EP0353976A1 - Detergents - Google Patents
Detergents Download PDFInfo
- Publication number
- EP0353976A1 EP0353976A1 EP89307771A EP89307771A EP0353976A1 EP 0353976 A1 EP0353976 A1 EP 0353976A1 EP 89307771 A EP89307771 A EP 89307771A EP 89307771 A EP89307771 A EP 89307771A EP 0353976 A1 EP0353976 A1 EP 0353976A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- powdered
- free flowing
- high active
- anionic
- 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.)
- Granted
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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0034—Fixed on a solid conventional detergent ingredient
Definitions
- This invention relates to detergents, and more particularly, to free flowing, high active anionic detergents.
- High active detergents for the purposes of the present invention, may be defined as detergents comprising more than 12% active matter.
- Free flowing for the purposes of the present invention, may be defined as sufficiently mobile as to be capable of being poured or dispensed reproducably as a measured quantity.
- detergent powders exemplify certain characteristics, namely, the detergent powder should be non-dusty, free flowing, easily handled, easily dissolved and stable under normal storage conditions.
- a large proportion of the worldwide detergent market uses high foaming powder surfactants, most of which are based on anionic active matter ingredients.
- a further method of manufacture of detergents in powder form is by so called 'dry neutralisation'. Dry neutralisation and associated agglomeration is normally regarded as a three part process:
- a method of producing a free flowing, high active, anionic detergent comprising the step of adsorbing an anionic surfactant acid onto a powdered or granular material to form an agglomerate without the addition of water in the agglomeration stage.
- the powdered or granular detergent composition derived from this method suprisingly has a substantially uniform particle size and may comprise high levels of surfactant acid successfully exceeding the maximum surfactant acid content of the prior art.
- a free flowing, high active, anionic powdered or granular detergent composition comprising an anionic surfactant acid adsorped onto a powdered or granular material, said detergent composition having a particle size distribution substantially within the range from 248 microns to 1752 microns.
- a free flowing, high active, anionic, powdered or granular detergent composition comprising a surfactant acid adsorped onto a powdered or granular material the surfactant acid being present in the range from 12 to 40% by weight of the total composition and the powdered or granular material being present within the range from 20 to 50% by weight of the total composition.
- the anionic surfactant acid is adsorbed onto heated, dry, powdered, or granular material. In a preferred embodiment of the invention the anionic surfactant acid is adsorbed onto heated dry powdered or granular form preferably in a fluidised bed.
- the agglomerate so formed is then coated by the application of a silicate and/or alkali, preferably in a fluidised bed.
- a silicate and/or alkali preferably in a fluidised bed.
- the temperature of the inital part of the fluidised bed is preferably above 50°C and more preferably in the range from 85 to 95°C.
- Any suitable anionic surfactant acid may be used. Suitable examples of such are as follows: alkyl aryl sulphonic acids, fatty acid sulphonic acids, olefin sulphonic acids, fatty alcohol ether sulphuric acid, fatty methyl ester sulphonic acid, alkane sulphonic acids. More particularly alkyl aryl sulphonic acids containing an alkyl group with 9-20 carbon atoms and a sulphonic acid or sulphuric acid ester group (included in the term alkyl is the alkyl portion of the aryl groups), or fatty acid sulphuric acids obtained by sulphating alcohols with 8-18 carbon atom chains.
- linear straight chain alkyl benzene sulphonic acids in which the average number of carbon atoms in the alkyl group is from 11 to 13.
- the amount of anionic surfactant acid added is preferably in the range 12% to 40%, more preferably from 12% to 35% and even more preferably from 12% to 30% of the final product weight for weight.
- the powdered or granular material may comprise any suitable alkali, or alkalies, alone, or in combination with other additional ingredients.
- suitable alkalies are as follows: Sodium phosphates, for example sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate or other similar alkalies including potassium or magnesium salts.
- the amount of alkali is preferably in the range 10% to 95% and more preferably 60% to 95% final product weight for weight.
- Additional ingredients may include the following: bleaching agents for example Sodium Perborate, corrosion inhibitors or alkaline additives, for example, Sodium Silicates, inert fillers, for example Sodium Sulphate, surfactants, optical brighteners, preventors of soil redeposition, (for example, sodium carboxy-methyl cellulose,) dedusting agents and solubilisers, such as sodium xylene sulphonate, enzymes, chelating agents, perfumes, softening agents, defoamers, bleach activators, soap, and non ionic active material.
