ES2210544T3 - PROCEDURE TO PRODUCE A DETERGENT COMPOSITION THROUGH A PROCEDURE WITHOUT TOWERS. - Google Patents

Abstract

THE INVENTION REFERS TO A PROCEDURE THAT DOES NOT USE TOWER, TO PREPARE A DETERGENT GRANULAR COMPOSITION OF APPROX DENSITY CONTINUOUSLY. OF 600 G / L. SUCH PROCEDURE UNDERSTAND THE FOLLOWING PHASES: (A) (I) DISPERSE A TENSIOACTIVE AND COVER THE SENSITIVE TENSIUM WITH FINE POWDER, WHICH DIAMETER IS UNDERSTANDED BETWEEN 0.1 AND 500 MICRONS, WETTING SIMULTANEOUSLY THROUGH A STRENGTHENED ENVIRONMENT (B) COMPLETELY MIXING THE CONCLUSIONS IN A MIXER. PHASE (B) MAY ALSO BE FOLLOWED BY AN ADDITIONAL PHASE (C), CONSISTING IN GRANULATING THE AGLOMERATES FROM STAGE (B) IN ONE OR MORE FLUIDIFICATION DEVICES.

Description

Procedure to produce a composition detergent by a procedure without towers.

Field of the Invention

The present invention generally relates to a procedure without towers to produce a detergent composition in particles. More particularly, the invention relates to a continuous procedure by which agglomerates are produced detergents feeding a surfactant and materials coating to a series of mixers. The procedure produces a flowing detergent composition whose density can be adjusted for a wide range of consumer needs and that You can sell commercially.

Background of the invention

Recently, in the detergent industry has there was considerable interest in detergents for washing clothes that are "compact" and therefore have volumes Low dosage. To facilitate the production of these so-called low dosage detergents, many have been made attempts to produce detergents of high apparent density, by example, 600 g / l or more. Low dosage detergents they are currently in high demand because they conserve resources and they can sell in small packages that are more convenient for consumers. However, the degree to which detergent products modern need to be of a "compact" nature is still undetermined. Actually, many consumers, especially in developing countries, continue to prefer levels of higher dosage in their respective washing operations of clothing.

Generally, there are two main types of procedures by which granules or powders can be prepared detergents The first type of procedure involves drying by sprinkling an aqueous suspension of the detergent on a tower of spray drying, to produce very porous detergent granules (for example, procedure with towers for compositions low density detergents). In the second type of procedure, The various detergent components are dry mixed after of which they agglomerate with a binding agent, such as a nonionic or anionic surfactant, to produce compositions high density detergents (for example, process of agglomeration for high density detergent compositions). In these two procedures, the important factors that determine the Density of the resulting detergent granules are the shape, porosity and distribution of particle sizes of those cited granules, density and shape of various starting materials and their respective chemical composition.

In the art there have been many attempts to provide procedures that increase granule density or detergent powders. Particular attention has been given to the densification, by treatment after towers, of granules spray dried. For example, an attempt implies a discontinuous process in which granulated detergent powders or spray dried containing sodium tripolyphosphate and sodium sulfate is densified or converted into spherical granules in a Marumerizer®. This apparatus comprises a rough turntable, substantially horizontal, located at the base of a cylinder substantially vertical smooth walls. However, this procedure is essentially a discontinuous procedure and, by Therefore, less suitable for the production of detergent powders at big scale. More recently, other attempts have been made to provide continuous procedures to increase density, after the towers, of detergent granules dried by aspersion. Typically, such procedures require a first apparatus that pulverizes or crushes the granules and a second apparatus which increases the density of the granules by agglomeration pulverized Although these procedures achieve the increase desired density by treating or densifying "after towers "spray dried granules, have a capacity limited to having higher levels of surfactant without a stage back coating. In addition, the treatment or densification "after the towers" is not favorable in terms of economy (higher capital cost) and complexity of operation. In addition, all The aforementioned procedures are mainly aimed at densify or process spray dried granules. At present, relative quantities and types of materials have been limited subjected to spray drying procedures for production of detergent granules. For example, it has been difficult achieve high levels of surfactant in the detergent composition resulting, a feature that facilitates the production of detergents in a more efficient way. Thus, it would be desirable to have a procedure by which compositions could be produced detergents without having the limitations imposed by techniques Conventional spray drying.

To this end, the technique is full of descriptions of procedures that involve agglomerating compositions detergents For example, attempts have been made to agglomerate detergency builders by mixing zeolite and / or silicates in layers in a mixer, to produce flowing agglomerates. Even if such attempts suggest that these procedures can be used to produce detergent agglomerates, they do not provide a mechanism whereby starting detergent materials in the form of pastes, liquids and dry materials can be effectively agglomerated forming agglomerates consistent flowing detergents.

Consequently, in the technique the need to have an agglomeration procedure (without towers) to continuously produce a detergent composition having a high density provided directly by the ingredients starting detergents and preferably the density adjusting the conditions of the procedure. Too, there remains a need for such a procedure to be more efficient, flexible and economical to facilitate the production of detergents to large scale (1) for flexibility in the final density of the final composition and (2) for flexibility in incorporating the procedure several different kinds of ingredients detergents especially liquid ingredients.

The following references are directed to densify spray dried granules: Appel et al , US Patent No. 5,133,924 (Lever); Bortolotti et al , U.S. Patent No. 5,160,657 (Lever); Johnson et al , British Patent No. 1,517,713 (Unilever); and Curtis, European Patent Application 451,894.

The following references are aimed at producing detergents by agglomeration: Beujean et al , published no.
WO93 / 23,523 (Henkel), Lutz et al , US Patent No. 4,992,079 (FMC Corporation); Porasik et al , US Patent No. 4,427,417 (Korex); Beerse et al , US Patent No. 5,108,646 (Procter &Gamble); Capeci et al , US Patent No. 5,366,652 (Procter &Gamble); Hollingsworth et al , European Patent Application 351,937 (Unilever); Swatling et al , US Patent No. 5,205,958; Dhalewadikar et al , published No.WO96 / 04359 (Unilever).

