EP1114138B1 - Kontinuierliches herstellungsverfahren für waschmittel - Google Patents

Kontinuierliches herstellungsverfahren für waschmittel Download PDF

Info

Publication number
EP1114138B1
EP1114138B1 EP99946732A EP99946732A EP1114138B1 EP 1114138 B1 EP1114138 B1 EP 1114138B1 EP 99946732 A EP99946732 A EP 99946732A EP 99946732 A EP99946732 A EP 99946732A EP 1114138 B1 EP1114138 B1 EP 1114138B1
Authority
EP
European Patent Office
Prior art keywords
mixer
detergent
binder
free
particle size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99946732A
Other languages
English (en)
French (fr)
Other versions
EP1114138A1 (de
Inventor
Paul R. Mort, Iii
Millard Edward Sullivan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1114138A1 publication Critical patent/EP1114138A1/de
Application granted granted Critical
Publication of EP1114138B1 publication Critical patent/EP1114138B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention generally relates to a continuous, non-tower process for producing a particulate detergent composition. More particularly, the invention is directed to a continuous process where a free-flowing dry neutralized detergent powder is agglomerated with a liquid or viscous paste binder to form agglomerates. The process produces detergent agglomerate having a reduced amount of fine particles and over-sized particles that require recycle.
  • the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules (e.g., tower process for low density detergent compositions).
  • the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant, to produce high density detergent compositions (e.g., agglomeration process for high density detergent compositions).
  • the important factors which govern the density of the resulting detergent granules are the shape, porosity and particle size distribution of said granules, the density of the various starting materials, the shape of the various starting materials, and their respective chemical composition.
  • one attempt involves a batch process in which spray-dried or granulated detergent powders containing sodium tripolyphosphate and sodium sulfate are densified and spheronized in a Marumerizer®.
  • This apparatus comprises a substantially horizontal, roughened, rotatable table positioned within and at the base of a substantially vertical, smooth walled cylinder.
  • This process is essentially a batch process and is therefore less suitable for the large scale production of detergent powders.
  • More recently, other attempts have been made to provide continuous processes for increasing the density of "post-tower" or spray dried detergent granules.
  • Laid Open No.WO96/04359 (Unilever).
  • Laid-open No.WO93/23,523 (Henkel) describes the process comprising pre-agglomeration by a low speed mixer and further agglomeration step by high speed mixer for obtaining high density detergent composition with less than 25 wt % of the granules having a diameter over 2 mm.
  • the U.S. Patent No. 4,427,417 (Korex) describes continuous process for agglomeration which reduces caking and oversized agglomerates.
  • the present invention provides a continuous process for preparing a granular detergent agglomerate comprising more than 15wt% surfactant, having a mean particle size of between 250 and 1200 micrometers, having a geometric standard deviation of less than 2.5, and having a density of at least 500g/l, comprising the steps of:
  • the present invention produces high density detergent agglomerates for use in granular detergent compositions, having a high level of detergent surfactant and a relatively narrow particle size distribution. Furthermore, the process is inherently efficient by significantly reducing the amount of agglomerate which is outside an acceptable particle range.
  • the present invention also meets the aforementioned needs in the art by providing a process which produces a granular detergent composition for flexibility in the ultimate density of the final composition from an agglomeration (e.g., non-tower) process. The process does not require the use of conventional spray drying towers which have limited capability to produce compositions having a high surfactant loading (concentration) at high bulk density of greater than 500 gm/l.
  • the process described herein provides a granular detergent agglomerate having a high density of at least 500 g/l and relatively narrow particle size distribution as measured by the geometric standard deviation of less than 2.5, with high throughput capability and increased production efficiency, and with less recycle of material having an unacceptable particle size. While it is recognized that other processes which include classification and recycle loops are capable of producing more narrow particle size distributions measured at the final product output, the advantage of the current invention is the narrowness of the particle size distribution before any classification is done.
  • agglomerates refers to particles formed by agglomerating particulate detergent materials with a binder such as surfactants and/or other solutions, whereby the agglomerate particle has a larger size than the particulate detergent materials contained therein.
  • the residence time can be easily and conveniently determined by measuring the steady-state weight of agglomerate powder and ingredients in a mixer (in kg), and dividing by the mass throughout (in kg/minute) of the mixer.
  • particle size distribution refers to the mass-basis distribution of agglomerate particle sizes, where the distribution is described by the geometric mean and geometric standard deviation.
  • the mass-basis geometric mean and standard deviation are most commonly measured using standard sieve analysis methods.
  • the present invention is directed to a continuous process which produces free-flowing, granular detergent agglomerates.
  • the process produces a product having a density of at least 500 g/l, a narrow product size distribution at the output of the agglomeration step, and improved process efficiency by virtue of its low recycle rate.
  • the first step of the process prepares a dry neutralized material in the form of a free-flowing powder.
  • the dry neutralized material is obtained by the dry neutralization of an acid precursor of an anionic detergent surfactant with a water-soluble alkaline inorganic particulate material in a high speed mixer, whereby the acid precursor is partially or completely neutralized to the anionic surfactant.
  • an excess of the alkaline inorganic particulate material is used to ensure that the acid precursor is sufficiently neutralized under the high speed mixing conditions.
  • a particulate water-soluble alkaline inorganic material is continuously introduced into the high speed mixer in the form of fine particles.