- bleaching agents for example Sodium Perborate, corrosion inhibitors or alkaline additives, for example, Sodium Silicates, inert fillers, for example Sodium Sulphate, surfactants, optical brighteners, preventors of soil redeposition, (for example, sodium carboxy-methyl cellulose,) dedusting agents and solubilisers, such as sodium xylene sulphonate, enzymes, chelating agents, perfumes,
- Any suitable apparatus may be used, but this may have to be adapted to run under the appropriate conditions so as to maintain dry conditions during the agglomeration stage. Examples of such apparatus are as follows:
- Sample powdered or granular detergents derived from this method exhibit the following characteristics: Particle Size no more than 3% by weight of the particles are larger than 1700 microns no more than 1% by weight of the particles are less than 250 microns average particle size 1100 to 1300 microns
- Bulk density untapped 600-720 gm/ml tapped: 730-830 gm/ml moisture content : less than 4% W/W angle of repose average: 37 to 38°C with minimum 36° maximum 41° sliding angle : minimum 25° maximum 28° flowrate : 30-41 cc/sec through standard orifice. compressibility : 7-15%
- composition of anionic detergent granulate
- the detergent composition comprises 5 to 40% preferably 10 to 35% and more preferably 12 to 30% by weight of the final composition of an anionic surfactant acid for example Sodium alkyl aryl sulphate.
- the detergent composition comprises 20 to 50% preferably 25 to 45% and more preferably 30 to 40% by weight of the final composition of the powdered or granular material such as the alkaline material sodium tripolyphoshphate.
- the detergent composition may also comprise any of the optical ingredients listed on page 5 including for example any of the following: soda ash, sodium sulphate, sodium carboxy methyl cellulose, optical bleaches, sequestering agents, sodium silicates etc.
- the angle of repose is defined as the angle from the horizontal to the line of slope of a heap of powder, the heap having been formed by directing powder through a funnel into the centre of a circular horizontal surface. The funnel is slowly raised to allow the heap to form immediately beneath it.
- the flow rate of the powder is defined as the rate in cubic centimetres per second that will flow through a 1.25cm diameter orifice with a smooth PVC funnel expanding at 10° to the vertical above the orifice.
- the angle of slide is defined as the minimum angle between the horizontal and an inclined surface when a powder slides by gravity en masse down that surface, the surface being a smooth, wooden unpolished medium.
- the powder is scattered as a layer no more than 20mm deep on the surface. The surface is raised slowly until the sliding condition is achieved
- the compressibility of the powder is defined as the percentage of initial volume lost when a sample is subjected to a compressive load, the compressive load being provided by a 10Kg weight which is applied to a cylinder of powder of 69mm diameter for a period of 3 minutes.
- LIQUID 1 Do Decyl Benzene Sulphonic Acid (DDBSA) at a spray rate of 390g/min.
- LIQUID 2. A solution comprising % W/W a) Sodium Silicate (2:1 SiO2:Na2O) 40.00 b) Pigment blue 15:1 (46% Dispersion 0.18 c) Tetra sodium salt of ethylene diamine tetra acetic acid 3.66 d) Water 56.16
- the product was a dust free, free flowing granular agglomerate.
- composition of the two liquids sprayed along the fluidised bed was as in EXAMPLE 1.
- LIQUID 1 was applied at a spray rate of 600g/min.
- LIQUID 2 was applied at a spray rate of 390g/min
- alkyl aryl sulphonic and silicate solultion equated to a combined percentage liquid addition of 35.0% W/W.
- the powder produced was a dust free, free flowing granular agglomerate.
- the method enabled a liquid addition of 35.0% W/W to the fluid bed which is comfortably in excess of the limit of 20% imposed by known methods.
- Active matter content was as high as 23.9%, which is almost twice the maximum amount of 12% of active matter achieved by known methods, utilising a fluid bed apparatus.
- the present invention provides a cost efficient method of producing a high active, non-dusty, free flowing, stable anionic detergent powder which may be easily handled and easily stored.
Abstract
Description
- This invention relates to detergents, and more particularly, to free flowing, high active anionic detergents.