For example, the published patent document WO93 / 3,523 (Henkel) describes the process comprising the pre-agglomeration by a low speed mixer and the subsequent agglomeration stage by a speed mixer high to obtain a high density detergent composition with less than 25% by weight of granules with a diameter greater than 2 mm U.S. Patent No. 4,427,417 (Korex) describes a continuous agglomeration procedure that reduces sedimentation compact and large agglomerates

Document US5554587 describes a procedure for preparing detergent compositions comprising introducing air in a mixer during the agglomeration of a paste surfactant and other detergent ingredients, so that at least a minimum amount of water of said surfactant paste is absorbed by said air.

WO9609370 describes a procedure to prepare high density detergent compositions that It comprises the steps of mixing a surfactant paste and dry detergent ingredients in a mixer to form ones first agglomerates, condition said first agglomerates to get agglomerated seconds that have a particle size specific, recycle any agglomerates that do not have the desired particle size for subsequent agglomeration to get a few seconds agglomerates that have particle size desired, mix detergent ingredients with said seconds agglomerates to form a high detergent composition density.

None of the existing techniques provide All the advantages and benefits of the present invention.

Summary of the invention

The present invention meets the needs mentioned above in the art by providing a procedure that It produces a high density granular detergent composition. The The present invention also meets the needs before mentioned in the art by providing a procedure that produces a granular detergent composition for flexibility in final density of the final composition by a process of agglomeration (for example, without towers). The procedure does not use the conventional conventional spray drying towers that are limited to producing compositions with high surfactant loading. In addition, the process of the present invention is more efficient, economical and flexible with respect to the diversity of compositions detergents that can be produced in the process. In addition, the procedure is more sensitive to environmental conditions because does not use spray drying towers that typically emit to the Atmosphere volatile organic compounds and particles.

Here, the term "agglomerates" refers to particles formed by agglomerating raw materials with binding agents, such as surfactants and / or inorganic solutions / organic solvents and solutions of polymers Here, the term "granulation" is refers to fluidize agglomerates to produce granulated agglomerates round shaped flowers. Here, the expression "average residence time" refers to the following definition:

Average residence time (h) = [mass (kg)] / [hourly production (kg / h)]

All percentages used herein memory are "percentages by weight", unless indicated contrary. All proportions are proportions by weight, except otherwise indicated. In this report, the expression "comprising" means that other ones can be added stages and other ingredients that do not affect the result. Is expression encompasses the expressions "consisting of" and "that it consists essentially of ".

According to a first aspect of the invention, a procedure for preparing a composition is provided granular detergent having a density of at least g / l

(to)

disperse a surfactant and coat the surfactant with a fine powder that has a diameter of 0.1 to 500 micrometers, while the surfactant coated with fine powder with finely liquid atomized, in a mixer in which the conditions of the mixer include (i) an average residence time of 0.2 to 5 seconds, (ii) a peripheral speed of 15 to 26 m / s and (iii) a condition of energy of 0.2 to 3 kJ / kg, in which first ones are formed agglomerates;

(b)

Mix perfectly the first agglomerates in a mixer with cutters in which the conditions of the mixer include (i) a average residence time of 0.5 to 15 minutes and (ii) a condition energy of 0.15 to 7 kJ / kg, in which a few seconds are formed agglomerates; Y

(c)

granulate the second agglomerated in a fluidized bed dryer and a fluidized bed cooler in which the conditions of each of the fluidization apparatus include (i) an average time of permanence of 1 to 10 minutes, (ii) a bed height not fluidized from 100 to 300 mm, (iii) a size of the droplets sprayed not exceeding 50 micrometers, (iv) a spray height of 175 to 250 mm, (v) a fluidization rate of 0.2 to 1.4 m / s and (vi) a bed temperature of 12 to 100 ° C, in which the average time d permanence of stage (c) is in total from 2 to 12 minutes, and in the that a coating agent selected from the group consisting in aluminosilicates, silicates, carbonates and mixtures thereof is added to stage (c) well: directly after the cooler of fluidized bed or fluidized bed dryer; and / or between fluidized bed dryer and fluidized bed cooler; I directly to the fluidized bed dryer.

The compositions are also provided granular detergents that have a high density of at least 600g / l, produced by any one of the embodiments of the procedures described herein.

Consequently, an objective of the present invention is to provide a process for continuous production a detergent composition that has flexibility with respect to the density of the final products controlling energy consumption, residence time and peripheral speed in the mixers. It is also an object of the invention to provide a method. make it more efficient, flexible and economical to facilitate the large scale production. These and other objectives, characteristics and related advantages of the present invention will be clear to Those skilled in the art from reading the following detailed description of the preferred embodiment and the attached claims.

Detailed description of the preferred embodiment

The present invention relates to a procedure that produces flowing detergent agglomerates granular having a density of at least 600 g / l. The procedure produces agglomerates of granular detergents from of an aqueous and / or non-aqueous surfactant that is then coated with a fine powder having a diameter of 0.1 to 500 micrometers, for obtain low density granules.

Process

First stage [stage (to)]

In the first stage of the procedure, feed a first mixer a surfactant (s) aqueous (s) and / or non-aqueous (s) that are in the form of powder, paste and / or liquid, and a fine powder that has a diameter of 0.1 to 500 micrometers, preferably 1 to 100 micrometers, for Prepare agglomerates. During the procedure, the surface of the surfactant that is coated with fine powder, moistened with finely atomized liquid to add more fine powder on the agglomerate surface. (The definition of surfactant and of fine powder and finely atomized liquid are described in more detail ahead). Optionally, in addition to the fine powder, it can be fed to the mixer an internal recirculated stream of dust, which has a diameter of 0.1 to 300 micrometers, generated in the apparatus of fluidization (for example, fluidized bed dryer and / or cooler fluidized bed). The amount of said recycled current Internal powder can be 0 to 60% by weight of the final product.

