EP0772671B1 - Method for preparing co-granules, co-granules thus obtained and use thereof as a component in detergent compositions - Google Patents
Method for preparing co-granules, co-granules thus obtained and use thereof as a component in detergent compositions Download PDFInfo
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- EP0772671B1 EP0772671B1 EP95926948A EP95926948A EP0772671B1 EP 0772671 B1 EP0772671 B1 EP 0772671B1 EP 95926948 A EP95926948 A EP 95926948A EP 95926948 A EP95926948 A EP 95926948A EP 0772671 B1 EP0772671 B1 EP 0772671B1
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- EP
- European Patent Office
- Prior art keywords
- granules
- acid
- compaction
- alkali metal
- slurry
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Classifications
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- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- 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
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
Definitions
- the present invention in the first place relates to a method for preparing co-granules as a component for and for incorporation in detergent compositions, which method comprises:
- granule is to be interpreted broadly and is intended to comprise various particulate forms such as granulate, coarse powder, tablets and noodles.
- Dishwashing compositions frequently consist of granules of one particular inorganic compound such as e.g. alkali silicate and these compositions often contain the other ingredients in the form of different particles e.g. of organic compounds etc.
- the granules, frequently silicate granules often dissolve only with difficulty. They lead to the formation of fines (dust).
- a method for the preparation of granular alkali detergent compositions comprising sodiummetasilicate, i.e. having an SiO 2 /Na 2 O molar ratio of 1, is described in EP-A-0 283 885, in which a mixture of the components is compacted, broken up and sieved. However, the ingredients are mixed together in dry form and subsequently compacted.
- finely powdered components such as pentasodiumtriphosphate and zeolite NaA
- at least two of the ingredients, including said finely powdered components are agglomerated and dried before being mixed with other dry components, like silicate, in the compaction step.
- sodium salts of nitrilotriacetic acid or polymeric carboxic acids may be incorporated.
- silicate granules segregation of different types of granular components (e.g. bleach system and enzymes or other usual ingredients) can take place.
- the problems are aggravated by the fact that silicate granules having a molar ratio SiO 2 /Na 2 O between 1.8 and 3.0 and a moisture content of below about 22% by weight dissolve only with considerable difficulty.
- alkali silicate granules with a homogeneous distribution of moisture are difficult to obtain. Usually less moisture is present in the outer skin than in the inside, which is a consequence of drying and which reduces solubility during use.
- EP-A-0 574 685 (Haarmann & Reimer Corp.) which relates to a method for the production of detergent builder formulations comprising granules of citric acid or an alkali metal salt thereof in combination with a detergent builder.
- Citric acid or a salt thereof is spray granulated form its partially purified fermentation broth in order to form free flowing granules.
- Detergent builders may be added to the fermentation broth of introduced during spray granulation in order to form granules which include such detergent builders.
- Another method for preparing co-granules useful in detergent compositions is known inter alia from EP-A-0 421 664 (Rohm and Haas Company) disclosing a method for preparing a polymer containing granulate containing 20% by weight of polymer and at least 20% by weight of a water soluble inorganic compound.
- Such compounds are preferably sulphates, carbonates or silicates.
- other phosphate replacing builders may be present such as zeolites, carbonates, nitrilotriacetic acid, citric acid, tartaric acid, salts thereof, phosphonates etc.
- the examples disclose granules containing polymer and sodium sulphate or sodium carbonate.
- the object of the present invention is to provide a method for preparing co-granules having a good solubility in water, giving less fines during handling, having a more even distribution of moisture, and preventing segregation of at least those ingredients included in the co-granules, which can be conveniently prepared.
- this object is achieved by a method for preparing co-granules as a component for and for incorporation in detergent compositions, at least comprising an alkali metal citrate and sodium disilicate, which method comprises preparing a solution or a slurry of the ingredients, drying the mixture, compacting the dried product and breaking up and sieving the compacted product.
- JP-A-54 106 509 disclosing the preparation of spray dried granulated detergent compositions comprising a surfactant, an alkali metal silica salt and a phosphate salt.
- a surfactant an alkali metal silica salt and a phosphate salt.
- an acid type surfactant or an organic acid such as citric acid is added to control the molar ratio of SiO 2 :M 2 O.