- High active detergents, for the purposes of the present invention, may be defined as detergents comprising more than 12% active matter.
- Free flowing, for the purposes of the present invention, may be defined as sufficiently mobile as to be capable of being poured or dispensed reproducably as a measured quantity.
- It is desirable that detergent powders exemplify certain characteristics, namely, the detergent powder should be non-dusty, free flowing, easily handled, easily dissolved and stable under normal storage conditions.
- A large proportion of the worldwide detergent market uses high foaming powder surfactants, most of which are based on anionic active matter ingredients.
- It has hitherto been common practice to produce detergents in powder form by making up a slurry of the various ingredients in water and subsequently spray drying the slurry to yield a powder of typical bulk density 0.2 to 0.5 gms/ml. This method of manufacture is expensive because heat is required to evaporate the water which was initially added and yet is not required in the final product.
- A further method of manufacture of detergents in powder form is by so called 'dry neutralisation'. Dry neutralisation and associated agglomeration is normally regarded as a three part process:
- 1. Dry adsorption of an alkyl aryl sulphonic acid onto the surface of an alkaline base.
- 2. Addition of water to affect the reaction of the alkali and sulphonic acid to form an alkaline sulphonate which binds the constituents to produce a neutralised detergent agglomerate; and
- 3. Coating the outside of the agglomerate with a layer of dessicant material such as sodium tripolyphosphate, sodium carbonate or silicate.
- It has previously been assumed that: there is a reasonably well described limitation on the amount of alkyl aryl sulphonic acid which can be adsorpted onto the surface of various alkaline bases without first causing over agglomeration or poor flow properties. For example it has been claimed that the adsorptive characteristics of tripolyphosphate or other adsorptive materials are a function of their surface area. Therefore, sodium tripolyphosphate (STPP) in powder form must have greater adsorptivity than in granular form. Definitive tables of the adsorptivity of STPP and other alkalies have been published in the past giving the adsorptivity of various powders with regard to the uptake of alkyl aryl sulphonic acid, for example do decyl benzene sulphonic acid (DDBSA.) This, theoretically, limits the amount of active matter which can be formulated into a detergent powder produced by dry neutralisation.
- The table (A) below shows commonly accepted limitations of the adsorptivity of various bases.
TABLE A g DDBSA/100g alkali salt STPP Powder 32.5 STPP low density granular 2.0 STPP regular density granular 2.1 soda ash (powder) 2.2 soda ash (granular) 0.2 Sodium metasilicate anhydrous 0.1 Sodium metasilicate 5H₂O 0.1 - It has previously been assumed that the addition of approximately 1-2 % of water was necessary to cause in situ neutralisation of sulphonic acids with alkaline bases. The product was not thought to be stable until this reaction had been completed. It has previously been assumed that a dessicant should be used to coat the outside of the agglomerate to adsorb free water, usually by hydration of the dessicant, to obtain a free flowing product.
- According to a first aspect of the present invention, there is provided a method of producing a free flowing, high active, anionic detergent comprising the step of adsorbing an anionic surfactant acid onto a powdered or granular material to form an agglomerate without the addition of water in the agglomeration stage.
- It has been discovered that the powdered or granular detergent composition derived from this method suprisingly has a substantially uniform particle size and may comprise high levels of surfactant acid successfully exceeding the maximum surfactant acid content of the prior art.
- According to a second aspect of the present invention there is provided a free flowing, high active, anionic powdered or granular detergent composition comprising an anionic surfactant acid adsorped onto a powdered or granular material, said detergent composition having a particle size distribution substantially within the range from 248 microns to 1752 microns.
- According to a third aspect of the present invention there is provided a free flowing, high active, anionic, powdered or granular detergent composition comprising a surfactant acid adsorped onto a powdered or granular material the surfactant acid being present in the range from 12 to 40% by weight of the total composition and the powdered or granular material being present within the range from 20 to 50% by weight of the total composition.
- In a preferred embodiment of the invention, the anionic surfactant acid is adsorbed onto heated, dry, powdered, or granular material. In a preferred embodiment of the invention the anionic surfactant acid is adsorbed onto heated dry powdered or granular form preferably in a fluidised bed.
- In a further preferred embodiment, the agglomerate so formed is then coated by the application of a silicate and/or alkali, preferably in a fluidised bed. The temperature of the inital part of the fluidised bed is preferably above 50°C and more preferably in the range from 85 to 95°C.