  • a liquid acid precursor of the anionic surfactant is introduced into the mixer and is well dispersed and adsorbed onto the surface of the fine particles of the alkaline inorganic material. Neutralization of the acid precursor to the corresponding salt occurs quickly. The rate and capacity for neutralization of the acid precursor to the salt increases as the alkaline inorganic material is reduced to a finer particle size with a higher reactive surface area. Because of the inherent binding capacity of the liquid, there is typically some intermediate agglomeration associated with the first step to form the dry neutralized material.
  • the extent of this intermediate agglomeration is controlled primarily by the amount of liquid addition and the shear rate of the mixer.
  • the mean particle size of the dry neutralized material is generally within the range of about 50 to 500 microns, preferably about 100 to 250 microns.
  • the bulk density of the dry neutralized material of the first mixer is at least 500 g/l, more typically at least 600 g/l, and preferably from about 650 to 800 g/l.
  • the mixer consists of a device with mixing tools operating at a tip speed of at least 10 m/s, and a narrow gap between the tool tip(s) and the mixer wall or other fixed element of less than 2 cm.
  • the mean residence time of the first mixer is in range from 0.2 to 50 seconds, more preferably from 1 to 30 seconds.
  • Examples of the high speed mixer for the first step are a Lödige CB Mixer manufactured by the Lödige company (Germany), a Turbilizer manufactured by Bepex Company (USA), and a Schugi Flexomatic (e.g., Model FX-160) manufactured by the Schugi company (Netherlands).
  • the particulate water-soluble alkaline material is preferably sodium carbonate, alone or in combination with other materials such as sodium bicarbonate or silicate. Alkaline materials having other salts, such as lithium and potassium, can also be used. While aqueous alkaline materials such as sodium hydroxide can also be used in combination with the particulate alkaline material, their use should minimized to prevent the resulting intermediate agglomerate from being sticky or poor flowability.
  • the carbonate is preferably of a finely divided powder having an mean diameter of from 0.1 to 100 microns, preferably from 2 to 25 microns, and more preferably from 5 to 15 microns. Typically the moisture content of the carbonate will be less than about 2%, more preferably less than 1%.
  • the carbonate can comprise from about 25% to about 80% by weight of the resulting agglomerate, preferably about 30% to about 60%.
  • a preferred method of reducing the carbonate to the finely divided size is by the use of a suitable grinder capable of producing such finely ground carbonate from commercially available carbonate stock, such as the process described in WO 98/20104, published May 14, 1998.
  • Commercially available carbonate typically has a median particle size of about 50-150 microns, and contains less than 2%, preferably less than 1% moisture.
  • a preferred grinder used for this purpose is an air-classifier mill, such as the Mikro-ACM CX Model 300 available from Hosokawa Micron Powder Systems, Summit, New Jersey.
  • the particle size distribution of the ground carbonate is determined by any instrument which approximates such particle size as the diameter of a spherical particle occupying the same volume as the particle being measured.
  • the median particle size is that size which has 50% by volume of the particles being smaller and 50% by volume being larger.
  • a suitable instrument for measuring the particle size of the ground carbonate is the Malvern Series 2600 Optical Laser, available from Malvern Instrument Company, Malvern, Pennsylvania.
  • the amount of alkaline inorganic material is preferably in an amount to neutralize at least 80% of the acid precursor by the time the material leaves the first mixer. Typically, the stoicheometric amount of alkaline inorganic material will be at least twice that needed to fully neutralize the acid precursor.
  • the neutralization of the acid precursor with alkaline powder by dispersion/adsorption is well known in the art. See “Synthetic Detergents", A.S. Davidsohn & B. Midlewsky, 7th ed., pp. 202-209.
  • the amount of liquid acid precursor that can be added in this step is up to about 30 weight %.
  • acid precursors of detergent surfactants that are more crystalline than alkylbenzene sulfonate, such as alkyl sulfuric acid generally more of acid precursor can be loaded into the mixer.
  • the liquid acid precursor preferably selected from a conventional C 11 -C 18 alkylbenzene sulfonic acid ("HLAS"), a primary, branched-chain and random C 10 -C 20 alkyl sulfuric acid (“HAS”), the C 10 -C 18 secondary (2,3) alkyl sulfuric acid of the formula CH 3 (CH 2 ) x (CHOSO 3 - H + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - H + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, unsaturated alkenyl sulfuric acid such as oleyl sulfuric acid, and a C 10 -C 18 alkyl alkoxy sulfuric acid (“HAE x S"; especially EO 1-7 ethoxy sulfuric acid).
  • HLAS conventional C 11 -C 18 alkylbenzene sulfonic acid
  • HAS primary, branched-chain and random C 10 -C 20 alkyl sulfur
  • the acid precursor comprises at least 50% of HLAS.
  • at least 50% by weight of the detergent surfactant in the final detergent product is derived from the neutralization of the acid precursor in the first step.
  • particulate inorganic and organic detergent ingredients can be added into the first step mixer.
  • Such other particulate detergent ingredients are described herein after.
  • the addition of the other particulate detergent ingredients into the process can improve the physical properties of the dry neutralized material.
  • the dry neutralized material will contain less than about 5% by weight of such particulate builder material.
  • the alkaline inorganic material carbonate
  • the moisture content of the reaction mixture defined as water not firmly bound as water of hydration or crystallization to inorganic salts at a temperature of 135°C, should not be so high that it can lead to substantial agglomeration of the powders.
  • the moisture content of the powder material in the first mixer will be less than about 5%, more preferably less than about 2%.
  • a detergent material is obtained containing the salt of the anionic surfactant, wherein preferably at least 80%, more preferably at least 90%, and most preferably all, of the acid precursor of the anionic surfactant has been neutralized.
  • the detergent material exiting the first mixer can optionally be processed in an optional intermediate step, before passing as the free-flowing powder into the agglomeration mixer of the second step.
  • Such intermediate step can be a mixing step where optional liquid or particulate materials can be added.
  • Such optional liquid material is generally added at a level of less than 10% by weight of the free-flowing powder, and can include nonionic surfactants or other binder liquids herein described.
  • Such optional particulate material can be a free-flow aid, such as zeolite or a carbonate.
