EA003404B1 - Process for preparing granular detergent compositions - Google Patents

Abstract

1. A process for preparing a granular detergent product comprising the steps of: (i) mixing and agglomerating a liquid binder with a solid starting material in a high-speed mixer; (ii) mixing the material from step (i) in a moderate or low-speed mixer; (iii) feeding the material from step (ii) and a liquid binder into a gas fluidization granulator and further agglomerating, and (iv) optionally, drying and/or cooling. 2. The process according to claim 1, in which the high speed mixer operates with tool tip speed of at least 5, preferably at least 10 and more preferably at least 15 m/s. 3. The process according to claim 1 or claim 2, in which the high-speed mixer operates at a Froude Number of at least 5, preferably at least 20, more preferably at least 40 and yet more preferably at least 50. 4. The process according to any preceding claim, in which the moderate-or low-speed mixer operates with a tool tip speed of less than 15, preferably less than 10, more preferably less than 8 and yet more preferably less than 6 m/s. 5. The process according to any preceding claim, in which the moderate-or low-speed mixer operates at a Froude Number of less than 30, preferably less than 15, more preferably less than 8, more preferably less than 5, and yet more preferably less than 4. 6. The process according to any preceding claim, in which less than 10 wt% of the total liquid binder added in the process is added in step (ii). 7. The process according to claim 6, in which no liquid binder is added in step (ii). 8. The process according to any of one of the preceding claims, in which the weight ratio of binder added in step (i) to that added in step (iii) is in the range from 20: 1 to 1: 20, preferably from 10: 1 to 1: 10. 9. The process according to any preceding claim, in which the liquid binder comprises one or more anionic surfactants or acid precursors thereof. 10. The process according to any preceding claim, in which the liquid binder comprises one or more nonionic surfactants. 11. The process according to any preceding claim, wherein the liquid binder is at a temperature of at least 50 degree C, when fed into the mixer or gas fluidization granulator. 12. The process according to any one of the preceding claims, in which the liquid binder is a structured blend. 13. The process according to claim 12, in which the structured blend contains a soap-based structurant builder. 14. The process according to any preceding claim, in which the liquid binder added in step (iii) is a structured blend, and the fluidizing gas temperature and/or the atomization gas temperature of the gas fluidization granulator is elevated, as the structured blend is being added, to a temperature within 35 degree C, preferably within 25 degree C and more preferably within 15 degree C, of the pumpable temperature of the structured blend. 15. The process according to claim 14, in which the fluidizing gas temperature and/or the atomization gas temperature is around the pumpable temperature of the structured blend. 16. The process according to any preceding claim, in which the solid starting material comprises an aluminosilicate builder. 17. The process according to claim 16, in which the aluminosilicate builder comprises zeolite MAP. 18. A granular detergent product of bulk density less than 900 g/1 obtained according to the process of the invention.

Description

Field of Invention

This invention relates to a method for producing granular detergent compositions with a medium to low bulk density. More specifically, the invention relates to a method in which a liquid binder is contacted with a solid starting material in a high speed mixer and the resulting mixture is processed in a medium or low speed mixer and finally in a gas fluidized granulator, to which a liquid binder is still added.

BACKGROUND OF THE INVENTION

Recently, the detergent industry has shown considerable interest in developing methods for the production of granular detergent powders with specific bulk densities. Traditionally, detergent compositions are prepared by a spray drying method, where the components of the composition are mixed with water to obtain an aqueous suspension, which is then sprayed in a tower and brought into contact with hot air to remove water. The resulting spray dried powders are highly porous and typically have a bulk density of 300 to 550 g / l.

Spray dried powders typically provide good powder delivery characteristics, such as distribution and dissolution. However, the capital and operating costs of the spray drying method are high. However, significant consumer demand remains for such low-density powders.

It is difficult to increase the bulk density of powders obtained only by spray drying to more than 600 g / l without deteriorating the performance of the detergent composition, for example, to increase bulk density, sodium sulfate in high concentrations can be added to the suspension, but such an ingredient does not increase the detergent ability. Therefore, flexibility with respect to real bulk density can only be achieved by using additional post-treatment stages that compact the powders.

In recent years, there has been a significant interest in the production of detergent powders in methods that mainly use mechanical mixing without the use of spray drying. In a method of this type, the various components are mixed in a dry state and, optionally, granulated with a liquid binder. Liquid binders commonly used in such granulation processes are anionic surfactants, acid precursors of anionic surfactants, nonionic surfactants, or any mixture thereof. Using such granulation processes, granular detergent products are obtained having a high bulk density, typically greater than 700 or 800 g / l.

Granular products having a high bulk density have a small packaging volume, which is beneficial for storage and distribution operations and also for the consumer. Moreover, if the spray drying step is not used, the capital and operating costs are usually much lower and the process consumes less energy and therefore is more advantageous in terms of environmental protection.

However, such high-density products typically have significantly lower porosity than conventional spray dried powder, which can degrade the quality of the wash. For example, concentrated powders of high bulk density may have slow and / or incomplete dissolution in the washing solution, which leads to the fact that the undissolved product is deposited on the washed fabric. More specifically, it is known that zeolite-containing concentrated powders pose a problem with undissolved zeolite-containing powder trapped in the fibers of the fabric. This is manifested in the form of white blotches (spots), clearly visible and unpleasant for the eyes.

Attempts have been made to use mixing methods without a spray drying step to produce materials with a lower bulk density. However, this has led to the use of unconventional cleaning ingredients, such as, for example, burkeite, which leads to a rise in price and therefore increases the cost of the product.

Subsequently, the detergent industry has sought methods for producing granular products with a medium to low bulk density, for example less than about 900 g / l, for example less than 800 g / l, preferably less than 750 g / l, without the need for a spray drying step. In particular, there remains a need for a method for producing zeolite-containing powders with a medium to low bulk density, where the spray drying step is not used, where the usual starting ingredients are used, and where a product with good powder properties is obtained.

Until recently, the development of the use of low shear mixers / granulators, such as, for example, gas fluidized granulators, has been less successful.

AO 98/58046, AO 98/58047, AO 98/58048 and AO 99/00475 (Ip Peueg) relate to low shear granulation methods, wherein the liquid binder is sprayed onto particulate fluidized material, preferably in a gas fluidized granulator. They describe how you can adjust the parameters of the gas-fluidized granulation process to obtain the desired powder properties, for example particle size distribution, bulk density, flow properties, and even yield to some extent.

Low shear granulation processes tend to produce lower bulk density powders, for example, typically less than 650 g / l. In order to provide greater flexibility with respect to bulk density, AO97 / 22685 (Ibbeueg) discloses a process where the particulate starting material is partially granulated with a liquid binder in a high or medium speed mixer before the low shear granulation step, for example in a fluidized bed a layer where additional liquid binder is added and where the granulation is completed.

