CA2242420C - Process for the production of a detergent composition - Google Patents
Process for the production of a detergent composition Download PDFInfo
- Publication number
- CA2242420C CA2242420C CA002242420A CA2242420A CA2242420C CA 2242420 C CA2242420 C CA 2242420C CA 002242420 A CA002242420 A CA 002242420A CA 2242420 A CA2242420 A CA 2242420A CA 2242420 C CA2242420 C CA 2242420C
- Authority
- CA
- Canada
- Prior art keywords
- bulk density
- process according
- detergent
- low
- detergent composition
- 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 - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000003599 detergent Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000007858 starting material Substances 0.000 claims abstract description 18
- 239000008187 granular material Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000011236 particulate material Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000005323 carbonate salts Chemical class 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract description 10
- 239000000843 powder Substances 0.000 description 25
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- 235000019832 sodium triphosphate Nutrition 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- -1 potassium alkyl sulphates Chemical class 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- VSXGXPNADZQTGQ-UHFFFAOYSA-N oxirane;phenol Chemical compound C1CO1.OC1=CC=CC=C1 VSXGXPNADZQTGQ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
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
-
- 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
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)
Abstract
A process for the production of a low to medium bulk density detergent composition by mixing a liquid binder and a particulate starting material in a high speed mixer/granulator to form granules which are then contacted with a particulate material having a bulk density of not more than 700g/l in very low shear mixing zone for example a fluid bed.
Compositions produced by this process are also disclosed.
Compositions produced by this process are also disclosed.
Description
PROCESS FOR THE PROD1~'r'rnN Og A DETERGENT COMPOSITION
' The present invention relates to a process for the production of a detergent composition. In particular the invention is concerned with a process for the production of a detergent composition having a medium bulk density without the use of a spray-drying step involving a high shear mixing step and a very low shear mixing step and to detergent compositions thereby produced.
Conventionally, detergent compositions have been produced by a spray-drying process in which the components of the composition are mixed with water to form an aqueous crutcher slurry which is then sprayed into a spray-drying tower and contacted with hot air to remove water whereby detergent particles, often referred to as a "base" powder are obtained. The particles so obtained, have a high porosity.
Thus powders produced by this method typically have a bulk density of 300 to 550 g/1 or even up to 650 g/l.
Spray-dried powders generally provide good powder delivery characteristics such as dispensing and dissolution.
However, the capital and operating costs of the spray-drying process are high. Nevertheless there remains a significant consumer demand for such low density powders.
In recent years, detergent powders having a high bulk density have been produced by mechanical mixing processes.
Bulk densities of 700 to 900 g/1 and even higher have been obtained. Typically such powders are produced by densifying a spray-dried base powder in one or more mechanical mixers, optionally with the addition of further components, or by mixing the components of the composition in a continuous or batch mixing process without the use of a spray-drying step.
' The present invention relates to a process for the production of a detergent composition. In particular the invention is concerned with a process for the production of a detergent composition having a medium bulk density without the use of a spray-drying step involving a high shear mixing step and a very low shear mixing step and to detergent compositions thereby produced.
Conventionally, detergent compositions have been produced by a spray-drying process in which the components of the composition are mixed with water to form an aqueous crutcher slurry which is then sprayed into a spray-drying tower and contacted with hot air to remove water whereby detergent particles, often referred to as a "base" powder are obtained. The particles so obtained, have a high porosity.
Thus powders produced by this method typically have a bulk density of 300 to 550 g/1 or even up to 650 g/l.
Spray-dried powders generally provide good powder delivery characteristics such as dispensing and dissolution.
However, the capital and operating costs of the spray-drying process are high. Nevertheless there remains a significant consumer demand for such low density powders.
In recent years, detergent powders having a high bulk density have been produced by mechanical mixing processes.
Bulk densities of 700 to 900 g/1 and even higher have been obtained. Typically such powders are produced by densifying a spray-dried base powder in one or more mechanical mixers, optionally with the addition of further components, or by mixing the components of the composition in a continuous or batch mixing process without the use of a spray-drying step.
EP 367 339 (Unilever) discloses a process for the production of a detergent composition having a high bulk density in which a particulate starting material is treated in a high speed mixer, a moderate speed mixer wherein the material is brought into or maintained in a deformable state, and then dried and/or cooled. The starting material may be a spray-dried base powder or the components of the composition may be employed without a prior spray-drying step in the detergent production process.
Powders having a high bulk density have a low packing volume which is advantageous for storage and distribution operations and also for the consumer. Furthermore, if a spray-drying step is not employed, the capital and operating costs are typically much lower and the process uses less energy and so provides an environmental benefit. The avoidance of a spray-drying step in the detergent production process is therefore desirable.