  • the mixer can be a static mixing device such as a baffled box mixer, or a mechanical mixer such as a Schugi, drum or cage mixer.
  • Such optional step can be advantageously used to add a liquid material (as in the case of a nonionic surfactant) that may interfere with effective dry neutralization of the acid precursor in the first step, or with effective agglomeration in the second step.
  • the second step prepares a granular detergent agglomerate from the free-flowing powder and an agglomerating binder.
  • the resultant free-flowing powder from the first step is fed into a second mixer:
  • the second mixer is preferably a completely separate mixer, though it can be a subsequent downstream zone of the first mixer, so long as it satisfies the mixing conditions.
  • the second step comprises dispersing an agglomeration binder onto the free-flowing powder of the first step to form the detergent agglomerate.
  • the amount of the agglomeration binder used can be from about 1 % to about 50% (active basis), preferably from 5% to about 35% (active basis) by weight of the detergent agglomerates.
  • the invention can accommodate a broad range of surfactant paste levels based on rheological properties and modifications thereof in the process.
  • the resulting detergent agglomerates have a mean particle size of 250 microns to 1200 microns, more preferably 400 microns to 1000 microns, and a relatively narrow particle size distribution at the output of the second agglomeration step having a geometric standard deviation of less than 2.5, preferably less than 2.0.
  • the second step of the process It is preferred to operate the second step of the process at an operating temperature sufficiently high to promote effective agglomeration of the free-flowing powder with the agglomeration binder, though not so high in temperature such that there is excessive agglomeration or "balling" of the powder into large clumps.
  • the operating temperature of combined material of the second step, within the second mixer is from about 30 to 70°C.
  • the temperature of the agglomeration binder can be controlled independently such that the agglomeration binder can be in the form of either a flowable liquid, which can be sprayed or dripped into the mixing zone of the second mixer, or a thick viscous paste which needs to be mechanically dispersed into particles within the mixing zone.
  • the flowable liquid agglomeration binder can be sprayed on the agglomerates in the second mixer using single fluid or air-atomizing spray nozzles, which can be easily selected for the service required.
  • the flowable liquid can also be dripped or introduced into the mixer as a stream of liquid from a pipe. It is important that the flowable liquid, though, be well dispersed and distributed within the powder in order for the powder particles to efficiently and effectively adhere to and coat the outer surface of the agglomeration binder.
  • Typical tip speed of the chopper blades is at least about 3 m/sec, preferably greater than about 15 m/sec, and more preferably greater than about 20 m/sec.
  • Typical chopper designs include at least four radial blade positions. This is well suited to the ploughshare design of mixers with internal choppers, for example a Lödige KM mixer manufactured by the Lödige company (Germany). Mixers can be equipped with lance tubes through which a binding fluid can be injected onto the chopper locations.
  • the lance tubes can be sub-divided into smaller diameter tube streams, where the cross sectional area of the openings of each (sub-divided) stream is less than about 80 mm 2 , most preferably less than about 1 mm 2 .
  • the combination of paste injection rate divided across the number of streams and the chopper cutting speed results in cutting of the individual streams into fine units of binder, where the calculated volume of paste in each stream per cut is less than about 1 ml, most preferably less than about 0.01 ml, and most preferably from about 0.00005 ml to about 0.01 ml, or an average equivalent diameter of less than about 13 mm, and more preferably less than about 4 mm.
  • Binder particles of this size are tom apart into smaller sizes within the second mixer as a result of the coating and embedding of the finely-divided powder onto the binder particle, until the agglomerate achieves a size within a range where the strength of the agglomerate particle will resist further reduction.
  • This agglomerate size range is generally from about 50 microns to about 2000 microns, and spans beyond the range of acceptable average detergent particle size, which is 250 to 1200 microns, to include both fines, agglomerates and particles less than 250 microns and overs agglomerates greater than 1400 microns.
  • agglomeration binder it is most preferable to form and disperse the agglomeration binder into droplets or particles having an equivalent diameter of from about 0.5 mm to about 1 mm. This particle size is comparable to the size of the desired detergent agglomerate. Binder particles within this size range will tend not to be tom into smaller sizes. The result of dispersing the agglomerate binder within this size range will be a resulting detergent agglomerate having a significantly narrower particle size range, with minimal amounts of overs and fines.
  • the binder volume per cut can be calculated from the cutting rate, and the binder volume rate.
  • the cutting rate, in cuts/sec is "chopper revolutions/sec x chopper blades/revolution", where each chopper blade makes a cut.
  • the binder volume rate, in ml/sec is "binder mass / binder density”, where the binder mass is in kg/sec, and the binder density is in kg/ml.
  • the binder volume per cut is then "binder volume rate / cutting rate”.
  • the tubes that are used to inject the (sub-divided) binder streams are located such that their discharge openings are slightly upstream of the choppers; in this way, the ploughshare tools in the mixer sweep the binder streams and intermediate particles into the choppers, where the binder is finely divided and coated with powder.
  • Another embodiment is to supplement the above sub-divided binder injectors with additional mechanisms to disperse the binder, such as by the addition of compressed air in the binder line at or before the opening of the binder tube into the mixer.
  • the air may be further pulsed to provide additional breakup of the binder stream into uniform pieces.
  • vibrating elements such as reeds can be used at the injection point to further improve the uniformity of the binder dispersion.
  • the most preferred embodiment uses a viscous surfactant paste binder, characterized by a shear-rate thinning viscosity that exhibits an apparent yield stress.
  • the shear-rate thinning property is advantageous to transport of the paste binder, typically from a storage tank, into the mixer/agglomerator.
  • the apparent yield stress property is important in mechanical cutting of the paste as well as in maintaining the structural integrity of the as-formed agglomerates, especially at high active levels of the binder.