AO 98/58046, AO 98/58047, AO 98/58048 and AO 99/00475 (Ipieueg) also disclose the use of a preliminary stage of partial granulation, as described in AO97 / 22685 (Ipueueg), in order to provide greater flexibility with respect to volumetric density. However, none of these references specifically describes or provides examples of the use of more than one mixing / granulating step prior to the gas fluidization granulating step.

AO 98/14551, AO98 / 14552, AO 98/14553, AO 98/14556, AO 98/14557 and AO 98/14558 (Rgoe1 apb SashYe), all relate to the non-towed method for producing granular detergent compositions of high bulk density. The surfactant, preferably in the form of a paste or liquid, is dispersed with a fine powder of particles with a diameter of from 0.1 to 500 μm in the first mixer under certain operating conditions and the agglomerates thus obtained are then further agglomerated in one or more mixing steps, the conditions of which are determined and finally granulated in a fluidized bed under specific conditions. An obvious difference is established between the agglomerating effect of the mixers and the granulating effect of the fluidized bed. The term granulating is defined as referring to the thorough fluidization of agglomerates to obtain free-flowing, round, granular agglomerates. Therefore, although the growth of agglomerates, for example, due to coating can take place in the fluidized bed, these cases clearly show that agglomeration of already formed agglomerates should not occur.

EP 264049 (Waueg) describes a continuous process for the progressive granulation of organic substances, preferably dyes. The method includes granulating the atomized material in a high-speed mixer with granulating liquid, further granulating in a medium-speed mixer, preferably with the addition of additional granulating liquid, and drying the product in a fluidized bed with simultaneous spraying with a forming auxiliary substance. At the final stage, the material is preferably dried in the first part of the fluidized bed and then in another part of the dryer sprayed with a forming auxiliary, such as, for example, a sugar solution. In other words, the dried material acts as a carrier, and the forming excipient is absorbed on the carrier, probably in the form of a coating. In EP 264049 there is no indication of additional agglomeration occurring in the fluidized bed.

AO 99/03964, AO 99/03966, and AO 99/03967 (Prgosl & SachYe) describe a method for producing detergent powders with a bulk density of 300-550 g / l, comprising agglomerating an anionic surfactant paste or its acid precursor with a dry starting material in a first high-speed mixer, mixing detergent agglomerates in a second high-speed mixer to obtain enlarged agglomerates, and further agglomerating the increased agglomerates with a binder in a fluidized bed dryer and drying in a pseudo-dryer fluidized bed. Low bulk densities are disclosed as achieved by adjusting the Stokes number at the agglomeration stage in the fluidized bed, adjusting the height of the nozzle at the agglomeration stage in the fluidized bed, or controlling particle sizes at all three stages.

It was found that the problem associated with the methods described in the prior art for producing powders with a medium to low bulk density, including combinations of the stages of mechanical mixing and granulation with fluidization by gas, is that the fines in the product powder are far from optimal. For example, the methods described in AO 99/03964, AO 99/03966 and AO 99/03967 (PrgosGeg & Sachye) produce 14% fines (defined as particles less than 150 microns) in the product. Indeed, a relatively high fines content is apparently a preferred feature of these inventions. The fines particles are of the correct size to act as starting material for the process and, therefore, they are returned to the first high-speed mixer.

It was unexpectedly discovered that powders with a medium to low bulk density with improved powder properties can be obtained in a method comprising contacting and mixing the liquid binder with the starting material in the form of particles in a high speed mixer, followed by mixing in a medium or low speed mixer and final mixing with an additional liquid binder in a gas fluidized granulator. More specifically, a significantly lower fines content is achieved compared to prior art methods. Moreover, the method provides powders with better flow properties than prior art powders.

Definition of invention

In a first aspect, the invention relates to a method for producing a granular detergent product comprising the steps of (ί) mixing and agglomerating a liquid binder with a solid starting material in a high speed mixer;

(i) mixing the mixture obtained in step (ί) in a medium or low speed mixer;

(iii) supplying the mixture obtained in step (ίί) and a liquid binder to a gas-fluidized granulator and further agglomerating and (ίν) optionally drying and / or cooling.

In a second aspect, this invention relates to a granular detergent product with a bulk density of less than 900 g / l, obtained according to the method of the invention.

DETAILED DESCRIPTION OF THE INVENTION Definitions

Further in the description, in the context of this invention, the term granular detergent product encompasses granular finished products for sale, as well as granular components or auxiliary additives to form finished products, for example, by subsequent dosing to or with, or some other form of mixture with additional components or auxiliary additives. Thus, the granular detergent product, as defined here, may or may not contain an active detergent material, such as a synthetic surfactant and / or soap. The minimum requirement is that it must contain at least one general material of a common component of granular detergent products, such as a surfactant (including soap), a modifier, a bleach or a component of a bleaching system, an enzyme, an enzyme stabilizer or a stabilizing component system enzyme, anti-re-precipitation agent, fluorescent or optical brightener, anti-corrosion agent, anti-foaming material, separate abalone or dye.

However, in a preferred embodiment of the present invention, granular detergent products contain an active detergent material, such as a synthetic surfactant and / or soap, in a concentration of at least 5 wt.%, Preferably at least 10 wt.% Of the product.

As used herein, the term “powder” refers to materials essentially consisting of particles of individual materials and mixtures of such particles. As used herein, the term “granule” refers to a small particle of agglomerated smaller particles, for example, agglomerated powder particles. The final product of the method according to this invention consists of or contains a high percentage of granules. However, additional granular and / or powder materials may optionally be subsequently dosed to such a product.

Trifle according to this invention is defined as particles with a diameter of less than 180 microns.

The coarse material according to this invention is defined as such particles with a diameter of more than 1400 microns.

The content of fines and coarse particles can be measured using a sieve analysis.

For the purposes of this invention, the flow properties of the granular product are determined based on the dynamic flow rate (ΌΡΚ.) In ml / s, measured by the following procedure. A cylindrical glass tube with an inner diameter of 35 mm and a length of 600 mm is securely clamped so that its longitudinal axis is in a vertical position. Its lower end is limited by a polyvinyl chloride cone having an internal angle of 15 ° and a lower outlet with a diameter of 22.5 mm. The first beam sensor is placed 150 mm above the outlet and the second beam sensor is placed 250 mm above the first sensor.

To determine the dynamic flow rate, the outlet is temporarily closed and the cylinder is filled with a granular detergent product to a point about 10 cm above the upper sensor. The hole is opened and the flow time ΐ (seconds), taken as the time of falling level of the powder from the upper sensor to the lower sensor, is measured electronically. This is repeated 2 or 3 times and take the average time. If V means the volume (ml) of the tube between the upper and lower sensors, ΌΕΒ is set as ν / ΐ.