In another embodiment of the invention, the surfactant for the first stage can initially be fed to a mixer or premixer (for example, a conventional extruder screw or other similar mixer) before the previous stage, after which the mixed detergent materials are fed to the first stage mixer, as described, for its agglomeration.

In general terms, preferably, time means of permanence in the first mixer is in the range of 0.2 to 5 seconds and the peripheral speed of the first mixer is in the range of 10m / s at 30m / s and energy per unit mass (energy condition) in the first mixer is in the range from 0.15kJ / kg to 5 kJ / kg, more preferably, the average time of permanence in the first mixer is in the range of 0.2 to 5 seconds and the peripheral speed of the first mixer is in the range of 10 m / s to 30 m / s, energy per unit mass (energy condition) in the first mixer is in the range from 0.15 kJ / kg to 5 kJ / kg, and most preferably, the average time of permanence in the first mixer is in the range of 0.2 to 5 seconds, the peripheral speed of the first mixer is in the range of 15 m / s to 26 m / s, energy per unit mass (energy condition) in the first mixer is 0.2 kJ / kg at 3 kJ / kg

Examples of the mixer can be any types of mixers known to those skilled in the art as long as the mixer can maintain the conditions before mentioned for the first stage. An example can be the model Flexomic manufactured by the company Schugi (Netherlands). How result of the first stage, you get then the first agglomerates

       \ newpage
    

Second stage [Stage (b)]

The product resulting from the first stage (is ie, the first agglomerates) is fed to a second mixer. Specifically, the first agglomerates are mixed and sheared to background to round and grow the agglomerates in the second mixer. Optionally, it can be added in the second stage 0-10%, more preferably 2-5% of powder detergent ingredients of the type used in the first stage and / or other detergent ingredients. Preferably to break undesirable agglomerates of larger size, cutters can be used which are coupled to the third mixer. Therefore the procedure that includes the second mixer with cutters is useful to obtain as final products a reduced amount of larger agglomerates and said procedure is an embodiment Preferred of the present invention.

In general terms, preferably time permanence medium in the second mixer is in the range of 0.5 to 15 minutes and energy per unit mass (condition of energy) in the second mixer is in the range of 0.15 to 7 kJ / kg, more preferably the average residence time in the second mixer is in the interval of 3 to 6 minutes and the energy per unit mass (energy condition) in the second Mixer is in the range of 0.15 to 4 kJ / kg.

Examples of the second mixer can be any types of mixers known to those skilled in the technique as long as the mixer can maintain the conditions mentioned above for the second stage. An example may be the Lödige KM mixer manufactured by the Lödige company (Germany). As a result of the second stage, the seconds are obtained round agglomerates.

Third stage [stage (c)]

If the second agglomerates are less than 600 g / l, or if an additional agglomeration is preferred to satisfy the optimal condition as the final product from the procedure of the present invention, the second agglomerates are fed to a fluidized apparatus, such as fluidized bed, to increase the granulation to produce high density fluids granules. The third stage can take place in one more than one devices fluidized (for example, combining different kinds of apparatus of fluidization, such as a fluidized bed dryer and a chiller fluidized bed). Optionally, it can be added in the second step 0 to 10%, more preferably 2-5% of powder detergent materials of the type used in the first stage and / or other detergent ingredients. Optionally, it can be added also in step 0 to 20%, more preferably 2 to 10% of liquid detergent materials of the type used in the first stage, the second stage and / or other detergent ingredients to increase granulation and coating on the surface of the granules.

In general terms, to achieve density of at least 600 g / l, preferably greater than 650 g / l, the fluidized apparatus conditions may be;

Average residence time: 1 to 10 minutes

Non-fluidized bed height: 100 to 300 mm

Spray droplet size: not more than 50 micrometers

Spray height: 175 to 250 mm

Fluidization speed: 0.2 to 1.4 m / s

Bed temperature: from 12 to 100ºC,

plus preferably;

Average residence time: from 2 to 6 minutes

Non-fluidized bed height: from 100 to 250 mm

Spray droplet size: less than 50 micrometers

Spray height: 175 to 200 mm

Fluidization speed: 0.3 to 1.0 m / s

Bed temperature: from 12 to 80ºC.

If two different kinds of device are used fluidization, the total average time spent in the third stage may be 2 to 20 minutes, more preferably 2 to 12 minutes

A coating agent is added to improve fluidity and / or minimize excessive agglomeration of the composition detergent, in one or more of the following points of the present Procedure: (1) The coating agent can be added directly after the fluidized bed cooler or dryer fluidized bed; (2) the coating agent can be added between the fluidized bed dryer and the bed cooler fluidized; and / or (3) the coating agent can be added directly to the fluidized bed dryer. The agent of coating is preferably selected from the group consisting in aluminosilicates, silicates, carbonates and mixtures thereof. The coating agent not only increases the fluidity of the resulting detergent composition that is desirable by consumers because it allows easy detergent dosing during use, it also serves to control the agglomeration avoiding or minimizing excessive agglomeration. How Those skilled in the art are well aware of excessive agglomeration may cause undesirable fluidity and aesthetic properties in the final detergent product.

Starting detergent materials

The total amount of surfactants in products prepared by the present invention, which are included in the following detergent materials, finely atomized liquid e auxiliary detergent ingredients, is generally 5% to 60%, more preferably from 12% to 40%, more preferably from 15 to 35%, in percentages The surfactants that are included in the materials mentioned above may come from any part of the method of the present invention, for example, of a any of the first stage, the second stage and / or the third stage step of the present invention.

Detergent surfactant (aqueous / non-aqueous)

The amount of surfactant in the present procedure can be from 5 to 60%, more preferably from 12% to 40%, more preferably from 15% to 35%, based on the amount Total final product obtained by the procedure herein invention.

The surfactant of the present process, which It is used as the starting detergent materials mentioned above in the first stage, it is in the form of liquid raw material, in Paste or powder.