- Any suitable anionic surfactant acid may be used. Suitable examples of such are as follows: alkyl aryl sulphonic acids, fatty acid sulphonic acids, olefin sulphonic acids, fatty alcohol ether sulphuric acid, fatty methyl ester sulphonic acid, alkane sulphonic acids. More particularly alkyl aryl sulphonic acids containing an alkyl group with 9-20 carbon atoms and a sulphonic acid or sulphuric acid ester group (included in the term alkyl is the alkyl portion of the aryl groups), or fatty acid sulphuric acids obtained by sulphating alcohols with 8-18 carbon atom chains. Especially valuable are linear straight chain alkyl benzene sulphonic acids in which the average number of carbon atoms in the alkyl group is from 11 to 13. The amount of anionic surfactant acid added is preferably in the range 12% to 40%, more preferably from 12% to 35% and even more preferably from 12% to 30% of the final product weight for weight.
- We have discovered that we can adsorb up to at least 50gm DDBDA/100gm STPP powder when operating under the conditions of the invention thus significantly exceeding the amounts known to have been adsorbed in previously published work, whilst still retaining the free flowing nature of the end product.
- The powdered or granular material may comprise any suitable alkali, or alkalies, alone, or in combination with other additional ingredients. Examples of suitable alkalies are as follows: Sodium phosphates, for example sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate or other similar alkalies including potassium or magnesium salts. The amount of alkali is preferably in the range 10% to 95% and more preferably 60% to 95% final product weight for weight.
- Additional ingredients may include the following: bleaching agents for example Sodium Perborate, corrosion inhibitors or alkaline additives, for example, Sodium Silicates, inert fillers, for example Sodium Sulphate, surfactants, optical brighteners, preventors of soil redeposition, (for example, sodium carboxy-methyl cellulose,) dedusting agents and solubilisers, such as sodium xylene sulphonate, enzymes, chelating agents, perfumes, softening agents, defoamers, bleach activators, soap, and non ionic active material.
- Any suitable apparatus may be used, but this may have to be adapted to run under the appropriate conditions so as to maintain dry conditions during the agglomeration stage. Examples of such apparatus are as follows:
- 1. Static or moving machines with dividers or blades or paddles to mix the powders. These include twin shell blenders or V blenders, baffled drums and ribbon or paddle blenders.
- 2. Air suspension machines which suspend the particles in air whilst liquid is sprayed onto said particles. The particle size increases until the particles are too heavy to be suspended at which time they fall from the air stream.
- 3. Apparatus in which air is used to fluidise the particles making them act in a similar manner to a liquid, for example, a fluidised bed.
- Sample powdered or granular detergents derived from this method exhibit the following characteristics:
Particle Size
no more than 3% by weight of the particles are larger than 1700 microns
no more than 1% by weight of the particles are less than 250 microns
average particle size 1100 to 1300 microns
Bulk density: untapped 600-720 gm/ml
tapped: 730-830 gm/ml
moisture content: less than 4% W/W
angle of repose average: 37 to 38°C
with minimum 36° maximum 41°
sliding angle: minimum 25° maximum 28°
flowrate: 30-41 cc/sec through standard orifice.
compressibility: 7-15% - The detergent composition comprises 5 to 40% preferably 10 to 35% and more preferably 12 to 30% by weight of the final composition of an anionic surfactant acid for example Sodium alkyl aryl sulphate. The detergent composition comprises 20 to 50% preferably 25 to 45% and more preferably 30 to 40% by weight of the final composition of the powdered or granular material such as the alkaline material sodium tripolyphoshphate. The detergent composition may also comprise any of the optical ingredients listed on page 5 including for example any of the following: soda ash, sodium sulphate, sodium carboxy methyl cellulose, optical bleaches, sequestering agents, sodium silicates etc.
- For the purpose of the present invention:-
the angle of repose is defined as the angle from the horizontal to the line of slope of a heap of powder, the heap having been formed by directing powder through a funnel into the centre of a circular horizontal surface. The funnel is slowly raised to allow the heap to form immediately beneath it. - The flow rate of the powder is defined as the rate in cubic centimetres per second that will flow through a 1.25cm diameter orifice with a smooth PVC funnel expanding at 10° to the vertical above the orifice.