The Froude criterion (Et) is used to evaluate the relative effects of gravitational and centrifugal forces on particles in a particular mixing device. The Froude criterion used here is defined as Er = ogb / 2d.

where ω = speed of rotation of the mixer [rad / s], b = diameter of the mixer [m], d = acceleration of gravity [m / s ² ].

Ί

Unless otherwise specified, values related to powder properties, such as bulk density, ΌΕΚ, moisture content, etc., refer to a granular detergent product that has been exposed to the atmosphere.

Way

The method of the present invention is carried out using a high speed mixer, a medium or low speed mixer, and a gas fluidized granulator.

High- and medium- or low-speed mixers: stages (ί) and (ίί).

The mixers used in the method of the invention, whether high, medium or low speed, essentially consist of a hollow static cylinder or reservoir, preferably horizontal, having a centrally located rotating axis with tools mounted on it.

The tools on the axis of the high-speed mixer should provide a thorough vigorous mixing action on the solids and liquids that are mixed at this stage. In this regard, the tools may be, for example, rod-like, like a blade (ploughshare), or a combination thereof, or any other suitable structure, as one skilled in the art would well know.

Suitable high-speed mixers are any of a variety of commercially available mixers, such as, for example, mixers available from LbLde, Ssid1 and Etak. Particularly preferred machines include the Lbbshche machine (trademark) CB K.Kesus1eg and Etak (trademark) K-TPP.

A suitable example of a medium- or low-speed mixer is the KM mixer (trademark) KM, also referred to as the Р ще Р Р Й Й аг аг аг е. This device has various plow-shaped tools mounted on its axis. Optionally, one or more cutting tools can be used to prevent the formation of larger or lumpy material. Another suitable machine for this stage is, for example, that way (trademark) KT.

The minimum tool tip speed in the high speed mixer is preferably at least 5, more preferably at least 10, and most preferably at least 15 m / s. The maximum tip speed is preferably not more than 60, more preferably not more than 55, even more preferably not more than 50, and most preferably not more than 45 m / s.

The high-speed mixer is preferably operated with a minimum Froude criterion of at least 5, more preferably at least 20, even more preferably at least 40, and most preferably at least 50. The maximum Froude criterion is preferably not more than 750, more preferably not more than 500, and more preferably not more than 400.

The maximum speed of the tip of the tool in the medium or low speed mixer is preferably less than 15, more preferably less than 10, even more preferably less than 8 and most preferably less than 6 m / s. The minimum tip speed is preferably at least 1, more preferably at least 1.5, and most preferably at least 2 m / s.

The medium or low speed mixer is preferably operated with a maximum Froude criterion of less than 30, more preferably less than 15, even more preferably less than 5, and most preferably less than 4. The minimum value of the Froude criterion is preferably at least 0.15, more preferably at least 0.30, even more preferably at least 0.50, and most preferably at least 0.60.

It should be noted that in the precise definition of any particular preferred tip speed or range of the Froude criterion here, for either a high speed mixer or a medium or low speed mixer, no specific maximum tip speed is associated with any particular minimum tip speed. Similarly, no specific maximum value of the Froude criterion is associated with any specific minimum value of the Froude criterion.

A significant difference between a medium or low speed mixer and a high speed mixer in the method of the present invention is that the medium or low speed mixer operates at a lower tip speed and / or lower value of the Froude criterion, preferably both.

The speed of rotation of the axis with the tools mounted on it depends to a large extent on the size of the mixer used. For example, the high-speed machine Lbsche CB 100 will preferably have an axis rotation speed in the range of 100 to 1100, and more preferably 200 to 750 rpm. Likewise, a medium speed machine KM 10000 will preferably have an axis rotation speed in the range of 20 to 200, more preferably 25 to 120, even more preferably 30 to 100, and most preferably 30 to 70 rpm. For other sizes of the mixer, the preferred rotation speed is controlled to maintain the speed of the tool tip and the values of the Froude criterion at the preferred levels indicated above.

In addition to the mixing / mixing action of the tools, the medium or low speed mixer may contain cutting tools (cutters) that can be driven independently of the axis of the tools. These cutters can be used to prevent the formation of lumpy or larger material. If used, they work preferably at a speed of 200-3000 and more preferably from 2000 to 3000 rpm.

The residence time in the mixers during stationary operation depends on the parameters, which include the axis rotation speed, throughput, tool position and the shutter at the outlet. The residence time in the high speed mixer should be relatively short, preferably from about 1 to 60 seconds, more preferably from 5 to 30 seconds, and even more preferably from 5 to 20 seconds. The residence time in a medium or low speed mixer should usually be longer than the time in a high speed mixer. Preferably, it is in the range of from about 30 seconds to 10 minutes, more preferably from about 30 seconds to 5 minutes, most preferably from 30 seconds to 3 minutes.

Other suitable machines that can be used in the method of this invention either as high-speed mixers or as medium or low-speed mixers include Eikae® E8-O series mixers; Buckpa® V series from B1egkk & 8oipe, Germany; Ryaga Mayth® by T.K. E1e1bb Yb, England; Eir® νθ-C series from Eu) 1 8apduo Co, Japan; Βοΐο® from 2apeyeya & Co. kg1, Italy, and granulator 8eiir® Е1ехош1х.

The temperature in high-, medium- or low-speed mixers can be raised and / or lowered by any suitable means, for example a heating / cooling jacket.

The process in the mixers may be batch or continuous, however, continuous is preferred.

Gas fluidized granulator: stage (w).

In a third step of the method of the invention, a gas fluidized granulator is used. In an apparatus of this kind, a gas (usually air) is blown through a mass of solid particulate matter into or onto which a liquid component is sprayed. A gas fluidized granulator is sometimes referred to as a granulator or fluidized bed mixer. This is not entirely accurate, since such mixers can operate at such a high gas flow rate that no classical fluidized bed is formed.

The gas granulation and agglomeration process step is preferably carried out essentially as described in No. 098/58046 and No. 098/58047 (Ipieueg), the contents of which are incorporated herein by reference.

The gas fluidization apparatus mainly comprises a chamber in which a gas stream (hereinafter referred to as fluidization gas), usually air, is used to create a turbulent flow of solid matter in the form of particles to form a suspension of solid particles, and to or from the suspension Liquid binder is sprayed to make it contact with individual particles. As the process proceeds, individual particles of the starting solid materials are agglomerated due to the liquid binder to form granules.

A gas fluidized gas granulator is typically operated at a surface air velocity of about 0.1-1.2 ms ^-1, either under positive or negative relative pressure and with an inlet air temperature (i.e., a fluidized gas temperature) ranging from -10 or 5 ° C up to 100 ° C. In some cases, it can be as high as 200 ° C.