The surfactant is preferably selected from anionic, nonionic, hybrid, ampholytic and cationic surfactants and compatible mixtures thereof. Detergent surfactants useful in the present invention are described in US Patents 3,664,961, Norris, issued May 23, 1972, and 3,929,678, Laughlin et al ., Issued December 30, 1975. Useful cationic surfactants. they also include those described in US Patents 4,222,905, Cockrell, issued on September 16, 1980, and 4,239,659, Murphy, issued on December 16, 1980. Of the surfactants, preferred are anionic and non Ionic and most preferred are anionic.

Non-limiting examples of surfactants Preferred anionics useful in the present invention include the (C 11 -C 18 alkyl) benzenesulfonates ("LAS") and (primary C 10 -C 20 alkyl), branched chain and random) sulfates ("AS") conventional; the [C 10 -C 18 alkyl] secondary (2,3)] sulfates of formula CH 3 (CH 2) x (CHOSO3 - M +) CH 3 Y CH 3 (CH 2) y (CHOSO 3 - M +) CH 2 CH 3 where x e (y + 1) are integers of at least approximately 7, preferably at least about 9, and M is a cation water solubilizer, especially sodium; unsaturated sulfates, as oleyl sulfates, and the (alkyl C 10 -C 18) - alkoxysulfates ("AE_ {x} S", especially EO ethoxy sulfates 1-7).

Useful anionic surfactants include also water soluble salts of acids 2-acyloxyalkano-1-sulfonic containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; water soluble salts of olefinsulfonates containing 12 to 24 carbon atoms; Y beta-alkyloxysulfonates containing 1 to 3 carbon atoms in the alkyl group and 8 to 20 carbon atoms in the rest alkane.

Optionally, other useful typical surfactants in the pulp of the invention include (alkyl C 10 -C 18) alkoxycarboxylates (especially EO 1-5 ethoxycarboxylates), (rent C 10 -C 18) - glycerol ethers, the (C 10 -C 18 alkyl) polyglycosides and the corresponding sulfated polyglycosides, and esters of C 12 -C 18 fatty acids α-sulphonates. If desired, you can also include in all the compositions non-ionic surfactants and conventional amphoteric, such as (alkyl) C 12 -C 18) - ethoxylates ("AE"), including so-called (peak alkyl) narrow) ethoxylates and (alkyl C 6 -C 12) Phenolalkoxylates (especially mixed ethoxylates and ethoxy / propoxy), amine oxides C 10 -C 18, and the like. Can also be use fatty acid N-alkylamides C 10 -C 18 polyhydroxylated. Typical examples include N-methylglucamides C_ {12} -C_ {18}. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxyamides of polyhydroxy fatty acids, such as N- (3-methoxypropyl) glucamide C_ {10} -C_ {18}. You can also use the N-propyl a N-hexyl glucamides C 12 -C 18 for low foaming. Conventional soaps can also be used C_ {10} -C_ {20}. If you want a lot of training foam, C 10 -C 16 soaps of branched chain Especially useful are mixtures of surfactants anionic and nonionic.

As detergent surfactants, cationic surfactants and suitable surfactants of the quaternary ammonium type can also be used herein from [mono-N-alkyl (or alkenyl) C 6 -C 16] surfactants, preferably C 6 -C 10] -ammonium, in which the remaining positions of N are substituted by methyl, hydroxyethyl or hydroxypropyl groups. As detergent surfactants, ampholytic surfactants may also be used herein, including aliphatic derivatives of secondary and tertiary heterocyclic amines; hybrid surfactants, including derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds; water soluble salts of α-sulphonated fatty acid esters; alkyl ether sufatos; water soluble salts of olefinsulfonates; β-alkyloxyalkanesulfonates; betaines having the formula R (R 1) 2 N + R 2 COO - in which R is a hydrocarbyl group
C 6 -C 18, preferably a C 10 -C 16 alkyl group or a (C 10 -C 16 acyl) amidoalkyl group, each R 1 is typically C_ alkyl 1-C 3, preferably methyl, and R 2 is a C 1 -C 5 hydrocarbyl group, preferably a C 1 -C 3 alkylene group, more preferably a group C 1 -C 2 alkylene. Examples of suitable betaines include cocoacylamidopropyl dimethyl betaine; hexadecyldimethyl betaine; (C 12 -C 14 acyl) amidopropyl betaine ;, (C 8 -C 14 acyl) -amidohexyldiethyl betaine; 4 - [(C 14 -C 16 acyl) methylamidodyethylammonium] -1-carboxybutane; (C 16 -C 18 acyl) amidodimethyl betaine; (C 12 -C 16 acyl) amidopentanediethylbetaine and (C 12 -C 16 acyl) methylamidodimethyl betaine. Preferred betaines are (C 12 -C 18) dimethylammonium hexanoate and the (C 10 -C 18 acyl) amido-propane (or ethane) dimethyl (or diethyl) betaines; and the sultaines having the formula R (R 1) 2 N + R 2 SO 3 - in which R is a C 6 -C 18 hydrocarbyl group , preferably a C 10 -C 16 alkyl group, more preferably a C 12 -C 13 alkyl group, each R 1 is typically C 1 -C 3 alkyl, preferably methyl, and R2 is a hydrocarbyl group
C 1 -C 6, preferably an alkylene group or, preferably, C 1 -C 3 hydroxyalkylene. Examples of suitable sultains include (C 12 -C 14) dimethyl-ammonium-2-hydroxypropylsulfonate, (C 12 -C 14) amidopropylammonium-2-hydroxypropyl-sultaine, (C 12 -C_ {14}) dihydroxyethylammoniumpropanesulfonate and (C16 -C18) dimethylammonium-hexanesulfonate, with the
(C 12 -C 14) amidopropylammonium-2-hydroxypropyl-sultaine.