- The angle of slide is defined as the minimum angle between the horizontal and an inclined surface when a powder slides by gravity en masse down that surface, the surface being a smooth, wooden unpolished medium. The powder is scattered as a layer no more than 20mm deep on the surface. The surface is raised slowly until the sliding condition is achieved
- The compressibility of the powder is defined as the percentage of initial volume lost when a sample is subjected to a compressive load, the compressive load being provided by a 10Kg weight which is applied to a cylinder of powder of 69mm diameter for a period of 3 minutes.
- The invention will now be described further by the following Examples:
- The following mixture was prepared by dry blending and then fed at a rate of typically 1.83 kg per minute onto a horizontal fluidised bed. No water was added. The inital part of the fluidised bed was heated to above 80°C and retained at this temperature during the experiment.
Material % W/W Sodium Tripolyphosphate 44.8 Sodium Carbonate 23.4 Sodium Carboxy-Methyl Cellulose 2.40 Sodium Sulphate 29.00 Optical Brightener (TINOPAL* CBS-X) 0.40 *TINOPAL is a Trade Mark of Ciba-Geigy. - Two liquids, as defined below, were sprayed sequentially along the fluidising bed onto the fluidised powder.
LIQUID 1. Do Decyl Benzene Sulphonic Acid (DDBSA) at a spray rate of 390g/min.
LIQUID 2. A solution comprising% W/W a) Sodium Silicate (2:1 SiO₂:Na₂O) 40.00 b) Pigment blue 15:1 (46% Dispersion 0.18 c) Tetra sodium salt of ethylene diamine tetra acetic acid 3.66 d) Water 56.16 - The solution was applied at a spray rate of 390g/min. The combined addition of alkyl aryl sulphonic acid and silicate solution equated to a 30.0% w/w combined percentage liquid additions.
- After processing, chemical analysis indicated the powders had the following chemical content.
% W/W Active Detergent (calculated as Sodium Alkyl Aryl Sulphonate - Molecular Weight 322) 15.6 Sodium Tripolyphosphate (calculated as P₂O₅) 32.4 Moisture 1.53 - The product was a dust free, free flowing granular agglomerate.
- The following powder mixtures were prepared and used as in EXAMPLE 1.
% W/W Sodium Tripolyphosphate 57.60 Sodium Carbonate 23.00 Sodium Carboxy-Methyl Cellulose 2.40 Sodium Sulphate 16.60 Optical Brightener (TINOPAL* CBS-X) 0.40 *TINOPAL is a Trade Mark of Ciba-Geigy. - The composition of the two liquids sprayed along the fluidised bed was as in EXAMPLE 1.
LIQUID 1 was applied at a spray rate of 600g/min.
LIQUID 2 was applied at a spray rate of 390g/min - The combined addition of alkyl aryl sulphonic and silicate solultion equated to a combined percentage liquid addition of 35.0% W/W.
- After processing, chemical analysis indicated the powder had the following chemical content.
% W.W. Active Detergent (calculated as Sodium Alkyl Aryl Sulphonate - Molecular Weight 332) 23.9 Sodium Tripolyphosphate (calculated as P₂O5) 41.7 Moisture 1.73 - The powder produced was a dust free, free flowing granular agglomerate.
- The method enabled a liquid addition of 35.0% W/W to the fluid bed which is comfortably in excess of the limit of 20% imposed by known methods.
- Active matter content was as high as 23.9%, which is almost twice the maximum amount of 12% of active matter achieved by known methods, utilising a fluid bed apparatus.
- The amount of alkyl aryl sulphonic acid adsorped onto the tripolyphosphate and other alkalies present was well in excess of the previously know adsorptive figures quoted in literature as shown in TABLE A.
- In EXAMPLE 1 the theoretical maximum for successful adsorption of alkyl aryl sulphonic acid is calculated to be 15.075g of sulphonic acid per 100 g of initial powder mixture. The practical result of use of the claimed method is calculated to be 21.311g of sulphonic acid per 100g of initial powder mixture which is well in excess of the results from previously known methods.
- Similarly in EXAMPLE 2 the figures for theoretical maximum and practical results are 19.226g and 32.311g of alkyl aryl sulphonic acid per 100g of initial powder mixture.