However, such high density powders typically have a much lower porosity than a conventional spray-dried powder which may impair the delivery of the powder into the wash liquor.
Additionally, the production of powders having a low to medium bulk density, for example less than about 700 g/1, has not hitherto been readily achievable on a commercial scale without the use of a spray-drying step.
EP 544 365 (Unilever) is concerned with the production of a high bulk density detergent composition and refers to the bulk density of a detergent powder being dependent upon the bulk density of the starting materials in the case of a mixing process.
Treating a porous spray-dried material in a mechanical mixing process typically leads to an increase in bulk density as the powder porosity is reduced. However, we have found that a powder having a surprisingly low bulk density, for ' example less than 700 g/l, may be obtained by a process in which a spray-drying step is not employed, involving a high shear mixing step and a very low shear mixing step if a component having a low bulk density is incorporated in the very low shear mixing step. Further, such a powder exhibits good powder properties.
A first aspect of the invention provides a process for the production of a detergent composition or component having a bulk density of less than 700 g/1 which. does not comprise a spray-drying step and which process comprises mixing a particulate starting material with a liquid binder in a mixer granulator, preferably having both a stirring and a cutting action, to form granules wherein the starting material and/or binder comprises a non-soap detergent active or a precursor thereof, feeding the said granules to a very low shear mixing zone and contacting the granules with a particulate material having a bulk density of not more than 700g/1 to produce a detergent composition or component having a bulk density of less than 700 g/l.
A second aspect of the invention provides a detergent composition or component having a bulk density of less than 700 g/1 obtainable by a process which does not comprise a spray-drying step and which comprises mixing a particulate starting material with a liquid binder in a mixer/granulator, preferably having both a stirring and cutting action, to form granules and feeding the said granules to a ve ry low shear mixing zone and contacting the granules with a particulate material having a bulk density of not more than 700g/1.
Unless stated otherwise, ~ figures are on a weight basis and based on the total weight of the detergent composition or component prior to the optional addition of post-dosed ingredients.
Suitably the detergent composition has a bulk density of 400 to 680 g/1, preferably 450 to 680 g/1 and more preferably 500 to less than 650 g/l. =t is further preferred that the detergent composition has a particle porosity of at least 0.2 and more preferably at least 0.25. The porosity may be determined by a mercury porosimetry method.
The component incorporated in the very low shear zone has a bulk density of not more than 700 g/1, and suitably has a bulk density of 200 to 600 g/1, preferably 250 to 550 g/1 and especially 350 to 500 g/1.
This low bulk density component is desirably an aluminosilicate, for example zeolite 4A or zeolite A24 or a salt, preferably an inorganic salt. Salts, preferab:Ly sodium, of phosphates, for example tripolyphosphate, carbonate, bicarbonate and sulphate are especially suitable.
Desirably the low bulk density component constitutes the detergency builder, or part thereof in the composition. 2f desired, this component may be a non-builder material, in which case the particulate starting material will suitably comprise a builder.
It is especially preferred that the low bulk density component comprises sodium tripolyphosphate having a bulk density of 380 to 500 g/1. This compares to a typical bulk density of 800 to 1000 g/1 for tripolyphosphate conventionally employed in detergent compositions.
Suitably the level of the low bulk density compt>nent is selected according to the desired density of the detergent composition. Preferably it is present at a level of 5 to WO 97/28246 PCTlEP97I00118 65 wt ~, preferably 10 to 40 wt ~ and optimally 10 to 30 wt of the composition.
If desired part of the low bulk density component may be ' 5 introduced into the high speed mixer/granulator. In a preferre-d embodiment, the level of this component in the very low shear mixing zone is at least 10g by~weight based on the detergent composition and additionally up to 80~ of the total amount of the low bulk density component may be dosed into the high speed mixer/granulator although it is preferred that up to 60~, more preferably 5 to 50~, especially 20 to 45~ of the low density material (as a percentage of the total amount of this material) be dosed into the high speed mixer granulator.
The process may be continuous but is preferably batch-wise.
A preferred type ofmixer/granulator for use in the process of the invention is bowl-shaped and preferably has a substantially vertical stirrer axis. Especially preferred are mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall. The stirrer and cutter may be operated independently of one another, and at separately variable speeds.
Other similar mixers found to be suitable for use in the process of the invention are the Diosna (Trade Mark) V series ex Dierks & Sohne, Germany; and the Pharma Matrix (Trade Mark) ex T K Fielder Ltd., England. Other similar mixers believed to be suitable for use in the process of the WO 97/28246 PCT/E1'97100118 invention include the Fuji (Trade Mark) VG-C series ~ex Fuji Sangyo Co., Japan; and the Roto (Trade Mark) ex Zanchetta &
Co srl, Italy.