  • the shear-rate thinning and apparent yield stress properties can be measured in accordance with accepted practice in the art of rheological characterization, for example, using a parallel plate or cone and plate viscometer.
  • the viscometer is typically determined using a stress ramp program, where stress ( ⁇ ) is increased from about 10 Pa to about 1000 Pa over a ramp time of about 10 minutes, and the resultant strain rate (y ⁇ ) is measured.
  • the logarithm of the calculated viscosity is then plotted against the logarithm of shear rate.
  • regression of log( ⁇ ) versus log( ⁇ ⁇ ) typically results in a good linear fit in the strain rate range from about 0.1 to about 10 sec -1 . More specifically, the correlation coefficient of the regression, r 2 , is typically greater than 0.99.
  • the downward (negative) slope of the log-log plot is indicative of shear-thinning behavior, i.e., the viscosity falls as the shear rate increases.
  • the viscosity of yield-stress fluids are typically dominated by the yield-stress effects in this range of shear rates.
  • the apparent yield stress ( ⁇ y ) is defined as the product of the viscosity and the shear rate at the shear rate value of 1 sec -1 .
  • the value of the apparent yield stress, ⁇ y should be greater than 20 Pa, preferably greater than 50 Pa, and more preferably greater than 100 Pa.
  • the apparent yield stress of paste binders increases with a reduction in temperature, whereby the agglomerates can have improved physical integrity and be more resistant to smearing as the product cools.
  • the preferred paste binder has a viscoelastic rheology that can be characterized by a complex shear modulus (G*), which is the vector sum of its elastic storage (G') and viscous loss (G") parts.
  • G* complex shear modulus
  • the preferred embodiment employs a paste binder with a tan( ⁇ ) value that is less than 1.0, more preferably less about 0.5, over the frequency range of about 2 Hz to about 20 Hz.
  • the decreasing value of tan( ⁇ ) below 1.0 means that the elastic storage modulus becomes increasingly dominant over the viscous loss modulus.
  • the dominance of the elastic storage modulus aids in the mechanical cutting the paste and dispersion of the paste as discrete units of binder.
  • Dispersion of highly viscoelastic binder as discrete mass units favors the formation of agglomerates by embedding powder into the discrete mass units of binder.
  • the low value of tan( ⁇ ) helps to reduce the tendency for the binder to smear over the surface of the agglomerates and the internal mechanical elements of the medium-shear mixer.
  • the reduction of smearing is advantageous in improving the operating efficiency of the process by reducing the tendency for product to make-up and adhere to the inside of the mixer.
  • the above viscoelastic rheology data can be measured by one skilled in the art of rheology using oscillatory parallel plate viscometers.
  • the high viscosity, apparent yield stress and viscoelastic nature of the viscous agglomeration binder is well suited to a mechanism of agglomeration wherein the solid particles coat, adhere and are embedded into the binder.
  • the mixing shear of the process needs to be sufficient only to coat and embed the particles into the finely divided droplets or particles of binder; as such, the mixing shear in the second mixer is intentionally kept below a point that would extensively spread the binder over the surface of the particles.
  • a viscous binder be well dispersed and distributed within the free-flowing powder in order for the powder particles to efficiently and effectively adhere to and coat the outer surface of the agglomeration binder.
  • the dispersion of the binder is accomplished by extruding the binder through a die plate with many small openings, producing noodles of binder which are then fed into the agglomeration mixer.
  • the noodles can be cut into pellets before being fed into the mixer, using a variety of cutter configurations that are well known in the art of extrusion/pelletization.
  • a more preferred embodiment uses a fine noodle size, with a noodle cross sectional area less than about 10 mm 2 and a chopper configured to chop the noodles into short lengths of less than about 4 mm.
  • a most preferred embodiment uses an even finer noodle size, with a noodle cross sectional area less than about 1 mm 2 and a chopper configured to chop the noodles into short lengths of less than about 1 mm.
  • the agglomeration binder can be selected from the group consisting of anionic surfactant paste (which is most preferred), liquid silicate, cationic surfactants, aqueous or non-aqueous polymer solutions, water, and mixtures thereof.
  • anionic surfactant solutions as the agglomeration binder are about 30 - 95% active NaLAS, having an alkyl chain of 12-18 carbons; about 30 - 95% active NaAS, having an alkyl chain of 12-18 carbons; about 30 - 95% active NaAS, having a branched alkyl chain of 10-20 carbons; and about 20-95% active NaAExS solution, having an alkyl chain of 10-18 carbons, and where x is from about 1-10, and a mixture of the above surfactant solutions having a net active level of 30 to 95%.
  • NaAS and NaLAS surfactants having an alkyl chain from about 14-15 carbons, and about 70-80% active
  • AExS surfactants having an alkyl chain from 12-14 carbons, an x of about 3, and about 70-80% active.
  • Other minor ingredients such as polyethylene glycol, organic polymers, silicates and alkaline salts may be present in the paste compositions.
  • Cationic surfactants can be quaternary ammonium surfactants are selected from mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Other binders can be those disclosed in U.S. Patent 5,108,646 (Beerse et al.).
  • Additional particulate detergent ingredients of the type used in the first step can optionally be added into the second step mixer, along with the free-flowing powder, and agglomerated with the binder.
  • About 0-10% particulate detergent ingredients, more preferably about 2-5%, by weight of the detergent agglomerate is typically added to the second mixer.
  • the second agglomeration mixer can be any types of mixer known to persons skilled in the art, as long as the mixer can maintain the above mentioned condition for the second step.
  • the second mixer which conducts the second step under conditions that include (i) from 10 seconds to 2 minutes, more preferably from 1 minute to 2 minutes, of mean residence time, (ii) a tip speed of a mixing tool mounted within the mixing zone of 0.5 to 5 m/s; and (iii) from 0.15 to 7 kj/kg of specific energy condition.
  • a preferred example of the second mixer is the Lödige KM Mixer manufactured by the Lödige company (Germany).
  • the free-flowing powder of the first step is introduced directly into the second mixer, though optionally is can first be handled or processed thorough other mixing or transporting equipment, as herein before described.