- Prior art methods of dry neutralisation in whatever apparatus have always assumed the presence of added water and have always restricted the ratio of the amount of alkyl aryl sulphonates to the amount of alkali to a limit which the invention successfully exceeds. The present invention provides a cost efficient method of producing a high active, non-dusty, free flowing, stable anionic detergent powder which may be easily handled and easily stored.
Claims (32)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89307771T ATE97951T1 (en) | 1988-08-05 | 1989-07-31 | LAUNDRY DETERGENT. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8818613 | 1988-08-05 | ||
GB888818613A GB8818613D0 (en) | 1988-08-05 | 1988-08-05 | Detergents |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0353976A1 true EP0353976A1 (en) | 1990-02-07 |
EP0353976B1 EP0353976B1 (en) | 1993-12-01 |
Family
ID=10641648
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89307771A Revoked EP0353976B1 (en) | 1988-08-05 | 1989-07-31 | Detergents |
EP89909029A Pending EP0404865A1 (en) | 1988-08-05 | 1989-07-31 | Detergents |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89909029A Pending EP0404865A1 (en) | 1988-08-05 | 1989-07-31 | Detergents |
Country Status (14)
Country | Link |
---|---|
EP (2) | EP0353976B1 (en) |
KR (1) | KR920009044B1 (en) |
AT (1) | ATE97951T1 (en) |
CA (1) | CA1323278C (en) |
DE (1) | DE68911053T2 (en) |
ES (1) | ES2047677T3 (en) |
GB (1) | GB8818613D0 (en) |
HK (1) | HK48495A (en) |
IE (1) | IE63797B1 (en) |
IN (1) | IN176172B (en) |
MY (1) | MY105001A (en) |
NZ (1) | NZ230218A (en) |
PT (1) | PT91386A (en) |
WO (1) | WO1990001536A1 (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994007990A1 (en) * | 1992-09-30 | 1994-04-14 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing granulated surfactants |
DE4415369C1 (en) * | 1994-05-02 | 1995-08-31 | Henkel Kgaa | Heterogeneous surfactant granulate useful in washing powder and detergent |
EP0688861A1 (en) * | 1994-06-22 | 1995-12-27 | SOCIETE FRANCAISE HOECHST Société anonyme dite: | Process for the preparation of anionic surfactant compositions in powder, bead or granular form and use of these compositions in cleaning and care products |
WO1996004359A1 (en) * | 1994-08-05 | 1996-02-15 | Unilever Plc | Granulation in a fluidised bed |
WO1997032005A1 (en) * | 1996-02-26 | 1997-09-04 | Unilever Plc | Anionic detergent particles |
WO1998058046A1 (en) * | 1997-06-16 | 1998-12-23 | Unilever Plc | Production of detergent granulates |
WO1999000475A1 (en) * | 1997-06-27 | 1999-01-07 | Unilever Plc | Production of detergent granulates |
US6077820A (en) * | 1995-12-20 | 2000-06-20 | Lever Brothers Company Division Of Conopco, Inc. | Process for preparing a granular detergent |
WO2000037604A1 (en) * | 1998-12-22 | 2000-06-29 | The Procter & Gamble Company | Process for preparing a granular detergent composition |
WO2000053719A1 (en) * | 1999-03-09 | 2000-09-14 | The Procter & Gamble Company | Detergent particles having coating or partial coating layers |
US6207635B1 (en) * | 1995-05-31 | 2001-03-27 | The Procter & Gamble Company | Process for manufacture of high density detergent granules |
US6274544B1 (en) | 1997-06-16 | 2001-08-14 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6596683B1 (en) | 1998-12-22 | 2003-07-22 | The Procter & Gamble Company | Process for preparing a granular detergent composition |
US6740632B1 (en) * | 2000-02-18 | 2004-05-25 | Glatt Ingenieurtechnik Gmbh | Process for manufacturing industrial detergent and components thereof |
US6858572B1 (en) | 1999-03-09 | 2005-02-22 | The Procter & Gamble Company | Process for producing coated detergent particles |
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 |