Another mixer found to be suitable for use in the process of the invention is the Lddige (Trade Mark) 1.~'M series batch mixer ex Morton Machine Co. Ltd., Scotland. This differs from the mixers mentioned above in that its stirrer has a horizontal axis.
Granulation is preferably effected by running the mixer using both stirrer and cutter; a relatively short residence time (for example, 5-8 minutes for a 35 kg batch) is generally sufficient. The final bulk density can be controlled by choice of residence time.
Suitably the stirrer is operated at a rate of 25 to 80 rpm, preferably 30 to 75 rpm. Independently the cutter is suitably operated at a rate of 200 to 2500 rpm, preferably 300 to 2200 rpm. A batch process typically involves pre-mixing of solid components, addition of liquids, granulation, optional addition of a layering material suitable for controlling the granulation end-point, and product discharge.
The rate of stirring and/or cutting is suitably adjusted according to the stage of the process.
The presence of a liquid binder is necessary for successful granulation. The precise nature of the binder is not critical provided that it enables successful granulation to be achieved. Suitably the binder comprises one or more of the following: liquid detergent-active compound(s), precursors thereof, water, solutions, non-aqueous or aqueous, of other ingredients or mixtures thereof. If water is employed the level is desirably controlled so that the moisture content of the detergent composition is not more than 10~ by weight and preferably not more than 6%.
The mixing step is preferably carried out at a controlled temperature somewhat above ambient, preferably above 30°C. Suitably the temperature is within the range 30 to 55°C although higher temperatures may be suitable, for example, where heat of reaction is generated by in situ neutralisation.
The very low shear mixing zone may be located within the r same apparatus as the high speed mixer granulation but desirably is in a separate apparatus for example a rotating bowl mixer and preferably a fluid bed. The fluid bed is suitably operated at a temperature of 30 to 90°C and at a superficial air velocity of about 0.25 to 1.2 ms-'. Suitable fluid beds are available from, for example NIRO~". The air flow in the fluid bed may be adjusted according to the desired level of shear and agitation of the low bulk density component. Suitably the low bulk density component is dosed into the bed and gently agitated using a small air flow which is then increased prior to feeding in the granules from the high speed mixer/granulator.
r 5 The detergent composition suitably comprises anionic detergent active. This may be incorporated as a pre-neutralised material, desirably as a component of the particulate starting material, or may be neutralised in situ.
In the latter case the acid precursor of the active is preferably neutralised using a solid neutralising agent, for example carbonate (preferably sodium carbonate), which is desirably a component of the particulate starting material.
The detergent active material present in the composition may be selected from anionic, ampholytic, zwitterionic or WO 97/28246 PCT/Ef97100118 nonionic detergent active materials or mixtures thereof.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium (C9-C2o) benzene sulphonates, particularly sodium linear secondary alkyl (Clo-Cls) benzene sulphonates; sodium or potassium alkyl sulphates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic aicohols derived from petroleum. Suitable nonionics which may be employed include, in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C22) phenol ethylene oxide condensates, generally having 5 to EO, ie 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic (C8-Cl8) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO. The level of detergent active material 20 present in the composition may be in the range from 1 to 50~
by weight depending on the desired applications. Nonionic material may be present in the particulate starting material at a level which is preferably less than 10~ by weight, more preferably less than 5~ by weight and/or employed as the 25 liquid binder optionally with another liquid component, for example water.
2n a preferred embodiment of the invention, the particulate starting material comprises one or more of a carbonate salt at a level.of 5 to 60 wt ~, a zeolite at a level of 5 to 60 wt ~ and, if present as the low bulk density component, a phosphate salt at a level of 5 to 20~ by weight of the total quantity of starting material.
Suitably the particulate starting material constitutes 30 to 70~ of the detergent composition.
Optionally, a layering material may be employed during the high speed mixing step to control granule formation and reduce or prevent over-agglomeration. Preferably a layering material is introduced into the very low shear mixing step.
Suitable materials include aluminosilicates, for example zeolite 4A and A24. The layering material is suitability present at a level of 1 to 4 wt ~ based on the co mposition.
The composition may be used as a complete composition in its own right or may be mixed with other components or mixtures and thus may form a major or minor part of a final product. The composition may be blended with for example a spray-dried base powder.
Conventional additional components such as enzymes, bleach and perfume may also be admixed with the composition as desired to produce a fully formulated product.
The invention is further illustrated by the following non-limiting Examples.