- a slurry is prepared in water and the mixture is dried by means of suitable drying techniques, like a turbine dryer e.g. a Turbogranulation dryer ex. Vomm-Turbo Technology, VOMM IMPIANTI E PROCESSI S.r.l., Milan, Italy.
- a turbine dryer e.g. a Turbogranulation dryer ex. Vomm-Turbo Technology, VOMM IMPIANTI E PROCESSI S.r.l., Milan, Italy.
- this dryer is less suited for the combined drying and granulation to produce co-granules containing substantial quantities of organic ingredients in conjunction with silicate. Due to the high attrition between the rotating blades and the film formed on the wall during the granulation phase, local overheating can cause partial decomposition of the organic ingredients, leading to (local-) coloring.
- Drying can also conveniently be achieved by spray drying the slurry by a conventional technique using a spray tower in which the slurry is atomized and dried in a hot air stream.
- the conditions in the spray tower, when drying silicate or mixtures, containing silicate can be controlled in such a manner, that the bulk density, the particle size and shape can be optimised.
- a powder product consisting of either small particles (below 100 microns) or hollow spheres with a particle size up to approximately 400 microns.
- the resulting powder can be granulated, optionally after milling in a granulation process, e.g. using a L ⁇ dige plow share mixer.
- a granulation process e.g. using a L ⁇ dige plow share mixer.
- For granulation usually a small amount of moisture is added.
- the powders obtained in a turbine dryer generally have a wider particle size distribution as part of the product is gathering at the wall creating larger particles.
- powder particles obtained in a turbine dryer are less homogeneously dried as a result of their larger particles being more effectively dried at the outside and as a result of the difference in residence time between particles remaining in the gas stream and those sticking on the (heated) wall of the dryer.
- Another possibility is to spray the slurry in a rotary drum granulator onto fines building up coarser particles followed by, or in conjunction with drying.
- the spray-on techniques lead to granules with a homogenous distribution of moisture and consequently a better solubility.
- Such granules however comprise a relatively poor attrition resistance and provide a considerable dust problem during handling thereof. Further disadvantages of such processes are that it is extremely difficult to avoid caking of the product leading to large lumps. these processes also lead to more massive particles with less homogeneous distribution of the residual moisture, leading to worse dissolution.
- the dried powder or the dried granulated product is subjected to a compacting treatment, an excellent product can be obtained, which shows no dust problem as a consequence of the high attrition resistance with a more homogeneous distribution of moisture, minimising the risk of segregation in the detergent compositions and in which the use of separate builders can be avoided.
- the product obtained shows no dust problems as a consequence of the high attrition resistance and also has a relatively high bulk density.
- compaction is performed at a temperature between 0 and 90°C and more preferably between 20 and 50°C. The pressure depends on the method of compaction, i.e. the device used and the material which is to be compacted.
- the moisture content of the dried product before compaction is adjusted to at least 5-25% (w/w), which further improves the bulk density and attrition resistance of the end product.
- Compacting can be performed by a number of methods, however for the present method it is preferred that compaction is performed by passing the dry mixture between rollers forming a film. Such a film will expediently have a thickness of 1-10 mm. Compaction can also expediently be performed by making tablets.
- Compaction can be carried out between two rollers in a continuous process as offered by the firm Alexanderwerke AG in Remscheid, Germany or in a tabletting operation.
- the effectiveness of the compaction process depends on the pressure exerted on the powder layer/film and the temperature.
- the pressure is exerted hydraulically on one of the rollers.
- the powder is pressed through the rollers and the dosing rate determines the thickness of the film, which is normally a few millimetres only.
- the minimum pressure needed to granulate the powders in a standard Alexanderwerke unit having rollers with a diameter of 48 cm and a length of 26 cm is about 130 bar.
- the maximum pressure the equipment tolerates is slightly above 200 bar.
- the temperature is controlled by internal cooling of the rollers.
- the temperature range that can be used is between 0 and 80% and preferably 20-50°C.
- the fines resulting from said sieve operation are returned to the dried product before compaction and the resulting oversize particles are returned to the breaking step.
- the fines are returned to the starting slurry.
- the oversize particles can advantageously be returned to the breaking operation.
- Part of the alkali metal salt of citric acid e.g. 30% can be replaced by a lower hydroxymonocarboxylic acid e.g. lactic acid.
