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
  • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions

Definitions

• the present invention relates to a process for the production of a detergent composition.
• the invention is concerned with a process for the production of a detergent composition having a medium or low bulk density and to detergent compositions thereby produced.
• 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.
• powders produced by this method typically have a bulk density of 300 to 550 g/1 or even up to 650 g/1.
• 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.
• 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.
• 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.
• 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 often desirable.
• EP-A-367 339 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.
• WO 97/02338 (Unilever : unpublished at the priority date of the present application) discloses that a low bulk density, for example less than 700 g/1, may be obtained by a process in which a spray-drying step is not employed, if the composition is formulated with a component having a low bulk density.
• this process is relatively unsuitable for use with starting materials which are either available commercially in a form in which the particle density is high or which are themselves produced by spray-drying (the latter normally producing relatively porous particles).
• medium or low bulk density powders may be obtained by a new process of mechanical mixing of a powder which contains little or no detergent active material and which consists of particles having a predetermined average particle size and high particle porosity together with a liquid component comprising a detergent active material or a precursor therefor.
• a first aspect of the present invention provides a process for the production of a detergent composition having a bulk density of no more than 750 g/1, e.g. no more than 700 or 650 g/1, the process comprising mixing a particulate starting material which contains no more than 10% by weight of the starting material of detergent active material and which starting material has a d 5f , average particle diameter of from lOO ⁇ m to lOOO ⁇ m and a particle porosity of at least 0.4, together with a liquid component comprising a detergent active material or a precursor therefor in a mixer/ granulator having both a stirring and a cutting action.
• the present invention further extends to a detergent composition prepared by a process according to the present invention. Detailed description of the invention
• the present invention derives from the unexpected observation that the bulk density of the resultant product is dependent upon the rotational speed of mixing. This is also a function of the particular mixer of choice but essentially, the lower the speed of the mixer, the lower the bulk density of the product.
• the first advantage is that by choosing a powder starting material which already possesses the required average particle size and porosity medium or low bulk density powders may be prepared.
• NTR non-tower route
• the detergent composition resulting from the process of the present invention has a bulk density of 400 to 650 g/1, preferably 450 to 650 g/1 and more preferably
• the resultant detergent composition has a particle porosity of at least 0.2 and more preferably at least 0.25.
• the particulate starting material is dosed at a level of from 10 to 75 wt%, preferably from 20 to 40 wt%, of the composition resulting from the mechanical mixing process .
• particle size distributions in terms of average (e.g. d 50 ) particle diameters, if they are capable of being fitted to a Rosin-Rammler distribution, they may be expressed in terms of their Rosin Rammler number. This is calculated by fitting the particle size distribution to an n-power distribution according to the following formula : -
• R is the cumulative percentage of powder above a certain size D.
• D ⁇ is the average granule size and n is a measure of the particle size distribution.
• D r and n are the
• a high n value means narrow particle size distribution and low values mean a broad particle size distribution.
• the process may be a continuous process or may be performed batch-wise .
• One type of equipment suitable for carrying out the mechanical mixing comprises a high-speed mixer/densifier into which are dosed the starting material and the liquid component, to form a granular detergent material.
• the equipment further comprises a moderate-speed granulator/densifier into which the granular detergent material from the high-speed mixer/densifier is dosed and is thereby brought into or maintained in a deformable state and the resultant product is subsequently dried and/or cooled.
• An example of such a high-speed mixer/densifier is the ⁇ dige (Trade Mark) CB 30 Recycler. This apparatus essentially consists of a large, static hollow cylinder having a diameter of about 30 cm which is horizontally placed.
• the middle it has a rotating shaft with several different types of blades mounted thereon. It can be rotated at speeds between 100 and 2500 rpm, dependent on the degree of densification and the particle size desired.
• the blades on the shaft provide a thorough mixing action of the solids and the liquids which may be admixed at this stage.
• the mean residence time is somewhat dependent on the rotational speed of the shaft, the position of the blades and the weir at the exit opening.
• a Shugi (Trade Mark) Granulator or a Drais (Trade Mark) K-TTP 80 may be used.
• the components of the feedstock are thoroughly mixed in a high-speed mixer/densifier , preferably for a relatively short time of about 5-30 seconds.
• the detergent material still possesses a considerable porosity, which can be desired for low density products.
• it is preferred that detergent material is treated in a second processing step for about 1-10 minutes, preferably for 2-5 minutes, in a moderate-speed granulator/densifier .
• the conditions are such that the powder is brought into, or maintained in, a deformable state. As a consequence, the particle porosity will be further reduced.
• the main differences from the first step reside in the lower mixing speed and the generally longer residence time of at least 30 seconds, for example 1-10 minutes, and the necessity for the powder to be deformable.
• This second mixing stage can be successfully carried out in a L ⁇ dige (Trade Mark) KM 300 mixer, also referred to as L ⁇ dige Ploughshare.
• This apparatus essentially consists of a hollow static cylinder having a rotating shaft in the middle. On this shaft various plough-shaped blades are mounted. It can be rotated at a speed of 40-160 rpm. Optionally, one or more high-speed cutters can be used to prevent excessive agglomeration.
• Another suitable machine for this step is, for example the Drais (Trade Mark) K-T 160.
• the densified detergent powder For use, handling and storage, the densified detergent powder must no longer be in a deformable state. Therefore, after the second mixing stage, the densified powder is dried and/or cooled. This step can be carried out in a known manner, for instance in a fluid bed apparatus (drying, cooling) or in an airlift (cooling) . It is advantageous if the powder needs a cooling step only, because the required equipment is relatively simple and more economical.
• the second and preferable for the first mixing stage is the attainment of a deformable state for the detergent powder in order to get optimal densification .
• the high-speed mixer/densifier and/or the moderate speed granulator/densifier are then able to effectively deform the particulate material in such a way that the particle porosity is reduced, and consequently the bulk density is increased.
• Another suitable type of mixer/granulator for use in the process of the invention is bowl-shaped and preferably has a substantially vertical stirrer axis.
• the stirrer and cutter may be operated independently of one another, and at separately variable speeds.
• 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 35kg batch) is generally sufficient.
• the final bulk density can be controlled by choice of residence time and stirrer rate.
• the stirrer is operated at a rate of 25 to 250 rpm, e.g. from 100 rpm to 200 rpm or even as low as 30 to 50 rpm. However, this speed is dependent on the size of the apparatus.
• the cutter is suitably operated at a rate of 200 to 3500 rpm, preferably 300 to 3000 rpm.
• 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 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 45°C.
• the amount of detergent active material in the particulate starting material is no more than 10% by weight of that material.
• the amount of detergent active material in the particulate starting material is suitably no more than 5% by weight thereof and preferably no more than 1% by weight thereof.
• the particulate starting material may be substantially or totally free of any detergent active material.
• the particulate starting material may be one prepared by spray-drying.
• starting materials having the required parameters may be obtained by other means, e.g. involving granulation.
• the d 50 average particle diameter of the particulate starting material is from lOO ⁇ m to lOOO ⁇ m. This is important for controlling the particle size distribution in the final product. Preferably though, this average particle diameter is from 150 ⁇ m to 800 ⁇ m, especially from 200 ⁇ m to 700 ⁇ m.
• 90% by weight of the particles in the starting material have a particulate diameter in the region of lOO ⁇ m to lOOO ⁇ m.
• the particle porosity of the particulate starting material is at least 0.4 but is preferably at least 0.45, e.g. from 0.45 to 0.55. Most preferably it is at least 0.50.
• such particulate starting material may comprise a spray-dried material, that is to say some or all of the starting material is formed by a spray-drying process.
• the measurement of particle porosity is based on the well known Kozeny-Carman relation for air flow through a packed bed of powder:
• the particle porosity can be derived from the following experiments:
• the height of the powder bed is recorded.
• An air flow of 375 cm /min is flowed through the bed of powder.
• the pressure drop over the bed is measured.
• the pressure drop over the empty tube should also be measured at the specified air flow.
• the solids density of the particles is needed (eq. 2) . This is measured using helium pycnometry, e.g. by using a penta pycnometer supplied by Quantachrome .
• the particle porosity can easily be derived.
• powder flow is defined in terms of the dynamic flow rate (DFR) , in ml/s, measured by means of the following procedure.
• the apparatus used consists of a cylindrical glass tube having an internal diameter of 35 mm and a length of 600 mm. The tube is securely clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 22.5 mm.
• a first beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor .
• the outlet orifice is temporarily closed, for example, by covering with a piece of card, and powder is poured through a funnel into the top of the cylinder until the powder level is about 10 cm higher than the upper sensor; a spacer between the funnel and the tube ensures that filling is uniform.
• the outlet is then opened and the time £. (seconds) taken for the powder level to fall from the upper sensor to the lower sensor is measured electronically. The measurement is normally repeated two or three times and an average value taken. If Y is the volume (ml) of the tube between the upper and lower sensors, the DFR (ml/s) is given by the following equation:
• the averaging and calculation are carried out electronically and a direct read-out of the DFR value obtained.
• the particulate starting material preferably comprises a builder, most preferably aluminosilicate, for example zeolite 4A or zeolite A24 or a salt, preferably an inorganic salt.
• Salts preferably sodium, of phosphates, for example sodium tripolyphosphate (STP), carbonate, bicarbonate and sulphate are also suitable.
• solid materials may also be incorporated in the particulate starting material, although they may alternatively or additionally be dosed at any appropriate stage (s) of the mechanical mixing.
• the liquid component preferably contains at least one liquid nonionic surfactant. It may also contain one or more acid precursors of anionic surfactants and/or fatty acids.
• the acid precursor (s) can then be neutralised to form the corresponding anionic surfactant ( s ) and the fatty acid(s) saponified by dosing one or more suitable alkaline materials at an appropriate stage during the mechanical mixing process.
• suitable alkaline materials include alkali metal carbonates, e.g. Na : CO, and hydroxides, e.g. NaOH . Such alkaline materials may be dosed in solid form or as aqueous solutions. It is also possible to partially neutralise/saponify such precursors or fatty acids in the liquid component prior to the mechanical mixing step.
• the detergent composition suitably comprise anionic detergent active.
• 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.
• the acid precursor of the active is preferably neutralised using a solid neutralising agent, for example carbonate, which is desirably a component of the particulate starting material.
• the detergent active material present in the composition may be selected for anionic, cationic, ampholytic, zwitterionic or nonionic detergent active materials or mixtures thereof.
• suitable synthetic anionic detergent compounds are sodium and potassium (C-C,,,) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates (LAS); sodium or potassium alkyl sulphates (PAS); and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols 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, amines or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
• Specific nonionic detergent compounds are alkyl (C 6 -C 22 ) phenol ethylene oxide condensates, generally having 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic (C Intel-C 1P ) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 50 EO.
• the level of detergent active material 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 particulate starting material at a level which is less than 10% by weight more preferably less than 5% by weight and/or employed as the liquid binder in the mixing process optionally with another liquid component, for example water.
• the particulate starting material constitutes 30 to 70% of the detergent composition.
• a layering material may be employed during the mixing step to control granule formation and reduce or prevent over-agglomeration.
• Suitable materials include aluminosilicates , for example zeolite 4A.
• the layering material is suitably present at a level of 1 to 4 wt %.
• 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 resulting powders had the following properties
• Sokalan CP5 is a polyacrylate/polymaleate copolymer.
• the spray-dried zeolite-based porous carriers were subsequently used as base powders in NTR processes as described in Examples 1-8.
• Base powder 2 was also used in a continuous NTR trial.
• Base Powder 1 43.4 Base Powder 2 46.4
• the PAS adjunct used in the trial had the following composition: PAS 45 wt%
• Base Powder 2 was also applied in a continuous NTR process, as a substitute for Zeolite A24.
• the following materials were fed into the Recycler CB30:
• Porous zeolite base powder was granulated in a continuous NTR process.
• RPM (CB30) 1800 1500 1200 1000 300 1500 RPM (KM300) 120 120 120 120 120 120 120 120 120 120 120 120 Results ex Recycler CB30
• a striking effect is caused by the speed of the Recycler CB30.
• the speed can be used to adjust the BD of the powder to the desired value, whereas at the same time still good particle size distributions are produced.
• the resulting powder had the following properties:
• the spray-dried STP-based carrier was used to formulate powders in Examples 9-13.
• the STP-based carrier was used in a batch NTR process using a Fukae FS30 mixer as follows:
• Zeolite 4A (Wessalith P) 1.0 1.0 1.0
• the STP-based carrier was used in a continuous NTR process using a Recycler CB30/Ploughshare KM300 as follows:
• Recycler CB30 RMP 1500 1000 1800

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• 1996
  • 1996-12-02 GB GBGB9625066.7A patent/GB9625066D0/en active Pending
• 1997
  • 1997-10-29 DE DE69709398T patent/DE69709398T3/de not_active Expired - Lifetime
  • 1997-10-29 EP EP97950085A patent/EP0942958B2/de not_active Expired - Lifetime
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  • 1997-10-29 BR BR9714494A patent/BR9714494A/pt not_active IP Right Cessation
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  • 1997-10-29 ES ES97950085T patent/ES2169882T3/es not_active Expired - Lifetime
  • 1997-10-29 WO PCT/EP1997/006073 patent/WO1998024876A1/en active IP Right Grant
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