The temperature of the fluidization gas, and therefore preferably the temperature of the bed, can be changed during the granulation process, as described in XVO 98/58048. It can be increased for the first period, for example, up to 100 ° C or even up to 200 ° C and then at one or several other stages (before or after) it can be lowered to a temperature slightly above ambient, equal to or lower than it, for example up to 30 ° C or lower, preferably 25 ° C or lower or even as low as 5 ° C or lower or -10 ° C or lower.

In a preferred embodiment, the temperature of the fluidization gas and preferably also the temperature of the bed is increased for the first period and subsequently reduced in the second period.

When the method is a batch process, the temperature will change over time. If the method is a continuous process, the temperature will vary along the path of the layer in the granulator (i.e., in the direction of the flow of powder through the layer in the granulator). In the latter case, this is usually carried out using a piston-type flow granulator, i.e. such where materials flow through the reactor from start to finish.

In a batch process, the temperature of the fluidization gas can be reduced over a relatively short period of time, for example from 10 to 50% of the process time.

Typically, the gas temperature can be lowered within 0.5-15 minutes. In a continuous process, the gas temperature can be lowered over a relatively short length of the layer path in the granulator, for example, over 10-50% of the path. In both cases, the gas may be pre-cooled.

Preferably, the temperature of the fluidized gas, and preferably also the temperature of the bed, is not reduced until essentially the agglomeration of the fluidized solid particulate material is completed.

In addition to the fluidization gas, a spray gas stream may also be used in the fluidized gas granulator. Thus, a spray gas stream is used to facilitate the dispersion of a liquid binder from the nozzle onto or into fluidized solids. If a spray gas stream is used, it usually operates at a pressure of 2 to 5 bar (200-500 kPa). The flow of atomizing gas, usually air, can also be heated.

In a preferred embodiment, the temperature of the layer is maintained near or close to a temperature that provides for the pumpability (as defined below) of the liquid binder for at least a portion of the time and preferably for substantially the entire time that the liquid binder is sprayed onto a fluidized solid substances. This is especially preferred when the liquid binder is a structured mixture (as described below).

Alternatively, it is preferable that the temperature of one and preferably both gases, and a fluidization gas, and a spray gas, is raised to a temperature within a tolerance of 15 ° C. (plus or minus) and preferably within a temperature of 10 ° C. to ensure the pumpability of the liquid binder, especially when liquid a binder is a structured mixture. The temperature should be raised at least during the portion, and preferably substantially throughout the entire period when the liquid binder mixture is sprayed onto the fluidized material.

In a preferred embodiment, the temperature of one and preferably both gases, and a fluidization gas, and a spray gas, is increased so that they are at least at a temperature that ensures the pumpability of the liquid binder, especially when the liquid binder is a structured mixture.

As used herein, the term bed temperature refers to the temperature of a fluidized gas around particulate solid material. The temperature of the layer can be measured, for example, with a thermocouple. Whether it is a distinguishable powder layer or an indistinguishable powder layer (i.e., because the mixer operates at such a high gas flow rate that a classical fluidized fluidized bed does not form), the temperature of the layer is taken to be the temperature measured at a point inside fluidization chambers at a distance of about 15 cm from the gas distribution plate.

A gas fluidized granulator may optionally be of the type provided with a vibrating bed, especially for continuous use.

Drying and / or cooling: stage (ίν).

For use, handling and storage, the granular detergent product must be in a free-flowing state. Therefore, at the final stage, the granules can be dried and / or cooled, if necessary. This step can be carried out in any known manner, for example, in an apparatus with a fluidized bed (drying and cooling) or in an ER elevator (cooling). Drying and / or cooling can be carried out in the same fluidized bed apparatus used for the final sintering step, simply by changing the process conditions used, as should be well known to one skilled in the art. For example, fluidization may be continued for a period after completion of the addition of a liquid binder, and the inlet air temperature may be reduced.

In a preferred embodiment, the entire process is continuous.

Liquid binder

In the method of the invention, a liquid binder is added in steps (ί) and (ίίί). A liquid binder may also be added in step (ίί) of the process, but preferably when little liquid is added or not added. If a liquid binder is added during step (ίί), it is preferred that less than 10 wt.%, Preferably less than 5 wt.%, Of the total amount of liquid binder added in the process is added in step (ίί).

The liquid binder added at each stage may be the same, or they may be different, and at any one stage more than one liquid binder may be added.

The mass ratio of the binder added in step (ί) to that added in step (ίίί) is preferably in the range from 20: 1 to 1:20, preferably from 10: 1 to 1:10, and more preferably from 9: 1 to 1: 2. Preferably, of the total amount of liquid binder added in steps (ί) and (ίίί), at least 5 wt.%, More preferably at least 10 wt.%, Is added in step (ίίί).

As a rule, for the same process conditions, the higher the mass ratio of the liquid binder added in stage (ί) to that added in stage (ίίί), the higher the resulting bulk density. Thus, the bulk density of the granular detergent product can be varied and adjusted to a certain extent by changing the binder addition ratio.

The liquid binder can simply be pumped into the mixer of stage (ί) and optionally to the mixer of stage (ίί) or can be introduced as a spray. The liquid binder is sprayed into the granulator with a gas fluidization stage (ίίί).

The liquid binder may contain one or more components of a granular detergent product. Suitable liquid components include anionic surfactants and their acid precursors, nonionic surfactants, fatty acids, water and organic solvents.

The liquid binder may also contain solid components dissolved or dispersed in the liquid component, such as, for example, inorganic neutralizing agents and detergent modifying additives. The only limitation is that with or without dissolved or dispersed solids, the liquid binder must be pumped and capable of being delivered to the mixer and / or granulator in the form of a liquid, including a paste form.

Preferably, the liquid binder contains an anionic surfactant. The content of the anionic surfactant in the liquid binder may be as high as possible, for example at least 98 wt.% Of the liquid binder, or it may be less than 75 wt.%, Less than 50 wt.% Or less than 25 wt.%. It, of course, may be 5 wt.% Or less, or may be absent altogether.

Suitable anionic surfactants are well known to those skilled in the art. Examples suitable for incorporation into a liquid binder include alkylbenzenesulfonates, especially linear alkylbenzenesulfonates having a C ₈ -C _{1 5} alkyl chain length; primary and secondary alkyl sulfates, especially C ₁₂ -C ₁₅ primary alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; and sulfonates of fatty acid esters. Sodium salts are generally preferred.

It is very preferable to obtain some or all of the anionic surfactant ίη zi in a liquid binder by reacting a suitable acid precursor and an alkaline material such as alkali metal hydroxide, for example ΝαΝ, since the latter usually needs to be metered in an aqueous solution, which inevitably accompanied by the introduction of a certain amount of water. Moreover, the reaction of an alkali metal hydroxide and an acid precursor also gives some water as a by-product.