Example 1 and A (Comnarativ~Z
A detergent composition was prepared by dosing the following components into a Fukae FS3500 mixer (in the 5 following sequence):
Sodium Tripolyphosphate (400- 80(kg) 440g/1) Fluorescer 1 Sodium Carbonate 530 LAS acid 170 l Fatty acid (pRISERENE"" 4918)/ 40/30 Nonionic mixture The process conditions employed are summarised below:
Process step Stirrer(rnm) Cutter(r~m) Solids premix 40 0 Liquids addition 75 1900 Granulation 70 1900 Discharge 30-45 1500 The mixer was operated at a temperature of 30-35°C. The mixer was operated for sufficient time to effect granulation in the granulation step (end point 60 amps) and the product was discharged over 240 seconds.
130kg of sodium tripolyphosphate (bd 400-440g/1) was dosed into a NIRO fluid bed and 'bubbled' at a low air velocity. Prior to discharge of the granules from the Fukae mixer, the air flow was increased to about 11000 m3/hr and the granules were fed into the fluid bed.
WO 97!28246 PCT/EP97/00118 20kg of zeolite 4A was then dosed into the fluid bed as a layering material. The detergent composition was then discharged from the fluid bed at a temperature below 30°C.
' S For comparative purposes the above procedure was repeated to produce Composition A, but conventional density STP (about 800g/1) was substituted for the low density STP.
All of the STP was dosed into the Fukae mixer and none into the fluid bed.
The properties of the two powders were measured and the results are detailed below:
Bulk density (g/1) 520 775 Dynamic Flow Rate (ml/s) >90 >90 Mean particle size (l.un) 520 750 Both powders were crisp and free flowing and white/cream in colour.
The results demonstrate that a medium bulk density powder is obtainable without the need for a spray-drying step in the production process. A reduction in bulk density may be expected to have an adverse effect on powder properties (compression, UCT). However these properties remain at an acceptable level for the powder of Example 1.
Powders having a high bulk density have a low packing volume which is advantageous for storage and distribution operations and also for the consumer. Furthermore, if a spray-drying step is not employed, the capital and operating costs are typically much lower and the process uses less energy and so provides an environmental benefit. The avoidance of a spray-drying step in the detergent production process is therefore desirable.
However, such high density powders typically have a much lower porosity than a conventional spray-dried powder which may impair the delivery of the powder into the wash liquor.
Additionally, the production of powders having a low to medium bulk density, for example less than about 700 g/1, has not hitherto been readily achievable on a commercial scale without the use of a spray-drying step.
EP 544 365 (Unilever) is concerned with the production of a high bulk density detergent composition and refers to the bulk density of a detergent powder being dependent upon the bulk density of the starting materials in the case of a mixing process.
Treating a porous spray-dried material in a mechanical mixing process typically leads to an increase in bulk density as the powder porosity is reduced. However, we have found that a powder having a surprisingly low bulk density, for ' example less than 700 g/l, may be obtained by a process in which a spray-drying step is not employed, involving a high shear mixing step and a very low shear mixing step if a component having a low bulk density is incorporated in the very low shear mixing step. Further, such a powder exhibits good powder properties.
A first aspect of the invention provides a process for the production of a detergent composition or component having a bulk density of less than 700 g/1 which. does not comprise a spray-drying step and which process comprises mixing a particulate starting material with a liquid binder in a mixer granulator, preferably having both a stirring and a cutting action, to form granules wherein the starting material and/or binder comprises a non-soap detergent active or a precursor thereof, feeding the said granules to a very low shear mixing zone and contacting the granules with a particulate material having a bulk density of not more than 700g/1 to produce a detergent composition or component having a bulk density of less than 700 g/l.
A second aspect of the invention provides a detergent composition or component having a bulk density of less than 700 g/1 obtainable by a process which does not comprise a spray-drying step and which comprises mixing a particulate starting material with a liquid binder in a mixer/granulator, preferably having both a stirring and cutting action, to form granules and feeding the said granules to a ve ry low shear mixing zone and contacting the granules with a particulate material having a bulk density of not more than 700g/1.
Unless stated otherwise, ~ figures are on a weight basis and based on the total weight of the detergent composition or component prior to the optional addition of post-dosed ingredients.
Suitably the detergent composition has a bulk density of 400 to 680 g/1, preferably 450 to 680 g/1 and more preferably 500 to less than 650 g/l. =t is further preferred that the detergent composition has a particle porosity of at least 0.2 and more preferably at least 0.25. The porosity may be determined by a mercury porosimetry method.
The component incorporated in the very low shear zone has a bulk density of not more than 700 g/1, and suitably has a bulk density of 200 to 600 g/1, preferably 250 to 550 g/1 and especially 350 to 500 g/1.
This low bulk density component is desirably an aluminosilicate, for example zeolite 4A or zeolite A24 or a salt, preferably an inorganic salt. Salts, preferab:Ly sodium, of phosphates, for example tripolyphosphate, carbonate, bicarbonate and sulphate are especially suitable.