US6992055B1 (en) * | 1996-09-06 | 2006-01-31 | Kao Corporation | Process for preparing detergent compositions having high bulk density |
US7022660B1 (en) | 1999-03-09 | 2006-04-04 | The Procter & Gamble Company | Process for preparing detergent particles having coating or partial coating layers |
US7098177B1 (en) * | 1998-10-16 | 2006-08-29 | Kao Corporation | Process for producing detergent particles |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9001285D0 (en) * | 1990-01-19 | 1990-03-21 | Unilever Plc | Detergent compositions and process for preparing them |
DE4216629A1 (en) * | 1992-05-20 | 1993-11-25 | Henkel Kgaa | Process for the production of detergents and cleaning agents containing anionic surfactants |
US5573697A (en) * | 1995-05-31 | 1996-11-12 | Riddick; Eric F. | Process for making high active, high density detergent granules |
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GB707994A (en) * | 1950-02-13 | 1954-04-28 | Ruhrchemie Ag | Process for the neutralization of sulphonic acids |
GB1369269A (en) * | 1971-02-01 | 1974-10-02 | Colgate Palmolive Co | Method for neutrlization of detergent acid |
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BE750648A (en) * | 1969-05-21 | 1970-11-20 | Stauffer Chemical Co | PROCESS FOR PREPARING DETERGENT COMPOSITIONS |
GB1404317A (en) * | 1971-10-23 | 1975-08-28 | Bell Chemicals Pty Ltd | Manufacture of detergent powders |
DD140987B1 (en) * | 1979-01-05 | 1982-06-30 | Manfred Mittelstrass | CONTINUOUS MANUFACTURING METHOD GRANULATED WASHING AND CLEANING AGENT IN SWIVEL LAYERED APPARATUS |
DD228458A1 (en) * | 1983-12-21 | 1985-10-16 | Genthin Waschmittelwerk | METHOD FOR THE CONTINUOUS PREPARATION OF DETERGENT GRANULATE PRODUCTS |
GB2166542B (en) * | 1984-11-02 | 1988-10-12 | British Aerospace | Air conditioning systems |
GB2209172A (en) * | 1987-08-28 | 1989-05-04 | Unilever Plc | Preparation of solid particulate components for detergents |
IN170991B (en) * | 1988-07-21 | 1992-06-27 | Lever Hindustan Ltd |
-
1988
- 1988-08-05 GB GB888818613A patent/GB8818613D0/en active Pending
-
1989
- 1989-07-28 MY MYPI89001029A patent/MY105001A/en unknown
- 1989-07-31 IN IN675DE1989 patent/IN176172B/en unknown
- 1989-07-31 WO PCT/GB1989/000873 patent/WO1990001536A1/en not_active Application Discontinuation
- 1989-07-31 CA CA000607122A patent/CA1323278C/en not_active Expired - Fee Related
- 1989-07-31 EP EP89307771A patent/EP0353976B1/en not_active Revoked
- 1989-07-31 KR KR1019900700616A patent/KR920009044B1/en not_active IP Right Cessation
- 1989-07-31 ES ES89307771T patent/ES2047677T3/en not_active Expired - Lifetime
- 1989-07-31 DE DE89307771T patent/DE68911053T2/en not_active Revoked
- 1989-07-31 AT AT89307771T patent/ATE97951T1/en not_active IP Right Cessation
- 1989-07-31 EP EP89909029A patent/EP0404865A1/en active Pending
- 1989-08-04 NZ NZ230218A patent/NZ230218A/en unknown
- 1989-08-04 IE IE253089A patent/IE63797B1/en not_active IP Right Cessation
- 1989-08-04 PT PT91386A patent/PT91386A/en not_active Application Discontinuation
-
1995
- 1995-03-30 HK HK48495A patent/HK48495A/en unknown
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GB707994A (en) * | 1950-02-13 | 1954-04-28 | Ruhrchemie Ag | Process for the neutralization of sulphonic acids |
US2671797A (en) * | 1951-02-15 | 1954-03-09 | Ruhrchemie Ag | Neutralization of sulfonic acids and sulfuric acid esters |
GB1369269A (en) * | 1971-02-01 | 1974-10-02 | Colgate Palmolive Co | Method for neutrlization of detergent acid |
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Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994007990A1 (en) * | 1992-09-30 | 1994-04-14 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing granulated surfactants |