Fine powder

The amount of the fine powder of the present process, which is used in the first stage, can be 94% to 30%, preferably 86% to 54%, based on the total amount of starting material for the first stage. The starting fine powder of the present process is preferably selected from the group consisting of ground sodium carbonate, powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground sodium sulfates, aluminosilicates, layered crystalline silicates, nitrilotriacetates (NTA), phosphates, silicates precipitates, polymers, carbonates, citrates, powdered surfactants (such as powdered alkanesulfonic acids) and an internal recycled stream of powder from the process of the present invention, wherein the average diameter of the powder is 0.1 to 500 micrometers, preferably 1 to 300 micrometers, more preferably 5 to 100 micrometers In the case of using hydrated STPP as the fine powder of the present invention, hydrated STPP at a level not less than 50% is preferred. The aluminosilicate type ion exchange materials used herein as detergency builders preferably have both a high calcium ion exchange capacity and a high calcium ion exchange rate. Without pretending to be limited by theory, it is believed that said capacity and high rate of calcium ion exchange are a function of several interrelated factors derived from the method by which the aluminosilicate type ion exchange material is produced. In this regard, the aluminosilicate type ion exchange materials used herein are preferably produced in accordance with Corkill et al ., US Patent No. 4,605,509 (Procter & Gamble).

Preferably, the exchange material ionic aluminosilicate type is in "sodium" form put that the hydrogenated and potassium forms of aluminosilicate do not have a capacity or exchange rate as high as the provided by the sodium form. Additionally, the material of ion exchange aluminosilicate type is preferably in dry form to facilitate the production of agglomerates of detergents such as those described herein. The aluminosilicate type ion exchange materials used in the present specification preferably have particle diameters which optimize their effectiveness as detergency builders. In the present memory, the expression "average particle diameter" represents the average particle diameter of a material of ion exchange of particular aluminosilicate type, determined by conventional analytical techniques, such as determination microscopic and scanning electron microscopy (SEM). The Preferred average diameter of aluminosilicate particles is 0.1 at 10 micrometers, more preferably 0.5 to 9 micrometers. The most preferably, the average particle diameter is 1 to 8 micrometers

Preferably, the exchange material aluminosilicate type ionic has the formula

Na_ {z} [(AlO_2) {z} \ cdot (Si0_2) y} xH_ {O}

in which z and y are whole numbers of at least 6, the molar ratio of z a y is approximately 1 a about 5 and x is from 10 to 264. More preferably, the aluminosilicate has the formula

Na 12 ((AlO2) 12 \ cdot (Si02) 12] xH2 O

wherein x is from about 20 to about 30, preferably about 27. These preferred aluminosilicates are commercially available, for example, under the designations of zeolite A, zeolite B and zeolite X. Alternatively, natural ioninosilicate-type ion exchange materials or Synthetic materials suitable for use herein can be prepared as described by Krummel et al ., US Patent No. 3,985,669.

The aluminosilicates used herein memory are also characterized by their exchange capacity ionic which is at least 200 mg equivalent of CaCO3 hardness per gram, calculated on an anhydrous basis, and found preferably in the range of 300 to 352 mg equivalent of CaCO 3 hardness per gram.

Finely atomized liquid

The amount of finely atomized liquid from the This procedure can be from 1% to 10% (active base), preferably from 2% to 6% (active base), based on the amount total of the final product obtained in the process herein invention. The finely atomized liquid of the present process It can be selected from the group consisting of liquid silicates, anionic or cationic surfactants, which are in liquid form, aqueous or non-aqueous polymer solutions, water and mixtures of the same. Other optional examples of finely atomized liquid from The present invention may be carboxymethyl cellulose solution sodium, polyethylene glycol (PEG) and acid solutions dimethylenetriaminepentamethylphosphonic acid (DETMP).

Preferred examples of solutions of anionic surfactants that can be used as a thin liquid atomized in the present invention are HLAS of 88-97% of active compound, NaLAS of 30-50% active compound, 28% AE3S solution of active compound, liquid silicate of 40-50% of active compound, etc.

As a finely atomized liquid herein memory can also be used cationic surfactants and the suitable surfactants of the quaternary ammonium type are select surfactants from [mono-N-alkyl (or alkenyl) C 6 -C 16, preferably C 6 -C 10 {] ammonium in which the remaining positions of N are substituted by methyl groups, hydroxyethyl or hydroxypropyl.

Preferred examples of aqueous solutions or not aqueous polymers that can be used as a finely liquid atomized in the present invention are modified polyamines that they comprise a polyamine main chain corresponding to the formula:

\uelm{N}{\uelm{\para}{H}}

-R]_{m}-[ \

\uelm{N}{\uelm{\para}{}}

-R]_{n}-NH_{2}[H 2 NR] n + 1} - [\

 \ uelm {N} {\ uelm {\ para} {H}} 

-R] m - [\

 \ uelm {N} {\ uelm {\ para} {}} 

-R] n -NH2

which has a modified polyamine formula V (n + 1) WmYnZ, or a polyamine main chain that corresponds to the formula:

\uelm{N}{\uelm{\para}{H}}

-R]_{m}-[ \

\uelm{N}{\uelm{\para}{}}

-R]_{n}-[ \

\uelm{N}{\uelm{\para}{\uelm{R}{\uelm{\para}{}}}}

-R]_{k}-NH_{2} [H 2 NR] n-k + 1} [\

 \ uelm {N} {\ uelm {\ para} {H}} 

-R] m - [\

 \ uelm {N} {\ uelm {\ para} {}} 

-R] n - [\

 \ uelm {N} {\ uelm {\ para} {\ uelm {R} {\ uelm {\ para} {}}}} 

-R] k -NH2

which has a modified polyamine formula V (n-k + 1) W_ {m} Y_ {n} Y {k} Z, where k is equal to or less than n, having the said main chain of polyamine a molecular weight, before modification, greater than approximately 200 daltons, in the what:

i)

the units V are terminal units that have the formula:

one

ii)

 W units They are units of the main chain that have the formula:

two

iii)

the units Y They are units of branches that have the formula:

3

iv)

Z units are terminal units that have the formula:

4

in which the linker units R of the chain Main are selected from the group consisting of alkylene C 2 -C 12, alkenylene C 4 -C 12, hydroxyalkylene C 3 -C 12, dihydroxyalkylene C 4 -C 12, dialkylarylene C 8 -C 12, - (R 1 O) x R 1 -, - (R 1 O) x R 5 (OR 1) x -, - (CH 2 CH (OR 2) CH 2 O) Z (R 1 O) and R 1 (OCH 2 CH (OR ^ {2}) CH2) w-, -C (O) (R 4) r C (O) -, -CH 2 CH (OR 2) CH 2 -, and mixtures of the themselves; in which R 1 is alkylene C 2 -C 6 and mixtures thereof; R2 is hydrogen, - (R 1 O) x B and mixtures thereof; R 3 is C 1 -C 18 alkyl, arylalkyl C 7 -C 12, alkyl substituted aryl C 7 -C 12, aryl C 6 -C 12, and mixtures thereof; R 4 it is C 1 -C 12 alkylene, alkenylene C 4 -C 12, arylalkylene C 8 -C 12, arylene C 6 -C 10 and mixtures thereof; R 5 is C 1 -C 12 alkylene, hydroxyalkylene C 3 -C 12, dihydroxyalkylene C 4 -C 12, dialkylarylene C_ {8} -C_ {12}, -C (O) -, - C (O) NHR 6 NHC (O) -, - R 1 (OR 1) -, - C (O) (R 4) r} C (O) -, -CH 2 CH (OH) CH 2 -, - CH 2 CH (OH) CH 2 O (R 1 O) and R 1 OCH 2 CH (OH) CH2 - and mixtures thereof; R 6 is alkylene C 2 -C 12 or arylene C 6 -C 12; E units are selected from group consisting of hydrogen, alkyl C 1 -C 22, alkenyl C 3 -C 22, arylalkyl C 7 -C 22, hydroxyalkyl C 2 -C 22, - (CH 2) pCO 2 M, - (CH 2) qSO 3 M, -CH (CH 2 CO 2 M) CO 2 M, - (CH 2) p PO 3 M, - (R 1 O) x B, -C (O) R3 and mixtures thereof; oxide; B is hydrogen, C 1 -C 6 alkyl, - (CH 2) q SO 3 M, - (CH 2) pCO 2 M, - (CH 2) q (CHSO 3 M) CH 2 SO 3 M, - (CH 2) q (CHSO 2 M) CH 2 SO 3 M, - (CH 2) pPO 3 M, -PO 3 M and mixtures thereof; M is hydrogen or a water soluble cation in sufficient quantity to balance the load; X is a water soluble anion; m has the value from 4 to 400; n has the value from 0 to 200; p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; and has the value from 0 to 100; z has the value 0 or 1. An example of the polyethyleneimines plus Preferred is a polyethyleneimine having a molecular weight of 1,800 and which has been modified by ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E7). It is it is preferable that the solution of the above polymer is a precomplex with an anionic surfactant, such as NaLAS.

Other preferred examples of the solutions aqueous or non-aqueous polymers that can be used as the liquid finely atomized in the present invention are the dispersants of Polycarboxylate type polymers that can be prepared polymerizing or copolymerizing suitable unsaturated monomers, preferably in its acid form. Monomeric Unsaturated Acids which can be polymerized to form polymeric polycarboxylates Suitable include acrylic acid, maleic acid (or anhydride maleic), fumaric acid, itaconic acid, aconitic acid, acid Mesaconic, citraconic acid and methylene bromonic acid. The presence of monomeric segments that do not contain carboxylate radicals, such as vinyl methyl ether, styrene, ethylene, etc., in Polymeric polycarboxylates herein are suitable with the condition that said segments do not constitute more than 40% in polymer weight

Preferred are polycarboxylates homopolymers that have molecular weights greater than 4,000 as those described below. Homopolymeric Polycarboxylates particularly suitable can be derived from acrylic acid. Such acrylic acid based polymers that are useful in the herein are the water soluble salts of acrylic acid polymerized The average molecular weight of said polymers in form acid preferably ranges from more than 4,000 to 10,000, preferably from more than 4,000 to 7,000 and most preferably from more than 4,000 to 5,000. The water soluble salts of said polymers Acrylic acid may include, for example, metal salts alkali, ammonium and substituted ammonium.

Polycarboxylates can also be used. copolymers, such as acrylic / acid based copolymers Maleic Such materials include water soluble salts of copolymers of acrylic acid and maleic acid. Molecular weight medium of said acidic copolymers generally varies from 2,000 to 100,000, more preferably 5,000 to 75,000 and most preferably from 7,000 to 65,000. The acrylate segment ratio to maleate segments in said copolymers will generally vary from 30: 1 to 1: 1, more preferably from 10: 1 to 2: 1. The soluble salts in water of said acrylic acid / maleic acid copolymers can include, for example, alkali metal salts, ammonium and substituted ammonium It is preferable that the polymer solution before mentioned above is complexed with an anionic surfactant, like LAS.

Auxiliary detergent ingredients

The starting detergent material of the present process may include additional detergent ingredients and / or any number of additional ingredients may be incorporated into the detergent composition during later stages of the present process. These auxiliary ingredients include other detergency builder additives, bleach, bleach activators, foam enhancers or suppressors, anti-corrosion and anti-glare agents, stain suspending agents, stain release agents, germicides, pH regulating agents, alkalinity sources which are not detergency enhancing additives, chelating agents, smectite clays, enzymes, enzyme stabilizing agents and perfumes. See US Patent No. 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al .

Other detergency builder additives are they can generally select from the various phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxysulfonates, polyacetates, carboxylates and polycarboxylates Water soluble alkali metal, ammonium or substituted ammonium. From these salts are preferred alkali metal salts, especially sodium. Preferred for use herein are phosphates, carbonates, C 10 -C 18 fatty acids, polycarboxylates and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and disuccinates and mixtures thereof (see more ahead).

In comparison with amorphous sodium silicates, layered crystalline sodium silicates have a clearly better ability to exchange calcium and magnesium ions. In addition, layered sodium silicates prefer magnesium ions to calcium ions, a characteristic necessary to ensure that substantially all "hardness" is removed from the wash water. However, these layered crystalline sodium silicates are generally more expensive than amorphous silicates and other detergency builder additives. Consequently, in order to provide an economically viable detergent, the proportion of crystalline sodium silicates in layers used must be properly determined. Such layered crystalline sodium silicates are discussed in US Patent No. 4,605,509, Corkill et al .