However, in principle, any alkaline inorganic material can be used to neutralize, but water-soluble alkaline inorganic materials are preferred. Another preferred material is sodium carbonate, alone or in combination with one or more other water-soluble inorganic materials, for example bicarbonate or sodium silicate. If desired, a stoichiometric excess of a neutralizing agent can be used to ensure complete neutralization or to provide an alternative action, for example, as a detergent modifying additive, for example, if the neutralizing agent contains sodium carbonate. Organic neutralizing agents can also be used.

Of course, if the liquid binder contains the acid precursor of the anionic surfactant, the acid precursor can be neutralized or the neutralization can be completed in a mixer and / or granulator, either by contacting with a solid alkaline material, or by adding a separate liquid neutralizing agent to the mixer and / or granulator. However, neutralization in the mixer and / or granulator is not a preferred feature of the present invention.

The liquid acid precursor may be selected from linear alkylbenzenesulfonic acids (L8), alpha olefinsulfonic acids, internal olefinsulfonic acids, sulfonic acids of fatty acid esters, and combinations thereof. The method of the invention is particularly applicable to the preparation of compositions containing alkylbenzenesulfonates by reaction of the corresponding alkylbenzenesulfonic acid, for example, dobanoic (EbOapo1C) acid from 8Pc11. Can also be used linear or branched primary alkyl sulfates (RL8) having from 10 to 15 carbon atoms.

In a preferred embodiment, the liquid binder comprises an anionic surfactant and a nonionic surfactant. The mass ratio of anionic surfactant to nonionic surfactant is in the range from 10: 1 to 1:15, preferably from 10: 1 to 1:10, more preferably from 10: 1 to 1: 5. If the liquid binder contains at least some of the acid precursor of the anionic surfactant and the nonionic surfactant, then the mass ratio of the anionic surfactant, including the acid precursor, to the nonionic surfactant may be higher. e.g. 15: 1.

The nonionic surface-active component of the liquid binder can be any one or more liquid nonionic substances selected from ethoxylates of primary and secondary alcohols, especially C ₈ -C ₂₀ aliphatic alcohols, ethoxylated on average from 1 to 2 moles of ethylene oxide per mole of alcohol, and more specifically C ₁₀ -C ₁₅ primary and secondary aliphatic alcohols, ethoxylated on average from 1 to 10 mol of ethylene oxide per mole of alcohol. Non-ethoxylated non-ionic surfactants include alkyl polyglycosides, glycerol monoesters and polyhydroxyamides (glucamide).

In a preferred embodiment, the liquid binder is substantially anhydrous. That is, the total amount of water in it is not more than 20 wt.% A liquid binder, preferably not more than 15 wt.% And more preferably not more than 10 wt.%. However, if desired, a controlled amount of water may be added to facilitate neutralization. Typically, water may be added in amounts of from 0.5 to 2% by weight of the final detergent product. Typically, from 3 to 4 wt.% Of the liquid binder can be represented by water as a by-product of the reaction, and the rest of the water present is in the solvent in which the alkaline material is dissolved. It is very preferable to exclude any other water from the liquid binder except the indicated sources, with the exception of possible trace amounts / impurities.

Alternatively, an aqueous liquid binder may be used. This is especially suitable for the preparation of products that are auxiliary additives for subsequent mixing with other components to obtain a full detergent product. Such auxiliary additives will usually, in addition to components derived from a liquid binder, consist mainly of one or a small number of components commonly found in detergent formulations, for example, a surfactant or modifier, such as zeolite or sodium tripolyphosphate. However, this does not preclude the use of aqueous liquid binders for granulating products of a substantially complete composition. In any case, typical aqueous liquid binders include aqueous solutions of alkali metal silicates, water-soluble acrylic / maleic polymers (for example, 8co1ap CP5) and the like.

The liquid binder may optionally contain dissolved solids and / or finely divided solids that are dispersed therein. The only limitation is that with or without solids dissolved or dispersed, the liquid binder must be pumped and sprayed at temperatures of 50 ° C or higher or, in any case, 60 ° C or higher, for example 75 ° C. It is preferably solid at a temperature below 50 ° C, preferably at 25 ° C or lower. The liquid binder is preferably at a temperature of at least 50 ° C, more preferably at least 60 ° C, when it is fed to a gas fluidized mixer or granulator.

According to the present invention, liquid binders are considered to be easily pumpable if they have a viscosity of not more than 1 Pa-s at a shear rate of 50 s ^-1 and at a transfer temperature. Higher viscosity liquid binders may still be suitable in principle for pumping, but an upper limit of 1 Pa-s at a shear rate of 50 s ^{-1 is} used here to indicate the possibility of easy pumping.

Viscosity can be measured, for example, using a Naake UT500 rotational viscometer. The viscosity measurement can be carried out as follows. The measuring cell 8У2Р is connected to a thermostatic water bath with a cooling unit. The plumb of the measuring cell rotates at a shear rate of 50 s ^-1 . The cured mixture is heated in a microwave oven to 95 ° C and poured into a sample cup. After conditioning for 5 min at 98 ° C, the sample is cooled at a speed of +/- 1 ° C / min. The temperature at which a viscosity of 1 Pa s is observed is recorded as the temperature ensuring pumpability.

The temperature ensuring pumpability of the liquid binder is thus defined here as the temperature at which the liquid binder exhibits a viscosity of 1 Pa-s at 50 s ⁻¹ .

A definition of solid can be found in Nabbok about С SешbstЩtu apb Ryuysk, SKS Rge55. Vosa K.a1op, Florida, 67th edition, 1986.

Structured Blends

In a preferred embodiment of the invention, the liquid binder contains a builder, and the liquid binders that contain a builder are referred to herein as structured mixtures. All disclosures made in the description with reference to liquid binders are equally applicable to structured mixtures.

In the context of the present invention, the term “builder” means any component that makes the liquid component capable of achieving cure in a granulator and therefore good granulation, even if the solid component has a low liquid bearing capacity.

It is believed that the builders can be divided into categories, depending on their structural (curing) action according to one of the following mechanisms, namely: recrystallization (for example, silicate or phosphates); creating a three-dimensional structure of finely divided solid particles (for example, silica or clay), the effect on steric effects at the molecular level (for example, soaps or polymers), such as types commonly used as detergent modifying additives. One or more builders may be used.

Structured mixtures have the advantage that they cure at lower ambient temperatures and, as a result, impart structure and strength to the solids in the form of particles on which they are sprayed. Therefore, it is important that the structured mixture is suitable for pumping and spraying at elevated temperatures, for example at a temperature of at least 50 ° C, preferably at least 60 ° C, and that it also cures at temperatures below 50 ° C, preferably below 35 ° C in order to provide its beneficial effect.