- Partial salts of the carboxylic acid in which one or more of the hydrogen ions of the carboxylic groups are replaced by metal ions are particularly useful. Especially sodium and potassium salts can be used with good results for the purpose of this invention. Potassium salts are sometimes preferred because of their higher solubility. The use of sodium citrate in the co-granules according to the present invention is preferred.
- Sodium disilicate is used with special advantage.
- the co-granules further comprise at least one polymeric compound being either an acid and/or a salt of a polycarboxylic acid polymer or a polypeptide.
- Suitable polycarboxylic acid polymers comprise e.g. a water-soluble homopolymer or copolymer having a molecular weight of at least 500. It may be derived from a monocarboxylic acid or from a di-, tri- or polycarboxylic acid. The polymer will normally be used in the form of its water-soluble alkali metal salt form.
- One group of polymer materials found to be of value comprises homopolymers derived from a monomer of the formula: wherein R 1 is hydrogen, hydroxyl, C 1 -C 4 alkyl or alkoxy, acetoxy, or -CH 2 COOM; R 2 is hydrogen, C 1 -C 4 alkyl or -COOM and M is an alkalimetal.
- R 1 is hydrogen, hydroxyl, C 1 -C 4 alkyl or alkoxy, acetoxy, or -CH 2 COOM
- R 2 is hydrogen, C 1 -C 4 alkyl or -COOM
- M is an alkalimetal.
- this group include the sodium and potassium salts of polyacrylic, polymethacrylic, polyitaconic, polymaleic and polyhydroxyacrylic acids and also the hydrolysis products of the corresponding polymerised acid anhydrides.
- Suitable polypeptides which can be incorporated in the co-granules according to the present invention are e.g. polyaspertate and poly
- a second group of suitable polymeric materials comprises the copolymers of two or more carboxylic monomers of the above formula.
- this group include the sodium and potassium salts of copolymers of maleic anhydride with acrylic acid, methacrylic acid, crotonic acids, itaconic acid and its anhydride and/or aconitic acid.
- a third group of suitable polymeric materials comprises the copolymers of one carboxylic monomer of the above formula and two or more non-carboxylic acid monomers such as ethylene, propylene, styrene, alphamethylstyrene, acrylonitrile, acrylamide, vinylacetate, methylvinylketone, acrolein and esters of carboxylic acid monomers such as ethyl acrylate and methacrylate.
- non-carboxylic acid monomers such as ethylene, propylene, styrene, alphamethylstyrene, acrylonitrile, acrylamide, vinylacetate, methylvinylketone, acrolein and esters of carboxylic acid monomers such as ethyl acrylate and methacrylate.
- the co-granule further comprises at least one inorganic salt of the group consisting of alkali metal tripolyphosphate, alkali metal carbonate/bicarbonate/sesquicarbonate, alkali metal sulphate.
- an inorganic salt of the group consisting of alkali metal tripolyphosphate, alkali metal carbonate/bicarbonate/sesquicarbonate, alkali metal sulphate.
- Non-phosphate inorganic salts as various carbonates especially alkali metal carbonate/bicarbonate/sesquicarbonate are preferred.
- the inorganic salts are usually present in the form of their lower stable hydrate(s).
- the solution or slurry is preferably prepared by adding citric acid to a solution containing sodium disilicate, neutralising the carboxylic acid with alkali, optionally adding further ingredients as to obtain a solution or slurry with a water content of 30-60% (w/w), which solution or slurry is subsequently dried and compacted.
- the various ingredients of the solution or slurry can be used in the form of solid dry of hydrated forms, to which water is added.
- An other aspect of the invention provides co-granules obtainable by the method according to the invention.
- co-granules have a bulk density of at least 700 g/dm 3 , more preferably above 800g/dm 3 , and most preferably a bulk density between 900 g/dm 3 and 1200 g/dm 3 .
- High bulk densities are desirable at present, to be able to provide final detergents compositions with a relatively high specific weight.
- the particle size of the co-granules according to the present invention is not critical however, it is preferred that the co-granules have an average particle size of 100 to 1500 micrometer, more preferably an average particle size of 400-900 micrometer and a Rosen Rammler N-value above 2.5. Particle size determination and the definition and determination of the Rosen Rammler N-value is described in detail in "Small Particle Statistics" by Herdan, C; second revised edition; Butterworth, London 1960, in particular page 86-101. Graph paper according to DIN 1171 (new) is often used to determine the N-value.