Specific examples of inorganic phosphates useful as detergency builders are tripolyphosphates, pyrophosphates, polymeric metaphosphates that have a degree of polymerization of approximately 6 to 21 and sodium orthophosphates and Potassium Examples of polyphosphonates useful as additives detergency builders are the sodium and potassium salts of ethylenediphosphonic acid, the sodium and potassium salts of the acid ethane-1-hydroxy-1-diphosphonic and the sodium and potassium salts of the acid ethane-1,1,2-triphosphonic. Others phosphorous builder detergent compounds are described in U.S. Patents No. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148.

Examples of additives improving the non-phosphorus inorganic detergents are tetraborate decahydrate and silicates having a weight ratio of SiO2 to oxide of alkali metal 0.5 to 4.0, preferably 1.0 to 2.4. Additives soluble non-phosphorous organic detergency builders in water, useful herein, include the various polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates alkali metal, ammonium and substituted ammonium. Examples of polyacetate type detergency builders and Polycarboxylates are the salts of sodium, potassium, lithium, ammonium and substituted ammonium of ethylenediaminetetraacetic acids, nitrilotriacetic, oxydisuccinic, melitic, benzene polycarboxylic and citrus

In U.S. Patent 3,308,067, Diehl, issued on March 7, 1967, additives are described to improve the detergency of polymeric polycarboxylate type. Sayings Materials include water soluble salts of homo- and copolymers of aliphatic carboxylic acids, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenomonic acid. Some of these Materials are useful as water-soluble anionic polymers, as described below, but only intimately mixed with an anionic surfactant that is not a soap.

Other suitable polycarboxylates for use herein are the polyacetalcarboxylates described in US Patents 4,144,226, issued March 13, 1979 to Crutchfield et al ., And 4,246,495, issued March 27, 1979 to Crutchfield et al . These polyacetalcarboxylates can be prepared by putting together a glyoxylic acid ester and a polymerization initiator under polymerization conditions. The resulting polyacetalcarboxylate ester is then attached to chemically stable end groups to stabilize the polyacetalcarboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt and added to the detergent composition. Particularly preferred polycarboxylate type detergency builders are the ethercarboxylate type detergency builder compositions comprising a combination of tartratomonosuccinate and tartratodisuccinate, described in US Patent No. 4,663,071, Bush et al ., Issued 5 May 1987.

Bleaching agents and bleaching activators are described in US Patent Nos. 4,412,934, Chung et al ., Issued November 1, 1983, and 4,483,781, Hartman, issued November 20, 1984. Agents are also described. Chelants in US Patent 4,663,071, Bush et al ., from column 17, line 54, to column 18, line 68. Foam modifiers are other optional ingredients and are described in US patents 3,933,672 , issued on January 20, 1976 to Bartoletta et al ., and 4,136,045, issued on January 23, 1979 to Gault et al .

Smectite clays suitable for use herein are described in US Patent No. 4,762,645, Tucker et al ., Issued August 9, 1988, from column 6, line 3, to column 7, line 24. Additional detergency builder additives suitable for use herein are listed in Baskerville's patent, column 13, line 54, column 16, line 16, and U.S. Patent No. 4,663,071, Bush et al ., issued on May 5, 1987.

Optional stages of the procedure

Optionally, the process may comprise the step of spraying an additional binding agent in one or more of one of the first, second and / or third mixers of the present invention. A binder is added in order to improve the agglomeration by providing a "binder" or "adherent" agent for the detergent components. The binding agent is preferably selected from the group consisting of water, anionic surfactants, non-ionic surfactants, liquid silicates, polyethylene glycol, polyvinylpyrrolidone, polyacrylates, citric acid and mixtures thereof. Other suitable binder materials, including those indicated herein, are described in Beerse et al ., U.S. Patent No. 5,108,646 (Procter & Gamble Co).

Other optional stages contemplated by the present process include screening the agglomerates of detergents larger than desired in a screening device that can take a variety of forms, including, but without limiting character, conventional sieves chosen for size of desired particles of the final detergent product. Other stages Optional include conditioning detergent agglomerates subjecting them to additional drying by means of described devices previously.

Another optional stage of the present procedure is finish the resulting detergent agglomerates by means of a diversity of procedures, including spraying and / or mixing with Other conventional detergent ingredients. For example, the stage Finishing includes spraying perfumes, optical brighteners and enzymes on the finished agglomerates, to provide a most complete detergent composition. These techniques and ingredients They are well known in the art.

Another optional stage of the procedure is a procedure of structuring a paste of a surfactant, by example, harden an aqueous paste of an anionic surfactant aqueous incorporating a paste hardener material using a extruder, before the process of the present invention.

Examples Example 1

The following is an example to get agglomerates that have a high density using a Schugi mixer FX-160 followed by a Lödige KM mixer (KM-600) and finally a bed apparatus fluidized to obtain greater agglomeration.

Stage one

They disperse in a stream of air extremely turbulent mixer Schugi FX-160, 120-160kg / h of HLAS [an acid precursor of a (C 11 -C 18 alkyl) benzenesulfonate; 96% active compound] with 220 kg / h of sodium tripolyphosphate (average particle size of 40-75 micrometers), 160-280 kg / h of ground sodium carbonate (size particle size 15 micrometers), 80-120 kg / h of ground sodium sulfate (average particle size 15 micrometers), and 200 kg / h of an internal recycled powder stream. The surfactant is fed at a temperature of about 50 to 60 ° C and the powders are fed at room temperature. Later disperse 30 kg / h of HLAS (an acid precursor of a (alkyl C 11 -C 18) benzenesulfonate; 94-97% active compound] as a thin liquid atomized in the FX-160 mixer at approximately 50 to 60 ° C. 20-80 kg / h of sodium carbonate are added ground (average particle size approximately 10-20 micrometers) in the Schugi mixer. The Schugi mixer conditions are as follows:

Average residence time: 0.2 - 5 seconds

Peripheral speed: 16 - 26 m / s

Power Condition: 0.15 - 2 kj / kg

Mixer Speed: 2000 - 3200 rpm

Stage two

The agglomerates from the Schugi mixer FX-160 is fed to the KM mixer to get a greater agglomeration, rounded and growth of the agglomerates. KM 30 kg / h of zeolite can also be added to the mixer. For reduce the amount of agglomerates larger than desired They can use KM mixer cutters. The conditions of KM mixer are as follows:

Average residence time: 3- 6 minutes

Power Condition: 0.15 - 2 kj / kg

Mixer speed: 100 - 150 rpm

Shirt temperature: 30 - 40 ° C

Stage 3

The agglomerates from the KM mixer are feed a fluidized bed drying apparatus for drying, rounding and growth of agglomerates. To the drying apparatus of fluidized bed at 35 ° C can also be added 20-80 kg / h of liquid silicate (43% solids; R 2.0). The conditions of the fluidized bed drying apparatus are the following:

Average residence time: 2 - 4 minutes

Bed height no fluidized: 200 mm

Droplet Size sprayed: less than 50 micrometers

Spray height: 175 - 250 mm (above the distribution board)

Fluidization Speed: 0.4 - 0.8 m / s

Bed temperature: 40 - 70ºC

The granules resulting from stage 3 have a density of approximately 700 g / l and can be subjected optionally to optional cooling procedures, size separation and / or crushing.

Example 2

The following is an example to get agglomerates that have a high density using a schugi mixer FX-160, followed by a Lödige KM mixer (KM-600)

Stage one

They disperse in a stream of air extremely turbulent mixer Schugi FX-160, 120-200kg / h of HLAS [an acid precursor of a (C 11 -C 18 alkyl) benzenesulfonate; 95% active compound] at approximately 50 ° C, with 220 kg / h of powdered sodium tripolyphosphate (average particle size 40-75 micrometers), 160-280 kg / h of ground sodium carbonate (average particle size 15 micrometers), 80-120 kg / h of ground sodium sulfate (medium size of particle 15 micrometers), and 200 kg / h of a recycled stream internal dust. The conditions of the Schugi mixer are the following:

Average residence time: 0.2 - 5 seconds

Peripheral speed: 16 - 26 m / s

Power Condition: 0.15 - 2 kj / kg

Mixer Speed: 2000 - 3200 rpm

Stage two

The agglomerates from the mixer FX-160 are fed to the mixer KM-600 to achieve greater agglomeration, rounded and growth of agglomerates. KM mixer is also add 60 kg / h of ground sodium carbonate (average size of 15 micrometer particle). To reduce the amount of agglomerates larger than desired size cutters can be used KM mixer. The conditions of the KM mixer are the following:

Average residence time: 3- 6 minutes

Power Condition: 0.15 - 2 kj / kg

Mixer speed: 100 - 150 rpm

Shirt temperature: 30 - 40 ° C

The granules resulting from stage 2 have a density of 650 g / l and can optionally be subjected to optional cooling procedures, size separation and / or crushing.

Thus, having described the invention in detail, it will be obvious to those skilled in the art that can be done various changes without departing from the scope of the invention, and the invention is not considered limited to what is described in the descriptive memory.

Claims (7)

1. A procedure without towers to prepare a granular detergent composition having a density of at least 600 g / l, comprising the steps of: (a) disperse a surfactant and coat the surfactant with a fine powder having a diameter of 0.1 to 500 micrometers, while wetting the surfactant coated with the fine powder with finely atomized liquid, in a mixer in the that the conditions of the mixer include (i) an average time of permanence of 0.2 to 5 seconds, (ii) a peripheral speed of 15 at 26 m / s and (iii) an energy condition of 0.2 to 3 kJ / kg, in the that first agglomerates are formed; (b) mix the first ones perfectly agglomerated in a mixer with cutters in which conditions of the mixer include (i) an average residence time of 0.5 to 15 minutes and (ii) an energy condition of 0.15 to 7 kJ / kg, in which form a few agglomerated seconds; Y (c) granulate the second agglomerates in a fluidized bed dryer and a fluidized bed cooler in the that the conditions of each fluidization apparatus include (i) an average residence time of 1 to 10 minutes, (ii) a height of the non-fluidized bed of 100 to 300 mm, (iii) a size of the droplets sprayed not exceeding 50 micrometers, (iv) a spray height from 175 to 250 mm, (v) a fluidization rate from 0.2 to 1.4 m / s and (vi) a bed temperature of 12 to 100 ° C, in The average residence time of stage (c) is in total 2 to 12 minutes, and in which a selected coating agent from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof are added to step (c) either: directly after fluidized bed cooler or bed dryer fluidized; and / or between the fluidized bed dryer and the cooler fluidized bed; and / or directly to the bed dryer fluidized 2. The method according to claim 1, in which said surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, surfactants cationic, hybrid, ampholytic and mixtures thereof. 3. The method according to claim 1, in which said surfactant is selected from the group consisting of alkylbenzenesulfonates, alkylalkoxysulfates, alkylethoxylates, alkyl sulfates, coconut fatty alcohol sulfates and mixtures of same. 4. The method according to claim 1, in which an aqueous or non-aqueous polymer solution is dispersed with said surfactant in step (a). 5. The method according to claim 1, in which the fine powder is selected from the group consisting of sodium carbonate, sodium tripolyphosphate powder, tripolyphosphate hydrated, sodium sulfates, aluminosilicates, crystalline silicates layered, phosphates, precipitated silicates, polymers, carbonates, citrates, nitrilotriacetates, powdered surfactants and mixtures of the same. 6. The method according to claim 1, in that the finely atomized liquid is selected from the group that It consists of liquid silicates, anionic surfactants, cationic surfactants, aqueous polymer solutions, solutions of non-aqueous polymer, water and mixtures thereof. 7. The method according to claim 1, in which is also added to step (a) a recirculated current internal powder from the fluidization apparatus.