particles are milled in a pulverizer before being recycled with the unacceptable particles back to step 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C11D 17/06 C11D 17/06 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, F I, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV , MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Millard, Edward, Sullivan North, Ohio, United States of America , Cherry view, rain, 3287 F term (reference) 4H003 AB18 AB19 AB27 AB31 BA10 CA20 DA01 EA16 ED02 FA28 FA41

Claims (10)

[Claims] (A) dispersing and mixing a liquid acid precursor of an anionic surfactant and a solid, granular water-soluble alkali substance in a high-speed mixer with an average residence time of about 0.2 to about 50 seconds; Dry neutralized material in the form of a free-flowing powder, which partially or totally neutralizes the acid precursor, thereby comprising a salt of the precursor of the anionic surfactant And (b) dispersing and mixing the agglomerated binder and the above-mentioned free-flowing powder in a medium-speed mixer, whereby the powder is agglomerated into a granular detergent agglomerate. A continuous process for preparing granular detergent agglomerates having a density of about 500 g / l or more, comprising the two steps: 2. The medium speed mixer is operated under the conditions of (i) an average residence time of about 20 to about 600 seconds, and (ii) a tip speed of about 0.5 to about 5 m / sec of a mixing tool installed in the mixing zone. And
The medium speed mixer according to claim 1, wherein the medium speed mixer further has a cutting element that moves at a tip speed of 3 m / sec or more to disperse the viscous surfactant paste as an agglomerated binder in discrete mass units. Method. Wherein agglomeration binder is apparent yield stress (t _y) is a viscous surfactant paste having a shear thinning rheology of greater than about 50 Pa, Process according to claim 2. 4. The viscous surfactant paste comprises an alkyl sulfate, an alkyl ethoxy (1) sulfate, an alkyl ethoxy (3) sulfate, a linear alkyl benzene sulfonate, a branched alkyl benzene sulfonate, and a mixture thereof. 4. The method according to claim 3, comprising an anionic surfactant selected from the group consisting of a mixture. 5. The method of claim 3, wherein the agglomerated binder is dispersed in the mixing zone of the second mixer together with the free-flowing powder as discrete mass units having an average equivalent diameter of about 0.5 to about 4 mm. the method of. 6. The method of claim 1, wherein the solid particulate water-soluble alkali material is fine sodium carbonate having an average particle size of less than about 20 μm. 7. The method of claim 1, wherein the average particle size of the particulate detergent agglomerates is about 400-1000 μm and the geometric standard deviation is less than 2.5. 8. The method of claim 1 wherein the dry neutralized material is transferred to a free-flowing powder as a free-flowing powder in a second-stage flocculation mixer, optionally in an intermediate mixing step, and optionally in a liquid detergent component and a granular detergent component. The method of claim 1, wherein mixing is performed. 9. The method of claim 1, wherein the dry neutralized material comprises less than about 5% by weight of a detergent builder material. 10. The method of claim 9, wherein the particulate detergent agglomerates comprise less than about 5% by weight of a detergent builder substance.