US5824633A (en) * | 1994-05-02 | 1998-10-20 | Henkel Kommanditgesellschaft Auf Aktien | Heterogeneous surfactant granules |
DE4415369C1 (en) * | 1994-05-02 | 1995-08-31 | Henkel Kgaa | Heterogeneous surfactant granulate useful in washing powder and detergent |
EP0688861A1 (en) * | 1994-06-22 | 1995-12-27 | SOCIETE FRANCAISE HOECHST Société anonyme dite: | Process for the preparation of anionic surfactant compositions in powder, bead or granular form and use of these compositions in cleaning and care products |
FR2721616A1 (en) * | 1994-06-22 | 1995-12-29 | Hoechst France | Compositions of anionic surfactants in powder, pearls or granules, process for their preparation and their use in cleaning and maintenance products |
WO1996004359A1 (en) * | 1994-08-05 | 1996-02-15 | Unilever Plc | Granulation in a fluidised bed |
CN1115403C (en) * | 1994-08-05 | 2003-07-23 | 尤尼利弗公司 | Granulation in a fluidised bed |
AU702808B2 (en) * | 1994-08-05 | 1999-03-04 | Unilever Plc | Granulation in a fluidised bed |
US6207635B1 (en) * | 1995-05-31 | 2001-03-27 | The Procter & Gamble Company | Process for manufacture of high density detergent granules |
US6077820A (en) * | 1995-12-20 | 2000-06-20 | Lever Brothers Company Division Of Conopco, Inc. | Process for preparing a granular detergent |
WO1997032005A1 (en) * | 1996-02-26 | 1997-09-04 | Unilever Plc | Anionic detergent particles |
US6992055B1 (en) * | 1996-09-06 | 2006-01-31 | Kao Corporation | Process for preparing detergent compositions having high bulk density |
WO1998058046A1 (en) * | 1997-06-16 | 1998-12-23 | Unilever Plc | Production of detergent granulates |
US6056905A (en) * | 1997-06-16 | 2000-05-02 | Lever Brothers Company Division Of Conopco, Inc. | Production of detergent granulates |
US6274544B1 (en) | 1997-06-16 | 2001-08-14 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US6429184B1 (en) | 1997-06-16 | 2002-08-06 | Lever & Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
WO1999000475A1 (en) * | 1997-06-27 | 1999-01-07 | Unilever Plc | Production of detergent granulates |
US6133223A (en) * | 1997-06-27 | 2000-10-17 | Lever Brothers Company, Division Of Conopco, Inc. | Production of detergent granulates |
US7098177B1 (en) * | 1998-10-16 | 2006-08-29 | Kao Corporation | Process for producing detergent particles |
WO2000037604A1 (en) * | 1998-12-22 | 2000-06-29 | The Procter & Gamble Company | Process for preparing a granular detergent composition |
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 |
US7022660B1 (en) | 1999-03-09 | 2006-04-04 | The Procter & Gamble Company | Process for preparing detergent particles having coating or partial coating layers |
WO2000053719A1 (en) * | 1999-03-09 | 2000-09-14 | The Procter & Gamble Company | Detergent particles having coating or partial coating layers |
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 |
US6740632B1 (en) * | 2000-02-18 | 2004-05-25 | Glatt Ingenieurtechnik Gmbh | Process for manufacturing industrial detergent and components thereof |
Also Published As
Publication number | Publication date |
---|---|
AU4049289A (en) | 1990-03-05 |
NZ230218A (en) | 1991-11-26 |
IE892530L (en) | 1990-02-05 |
DE68911053T2 (en) | 1994-03-31 |
GB8818613D0 (en) | 1988-09-07 |
CA1323278C (en) | 1993-10-19 |
AU622925B2 (en) | 1992-04-30 |
WO1990001536A1 (en) | 1990-02-22 |
EP0353976B1 (en) | 1993-12-01 |
KR900701997A (en) | 1990-12-05 |
ES2047677T3 (en) | 1994-03-01 |
HK48495A (en) | 1995-04-07 |
IN176172B (en) | 1996-02-17 |
MY105001A (en) | 1994-07-30 |
KR920009044B1 (en) | 1992-10-13 |
PT91386A (en) | 1990-03-08 |
IE63797B1 (en) | 1995-06-14 |
DE68911053D1 (en) | 1994-01-13 |
EP0404865A1 (en) | 1991-01-02 |
ATE97951T1 (en) | 1993-12-15 |
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