  • a resultant product is obtained having a bulk density of at least 500 g/l.
  • the resultant product can be further subjected to drying, coating, fluid bed agglomeration, and/or cooling.
  • the particle size distribution of the product exiting the second stage mixer is more narrow, particularly compared to the free-flowing powder.
  • the narrow particle size distribution means that the product exits the second mixer with a higher weight fraction of particles in the acceptable size range; thus, the overall process can be run with a lower rate of recycle for fines (very small size particles) and overs (larger sized particles), providing higher throughput and more efficient operation.
  • the resultant agglomeration product can be made with a significantly higher active level of surfactant, compared to single stage agglomeration using only one type of binder.
  • the total amount of the detergent surfactants in the detergent agglomerates made by the present invention, which are included via the first step acid precursor, the second step surfactant paste agglomeration binder, and adjunct detergent ingredients, is from 5% to 80%, more preferably from 10% to 60%, more preferably, from 15 to 50%, by weight.
  • the amount of the surfactant that is formed by dry neutralization of acid precursor in the present process can be from 5% to 40%, though is more preferably from 10% to 30%, and most preferably from 15% to 25%, by weight of the agglomerate product.
  • Nonlimiting examples of the preferred anionic surfactants formed by the dry neutralization of the acid precursor in the first step of the present invention include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS"), primary, branched-chain and random C 10 -C 20 alkyl sulfates ("AS"), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and the C 10 -C 18 alkyl alkoxy sulfates ("AE x S"; especially EO 1-7 ethoxy sulfates).
  • LAS
  • the process of the present invention is carried out using (1) CB and/or Schugi mixer(s) which have flexibility to inject at least one liquid ingredient per mixer, (2) KM mixer with chopper blades which has flexibility to inject at least one paste binder ingredient, (3) an optional extruder/pelletizer which has flexibility to inject at least one additional paste binder ingredient into the KM, the process can incorporate at least four different kinds of liquid ingredients over a wide range of viscosity and other rheological properties in the process. Therefore, the proposed process is beneficial for persons skilled in the art in order to incorporate into a granule making process starting detergent materials which are in liquid form and are rather expensive and sometimes more difficult in terms of handling and/or storage than solid materials.
  • Optional other detergent surfactant can also be included in the detergent product, such as other anionic surfactants, nonionic surfactants, zwitterionic surfactants, ampholytic surfactants and cationic surfactants, and compatible mixtures thereof.
  • Such other detergent surfactants can be added as liquids or powders in small amounts (generally, 10% or less) in the first or second step, or in any optional intermediate or finishing step.
  • Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975.
  • Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980.
  • Cationic surfactants can also be used as a detergent surfactant herein and suitable quaternary ammonium surfactants are selected from mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the particulate inorganic or organic detergent ingredients that can be introduced into either one or more of the first step, the second step, or other optional step, are preferably in the form of a finely divided, free-flowing powder, and are preferably selected from the group consisting of ground soda ash or carbonates (including the excess of alkaline inorganic particulate material added in the first step), powdered sodium tripolyphosphate (STPP), hydrated tripolyphosphate, ground or powdered sodium sulphate, aluminosilicate, crystalline layered silicates, nitrilotriacetates (NTA), pyrophosphates, orthophosphates, precipitated silicates, polymers, other carbonates, citrates, the above-mentioned powdered surfactants (such as powdered alkane sulfonic acids) and internal recycle stream of powder occurring from the process of the present invention, wherein the mean diameter of the powder is from 0.1 to 500 microns, preferably from 1 to 300 microns
  • the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble).
  • the particulate inorganic or organic detergent ingredients can also serve as a coating agent when added to the second mixer.
  • Preferred as coating agents are phosphates, carbonates and aluminosilicates.
  • the coating agent enhances the free flowability of the resulting agglomerate and can prevent or minimize over-agglomeration in the second mixer. It can be advantageous to include only carbonate or other particulate material that is not a builder material, whereby a detergent agglomerate can be made that contains little (less than 10%, preferably less than 5%, by weight) or no detergent builders. This can enable the manufacturer to process a single detergent agglomerate for use in either phosphate-built or non-phosphate built detergents.
  • the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
  • the aluminosilicate ion exchange material preferably can be in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
  • the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
  • particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
  • the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
  • the aluminosilicate ion exchange material has the formula Na z [(AlO 2 ) z .(SiO 2 ) y ]xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula Na 12 [(AlO 2 ) 12 .(SiO 2 ) 12 ]xH 2 O wherein x is from about 20 to about 30, preferably about 27.
  • These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
  • naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669.
  • aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO 3 hardness/gram.
  • the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least 0.13 g/l/min (2 grains Ca ++ /gallon/minute/-gram/gallon), and more preferably in a range from 0,13 g/l/min to 0,39g/l/min (2 grains Ca ++ /gallon/minute/-gram/gallon to 6 grains Ca ++ /gallon/minute/gram/gallon).
  • the amount of the particulate inorganic or organic detergent ingredients that can be present in the first step comprise from about 30 to 94%, preferably from 50% to 90%, by weight of the detergent agglomerate exiting the second step.
  • An additional amount of the particulate inorganic or organic detergent ingredients can be added in any optional intermediate step, or in the second step, as to provide a dusting or free-flow material.
  • adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al.