- compositions of the co-granules according to the invention is: 5-90% (w.w.) sodium disilicate; 5-90% (w.w.) alkali metal salt of citric acid; 0-20% (w.w.) polymer; 0-40% (w.w.) alkali metal tripolyphosphate; 0-40% (w.w.) alkali metal (bi)carbonate, or sesquicarbonate; 0-10% (w.w.) organic phosphonate; 0-60% (w.w.) alkali metal sulphate; 5-25% (w.w.) moisture.
- the organic phosphonates which can be present in the co-granules according to the present invention are e.g. the various organic polyphosponates, e.g. of the Dequest® range, which are especially added to phosphate-free machine dishwashing compositions.
- a drawback of these polymers is that some of them are not quite biodegradable and therefore environmentally less acceptable. Therefore some of the polyphosphonates, whilst being effective, are less acceptable as being P-containing products.
- ingredients may be incorporated in the composition.
- Said ingredients are here to be understood compounds like, the well-known enzyme stabilizers such as the polyalcohols, e.g. glycerol, and borax; anti-scaling agents; crystal-growth inhibitors, threshold agents; thickening agents; perfumes and dyestuffs and the like.
- a small amount of low- to non-foaming nonionic surfactant which includes any alkoxylated nonionic surface-active agent wherein the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof, is preferably used to improve the detergency and to suppress excessive foaming due to some protein soil.
- an excessive proportion of nonionic surfactant should be avoided.
- an amount of 0.1 to 5% by weight preferably from 0.5 to 4% by weight, is quite sufficient.
- nonionic surfactants for use in the invention are the low- to non-foaming ethoxylated straight-chain alcohols of the Plurafac® RA series, supplied by the Eurane Company; of the Lutensol® LF series, supplied by the BASF Company and of the Triton® DF series, supplied by the Rohm & Haas Company.
- the present invention in a third aspect provides a detergent composition comprising co-granules according to the invention.
- a detergent composition comprises at least 40% of co-granules according to the invention and a bleach system and/or an enzyme system.
- the bleach system and/or an enzyme system is then usually added in the form of separate particles which may have the same particle size distribution as the co-granules; also it is usually advantageous if the bulk density of these particles is comparable to that of the co-granules.
- the detergent composition consists for at least 50% of co-granules according to the invention, and less than 30% of a bleach system and an enzyme system.
- Enzymes are used for many purposes in various fields where biochemical reactions occur.
- an enzyme can be described as a catalyst capable of permitting a biochemical reaction to quickly occur and can be classified according to the type of reaction they catalyze.
- Enzymes are characterized by a high specificity, that is to say, each enzyme can catalyze a single reaction of one substance or a very small number of closely related substances.
- enzymes suitable for use in the cleaning compositions of this invention include lipases, peptidases, amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removability.
- lipases are classified as EC class 3, hydrolases, subclass EC 3.1., preferably carboxylic ester hydrolases EC 3.1.1.
- lipase 3.1.1.3 with the systematic name glycerol ester hydrolases.
- Amylases belong to the same general class as lipases, subclass EC 3.2, especially EC 3.2.1 glycose hydrolases such as 3.2.1.1 alpha-amylase with the systematic name alpha-1,4-glucan-4-glucanohydrolase; and also 3.2.1.2, beta-amylase with the systematic name alpha-1,4-glucan maltohydrolase.
- Proteases belong to the same class as lipases and amylases, subclass EC 3.4, particularly EC 3.4.4. peptide peptido-hydrolases such as EC 3.4.4.16 with the systematic name subtilopeptidase A.
- Enzymes serving different functions can also be used in the practice of this invention, the selection depending upon the composition of biochemical soil, intended purpose of a particular composition, and the availability of an enzyme to degrade or alter the soil.
- Lipases sometimes called esterases, hydrolyse fatty soils. Lipases suitable for the use herein include those of animal, plant and microbiological origin. Suitable lipases are also found in many strain of bacteria and fungi. For example, lipases suitable for use herein can be derived from Pseudomonas, Aspergillus, Pneumococcus, Staphylococcus, Toxins, Mycobacterium Tuberculosis, Mycotorula Lipolytica, and Sclerotinia microorganisms, and can. be made using recombinant DNA manufacturing techniques.
- Suitable animal lipases are found in the body fluids and organs of many species.
- a preferred class of animal lipase herein is the pancreatic lipase.
- Lipase can be employed in the present cleaning compositions in an amount from about 0.005% to about 10%, preferably from 0.01 to 5% of the cleaning composition, on a pure enzyme basis.
- the enzymes most commonly used in machine dishwashing compositions are amylolytic enzymes.
- amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi.
- Preferred amylolytic enzymes are those prepared and described in British patent specification No. 1,296,839, cultivated from the strains of Bacillus lichenifonrmis NCIB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11 945, ATCC 8480 and ATCC 9945 A.
- Examples of such amylolytic enzymes are amylolytic enzymes produced and distributed under the trade name of SO-95® or Termamyl® by Novo Industri A/S, Copenhagen, Denmark. These amylolytic enzymes are generally presented as granules and may have enzyme activities of from about 2 to 10 Maltose units/milligram.
- amylolytic activity can be determined by the method as described by P. Bernfeld in "Method of Enzymology", Vol. I (1955), page 149.
- compositions of the invention preferably also contain a proteolytic enzyme.
- subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available subtilisins Maxatase® supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase®, supplied by Novo Industri A/S, Copenhagen, Denmark.
- protease obtained form a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available from Novo Industri A/S under registered trade names of Esperase® and Savinase®.
- the preparation of these and analogous enzymes is described in GB-A-1 243 784.
- protease useful herein is a fairly recent commercial product sold by Novo Industri A/S under the trade name Durazym®, as described in WO-A-89/06279.
- the enzymes are generally presented as granules, e.g. marumes, prills, T-granules etc., and may have enzyme activities of from about 500 to 1700 glycine units/milligram.
- All these enzymes can each be present in a weight percentage amount of from 0.2 to 5% by weight, such that for amylolytic enzymes the final composition will have amylolytic activity of from 10 2 to 10 6 Maltose units/kg, and for proteolytic enzymes the final composition will have proteolytic enzyme activity of from 10 6 to 10 9 Glycine Units/kg.
- the detergent composition may also comprise a bleach system encapsulated or not.
- the bleach system may be a chlorine-or bromine-releasing agent or a peroxygen compound.
- suitable reactive chlorine- or bromine-oxidizing materials are heterocyclic N-bromo- and N-chloro imides such as trichlorosio-cyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric acids, and salts thereof with watersolubilizing cations such as potassium and sodium.
- Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also quite suitable.
- Dry, particulate, water-soluble anhydrous inorganic salts are likewise suitable for use herein such as lithium, sodium or calcium hypochlorite and hypobromite.
- Chlorinated trisodium phosphate is another suitable material.
- Chloroisocyanurates are, however, the preferred bleaching agents. Potassium dichloroisocyanurate is sold by Monsanto Company as ACL-59®.
- Sodium dichloroisocyanurates are also available from Monsanto as ACL-60®, and in the dihydrate form, from the Olin Corporation as Clearon CDB-56®, available in powder form (particle diameter of less than 150 microns); medium particle size (about 50 to 400 microns); and coarse particle size (150-850 microns). Very large particles (850-1700 microns) are also found to suitable.
- peroxyacids usable in the present invention are solid and, preferably, substantially water-insoluble compounds.
- substantially water-insoluble is meant herein a water-solubility of less than about 1% by weight at ambient temperature.
- peroxyacids containing at least about 7 carbon atoms are sufficiently insoluble in water for use herein.
- Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxyacids such as:
- Peroxyacid bleach precursors are well known in the art. As nonlimiting examples can be named N,N,N 1 ,N 1 -tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4 751 015.
- TAED N,N,N 1 ,N 1 -tetraacetyl ethylene diamine
- SNOBS sodium nonanoyloxybenzene sulphonate
- SBOBS sodium benzoyloxybenzene sulphonate
- SPCC cationic peroxyacid precursor
- Inorganic peroxygen-generating compounds are also suitable for preparing the co-granules of the present invention.
- these materials are salts of monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
- a bleach catalyst such as the manganese complex, e.g. Mn-Me TACN, as described in EP-A-0 458 397, or the sulphonimines of US Patents 5,041,232 and 5,047,163 can be incorporated.
- the amount used in the co-granules of the invention may vary within the range of about 0,5% to about 3% as available chlorine (Av Cl).
- Av Cl available chlorine
- peroxygen bleaching agents a suitable range will be from 0,5% to 3% av 0 (available oxygen) .
- the invention in a fourth aspect relates to the use of a co-granule according to the invention as a component in detergent compositions, more preferably in dishwashing compositions. More in particular the invention provides non-irritant detergent composition in which the amount of peroxygen bleach, protease and surfactant taken together is at most 20%, more in particular between 10 and 19.95% (w.w.) of the total composition.
- composition Dry basis As Is (kg) (kg) Citric acid. Oaq. 189.5 189.5 Water 189.5 NaOH (50%) 118.5 237 Sokalan CP 5 (40%) 21.6 54 Sodium silicate (45%) 150.8 335 Total 480.4 1005
- the citric acid was first mixed with water and under stirring and cooling it was neutralised by slowly adding caustic soda. The solution was kept at about 70°C while successively the polymer and the silicate liquor were added. The solution obtained was clear at 70°C.
- composition Dry basis As Is (kg) (kg) Sodium citrate.2.aq 254.6 290.2 Water 325.8 Sokalan CP-5 (40%)* 21.6 54 Sodium silicate (45%)** 150.8 335 Total 427 1005
- citrate was dissolved under stirring in water, which was preheated at 70°C. The polymer and the silicate solution were then added. The solution was again clear.
- Spray-drying was carried out in a co-current manner in a standard spray-tower.
- the gas was pre-heated to max. 230°C and the solution was introduced (sprayed) at about 70°C in order to save energy/maximize capacity.
- the powders obtained varied in properties as summarized below, which could be adjusted by varying the conditions within the ranges given.
- Compaction was carried out in a standard compaction-roller unit as marketed by the firm Alexanderwerke AG in Remscheid, Germany.
- Type Walzenpresse Type WP 480 x 260 V.
- the equipment consists of 2 rollers.
- the powder was pressed between the rollers by a screw.
- the powder flow could be controlled by the screw.
- the pressure of the rollers was controlled hydraulically as the upper roller was not in a fixed position.
- the maximum pressure was about 150 t, which is equivalent to a hydraulic pressure of about 200 bar and about 6 t per cm length of the roller.
- the rollers rotated at a speed of 14 - 18 revolutions per min.
- the rollers were kept at about 25°C by water cooling.
- the sheet formed was broken down and sieved, using sieves of 200 and 1200 micrometers. The finer particles were returned to the compactor and the larger particles were returned to the breaker..
Abstract
Description
- preparing a solution or a slurry of at least
- an alkali metal citrate, and
- sodium disilicate,
- drying the mixture,
- compacting the dried product, and
- breaking up and sieving the compacted product.
In EP-A-0 526 978 it is disclosed that silicates can be simultaneously dried and granulated in this dryer. However, this dryer is less suited for the combined drying and granulation to produce co-granules containing substantial quantities of organic ingredients in conjunction with silicate. Due to the high attrition between the rotating blades and the film formed on the wall during the granulation phase, local overheating can cause partial decomposition of the organic ingredients, leading to (local-) coloring.
Preferably compaction is performed at a temperature between 0 and 90°C and more preferably between 20 and 50°C. The pressure depends on the method of compaction, i.e. the device used and the material which is to be compacted.
5-90% | (w.w.) | sodium disilicate; |
5-90% | (w.w.) | alkali metal salt of citric acid; |
0-20% | (w.w.) | polymer; |
0-40% | (w.w.) | alkali metal tripolyphosphate; |
0-40% | (w.w.) | alkali metal (bi)carbonate, or sesquicarbonate; |
0-10% | (w.w.) | organic phosphonate; |
0-60% | (w.w.) | alkali metal sulphate; |
5-25% | (w.w.) | moisture. |
Typical diperoxy acids useful therein include alkyl diperoxy acids and aryldiperoxy acids, such as:
Composition: | ||
Dry basis | As Is | |
(kg) | (kg) | |
Citric acid. Oaq. | 189.5 | 189.5 |
Water | 189.5 | |
NaOH (50%) | 118.5 | 237 |
Sokalan CP 5 (40%) | 21.6 | 54 |
Sodium silicate (45%) | 150.8 | 335 |
Total | 480.4 | 1005 |
Composition: | ||
Dry basis | As Is | |
(kg) | (kg) | |
Sodium citrate.2.aq | 254.6 | 290.2 |
Water | 325.8 | |
Sokalan CP-5 (40%)* | 21.6 | 54 |
Sodium silicate (45%)** | 150.8 | 335 |
Total | 427 | 1005 |
Gas temperature inlet | 200 - 230°C |
Gas temperature exit | 120 - 140°C |
Temperature solution | 65 - 75°C |
Bulk density (g/cm3) | 200 - 680 |
Free moisture content (%, w.w.) | 7- 12 |
Particle size | 90% below 250 micrometers. |
At higher temperatures, the pressures can be reduced.
Bulk density (g/cm3) | 870 - 900 |
Attrition test (fluid bed) (%,w.w.) | 3.6 - 5.2 |
Dissolution time at 20°C | 0'50"-1'20" |
Particles below 200 micrometers | 0 - 0.2% (w.w.) |
Particles above 1000 micrometers | 10 - 25% (w.w.) |
N Value (Rosen Rammler) | 3.5 - 4.5 |
Bulk density (g/cm3) | 770 - 820 |
Attrition test (fluid bed) (% w.w.) * | 10 - 30 |
Dissolution time at 20°C ** | 3'-5' |
Bulk density (g/cm3) | 870 - 900 |
Attrition test (fluid bed) (%,w.w.) | 3.6 - 5.2 *) |
Dissolution time at 20°C | 0'50"-1'20" |
Particles below 200 micrometers | 0 - 0.2% (w.w.) |
Particles above 1000 micrometers | 10 - 25% (w.w.) |
N Value (Rosen Rammler) | 3.5 - 4.5 |
Bulk density (g/cm3) | 770 - 820 |
Attrition test (fluid bed) (% w.w.) * | 10 - 30 |
Dissolution time at 20°C ** | 3'-5' |
Bulk density (g/cm3) | 850 - 950 |
Attrition test (fluid bed)(% w.w.) * | 4 - 8 |
Dissolution time at 20°C ** | 7'-10' |
Claims (16)
- Method for preparing co-granules as a component for and for incorporation in detergent compositions, which method comprises:preparting a solution or a slurry of at leastan alkali metal citrate, andsodium disilicate,drying the mixture,compacting the dried product, andbreaking up and sieving the compacted product.
- Method according to claim 1, characterised in that compaction is performed at a temperature between 0 and 90° C
- Method according to claim 1 or 2, characterized in that the moisture content of the dried product before compaction is adjusted to at least 5-25% (w/w).
- Method according to one or more claims 1-3, characterised in that compaction is performed by passing the dried mixture between rollers.
- Method according to one or more claims 1-4, characterised in that compaction is performed by making tablets.
- Method according to one or more of claims 1-5, characterised in that the fines resulting form breaking up and sieving are returned to the dried product before compaction and the resulting oversized particles are returned to the breaking step.
- Method according to one or more of the preceding claims, characterised in that the co-granules further comprise at least one polymeric compound, being either an acid and/or a salt of a polycarboxylic acid polymer or a polypeptide.
- Method according to one or more of the preceding claims, characterised in that the co-granules further comprise at least one inorganic salt of alkali metal tripolyphosphate, alkali metal carbonate/bicarbonate/sesquicarbonate or alkali metal sulphate.
- Method according to one or more of the preceding claims, characterised in that the slurry is prepared by adding citric acid to a solution containing the inorganic salt, neutralising the carboxylic acid with alkali, optionally adding further ingredients, as to obtain a solution or a slurry with a water content of 30-60% (w/w).
- Co-granules obtainable by the method according to one or more of the claims 1-9.
- Co-granules according to claim 10, characterised by having a bulk density of at least 700 g/dm3, preferably above 800 g/dm3.
- Co-granules according to claim 11, characterised in that the bulk density of the co-granules is between 900 g/dm3 and 1200 g/dm3.
- Co-granules according to one or more of claims 10-12, characterised in that the average particle size of the co-granules is 100 to 1500 µm.
- Co-granules according to claim 13, characterised in that the average particle size of the co-granules is comprised between 400 and 900 µm and that the Rosen Rammler N-value thereof is above 2.5.
- Detergent composition comprising co-granules according to one or more of claims 10-14.
- Use of a co-granules according to one or more of claims 10-14 as a component in detergent compositions.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9414576A GB9414576D0 (en) | 1994-07-19 | 1994-07-19 | Method for preparing cogranules by compaction |
GB9414576 | 1994-07-19 | ||
PCT/EP1995/002835 WO1996002621A1 (en) | 1994-07-19 | 1995-07-14 | Method for preparing co-granules, co-granules thus obtained and use thereof as a component in detergent compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0772671A1 EP0772671A1 (en) | 1997-05-14 |
EP0772671B1 true EP0772671B1 (en) | 2003-08-27 |
Family
ID=10758575
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95926948A Expired - Lifetime EP0772671B1 (en) | 1994-07-19 | 1995-07-14 | Method for preparing co-granules, co-granules thus obtained and use thereof as a component in detergent compositions |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0772671B1 (en) |
AT (1) | ATE248214T1 (en) |
AU (1) | AU3115095A (en) |
DE (1) | DE69531621D1 (en) |
GB (1) | GB9414576D0 (en) |
WO (1) | WO1996002621A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5914307A (en) * | 1996-10-15 | 1999-06-22 | The Procter & Gamble Company | Process for making a high density detergent composition via post drying mixing/densification |
GB2318584A (en) * | 1996-10-25 | 1998-04-29 | Procter & Gamble | Process for preparing detergent compositions by spray drying |
BR9808551C1 (en) * | 1997-04-14 | 2002-03-05 | Procter & Gamble | Sparkling component |
EP0872544A1 (en) * | 1997-04-14 | 1998-10-21 | The Procter & Gamble Company | Dry effervescent granules and granular compositions comprising the same |
MA24525A1 (en) | 1997-04-14 | 1998-12-31 | Procter & Gamble | DETERGENT PARTICLE |
DE102004050562A1 (en) * | 2004-10-15 | 2006-05-04 | Henkel Kgaa | Absorbable particles |
GB2548331B (en) * | 2016-03-07 | 2018-07-18 | Reckitt Benckiser Calgon Bv | Detergent granule and process of production |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3624336A1 (en) * | 1986-07-18 | 1988-01-28 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF GIANT ALKALINE CLEANING AGENTS BY COMPACTING GRANULATION |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5934758B2 (en) * | 1978-02-10 | 1984-08-24 | ライオン株式会社 | Manufacturing method of granular detergent |
US5268283A (en) * | 1990-10-05 | 1993-12-07 | Miles Inc. | Method for the production of detergent builder formulations utilizing spray granulated citric acid and salts thereof |
DE69502701T3 (en) * | 1994-01-25 | 2002-05-29 | Unilever Nv | METHOD FOR PRODUCING DETERGENT TABLETS |
-
1994
- 1994-07-19 GB GB9414576A patent/GB9414576D0/en active Pending
-
1995
- 1995-07-14 DE DE69531621T patent/DE69531621D1/en not_active Expired - Lifetime
- 1995-07-14 AT AT95926948T patent/ATE248214T1/en not_active IP Right Cessation
- 1995-07-14 EP EP95926948A patent/EP0772671B1/en not_active Expired - Lifetime
- 1995-07-14 AU AU31150/95A patent/AU3115095A/en not_active Abandoned
- 1995-07-14 WO PCT/EP1995/002835 patent/WO1996002621A1/en active IP Right Grant
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3624336A1 (en) * | 1986-07-18 | 1988-01-28 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF GIANT ALKALINE CLEANING AGENTS BY COMPACTING GRANULATION |
Non-Patent Citations (3)
Title |
---|
J.G. Vail Soluble Silicates, Einhold Pub. Corp. edit., vol. 1, pages 72 and 98 (1952) * |
Kirk-Othmer Encyclopedia of Chemical Technology, 3rd. ed., J. Wiley & Sons edit., vol. 20, page 855 * |
Römpp Chemie Lexikon, 9th. ed., Georg Thieme Verlag edit., page 4719 (1992) * |
Also Published As
Publication number | Publication date |
---|---|
EP0772671A1 (en) | 1997-05-14 |
DE69531621D1 (en) | 2003-10-02 |
ATE248214T1 (en) | 2003-09-15 |
GB9414576D0 (en) | 1994-09-07 |
WO1996002621A1 (en) | 1996-02-01 |
AU3115095A (en) | 1996-02-16 |
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