Desirably the low bulk density component constitutes the detergency builder, or part thereof in the composition. 2f desired, this component may be a non-builder material, in which case the particulate starting material will suitably comprise a builder.
It is especially preferred that the low bulk density component comprises sodium tripolyphosphate having a bulk density of 380 to 500 g/1. This compares to a typical bulk density of 800 to 1000 g/1 for tripolyphosphate conventionally employed in detergent compositions.
Suitably the level of the low bulk density compt>nent is selected according to the desired density of the detergent composition. Preferably it is present at a level of 5 to WO 97/28246 PCTlEP97I00118 65 wt ~, preferably 10 to 40 wt ~ and optimally 10 to 30 wt of the composition.
If desired part of the low bulk density component may be ' 5 introduced into the high speed mixer/granulator. In a preferre-d embodiment, the level of this component in the very low shear mixing zone is at least 10g by~weight based on the detergent composition and additionally up to 80~ of the total amount of the low bulk density component may be dosed into the high speed mixer/granulator although it is preferred that up to 60~, more preferably 5 to 50~, especially 20 to 45~ of the low density material (as a percentage of the total amount of this material) be dosed into the high speed mixer granulator.
The process may be continuous but is preferably batch-wise.
A preferred type ofmixer/granulator for use in the process of the invention is bowl-shaped and preferably has a substantially vertical stirrer axis. Especially preferred are mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall. The stirrer and cutter may be operated independently of one another, and at separately variable speeds.
Other similar mixers found to be suitable for use in the process of the invention are the Diosna (Trade Mark) V series ex Dierks & Sohne, Germany; and the Pharma Matrix (Trade Mark) ex T K Fielder Ltd., England. Other similar mixers believed to be suitable for use in the process of the WO 97/28246 PCT/E1'97100118 invention include the Fuji (Trade Mark) VG-C series ~ex Fuji Sangyo Co., Japan; and the Roto (Trade Mark) ex Zanchetta &
Co srl, Italy.
Another mixer found to be suitable for use in the process of the invention is the Lddige (Trade Mark) 1.~'M series batch mixer ex Morton Machine Co. Ltd., Scotland. This differs from the mixers mentioned above in that its stirrer has a horizontal axis.
Granulation is preferably effected by running the mixer using both stirrer and cutter; a relatively short residence time (for example, 5-8 minutes for a 35 kg batch) is generally sufficient. The final bulk density can be controlled by choice of residence time.
Suitably the stirrer is operated at a rate of 25 to 80 rpm, preferably 30 to 75 rpm. Independently the cutter is suitably operated at a rate of 200 to 2500 rpm, preferably 300 to 2200 rpm. A batch process typically involves pre-mixing of solid components, addition of liquids, granulation, optional addition of a layering material suitable for controlling the granulation end-point, and product discharge.
The rate of stirring and/or cutting is suitably adjusted according to the stage of the process.
The presence of a liquid binder is necessary for successful granulation. The precise nature of the binder is not critical provided that it enables successful granulation to be achieved. Suitably the binder comprises one or more of the following: liquid detergent-active compound(s), precursors thereof, water, solutions, non-aqueous or aqueous, of other ingredients or mixtures thereof. If water is employed the level is desirably controlled so that the moisture content of the detergent composition is not more than 10~ by weight and preferably not more than 6%.
The mixing step is preferably carried out at a controlled temperature somewhat above ambient, preferably above 30°C. Suitably the temperature is within the range 30 to 55°C although higher temperatures may be suitable, for example, where heat of reaction is generated by in situ neutralisation.
The very low shear mixing zone may be located within the r same apparatus as the high speed mixer granulation but desirably is in a separate apparatus for example a rotating bowl mixer and preferably a fluid bed. The fluid bed is suitably operated at a temperature of 30 to 90°C and at a superficial air velocity of about 0.25 to 1.2 ms-'. Suitable fluid beds are available from, for example NIRO~". The air flow in the fluid bed may be adjusted according to the desired level of shear and agitation of the low bulk density component. Suitably the low bulk density component is dosed into the bed and gently agitated using a small air flow which is then increased prior to feeding in the granules from the high speed mixer/granulator.
r 5 The detergent composition suitably comprises anionic detergent active. This may be incorporated as a pre-neutralised material, desirably as a component of the particulate starting material, or may be neutralised in situ.
In the latter case the acid precursor of the active is preferably neutralised using a solid neutralising agent, for example carbonate (preferably sodium carbonate), which is desirably a component of the particulate starting material.