  • the process of the present invention can be used ot make detergent agglomerates which are suitable for use as-is, after addition of any adjunct detergent ingredients, as a detergent product. However, it may be preferred to further condition or treat the detergent agglomerate via optional process steps. Such optional process steps can include screening any oversized detergent agglomerates in a screening apparatus which can take a variety of forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product.
  • Another optional step, particularly when loading high levels of anionic paste in the agglomeration step includes conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying, such as can be accomplished with an airlift or a fluid bed dryer.
  • an internal recycle stream of fine agglomerates having a mean diameter of about 75 to 400 microns generated by elutriation from a device such as a fluidized bed dryer, fluidized bed cooler, or other classification device, can be fed into the first step mixer or second step mixer as one of the fine powders.
  • the amount of such internal recycle stream can be 0 to about 60 % by weight of final product stream on an instantaneous basis, and preferably less than about 20 % by weight on an average production basis.
  • the process generally entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients.
  • the finishing step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition.
  • Such techniques and ingredients are well known in the art.
  • Step 1 222 kg/hr of liquid acid precursor HLAS (97% active) is continuously dispersed and mixed by the pin tools of a Lödige CB-30 mixer along with 297 kg/hr of ground soda ash (mean particle size of 15 microns), 295 kg/hr of powdered zeolite (mean particle size of about 5 microns), 10 kg/hr of ground sodium sulfate (mean particle size of 15 microns), and less that 20% (by weight of the CB mixer throughput) an internal recycle stream of powder from step 2.
  • the acid precursor is fed at about 40°C, and the powders are fed at room temperature.
  • the conditions of the CB-30 mixer are as follows:
  • Step 2 The free-flowing powder from the CB-30 mixer is fed continuously to a Lödige KM-600 mixer having four internal chopper assemblies along its length, each chopper assembly having three levels choppers of 4 blades each (4 cuts per chopper assembly level per chopper revolution).
  • a surfactant paste blend of about 48% NaAS paste (C14.5 sulfate, sodium salt; 75% active) and about 52% NaAES paste (C14.5 ethoxy-1 sulfate, sodium salt; 75% active) is prepared.
  • Such a surfactant paste blend has been determined to have an apparent yield stress of 78 Pa at a shear rate of 1 sec -1 and a temperature of 60°C, as measured using a Carrimed CSL-100 Controlled Stress Rheometer.
  • the paste binder is continuously injected at a temperature of about 60°C across the first three choppers assemblies at a total rate of 175 kg paste/hr.
  • Each paste stream to each chopper assembly is sub-divided into three smaller streams, each directed at a separate level of chopper, where each smaller stream has a discharge opening of 2 mm diameter.
  • Each chopper turns at about 3500 RPM.
  • the calculated mass of the discrete mass units of paste is about 0.023 grams, which is equivalent to a equivalent spherical diameter of about 3.4 mm.
  • the conditions of the KM-600 mixer are as follows:
  • Step 1 231 kg/hr of liquid acid precursor HLAS (97% active) is continuously dispersed and mixed by the pin tools of a Lödige CB-30 mixer along with 586 kg/hr of ground soda ash (mean particle size of 15 microns), and less that 20% (by weight of the CB mixer throughput) an internal recycle stream of powder from step 2.
  • the acid precursor is fed at about 40°C, and the powders are fed at room temperature.
  • the conditions of the CB-30 mixer are as follows:
  • Step 2 The free-flowing powder from the CB-30 mixer is fed continuously to a Lödige KM-600 mixer having four internal chopper assemblies along its length, each chopper assembly having three levels choppers of 4 blades each (4 cuts per chopper assembly level per chopper revolution).
  • a surfactant paste blend of 48% NaAS paste (C14.5 sulfate, sodium salt; 75% active) and 58% NaAES paste (C14.5 ethoxy-1 sulfate, sodium salt; 75% active) is prepared, and is determined to have an apparent yield stress of 78 Pa at a shear rate of 1 sec -1 and a temperature of 60°C, as measured using a Carrimed CSL-100 Controlled Stress Rheometer.
  • the paste binder is continuously injected at a temperature of about 60°C across the first three chopper assemblies at a total rate of about 182 kg paste/hr.
  • Each paste stream to each chopper is sub-divided into three smaller streams, each directed at a separate level of chopper, where each smaller stream has a discharge opening of 2 mm diameter.
  • Each chopper turns at about 3500 RPM.
  • the calculated mass of the discrete mass units of paste is about 0.024 grams, which is equivalent to a equivalent spherical diameter of about 3.5 mm.
  • the conditions of the KM-600 mixer are as follows:
  • Step 1 5400 kg/hr of liquid acid precursor HLAS (97% active) was continuously dispersed and mixed by the pin tools of a Littleford CB-100 mixer along with 12,040 kg/hr of finely ground soda ash (mean particle size of about 15 microns), 7200 kg/hr of powdered STPP, 3885 kg/hr of powdered sodium sulfate, and less that 20% (by weight of the CB mixer throughput) an internal recycle stream of powder from step 2.
  • the acid precursor was fed at about 40° C, and the powders were fed at room temperature.
  • the conditions of the CB-30 mixer were as follows:
  • Step 2 The free-flowing powder from the CB-100 mixer was fed continuously to a Lödige KM-15000 mixer with forward facing half-plows (i.e., Becker Blades), and having six internal chopper assemblies along its length, each chopper assembly having three levels of choppers, each chopper having 4 blades each (4 cuts per chopper assembly level per chopper revolution).
  • a surfactant paste of NaAES paste was used as the agglomeration binder.
  • the NaAES paste was the sodium salt of C14.5 ethoxy-3 sulfate (70% active) with an apparent yield stress of 135 Pa at a shear rate of 1 sec -1 and a temperature of 25°C, as measured using a Carrimed CSL-100 Controlled Stress Rheometer.
  • the paste binder was continuously injected at a temperature of about 30°C across the first four chopper assemblies at a total rate of 1224 kg paste/hr. Each paste stream to each chopper assembly was sub-divided into three smaller streams, each directed at a separate level of chopper, where each smaller stream had a discharge opening of 2 mm diameter. Each chopper turned at about 3500 RPM.
  • the calculated average mass of the discrete mass units of paste was about 0.12 grams, which is equivalent to a equivalent spherical diameter of about 6 mm.
  • the conditions of the KM-15000 mixer are as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Glanulating (AREA)