Typically, in high speed and medium or low speed mixers, the temperature is more than 10 ° C., preferably more than 20 ° C. lower than the temperature at which the mixture is prepared and pumped to the granulator.

The builders cause curing in the liquid binder component, preferably in order to impart strength to the mixture as follows. The strength (hardness) of the cured liquid component can be measured using a аппаратаηκΙgop pressure apparatus. A tablet of the cured liquid component taken from the process before it contacts the solid component is formed with dimensions of 14 mm in diameter and 19 mm in height. The tablet is then destroyed between the fixed and movable plates, the movable plate moves towards the fixed plate. The speed of the movable plate is set to 5 mm / min, which gives a measurement time of about 2 s. The pressure curve is recorded on a computer. Thus, determine the maximum pressure (at the time of destruction of the tablet) and the E-module is calculated from the slope of the curve.

For the cured liquid component, P _max at 20 ° C is preferably at least 0.1 MPa, more preferably 0.2 MPa, for example from 0.3 to 0.7 MPa. At 55 ° C, a typical range is from 0.05 to 0.4 MPa. At 20 ° C

E _{then <1} for the liquid mixture is preferably at least 3 MPa, for example from 5 to 10 MPa.

The structured mixture is preferably prepared in a shear dynamic mixer to pre-mix its components and neutralize the anionic acid precursor in some way.

Soaps represent one preferred class of builders, especially when the structured mixture contains a liquid non-ionic surfactant. In many cases, it may be desirable for the soap to have an average chain length greater than the average chain length of a liquid nonionic surfactant, but less than twice the average chain length of the latter.

It is very preferable to obtain some or all of the soap-forming agent ίη 511p in a liquid binder by reacting a suitable fatty acid precursor and an alkaline material such as alkali metal hydroxide, for example ΝαΟΗ. However, in principle, any alkaline inorganic material can be used to neutralize, but water-soluble alkaline inorganic materials are preferred. In a liquid binder containing an anionic surfactant and soap, it is preferable to obtain both an anionic surfactant and soap from their respective acidic precursors. All disclosures made in the description regarding the preparation of an anionic surfactant by neutralizing ίη 511п in a liquid binder of its acid precursors are equally applicable to the preparation of soaps in structured mixtures.

If desired, the solid components may be dissolved or dispersed in a structured mixture. Typical amounts of ingredients in an essential component of a structured mixture, as% by weight of a structured mixture, are as follows:

preferably from 98 to 10 wt.% anionic surfactants, more preferably from 70 to 30 wt.% and especially from 50 to 30 wt.%;

preferably from 10 to 98 wt.% non-ionic surfactant, more preferably from 30 to 70 wt.% and especially from 30 to 50 wt.%;

preferably from 2 to 30 wt.% builder, more preferably from 2 to 20 wt.%, even more preferably from 2 to 15 wt.% and especially from 2 to 10 wt.%.

In addition to the anionic surfactant or its precursor, non-ionic surfactant and builder, the structured mixture may also contain other organic solvents.

Solid source material

The starting solid materials of the present invention are in the form of particles and can be powder and / or granular. As such, the starting solid material may be any component of a granular detergent product that is available in particulate form. Preferably, the starting solid material with which the liquid binder is mixed contains a detergent modifying additive. In a particularly preferred embodiment of the present invention, the starting solid material contains modifying agents selected from crystalline and amorphous aluminosilicates.

If the starting solid material contains or essentially consists of an aluminosilicate modifying additive, the mass ratio of the liquid binder to the solid component is preferably from 0.2: 1 to 0.8: 1. If the solid component contains a phosphate modifying additive or essentially consists of it, this ratio is preferably equal to from 0.2: 1 to 5: 1.

Product

The present invention also relates to a granular detergent product obtained by the method of the invention (prior to any subsequent dosing or the like).

The granular detergent products according to the invention have a bulk density of less than 900 g / l, preferably less than 800 g / l, more preferably less than 750 g / l and even more preferably less than 700 g / l. Bulk density can be as low as 450 g / l, however, preferably it is more than 550 g / l. Preferably, it is in the range of 550-800 g / l, more preferably 550-750 g / l, even more preferably 550-700 g / l.

The product will have a bulk density determined by the exact nature of the process, but it can be controlled to some extent by changing the ratio of adding a liquid binder in stages (ί) and (w).

The granular detergent products of the process of this invention have a low fines content and have good flow properties.

More specifically, the method of the invention provides granular detergent products with improved fines compared to similar powders prepared by prior art methods. Preferably, not more than 10% by weight of the granules have a diameter of less than 180 microns, more preferably not more than 8% by weight. Moreover, the granular detergent product preferably contains not more than 10% by weight of granules with a diameter of more than 1400 microns and more preferably not more than 5% by weight of granules exceeds this limit.

A granular product is considered free-flowing if it has ΌΕΚ at least 80 ml / s. Preferably, the granular products of this invention have ΌΕΚ values of at least 80 ml / s, preferably at least 90 ml / s, more preferably at least 100 ml / s, and most preferably at least 110 ml /from. The indicated values are ΌΕΚ. applicable to the product exposed to the weather, and preferably also to the non-exposed product.

And finally, the granules can be distinguished from granules obtained by other methods using mercury porosimetry. The latter technique is ideal for characterizing granules that are produced by a process involving gas agglomeration.

Detergent formulations and ingredients

As indicated previously, the granular detergent product obtained by the method of the invention, by itself, can be a detergent composition of the complete formulation, or it can be a component or auxiliary additive that forms only part of such a composition. This section applies to final, fully formulated detergent formulations.

The total amount of the detergent modifying additive in the finished (final) detergent composition is suitably from 10 to 80 wt.%, Preferably from 15 to 60 wt.%. The modifying additive may be present in the auxiliary additive with other components, or, if desired, individual particles of the modifying additive containing one or more modifying materials may be used.

The present invention is particularly suitable for use where the starting solid material contains modifying additives selected from crystalline and amorphous aluminosilicates, for example zeolites, as disclosed in OV-L-1473201, amorphous aluminosilicates, as disclosed in OV-L-1473202, and mixed crystalline amorphous aluminosilicates as disclosed in CB-L-1470250; and layered silicates as disclosed in EP-B164514.

Aluminosilicates, if used as exfoliating agents and / or as incorporated into the particle mass, may suitably be present in a total amount of 10 to 60 wt.% And preferably in an amount of 15 to 50 wt.% Based on the final detergent composition. The zeolite used in most commercial powder detergent formulations is zeolite A. It is advantageous, however, to use aluminum maximum zeolite P (MAP zeolite) described and claimed in EP-A-384070. Zeolite MAP is an alkaline metal enriched alkali metal derivative of type P having a silicon to aluminum ratio of not more than 1.33, preferably not more than 1.15, and more preferably not more than 1.07.