The detergent active material present in the composition may be selected from anionic, ampholytic, zwitterionic or WO 97/28246 PCT/Ef97100118 nonionic detergent active materials or mixtures thereof.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium (C9-C2o) benzene sulphonates, particularly sodium linear secondary alkyl (Clo-Cls) benzene sulphonates; sodium or potassium alkyl sulphates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic aicohols derived from petroleum. Suitable nonionics which may be employed include, in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C22) phenol ethylene oxide condensates, generally having 5 to EO, ie 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic (C8-Cl8) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO. The level of detergent active material 20 present in the composition may be in the range from 1 to 50~
by weight depending on the desired applications. Nonionic material may be present in the particulate starting material at a level which is preferably less than 10~ by weight, more preferably less than 5~ by weight and/or employed as the 25 liquid binder optionally with another liquid component, for example water.
2n a preferred embodiment of the invention, the particulate starting material comprises one or more of a carbonate salt at a level.of 5 to 60 wt ~, a zeolite at a level of 5 to 60 wt ~ and, if present as the low bulk density component, a phosphate salt at a level of 5 to 20~ by weight of the total quantity of starting material.
Suitably the particulate starting material constitutes 30 to 70~ of the detergent composition.
Optionally, a layering material may be employed during the high speed mixing step to control granule formation and reduce or prevent over-agglomeration. Preferably a layering material is introduced into the very low shear mixing step.
Suitable materials include aluminosilicates, for example zeolite 4A and A24. The layering material is suitability present at a level of 1 to 4 wt ~ based on the co mposition.
The composition may be used as a complete composition in its own right or may be mixed with other components or mixtures and thus may form a major or minor part of a final product. The composition may be blended with for example a spray-dried base powder.
Conventional additional components such as enzymes, bleach and perfume may also be admixed with the composition as desired to produce a fully formulated product.
The invention is further illustrated by the following non-limiting Examples.
Example 1 and A (Comnarativ~Z
A detergent composition was prepared by dosing the following components into a Fukae FS3500 mixer (in the 5 following sequence):
Sodium Tripolyphosphate (400- 80(kg) 440g/1) Fluorescer 1 Sodium Carbonate 530 LAS acid 170 l Fatty acid (pRISERENE"" 4918)/ 40/30 Nonionic mixture The process conditions employed are summarised below:
Process step Stirrer(rnm) Cutter(r~m) Solids premix 40 0 Liquids addition 75 1900 Granulation 70 1900 Discharge 30-45 1500 The mixer was operated at a temperature of 30-35°C. The mixer was operated for sufficient time to effect granulation in the granulation step (end point 60 amps) and the product was discharged over 240 seconds.
130kg of sodium tripolyphosphate (bd 400-440g/1) was dosed into a NIRO fluid bed and 'bubbled' at a low air velocity. Prior to discharge of the granules from the Fukae mixer, the air flow was increased to about 11000 m3/hr and the granules were fed into the fluid bed.
WO 97!28246 PCT/EP97/00118 20kg of zeolite 4A was then dosed into the fluid bed as a layering material. The detergent composition was then discharged from the fluid bed at a temperature below 30°C.
' S For comparative purposes the above procedure was repeated to produce Composition A, but conventional density STP (about 800g/1) was substituted for the low density STP.
All of the STP was dosed into the Fukae mixer and none into the fluid bed.
The properties of the two powders were measured and the results are detailed below:
Bulk density (g/1) 520 775 Dynamic Flow Rate (ml/s) >90 >90 Mean particle size (l.un) 520 750 Both powders were crisp and free flowing and white/cream in colour.
The results demonstrate that a medium bulk density powder is obtainable without the need for a spray-drying step in the production process. A reduction in bulk density may be expected to have an adverse effect on powder properties (compression, UCT). However these properties remain at an acceptable level for the powder of Example 1.
Claims (10)
1. A process for the production of a detergent composition or component having a bulk density of less than 700 g/l which does not comprise a spray-drying step and which process comprises mixing a particulate starting material with a liquid binder in a mixer granulator to form granules wherein at least one of the starting material and binder comprises a non-soap detergent active or a precursor thereof feeding the said granules to a very low shear mixing zone and contacting the granules with a particulate material having a bulk density of not more than 700 g/l to produce a detergent composition or component having a bulk density of less than 700 g/l.
2. A process according to claim 1, wherein the particulate material having a low bulk density comprises alumino-silicate, an inorganic salt or mixtures thereof.
3. A process according to claim 2, wherein low bulk density particulate material comprises a phosphate, carbonate, bicarbonate or sulphate salt.
4. A process according to any one of claims 1 to 3, wherein the particulate material having low bulk density comprises a builder material.
5. A process according to any one of claims 1 to 4, wherein 5-65% by weight of the low bulk density particulate material based on the composition is added.
6. A process according to any one of claims 1 to 5, wherein at least 10% by weight based on the detergent composition of low bulk density particulate material is added in the very low shear mixing zone.