Claims (8)

  1. Kontinuierliches Verfahren zur Zubereitung eines granulösen Waschmittelagglomerats, umfassend mehr als 15 Gew.-% Tensid, mit einer durchschnittlichen Teilchengröße von zwischen 250 und 1200 µm, einer geometrischen Standardabweichung von weniger als 2,5 und einer Dichte von mindestens 500 g/l, umfassend die Schritte:
    (a) in einem ersten Schritt Verteilung und Mischung eines flüssigen Säurevorläufers eines anionischen Tensides mit einem festen teilchenförmigen, wasserlöslichen, anorganischen, alkalischen Material in einem Schnellmischer mit einer mittleren Verweilzeit von 0,2 bis 50 Sekunden, worin der Säurevorläufer ganz oder teilweise neutralisiert wird und dadurch ein trockenes, neutralisiertes Material, umfassend ein Salz eines anionischen Tensidvorläufers in der Form eines frei fließenden Pulvers, bildet, worin der flüssige Säurevorläufer eines anionischen Tensides und das feste teilchenförmige, wasserlösliche, alkalische Material gleichzeitig dem Schnellmischer zugeführt werden und worin der Schnellmischer aus einem Gerät mit Mischwerkzeugen besteht, deren Werkzeugspitzen mit einer Geschwindigkeit von mindestens 10 ms-1 arbeiten, und worin ein enger Zwischenraum zwischen den Werkzeugspitzen und der Mischerwand oder anderem fest montierten Element von weniger als 2 cm ist und
    (b) in einem zweiten Schritt Verteilung und Mischung eines Agglomerationsbindemittels, ausgewählt aus der Gruppe, bestehend aus anionischer Tensidpaste, flüssigem Silikat, kationenaktivem Tensid, wässrigen oder nichtwässrigen Polymerlösungen, Wasser und Mischungen davon, mit dem frei fließenden Pulver in einem mittelschnelllaufenden Mischer, wobei das Pulver in granulöse Waschmittelagglomerate agglomeriert wird, wobei der mittelschnelllaufende Mischer den zweiten Schritt unter Bedingungen, umfassend (i) eine mittlere Verweilzeit von 10 Sekunden bis 2 Minuten, (ii) eine Geschwindigkeit der im Mischbereich montierten Mischwerkzeugspitzen von 0,5 bis 5 ms-1 und (iii) eine spezifische Energiebedingung von 0,15 bis 7 kJ/kg, ausführt.
  2. Verfahren nach Anspruch 1, worin das Agglomerationsbindemittel eine viskose Tensidpaste ist, die eine scherungsverdünnende Rheologie mit einer scheinbaren Fließspannung (ty) von mehr als 50 Pa aufweist.
  3. Verfahren nach Ansprüchen 1-2, worin die viskose Tensidpaste ein anionisches Tensid, ausgewählt aus der Gruppe, bestehend aus Alkylsulfat, Alkylethoxy(1)sulfat, Alkylethoxy(3)sulfat, linearem Alkylbenzolsulfonat, verzweigtem Alkylbenzolsulfonat und Mischungen davon, umfasst.
  4. Verfahren nach einem der vorstehenden Ansprüche, worin das Agglomerationsbindemittel mit dem frei fließenden Pulver als gesonderte Masseneinheiten im Mischbereich des zweiten Mischers fein verteilt wird, wobei die Einheiten einen durchschnittlichen äquivalenten Durchmesser von 0,5 bis 4 mm haben.
  5. Verfahren nach einem der vorstehenden Ansprüche, worin das feste teilchenförmige, wasserlösliche, alkalische Material fein verteiltes Natriumcarbonat mit einer durchschnittlichen Teilchengröße von weniger als 20 µm ist.
  6. Verfahren nach einem der vorstehenden Ansprüche, worin das trockene, neutralisierte Material in einem optionalen Zwischenmischschritt mit einer fakultativen Flüssigkeit und teilchenförmigen Waschmittelbestandteilen vermischt wird, bevor es als frei fließendes Pulver in den Agglomerationsmischer des zweiten Schritts befördert wird.
  7. Verfahren nach einem der vorstehenden Ansprüche, worin das trockene, neutralisierte Material weniger als 5 Gew.-% Waschmittelbuildermaterial enthält.
  8. Verfahren nach einem der vorstehenden Ansprüche, worin die granulösen Waschmittelagglomerate weniger als 5 Gew.-% Waschmittelbuildermaterial enthalten.
EP99946732A 1998-09-18 1999-09-03 Kontinuierliches herstellungsverfahren für waschmittel Expired - Lifetime EP1114138B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10096098P 1998-09-18 1998-09-18
US100960P 1998-09-18
PCT/US1999/020182 WO2000017304A1 (en) 1998-09-18 1999-09-03 Continuous process for making a detergent composition

Publications (2)

Publication Number Publication Date
EP1114138A1 EP1114138A1 (de) 2001-07-11
EP1114138B1 true EP1114138B1 (de) 2005-05-11

Family

ID=22282421

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99946732A Expired - Lifetime EP1114138B1 (de) 1998-09-18 1999-09-03 Kontinuierliches herstellungsverfahren für waschmittel

Country Status (9)

Country Link
EP (1) EP1114138B1 (de)
JP (1) JP2002526602A (de)
CN (1) CN1191348C (de)
AT (1) ATE295409T1 (de)
AU (1) AU5907499A (de)
BR (1) BR9913862B1 (de)
CA (1) CA2341405A1 (de)
DE (1) DE69925286T2 (de)
WO (1) WO2000017304A1 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050181969A1 (en) 2004-02-13 2005-08-18 Mort Paul R.Iii Active containing delivery particle
DE102005005499A1 (de) * 2005-02-04 2006-08-17 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln
JP4785405B2 (ja) * 2005-04-14 2011-10-05 花王株式会社 洗剤粒子
US20090124532A1 (en) * 2005-07-12 2009-05-14 Yushi Sakata Detergent Granule and Process for Production Thereof
ATE467674T1 (de) * 2008-05-22 2010-05-15 Unilever Nv Herstellung von waschmittelgranulat durch trockenneutralisierung
US8727963B2 (en) 2008-07-31 2014-05-20 Ams Research Corporation Methods and implants for treating urinary incontinence
BR112012000460A2 (pt) * 2009-07-09 2016-02-16 Procter & Gamble processo contínuo para produção de uma composição detergente para lavagem de roupas
WO2011061045A1 (en) * 2009-11-20 2011-05-26 Unilever Nv Detergent granule and its manufacture
WO2015154277A1 (en) 2014-04-10 2015-10-15 The Procter & Gamble Company Composite detergent granules and laundry compositions comprising the same
CN115916940A (zh) * 2020-07-03 2023-04-04 宝洁公司 粒状衣物洗涤组合物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8922018D0 (en) * 1989-09-29 1989-11-15 Unilever Plc Detergent compositions and process for preparing them
WO1997032954A1 (en) * 1996-03-08 1997-09-12 The Procter & Gamble Company Agglomerated high density detergent composition containing secondary alkyl sulfate surfactant and processes for making same
GB9618876D0 (en) * 1996-09-10 1996-10-23 Unilever Plc Process for preparing high bulk density detergent compositions
BR9712885A (pt) * 1996-11-06 2000-02-01 Procter & Gamble Processo de neutralização para a fabricação de grânulos de aglomerado de detergente
GB9625066D0 (en) * 1996-12-02 1997-01-22 Unilever Plc Process for the production of a detergent composition

Also Published As

Publication number Publication date
CA2341405A1 (en) 2000-03-30
DE69925286T2 (de) 2006-02-23
JP2002526602A (ja) 2002-08-20
AU5907499A (en) 2000-04-10
BR9913862A (pt) 2001-06-05
EP1114138A1 (de) 2001-07-11
ATE295409T1 (de) 2005-05-15
WO2000017304A1 (en) 2000-03-30
DE69925286D1 (de) 2005-06-16
CN1191348C (zh) 2005-03-02
CN1354782A (zh) 2002-06-19
BR9913862B1 (pt) 2009-05-05

Similar Documents

Publication Publication Date Title
EP0782612B1 (de) Verfahren zur herstellung eines kompaktwaschmittels in einem rührkessel mit ausgewählten rücklaufströmen
US5516448A (en) Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate
US5576285A (en) Process for making a low density detergent composition by agglomeration with an inorganic double salt
EP0929648B1 (de) Verfahren zur herstellung von einer waschmittelzusammensetzung nach ohne-turm-verfahren
JPH11508313A (ja) 低密度洗剤組成物の製造法
CA2245933C (en) Process for making a low density detergent composition by agglomeration with an inorganic double salt
WO2000017304A1 (en) Continuous process for making a detergent composition
US6794354B1 (en) Continuous process for making detergent composition
JP2003521548A (ja) 流動床乾燥器内のノズルの高さの調整による低密度洗浄剤組成物の製造法
WO1998014550A1 (en) Process for making a low density detergent composition
EP1187904B1 (de) Verfahren zur herstellung granularer waschmittelzusammensetzungen
US6281188B1 (en) Process for making a low density detergent composition
MXPA02000027A (es) Procedimiento para elaborar detergente granular en un granulador de cama fluida que tiene reciclado de particulas de tamano no apropiado.
US6156719A (en) Process for making a low density detergent composition by non-tower process
JP2010138223A (ja) 洗剤粒子群の製造方法
MXPA01002871A (en) Continuous process for making a detergent composition
WO2000037605A1 (en) Process for making a low bulk density detergent composition by agglomeration
EP1115837B1 (de) Körnige waschmittelzusammensetzungen mit homogenen teilchen sowie verfahren zu ihrer herstellung
CA2346340A1 (en) Process for making a free flowing detergent composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010326

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20030605

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050511

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050511

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050511

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050511

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050511

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050511

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050511

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69925286

Country of ref document: DE

Date of ref document: 20050616

Kind code of ref document: P

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050809

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050811

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050811

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050811

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050822

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050902

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050903

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050905

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050930

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050930

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050930

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051019

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

ET Fr: translation filed
26N No opposition filed

Effective date: 20060214

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20061130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070403

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060903

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060903

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061002