Other suitable modifying additives include hydratable salts, preferably in substantial amounts, such as at least 25% by weight of the solid component, preferably at least 10% by weight. Hydratable solids include inorganic sulfates and carbonates, as well as inorganic phosphate builders, for example, orthophosphate, pyrophosphate and sodium tripolyphosphate.

Other inorganic modifying additives that may be present include sodium carbonate (as mentioned above, an example of a hydratable solid), if desired, in combination with a crystallization seed for calcium carbonate, as disclosed in CB-A-1437950. As mentioned above, such sodium carbonate may be the residue of an inorganic alkaline neutralizing agent used to form an anionic surfactant ίη Shi.

Organic modifying additives that may be present include polycarboxylate polymers, such as polyacrylates, acrylic / maleic copolymers and acrylic phosphinates, monomeric polycarboxylates, such as citrates, gluconates, oxydisuccinates, mono-, di- and trisuccinates, glycerol, carboxymethyloxy sulfonates, carboxymethyloxy sulfonates, hydroxyethyliminodiacetates, aminopolycarboxylates such as nitrilotriacetates (ΝΤΑ), ethylenediaminetetraacetate (ΕΌΤΑ) and iminodiacetates, alkyl and alkenyl malonates and succinate s and salts of sulfonated fatty acids. A copolymer of maleic acid, acrylic acid and vinyl acetate is particularly preferred since it is biodegradable and therefore desirable from an environmental point of view. This list should not be considered exhaustive.

Particularly preferred organic modifying additives are citrates, suitably used in amounts of from 2 to 30 wt.%, Preferably from 5 to 25 wt.%; and acrylic polymers, more particularly acrylic / maleic copolymers, suitably used in amounts of from 0.5 to 15 wt.%, preferably from 1 to 10 wt.%. The modifier is preferably present in the form of an alkali metal salt, especially a sodium salt.

Granular detergent compositions may contain, in addition to any anionic and / or nonionic surfactants of a liquid binder, one or more other detergent compounds that can be selected from soap and non-soap anionic, cationic, nonionic, ampere and zwitterionic surfactants substances and their mixtures. They can be dosed (added) at any suitable stage before or during the process. Many suitable detergent active compounds are available and fully described in the literature, for example, in the publication ZigGase-AsOme Adep18 apy Pe1egdep18, volumes I and II, 8c11 \\ 'ag1x. Turnip and Vegs. Preferred detergent actives that can be used are soaps and synthetic non-soap anionic and nonionic compounds.

Detergent compositions may also contain a whitening system, preferably a peroxy bleach, for example, an inorganic persol or organic peroxyacid capable of releasing hydrogen peroxide in an aqueous solution. The bleaching peroxy compound can be used in combination with a bleach activator (bleach precursor) to improve the bleaching effect at low washing temperatures. A particularly preferred whitening system comprises a peroxy bleach (preferably sodium percarbonate) optionally together with a bleach activator.

Typically, any whitening and other sensitive ingredients, such as enzymes and perfumes, will be dispensed after granulation along with other small ingredients.

Typical small ingredients include sodium silicate, corrosion inhibitors including silicates, anti-redeposition agents such as cellulose polymers, fluorescents, inorganic salts such as sodium sulfate, foaming control agents, or foaming enhancers, as appropriate; proteolytic and lipolytic enzymes; dyes; painted specks, perfumes, foam control agents; and tissue softening compounds. This list should not be considered exhaustive.

Optionally, an exfoliating agent or a flow promoting agent may be introduced at any suitable stage of the process of the invention. This is done to improve the graininess of the product, for example, by preventing aggregation and / or caking of the granules. The flowability additive / any delaminating agent is suitably present in an amount of from 0.1 to 15% by weight of the granular product, and more preferably in an amount of from 0.5 to 5% by weight.

Suitable delaminating agents / flow improvers include crystalline or amorphous alkali metal silicates, aluminosilicates including zeolites, citrates, O1casho1, calcite, diatomaceous earths, silica, for example precipitated silica, chlorides such as sodium chloride, sulfates such as magnesium sulfate, carbonates, such as calcium carbonate, and phosphates, such as sodium tripolyphosphate. When desired, mixtures of these materials may be used.

Zeolite MAP, also a preferred modifying additive, is particularly useful as an exfoliating agent. Layered silicates, such as 8K8-6 from the company S1AG1AP1. also applicable as exfoliating agents.

Powder fluidity can also be improved by introducing a small amount of an additional powder builder, for example a fatty acid (or fatty acid soap), sugar, acrylate or acrylate / maleate polymer, or sodium silicate, which is suitably present in an amount of from 1 to 5 wt.%.

Typically, additional components may be included in the liquid binder or mixed with the starting solid material at a suitable stage of the process. However, the solid components may be dosed (added) subsequently to the granular detergent product.

The granular detergent composition may also contain a powdery filler (or some other component that improves the washing process), which suitably contains an inorganic salt, for example sodium sulfate and sodium chloride. The filler may be present in an amount of 5 to 70% by weight of the granular product.

The invention will now be described in more detail by means of the following non-limiting examples, where parts and percentages are given by weight, unless otherwise stated. Examples indicated by numbers are in accordance with the invention, and those indicated by a letter are comparative.

Examples

Examples 1-6, comparative examples A and B.

The main powders of the granular detergent product of the compositions detailed in the table are prepared.

The main powders of examples 1-6 are obtained by (ί) mixing and granulating the starting solid materials consisting of zeolite, light soda ash, sodium carboxymethyl cellulose (8СМС) and citrate, with a liquid binder in the Bbbschs Kesus1eg apparatus (CB 30);

(ίί) transferring material from Kesus1eg to the mixer Bbbsche P1oidykyate (KM 300);

(ίίί) transferring the material from P1oidbase to the Wauchec fluidized bed (trademark), operating as a gas-fluidized granulator, adding additional liquid binder and agglomerating; and (ίν) finally drying / cooling the product in a fluidized bed.

Stage conditions (() - (() are as follows:

(ί) Mostly Kesus1eg (CB 30).

Stay time: about 15 s

Axis rotation speed: 1000 rpm

Tip Speed: 15.7 m / s

Froude's criterion: 168 (ίί) Bigger P1oid11k11age (KM 300).

Stay time: about 3 minutes

Axis rotation speed: 100 rpm

Choppers: Disabled

Tip Speed: 2.62 m / s

Froude Criterion: 2.8

Liquid binder: not added (ίίί) Fluidized bed (batch apparatus Washr1es, load size 10 kg).

Surface air speed: 1.0 m / s

Fluidization gas temperature: 75 ° C

Atomizing Gas Temperature: Hot

Atomizing pressure 3.5 bar air: (350 kPa)

Nozzle height (above the distribution plate): 47 cm

Binder Spray Speed: 800 g / min

Basic powders of comparative examples A and B are prepared in the same way, except that stage (ίί) is excluded.

The liquid binder used in steps (ί) and (ίίί) is a structured mixture containing an anionic surfactant, a nonionic surfactant and soap components of the base powder. The mixture is prepared by mixing 38.44 parts by weight of the acid precursor LAB8 and 5.20 parts by weight of the fatty acid soap precursor in the presence of 41.60 parts by weight of a non-ionic surfactant in the mixer (Lepb1oop) and neutralizing 14.75 parts of sodium hydroxide solution . The temperature of the mixture in the circuit is controlled by a heat exchanger. The neutralizing agent is sodium hydroxide solution. The resulting mixture has the following composition:

%

Linear sodium alkylbenzenesulfonate: 39.9

Nonionic Surfactant (7EO): 41.6

Soap: 5.6

Water: 12.9

The mass ratio of the mixture added to the recirculator and gas fluidized granulator is changed, as detailed in the table.

The values of bulk density and ΌΕΚ. for both fresh and weather-affected product are given in the table, as well as the content of fine and coarse material in the product.

ΌΕΚ. for both exposed and fresh granular detergent products of Examples 1-6 are at least 100 ml / s. In fact, the smallest ΌΕΚ observed in Example 1 is 108 ml / s.

The fines content in all examples 1-6 is less than 10 wt.%.

The products of comparative examples A and B are obtained in the same manner as used in examples 1 and 2, respectively, except that the second stage in the medium speed mixer is omitted in examples A and B. When comparing example A with example 1 and example B with example 2 clearly shows the benefits of using a medium-speed mixer (i.e. stage (s)) based on improved ΌΕΚ values. (for both fresh and weather-exposed product) and reduced fines in granular detergent products.

The results in the table also clearly demonstrate the main decrease in bulk density of the product when the ratio of the binder added in step (ί) to that added in step (ίίί) decreases. Bulk density is observed in the range from 739 to 579 g / l.

Example one BUT 2 IN 3 4 5 6 Basic powder U1-1.A8 11.35 11.35 11.66 11.66 12.08 12.23 12.77 13.30 Nonionic 7EO 11.72 11.72 12.04 12.04 12.47 12.63 13.19 13.73 Soap 1,58 1,58 1,62 1,62 1.68 1.70 1.78 1.85 Zeolite A24 37.47 37.47 37.07 37.07 36.53 36.32 35.63 34.95 Light Soda Ash 25.90 25.90 25.63 25.63 25.25 25.12 24.64 24.17 8 SMS 0.84 0.84 0.83 0.83 0.82 0.81 0.80 0.78 Citrate 3.45 3.45 3.41 3.41 3.36 3.35 3.28 3.22 Moisture, salt, ΝΌΟΜ 7.69 7.69 7.74 7.74 7.81 7.84 7.91 8.00 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Processing conditions The mixture in the recirculator,% 80 80 78 78 74 68 55 40 The mixture in the fluidized bed,% twenty twenty 22 22 26 32 45 60 Using P1oidY8Yage Yes not Yes not Yes Yes Yes Yes Properties of fresh About. pl., g / l 740 665 703 685 712 639 612 571 ΌΡΚ, ml / s 108 one hundred 115 one hundred 122 123 125 115 Properties exposed atm. the impact About. pl., g / l 739 674 719 690 658 655 615 579 ΌΡΚ, ml / s 115 85 110 95 122 130 120 112 YaB 626 442 546 561 496 519 524 557 Yaki 1.77 1.7 1.96 1.66 2.07 2.21 2,55 2,39 Trifle (<180),% 8.3 17.5 8.6 11.7 9.1 6.7 4.2 4.2 Coarse material (> 1400),% 2.6 0.4 1,5 2,3 one 0.9 one 1.8

CLAIM

Claims (18)

1. A method for producing a granular detergent product, comprising the steps of (ί) mixing and agglomerating a liquid binder with a solid starting material in a high speed mixer; (ίί) mixing the material from step (ί) in a medium or low speed mixer; (ίίί) feeding the material from step (ίί) and a liquid binder to a gas-fluidized granulator and further agglomerating; and (ίν) optionally drying and / or cooling - 2. The method according to claim 1, in which the high-speed mixer operates at a tip speed of at least 5, preferably at least 10, and more preferably at least 15 m / s. 3. The method according to claim 1 or 2, in which the high-speed mixer operates with a Froude criterion of at least 5, preferably at least 20, more preferably at least 40 and even more preferably at least , fifty. Niya. 4. The method according to any one of the preceding paragraphs, in which the medium or low speed mixer operates at a tip speed of less than 15, preferably less than 10, more preferably less than 8 and even more preferably less than 6 m / s. 5. The method according to any one of the preceding paragraphs, in which the medium or low speed mixer operates with a Froude criterion of less than 30, preferably less than 15, more preferably less than 8, more preferably less than 5 and even more preferably less than 4. 6. The method according to any one of the preceding paragraphs, in which less than 10 wt.% Of the total liquid binder added in the method is added in step (ίί). 7. The method according to claim 6, in which no liquid binder is added at stage (ίί). 8. The method according to any one of the preceding paragraphs, in which the mass ratio of the binder added in stage (ί) to the binder added in stage (ίίί) is in the range from 20: 1 to 1:20, preferably from 10: 1 to 1:10. 9. The method according to any one of the preceding paragraphs, in which the liquid binder contains one or more anionic surfactants or their acid precursors. 10. The method according to any one of the preceding paragraphs, in which the liquid binder contains one or more non-ionic surfactants. 11. The method according to any one of the preceding claims, wherein the liquid binder is at a temperature of at least 50 ° C when it is fed to a mixer or granulator with gas fluidization. 12. The method according to any one of the preceding paragraphs, in which the liquid binder is a structured mixture. 13. The method of claim 12, wherein the structured mixture comprises a soap-based builder. 14. The method according to any one of the preceding paragraphs, in which the liquid binder added in stage (ίίί) is a structured mixture and the temperature of the fluidization gas and / or the temperature of the spray gas of the granulator fluidized gas is increased when the structured mixture is added to a temperature within 35 ° C, preferably within 25 ° C and more preferably within 15 ° C, temperature, ensuring the pumpability of the structured mixture. 15. The method according to 14, in which the temperature of the fluidized gas and / or the temperature of the spray gas is approximately equal to the temperature that ensures the pumpability of the structured mixture. 16. The method according to any one of the preceding paragraphs, in which the source solid material contains aluminosilicate modifying additive. 17. The method according to clause 16, in which the aluminosilicate modifying additive contains a MAP zeolite. 18. Granular detergent product with a bulk density of less than 900 g / l, obtained according to the method according to claims 1-17.