7. A process according to any one of claims 1 to 6, wherein the binder comprises liquid detergent-active, liquid detergent-active precursor, water, solutions, non-aqueous or aqueous, of other ingredients, or mixtures thereof.
8. A process according to any one of claims 1 to 7, wherein the active comprises anionic detergent active.
9. A process according to claim 8, wherein an acid precursor of anionic detergent is added and neutralized in situ.
10. A process according to any one of claims 1 to 9, wherein the particulate starting material comprises one or more of a carbonate salt at a level of 5-60 wt%, a zeolite at a level of 5-60 wt% and if present as the low bulk density component, a phosphate salt at a level of 5-20% by weight of the total quantity of starting material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9601920.3 | 1996-01-31 | ||
| GBGB9601920.3A GB9601920D0 (en) | 1996-01-31 | 1996-01-31 | Process for the production of a detergent composition |
| PCT/EP1997/000118 WO1997028246A1 (en) | 1996-01-31 | 1997-01-06 | Process for the production of a detergent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2242420A1 CA2242420A1 (en) | 1997-08-07 |
| CA2242420C true CA2242420C (en) | 2005-08-30 |
Family
ID=10787857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002242420A Expired - Fee Related CA2242420C (en) | 1996-01-31 | 1997-01-06 | Process for the production of a detergent composition |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0882126B1 (en) |
| CN (1) | CN1191351C (en) |
| AR (1) | AR005576A1 (en) |
| AU (1) | AU1440997A (en) |
| BR (1) | BR9707474A (en) |
| CA (1) | CA2242420C (en) |
| DE (1) | DE69701731T2 (en) |
| EA (1) | EA001314B1 (en) |
| ES (1) | ES2145567T3 (en) |
| GB (1) | GB9601920D0 (en) |
| HU (1) | HUP9901180A3 (en) |
| IN (1) | IN188387B (en) |
| PL (1) | PL184656B1 (en) |
| TR (1) | TR199801444T2 (en) |
| WO (1) | WO1997028246A1 (en) |
| ZA (1) | ZA97255B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9513327D0 (en) * | 1995-06-30 | 1995-09-06 | Uniliver Plc | Process for the production of a detergent composition |
| GB9526097D0 (en) * | 1995-12-20 | 1996-02-21 | Unilever Plc | Process |
| US6150323A (en) * | 1996-10-04 | 2000-11-21 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| US6391844B1 (en) | 1996-10-04 | 2002-05-21 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| US6211138B1 (en) | 1996-10-04 | 2001-04-03 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| US6121229A (en) * | 1996-10-04 | 2000-09-19 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| US6136777A (en) * | 1996-10-04 | 2000-10-24 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| US6172034B1 (en) | 1996-10-04 | 2001-01-09 | The Procter & Gamble | Process for making a detergent composition by non-tower process |
| US6211137B1 (en) | 1996-10-04 | 2001-04-03 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| US6143711A (en) * | 1996-10-04 | 2000-11-07 | The Procter & Gamble Company | Process for making a detergent composition by non-tower process |
| GB9712580D0 (en) * | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
| GB9712583D0 (en) | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
| GB9713748D0 (en) * | 1997-06-27 | 1997-09-03 | Unilever Plc | Production of detergent granulates |
| US6555514B1 (en) | 1998-10-26 | 2003-04-29 | The Procter & Gamble Company | Processes for making granular detergent composition having improved appearance and solubility |
| WO2000037605A1 (en) * | 1998-12-22 | 2000-06-29 | The Procter & Gamble Company | Process for making a low bulk density detergent composition by agglomeration |
| US6596683B1 (en) | 1998-12-22 | 2003-07-22 | The Procter & Gamble Company | Process for preparing a granular detergent composition |
| US6858572B1 (en) | 1999-03-09 | 2005-02-22 | The Procter & Gamble Company | Process for producing coated detergent particles |
| GB9913544D0 (en) * | 1999-06-10 | 1999-08-11 | Unilever Plc | Process for preparing granular detergent compositions |
| GB9913546D0 (en) | 1999-06-10 | 1999-08-11 | Unilever Plc | Granular detergent component containing zeolite map and laundry detergent compositions containing it |
| US6894018B1 (en) | 1999-06-21 | 2005-05-17 | The Procter & Gamble Company | Process for making granular detergent in a fluidized bed granulator having recycling of improperly sized particles |
| CN102471740A (en) * | 2009-07-09 | 2012-05-23 | 宝洁公司 | Continuous process for making a laundry detergent composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59157198A (en) * | 1983-02-28 | 1984-09-06 | ライオン株式会社 | Manufacture of small bulk density detergent builder granules |
| JPS6072998A (en) * | 1983-09-30 | 1985-04-25 | 花王株式会社 | Manufacture of surfactant powder composition with high powder properties |
| JPS6072999A (en) * | 1983-09-30 | 1985-04-25 | 花王株式会社 | Manufacture of super concentrated powder detergent |
| JPH06128594A (en) * | 1992-10-16 | 1994-05-10 | Lion Corp | Production of particulate surfactant composition |
| DE69405238T2 (en) * | 1993-07-02 | 1998-01-02 | Unilever Nv | METHOD FOR PRODUCING A DETERGENT COMPOSITION |
| JPH0813000A (en) * | 1994-06-28 | 1996-01-16 | Lion Corp | Production of granular detergent composition having high bulk density |
-
1996
- 1996-01-31 GB GBGB9601920.3A patent/GB9601920D0/en active Pending
-
1997
- 1997-01-06 CA CA002242420A patent/CA2242420C/en not_active Expired - Fee Related
- 1997-01-06 BR BR9707474A patent/BR9707474A/en not_active IP Right Cessation
- 1997-01-06 DE DE69701731T patent/DE69701731T2/en not_active Revoked
- 1997-01-06 CN CNB971919607A patent/CN1191351C/en not_active Expired - Fee Related
- 1997-01-06 WO PCT/EP1997/000118 patent/WO1997028246A1/en not_active Application Discontinuation
- 1997-01-06 EA EA199800668A patent/EA001314B1/en not_active IP Right Cessation
- 1997-01-06 AU AU14409/97A patent/AU1440997A/en not_active Abandoned
- 1997-01-06 ES ES97901008T patent/ES2145567T3/en not_active Expired - Lifetime
- 1997-01-06 HU HU9901180A patent/HUP9901180A3/en unknown
- 1997-01-06 TR TR1998/01444T patent/TR199801444T2/en unknown
- 1997-01-06 EP EP97901008A patent/EP0882126B1/en not_active Revoked
- 1997-01-06 PL PL97328022A patent/PL184656B1/en not_active IP Right Cessation
- 1997-01-13 ZA ZA97255A patent/ZA97255B/en unknown
- 1997-01-28 AR ARP970100333A patent/AR005576A1/en unknown
- 1997-01-31 IN IN61BO1997 patent/IN188387B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUP9901180A2 (en) | 1999-08-30 |
| DE69701731T2 (en) | 2000-08-10 |
| HUP9901180A3 (en) | 2002-04-29 |
| CN1209835A (en) | 1999-03-03 |
| IN188387B (en) | 2002-09-14 |
| BR9707474A (en) | 1999-07-27 |
| GB9601920D0 (en) | 1996-04-03 |
| TR199801444T2 (en) | 1998-10-21 |
| EA001314B1 (en) | 2001-02-26 |
| EP0882126A1 (en) | 1998-12-09 |
| AR005576A1 (en) | 1999-06-23 |
| WO1997028246A1 (en) | 1997-08-07 |
| CA2242420A1 (en) | 1997-08-07 |
| ZA97255B (en) | 1998-07-14 |
| EA199800668A1 (en) | 1999-02-25 |
| CN1191351C (en) | 2005-03-02 |
| ES2145567T3 (en) | 2000-07-01 |
| EP0882126B1 (en) | 2000-04-19 |
| AU1440997A (en) | 1997-08-22 |
| PL328022A1 (en) | 1999-01-04 |
| DE69701731D1 (en) | 2000-05-25 |
| PL184656B1 (en) | 2002-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2242420C (en) | Process for the production of a detergent composition | |
| AU702278B2 (en) | A process for preparing a granular detergent | |
| EP0451894B1 (en) | High bulk density granular detergent compositions and process for preparing them | |
| KR920000114B1 (en) | Detergent compositions and process for preparing them | |
| KR960000207B1 (en) | Detergent compositions and process for preparing them | |
| EP0510746A2 (en) | Process for preparing condensed detergent granules | |
| EP0508543A1 (en) | Chemical structuring of surfactant pastes to form high active surfactant granules | |
| US5736502A (en) | Process for preparing detergent compositions | |
| US5494599A (en) | Agglomeration of high active pastes to form surfactant granules useful in detergent compositions | |
| AU721831B2 (en) | Process for the production of a detergent composition | |
| JPH0762160B2 (en) | Process for producing high bulk density detergent powder containing clay | |
| US5990073A (en) | Process for the production of a detergent composition | |
| AU1878592A (en) | Agglomeration of high active pastes to form surfactant granules useful in detergent compositions | |
| WO1998011193A1 (en) | Process for preparing high bulk density detergent compositions | |
| AU731828B2 (en) | Process for preparing high bulk density detergent compositions | |
| AU739651B2 (en) | Process for the production of a detergent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |