EP0352135B1 - Waschmittelzusammensetzungen und Verfahren zu deren Herstellung - Google Patents

Waschmittelzusammensetzungen und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0352135B1
EP0352135B1 EP89307452A EP89307452A EP0352135B1 EP 0352135 B1 EP0352135 B1 EP 0352135B1 EP 89307452 A EP89307452 A EP 89307452A EP 89307452 A EP89307452 A EP 89307452A EP 0352135 B1 EP0352135 B1 EP 0352135B1
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Prior art keywords
water
mixer
particulate
amount
granulator
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EP89307452A
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English (en)
French (fr)
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EP0352135A1 (de
Inventor
Vijay Venkat Bhujle
Shashank Vaman Dhalewadikar
Vinodkumar Ramniranjan Dhanuka
Robert Donaldson
David George Evans
Andrew Timothy Hight
Michael William Hollingsworth
Stephen Thomas Keningley
Gordon George Mcleod
Donald Peter
Timothy John Price
Chandulal Kantioal Ranpuria
Peter John Russell
Thomas Taylor
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GB888817386A external-priority patent/GB8817386D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0352135A1 publication Critical patent/EP0352135A1/de
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 granular detergent compositions and components of high bulk density, and their preparation by a dry neutralisation process.
  • Such powders containing anionic surfactants may be prepared by methods involving in-situ neutralisation of an acid precursor of the anionic surfactant with an alkali such as sodium hydroxide or sodium carbonate.
  • JP 60 072 999A (Kao) and GB 2 166 452B (Kao) disclose a process in which detergent sulphonic acid, sodium carbonate and water are mixed in a strongly shearing apparatus; the solid mass obtained is cooled to 40 ° C or below and pulverised; and the fine powder thus obtained is granulated.
  • This process is typical of those disclosed in the art in that the product of the neutralisation reaction is a doughy mass, and the reaction requires apparatus such as a kneader with a very high energy requirement; and separate pulverisation and granulation steps in different apparatus are required in order to obtain an acceptable granular detergent product.
  • EP 158 419B discloses a process in which nonionic surfactant and soda ash are mixed and granulated in a reactor having horizontal and vertical blades rotating at different speeds, to give a detergent powder built with sodium carbonate and containing a high level of nonionic surfactant.
  • GB 1 404 317 discloses the preparation of a detergent powder of low or moderate bulk density by a dry neutralisation process.
  • Detergent sulphonic acid is mixed with an excess of soda ash in the presence of sufficient water to initiate the neutralisation reaction but not enough to wet the resultant product, which is in the form of a free-flowing powder.
  • the process is carried out in apparatus, for example a ribbon blender, planetary mixer or air transfer mixer, in which the reactants are "tossed and fluffed", and carbon dioxide liberated during the neutralisation is entrapped in the product particles.
  • the process is thus directed towards the production of light, porous particles comparable to those obtained by spray-drying.
  • GB 1 369 269 discloses a process for the production of anionic detergent, by vigorously mixing detergent sulphonic acid with powdered sodium carbonate in a mixer with a cutting arrangement, for example a Lodige ploughshare mixer.
  • a cutting arrangement for example a Lodige ploughshare mixer.
  • the temperature during neutralisation typically rises to about 85 ° C.
  • US 4 690 785 discloses a process for the production of alkylbenzene sulphonate powder by the neutralisation of alkylbenzene sulphonic acid with a base in solid or solution form. A substantial amount of water is present at the beginning of the process, and the heat generated by the exothermic reaction is used to drive off this, and the water generated by the reaction itself; reaction temperatures of about 100 ° C are typical.
  • the present inventors have now discovered that free-flowing detergent powders and detergent powder components of high bulk density and small particle size can be produced by dry neutralisation at relatively low temperatures, using only a single piece of apparatus: a high-speed mixer/granulator having both a stirring action and a cutting action.
  • the present invention accordingly provides a process for the preparation of a granular detergent composition or component having a bulk density of at least 650 g/litre, which process includes the step of neutralising a liquid acid precursor of an anionic surfactant with a solid water-soluble alkaline inorganic material, the process being characterised by the steps of:
  • the invention also provides a granular detergent composition or component prepared by this process.
  • the subject of the invention is the preparation of high-bulk-density detergent powder by a process involving the dry neutralisation of the acid precursor of an anionic surfactant with an alkaline solid.
  • the process is carried out in a high-speed mixer/granulator and involves the previously defined process steps (i), (ii) and (iii).
  • a very important characteristic of the process of the invention is that the reaction mixture remains throughout in particulate or granular form. Caking, balling and dough formation are avoided, and the product at the end of the granulation step needs no further particle size reduction.
  • the process of the invention generally produces a granular product containing at least 50 wt%, preferably at least 70 wt%, of particles smaller than 1700 am. This is achieved by ensuring that liquid components, particularly the acid anionic surfactant precursor, do not have an opportunity to act as binders or agglomerating agents.
  • step (i) ensures that there is initially a large amount of particulate solids present, relative to the liquids to be added, in the mixer before the introduction of the liquids.
  • the total solids present in step (i) amount to at least 60 wt%, more preferably at least 67 wt%, of the total composition present in step (ii). It is therefore advantageous to add as high a proportion as possible of the solid ingredients of the final product at this stage.
  • the liquids to solids ratio at the end of the neutralisation step (ii) does not exceed 0.60; more preferably it does not exceed 0.55, and desirably it does not exceed 0.50.
  • the solids must of course include a particulate water-soluble alkaline inorganic material (neutralising agent), in at least slight excess over the amount required for neutralisation.
  • a particulate water-soluble alkaline inorganic material neutralising agent
  • the neutralising agent comprises sodium carbonate, either alone or in admixture with one or more other particulate water-soluble alkaline inorganic materials, for example, sodium bicarbonate and/or sodium silicate.
  • Sodium carbonate is of course also useful as a detergency builder and provider of alkalinity in the final composition.
  • This embodiment of the invention may thus advantageously be used to prepare detergent powders in which sodium carbonate is the sole or principal builder, and in that case substantially more sodium carbonate than is required for neutralisation may be present.
  • the sodium carbonate embodiment of the invention is also suitable, however, for the preparation of detergent compositions in which substantial amounts of other builders are present.
  • Those other builders may also advantageously be present in the high-speed mixer/granulator in step (i).
  • Examples of such builders include crystalline and amorphous alkali metal aluminosilicates, alkali metal phosphates, and mixtures thereof.
  • Sodium carbonate may nevertheless be present in excess of the amount required for neutralisation, in order to provide alkalinity in the product: an excess of about 10 to 15 wt% is then suitable.
  • the solids present in step (i) may also include any other desired solid ingredients, for example, fluorescers; polycarboxylate polymers; antiredeposition agents, for example, sodium carboxymethyl cellulose; fatty acids for in-situ neutralisation to form soaps; or fillers such as sodium sulphate, diatomaceous earth, calcite, kaolin or bentonite.
  • fluorescers for example, fluorescers
  • polycarboxylate polymers for example, sodium carboxymethyl cellulose
  • fatty acids for in-situ neutralisation to form soaps or fillers such as sodium sulphate, diatomaceous earth, calcite, kaolin or bentonite.
  • solid particulate surfactants for example, alkylbenzene sulphonate and/or alkyl sulphate in powder form, may form part of the solids charge in step (i).
  • a detergent powder prepared by the process of the invention may contain alkylbenzene sulphonate in part introduced as a powder in step (i), and in part prepared in situ in step (ii).
  • a spray-dried detergent base powder may form part of the solids charge in step (i).
  • the solids present in step (i) include a finely divided particulate flow aid. This is suitably present in an amount of from 2 to 8 wt%, more preferably from 5 to 7 wt%, based on the final composition.
  • Suitable flow aids include crystalline or amorphous alkali metal aluminosilicate, thermally treated perlite, calcite, diatomaceous earth, and combinations of these.
  • Preferred flow aids are diatomaceous earth, and, in particular, Dicamol (Trade Mark) 424 thermally treated perlite.
  • This material has a silica content of 80-87 wt% and a water absorbance capacity of 250-300 wt%. Its presence in the solids mix before and during the addition of the acid anionic surfactant precursor appears to assist in preventing excessive agglomeration and maintaining the reaction mix in particulate form.
  • the term "fluidisation” as used herein means a state of mechanically induced vigorous agitation in which the mass of particles is to some extent aerated, but does not necessarily imply the blowing in of a gas.
  • a high-speed mixer/granulator having both a stirring action and a cutting action.
  • the high-speed mixer/granulator has rotatable stirrer and cutter elements that can be operated independently of one another, and at separately changeable or variable speeds.
  • Such a mixer is capable of combining a high- energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operation.
  • a preferred type of high-speed mixer/granulator for use in the process of the invention is bowl-shaped and preferably has a substantially vertical stirrer axis.
  • mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another, and at separately variable speeds.
  • the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
  • a similar mixer manufactured in India is the Sapphire (Trade Mark) RMG series of rapid mixer/granulator, which like the Fukae mixer is available in a range of different sizes.
  • This apparatus is essentially in the form of a bowl-shaped vessel raised up pneumatically to seal against a fixed lid.
  • a three- bladed stirrer and a four-bladed cutter share a single substantially vertical axis of rotation mounted on the lid.
  • the stirrer and cutter may be operated independently of one another, the stirrer at speeds of 75 or 100 revolutions per minute (rev/min), and the cutter at speeds of 1440 rev/min or 2880 rev/min.
  • the vessel can be fitted with a cooling water jacket.
  • the Sapphire RMG-100 mixer which is suitable for handling a 60 kg batch of detergent powder, has a bowl of about 1 metre diameter and 0.3 metres deep; the working capacity is 200 litres.
  • the stirrer blades are of 1 metre diameter and the cutter blades are of 0.1 metre diameter.
  • mixers found to be suitable for use in the process of the invention include the Diosna (Trade Mark) V series ex Dierks & Söhne, Germany; and the Pharma Matrix (Trade Mark) ex T K Fielder Ltd., England.
  • Other mixers believed to be suitable for use in the process of the invention are the Fuji (Trade Mark) VG-C series ex Fuji Sangyo Co., Japan; and the Roto (Trade Mark) ex Zanchetta & Co srl, Italy.
  • step (ii) - is the introduction of the acid surfactant precursor.
  • the way in which this step is conducted is crucial to the success of the process. In particular, it is important that throughout the neutralisation step the amount of liquid present never rises to a level where it can cause substantial agglomeration.
  • step (ii) The amount of free water present in step (ii) is therefore believed to be very important.
  • free water is used herein to mean water that is not firmly bound as water of hydration or crystallisation to inorganic materials. If insufficient is present, the reaction will not proceed rapidly, and unreacted detergent acid precursor will accumulate in the mixer and act as a binder, causing substantial agglomeration, balling up and even dough formation. Thus it would appear that enough water to wet all the solids should be present, but not so much that the water itself will act as a binder.
  • the solids themselves may contain sufficient free water for these conditions to be attained.
  • a spray-dried detergent base powder blown to a relatively high moisture content could provide most or all of the free water required.
  • a carefully controlled amount of water should be added either prior to or concurrently (together or separately) with the addition of the acid precursor. To ensure thorough wetting of the solids before the introduction of the acid precursor, all the water may be added before addition of the acid precursor commences. Alternatively, the acid precursor and the water may be introduced simultaneously into the mixer.
  • a small amount of water sufficient to initiate the neutralisation reaction but not sufficient to cause substantial agglomeration, may be premixed with the acid precursor before the latter is introduced into the high-speed mixer/granulator. If a coloured product is desired, dyestuff may conveniently be premixed with the acid precursor and water before addition to the high-speed mixer/granulator.
  • the amount of water to be added will depend on the nature of the solids present. It has been found that an amount within the range of from 0.5 to 2.0 wt%, preferably from 0.5 to 1.5 wt%, based on the total solids present in steps (i) and (ii), gives good results in the preferred embodiment of the invention in which the neutralising agent is sodium carbonate.
  • step (ii) Another important condition for step (ii) is that the acid precursor be added gradually, so that it will be consumed immediately and will not accumulate in the mixer in unreacted form.
  • the time required and preferred for addition of the acid precursor is of course dependent on the amount to be added, but in general addition preferably takes place over a period of at least 1 minute, more preferably over a period of from 2 to 12 minutes, more preferably from 3 to 10 minutes.
  • liquid detergent ingredients may be introduced during step (ii).
  • examples of such ingredients include nonionic surfactants, and low-melting fatty acids which may be also be neutralised in situ, to form soaps.
  • the neutralisation step (ii) may typically take 2 to 12 minutes, and, as indicated above, the gradual addition of the acid precursor (optionally plus other liquid ingredients) may or may not be preceded by a separate step in which water (optionally plus other liquid ingredients) is added to the mixer.
  • the temperature of the powder mass in the high-speed mixer/granulator should be maintained throughout step (ii) at 55 ° C or below, preferably below 50 ° C, more preferably below 47 ° C, and desirably below 40 ° C.
  • a water jacket may be sufficient, for example, a jacket supplied with water at 25 ° C is generally adequate to achieve temperatures below 47 ° C; but in some cases it may be necessary to provide a cryogenic unit to inject cooling liquid or gas, for example, liquid nitrogen, into the mass of powder. If the temperature is allowed to rise, agglomeration and lump formation may occur.
  • a very important feature of the process of the invention is granulation in the high-speed mixer/granulator. This will generally take the form of a separate granulation step (iii) after addition of the acid precursor and neutralisation are complete. If, however, addition of the liquids takes place over a relatively long period, granulation can occur before addition is complete, and then a separate granulation step (iii) may be unnecessary. In this case, steps (ii) and (iii) of the process may be regarded as having coalesced to form a single continuous step (ii)/(iii).
  • the granulation or densification process leads to a product of very high bulk density.
  • Granulation in the process of the invention requires the presence of a liquid binder, but in an amount significantly lower than that used when granulating a powder in conventional apparatus such as a pan granulator: for example, from 3 to 8 wt% of the total composition, especially about 5 wt%, as compared to 10-15 wt%.
  • the binder is added prior to granulation but after neutralisation is complete. It will generally comprise water and/or a liquid detergent ingredient, for example, an aqueous solution of a polycarboxylate polymer, or a nonionic surfactant, or a mixture of any of these.
  • any free water already present in the composition and releasable at the process temperature generally about 30-50 ° C.
  • hydrated zeolite which contains 27 moles of water per mole, or about 20 wt% of bound water
  • sodium tripolyphosphate hexahydrate would probably release little or no water.
  • the total amount of free water that can be tolerated in the whole process is limited, and generally should not amount to more than 8 wt% of the total composition, preferably not more than 4 wt%.
  • the product of the granulation step (iii) is a particulate solid of high bulk density - at least 650 g/litre, preferably at least 750 g/litre, and more preferably at least 800 g/litre.
  • the particle size distribution is generally such that at least 50 wt%, preferably at least 70 wt% and more preferably at least 85 wt%, of particles are smaller than 1700 am, and the level of fines is low. No further treatment has generally been found to be necessary to remove either oversize particles or fines.
  • step (iii) further ingredients may be admixed to the granulated product of step (iii).
  • minor solid ingredients such as fluorescer and sodium carboxymethylcellulose may be added at this stage rather than included in the initial solids mix.
  • the product generally has good flow properties, low compressibility and little tendency towards caking, those powder properties may be improved further and bulk density further increased by the admixture of a builder salt or a finely divided particulate flow aid after granulation is complete.
  • a preferred builder salt that may be postdosed is sodium tripolyphosphate. This option is of especial interest for powders in which the principal or sole builder is sodium carbonate.
  • the flow aids mentioned above are also suitable for addition at this later stage in the process. Depending on the flow aid chosen, it may suitably be added in an amount of from 0.2 to 12.0 wt%, based on the total product.
  • Suitable flow aids include crystalline and amorphous alkali metal aluminosilicates having an average particle size within the range of from 0.1 to 20 am, preferably from 1 to 10 ⁇ rn.
  • the crystalline material zeolite
  • the amorphous material which is more weight-effective, is preferably added in an amount of from 0.2 to 5.0 wt%, more preferably from 0.5 to 3.0 wt%, based on the total product.
  • a suitable amorphous material is available commercially from Crosfield Chemicals Ltd, Warrington, Cheshire, England, under the trade mark Alusil. If desired, both crystalline and amorphous aluminosilicates may be used, together or sequentially, as flow aids.
  • thermally treated perlite, calcite, and diatomaceous earth are also suitably used in amounts of from 0.2 to 5.0 wt%, preferably from 0.5 to 3.0 wt%, based on the total product.
  • flow aids suitable for use in the process of the invention include precipitated silica, for example, Neosyl (Trade Mark), and precipitated calcium silicate, for example, Microcal (Trade Mark), both commercially available from Crosfield Chemicals Ltd.
  • precipitated silica for example, Neosyl (Trade Mark)
  • precipitated calcium silicate for example, Microcal (Trade Mark)
  • a process which comprises admixing finely divided amorphous sodium aluminosilicate to a dense granular detergent composition containing surfactant and builder and prepared and/or densified in a high speed mixer/granulator is described and claimed in our copending EP-A-339996 filed on 27 April 1989.
  • the process of the invention produces a granular high-bulk-density solid, containing surfactant and builder, and having a bulk density of at least 650 g/litre and preferably at least 700 g/litre. It is also characterised by an especially low particle porosity, preferably not exceeding 0.25 and more preferably not exceeding 0.20, which distinguishes it from even the densest powders prepared by spray-drying.
  • This final granulate may be used as a complete detergent composition in its own right. Alternatively, it may be admixed with other components or mixtures prepared separately, and may form a major or minor part of a final product. Generally, any additional ingredients such as enzymes, bleach and perfume that are not suitable for undergoing the granulation process and the steps that precede it may be admixed to the granulate to make a final product.
  • the densified granulate may typically constitute from 40 to 100 wt% of a final product.
  • the densified granulate prepared in accordance with the present invention is an "adjunct" comprising a relatively high level of detergent-active material on an inorganic carrier; and this may be admixed in a minor amount with other ingredients to form a final product.
  • the process may with advantage be used to prepare detergent compositions containing from 5 to 45 wt%, especially from 5 to 35 wt%, of anionic surfactant, this anionic surfactant being derived wholly or in part from the in-situ neutralisation reaction of step (ii).
  • the process of the invention is of especial interest for the production of detergent powders or components containing relatively high levels of anionic surfactant, for example, 15 to 30 wt%, more especially 20 to 30 wt%, but it is equally useful for the preparation of powders containing lower levels of anionic surfactant.
  • the anionic surfactant prepared at least in part by in-situ neutralisation may, for example, be selected from linear alkylbenzene sulphonates, alpha-olefin sulphonates, internal olefin sulphonates, fatty acid ester sulphonates and combinations thereof.
  • the process of the invention is especially useful for producing compositions containing alkylbenzene sulphonates, by in-situ neutralisation of the corresponding alkylbenzene sulphonic acid.
  • anionic surfactants that may be present in compositions prepared by the process of the invention include primary and secondary alkyl sulphates, alkyl ether sulphates, and dialkyl sulphosuccinates.
  • Anionic surfactants are of course well known and the skilled reader will he able to add to this list by reference to the standard textbooks on this subject.
  • anionic surfactant in salt form (generally aqueous paste or solution) rather than in acid precursor form, may be added after granulation.
  • the post-added anionic surfactant is alpha-olefin sulphonate.
  • solid particulate anionic surfactant at an earlier stage in the process has already been mentioned.
  • the process of the invention represents a versatile route for incorporating high levels of anionic surfactant in powders of high bulk density.
  • nonionic surfactants may also be present. These too are well known to those skilled in the art, and include primary and secondary alcohol ethoxylates.
  • non-soap surfactant for example, cationic, zwitterionic, amphoteric or semipolar surfactants, may also be present if desired.
  • suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • soap may also be present, to provide foam control and additional detergency and builder power.
  • detergent compositions produced by the process of the invention may comprise from 10 to 35 wt% of anionic surfactant, from 0 to 10 wt% of nonionic surfactant, and from 0 to 5 wt% of fatty acid soap.
  • compositions preferably contain a total of from 15 to 70 wt% of water-soluble crystalline inorganic salts, which may comprise, for example, sodium sulphate, sodium ortho- or pyrophosphate, or sodium meta- or orthosilicate.
  • Especially preferred compositions contain from 15 to 50 wt%, more preferably from 20 to 40 wt%, of sodium tripolyphosphate.
  • all these preferred classes of detergent composition may contain conventional amounts of other conventional ingredients, for example, bleaches, enzymes, lather boosters or lather controllers as appropriate, antiredeposition and anti incrustation agents, perfumes, dyes and fluorescers. These may be incorporated in the product at any suitable stage, and the skilled detergent formulator will have no difficulty in deciding which ingredients are suitable for admixture in the high-speed mixer/granulator, and which are not.
  • the process of the invention has the advantage over conventional spray-drying processes that no elevated temperatures are involved, so fewer restrictions are imposed on the way in which heat-sensitive ingredients such as bleaches and enzymes are incorporated into the product.
  • a 750 kg batch of high-bulk-density detergent powder having the following nominal formulation was prepared using a Fukae (Trade Mark) FS-1200 high-speed mixer/granulator:
  • the ratio of zeolite (anhydrous) to total non-soap surfactant in this composition was 1.29:1.
  • the resulting powder was free-flowing, had a bulk density of 850 g/litre, and contained 73 wt% of particles ⁇ 1700 ⁇ m.
  • the particle porosity was 0.15.
  • Coloured speckles of the same powder (0.8 parts) and enzyme granules (0.6 parts) were mixed with the powder using a rolling drum, and perfume (0.25 parts) were sprayed on, to give a fully formulated high-bulk-density detergent powder having excellent powder properties.
  • Example 1 The procedure of Example 1 was repeated, with the difference that the nonionic surfactant was added as a mixture with the acid, instead of during step (iii). A similar powder was obtained.
  • Example 1 The procedure of Example 1 was repeated, with the difference that 5 parts of zeolite were added to the mixer during step (iii), after addition of the binder but before granulation, and only 6 parts of zeolite were added as a flow aid in step (iv). A similar powder was obtained.
  • Example 2 The procedure of Example 2 was repeated, with the difference that half the anionic surfactant was added in step (i) as a powder (Marlon (Trade Mark) A390 ex Hüls). A similar powder was obtained.
  • This Example illustrates a procedure in which in-situ neutralisation is followed by the addition of a spray-dried base powder, and the mix is granulated together in the high-speed mixer/granulator.
  • a 750 kg batch of high-bulk-density detergent powder having the following nominal formulation was prepared using a Fukae (Trade Mark) FS-1200 high-speed mixer/granulator:
  • the ratio of zeolite (anhydrous) to total non-soap surfactant in this composition was 1.29:1.
  • the resulting powder was free-flowing, had a bulk density of 891 g/litre, and contained 80 wt% of particles ⁇ 1700 am.
  • Example 6 Two 750 kg batches (Examples 6 and 7) of high-bulk-density detergent powder having the nominal formulation given in Example 5 was prepared using the Fukae FS-1200 high speed mixer/granulator. The process was carried out as follows:
  • the powder of Example 6 was free-flowing, had a bulk density of 821 g/litre, and contained 81 wt% of particles ⁇ 1700 ⁇ m.
  • the powder of Example 7 was a product of similar bulk density but containing only 69 wt% of particles ⁇ 1700 ⁇ m.
  • a 20 kg batch of high-bulk-density detergent powder having the following nominal formulation was prepared using a Fukae FS-30 high-speed mixer/granulator: The ratio of zeolite (anhydrous) to total non-soap surfactant in this composition was 1.44:1. The process was carried out as follows:
  • the resulting powder was free-flowing, had a bulk density of 830 g/litre, and contained 85 wt% of particles ⁇ 1700 am.
  • Coloured speckles of the same powder (0.8 parts) and enzyme granules (0.61 parts) were mixed with the powder using a rolling drum, and perfume (0.25 parts) were sprayed on, to dive a fully formulated high-bulk-density detergent powder having excellent powder properties.
  • a 20 kg batch of high-bulk-density detergent powder built with sodium tripolyphosphate and sodium carbonate and having the following nominal formulation was prepared using a Fukae FS-30 high-speed mixer/granulator: The ratio of crystalline water-soluble inorganic salts to total non-soap surfactant in this composition was 1.9:1.
  • sodium carbonate was present as a major part of the building system.
  • the sodium carbonate introduced during step (i) (see below) amounted to an approximately 8x excess over the amount required for neutralisation of the alkylbenzene sulphonic acid (see paragraph (ii) below).
  • the process was carried out as follows:
  • the resulting detergent powder was free-flowing, had a bulk density of 875 g/litre, and contained 75 wt% of particles ⁇ 1700 am. Powder properties were excellent: dynamic flow rate was 133 ml/s and compressibility was 2% v/v.
  • a 750kg batch of high-bulk-density detergent powder built with sodium tripolyphosphate and sodium carbonate and having the following nominal formulation was prepared using a Fukae FS-1200 high-speed mixer/granulator: The ratio of crystalline water-soluble inorganic salts to total non-soap surfactant in this composition was 2.5:1. The process was carried out as follows:
  • the resulting detergent powder was free-flowing, had the extremely high bulk density of 1050 g/litre, and contained about 70 wt% of particles ⁇ 1700 ⁇ m. Dynamic flow rate was 71 ml/s and compressibility was 4.7% v/v.
  • a 60 kg batch of high-bulk-density detergent powder having the following nominal formulation was prepared using a Sapphire (Trade Mark) RMG-100 high-speed mixer/granulator: The process was carried out as follows:
  • the resulting powder was free-flowing, homogeneously blue coloured, had a bulk density of 800 g/litre, and contained 90 wt% of particles ⁇ 1700 ⁇ m.
  • the mean particle size was 539 ⁇ m.
  • Dynamic flow rate was 81.1 ml/s, and compressibility was 9.2% v/v.
  • the powder had a rapid rate of dissolution comparable with the best high-bulk-density powders presently on the market:
  • liquid to solid ratios at the end of the neutralisatior step in these Examples were therefore 0.55, 0.57 and 0.60 respectively.
  • Example 20 The powder properties of Examples 20 and 21, as shown in the following table, were not significantly different from those of Example 19.
  • the powder of Example 22 had a higher bulk density but inferior flow properties.
  • Example 27 The general procedure of earlier Examples was used to produce 60 kg batches of sodium carbonate- built powders to the formulations shown below.
  • the alpha-olefin sulphonate was post-added in the form of 70 wt% paste; in Example 29 it was added as 40 wt% solution, after neutralisation but before the addition of the greater part of the calcite.

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Claims (19)

1. Verfahren zur Herstellung einer gekörnten Waschmittelzusammensetzung oder -komponente mit einer Schüttdichte von mindestens 650 g/I, wobei das verfahren den Schritt der Neutralisierung einer flüssigen sauren Vorstufe eines anionischen Tensids mit einem festen wasserlöslichen alkalischen anorganischen Material einschließt, und wobei das Verfahren gekennzeichnet ist durch die Schritte:
(i) Aufwirbeln eines teilchenförmigen festen wasserlöslichen, alkalischen, anorganischen Materials in einer Menge im Überschuß zu jener, die für eine Neutralisation erforderlich ist, gegebenenfalls in Anmischung mit einem oder mehreren anderen teilchenförmigen Feststoffen in einem Hochgeschwindigkeitsmischer/Granulator, der sowohl eine Rührwirkung als auch Schneidwirkung aufweist;
(ii) allmähliche Zugabe der sauren Vorstufe zu dem Hochgeschwindigkeitsmischer/Granulator unter Beibehalten einer Temperatur von nicht mehr als 55 ° C, wodurch Neutralisation der sauren Vorstufe durch das wasserlösliche alkalische anorganische Material stattfindet, während das Gemisch in Teilchenform verbleibt;
(iii) Granulieren des Gemisches in dem Hochgeschwindigkeitsmischer/Granulator in Gegenwart eines flüssigen Bindemittels,

wodurch eine gekörnte Waschmittelzusammensetzung oder -komponente mit einer Schüttdichte von mindestens 650 g/I gebildet wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das teilchenförmige, wasserlösliche, alkalische, anorganische Material Natriumcarbonat umfaßt.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das teilchenförmige, wasserlösliche, alkalische, anorganische Material Natriumcarbonat in Anmischung mit Natriumbicarbonat und/oder Natriumsilicat umfaßt.
4. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß die saure Vorstufe eine lineare Alkylbenzolsulfonsäure ist.
5. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß das Verhältnis von Flüssigkeiten zu Feststoffen am Ende des Schrittes (ii) nicht größer als 0,60 ist.
6. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß in Schritt (ii) die saure Vorstufe innerhalb eines Zeitraums von 2 bis 12 Minuten zugegeben wird.
7. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß Wasser vor oder zusammen mit der sauren Vorstufe in Schritt (ii) in einer Menge von 0,5 bis 2,0 Gew.-%, bezogen auf die in Schritten (i) und (ii) vorliegende Trockenmasse, zugegeben wird.
8. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß die in Schritt (i) vorliegenden Feststoffe Natriumcarbonat in Anmischung mit einem oder mehreren Waschmittelbuildern, ausgewählt aus kristallinen und amorphen Alkalimetallaluminosilicaten, Alkalimetallphosphaten und Gemischen davon, umfassen.
9. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß die in Schritt (i) vorliegenden Feststoffe zusätzlich ein Tensid in Pulverform umfassen.
10. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß die in Schritt (i) vorliegenden Feststoffe ein sprühgetrocknetes Waschmittelgrundpulver umfassen.
11. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß die während Schritt (i) vorliegenden teilchenförmigen Feststoffe eine fein verteilte teilchenförmige Fließhilfe einschließen.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Fließhilfe Zeolith, amorphes Alkalimetallaluminosilicat, thermisch behandelter Perlit, Calcit, Diatomeenerde oder eine beliebige Kombination von diesen ist und in einer Menge von 2 bis 8 Gew.-%, bezogen auf die fertige Zusammensetzung, zugegeben wird.
13. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß die in Schritt (i) vorliegende Menge an gesamten Feststoffen mindestens 60 Gew.-% der in Schritt (ii) vorliegenden gesamten Zusammensetzung beträgt.
14. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß die Gesamtmengen an in den Schritten (i), (ii) und (iii) vorliegendem freiem Wasser 8 Gew.-%, bezogen auf die gesamte Zusammensetzung, nicht übersteigt.
15. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß die Temperatur in dem Hochgeschwindigkeitsmischer/Granulator unterhalb 47 ° C während Schritt (ii) beibehalten wird.
16. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß der Hochgeschwindigkeitsmischer/Granulator Schalenform aufweist und eine im wesentlichen vertikale Rührerachse aufweist.
17. Verfahren nach einem vorangehenden Anspruch, dadurch gekennzeichnet, daß es zusätzlich den Schritt des Anmischens einer fein verteilten teilchenförmigen Fließhilfe in einer Menge von 0,2 bis 12,0 Gew.-% zu der gekörnten Waschmittelzusammensetzung oder -komponente, nachdem der Granulierungschritt (iii) beendet ist, umfaßt.
18. Verfahren nach Anspruch 17, dadurch gekennzeichnet, daß die Fließhilfe fein verteiltes amorphes Natriumaluminosilicat, thermisch behandelter Perlit, Calcit, Diatomeenerde oder eine Kombination davon ist und in einer Menge von 0,2 bis 5,0 Gew.-%, bezogen auf die gesamte Zusammensetzung, zugegeben wird.
19. Verfahren nach Anspruch 17, dadurch gekennzeichnet, daß die Fließhilfe fein verteiltes kristallines Natriumaluminosilicat ist und in einer Menge von 3,0 bis 12,0 Gew.-%, bezogen auf die gesamte Zusammensetzung, zugegeben wird.
EP89307452A 1988-07-21 1989-07-21 Waschmittelzusammensetzungen und Verfahren zu deren Herstellung Revoked EP0352135B1 (de)

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EP0438320A2 (de) * 1990-01-19 1991-07-24 Unilever Plc Reinigungsmittel und Verfahren zu deren Herstellung
WO1992006170A1 (en) * 1990-10-03 1992-04-16 The Procter & Gamble Company Process for preparing high density detergent compositions containing particulate ph sensitive surfactant
EP0506184A1 (de) * 1991-03-28 1992-09-30 Unilever N.V. Waschmittel und Verfahren zu ihrer Herstellung
EP0555622A1 (de) * 1992-02-14 1993-08-18 The Procter & Gamble Company Verfahren zur Herstellung von Detergenskörnchen durch Neutralisation von Sulfonsäuren
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
EP0578872A1 (de) * 1992-07-15 1994-01-19 The Procter & Gamble Company Waschmittelzusammensetzungen
US5298183A (en) * 1990-06-06 1994-03-29 Lever Brothers Company, Division Of Conopco, Inc. Soap powder compositions
WO1995029215A1 (en) * 1994-04-20 1995-11-02 The Procter & Gamble Company Process for the manufacture of free-flowing detergent granules
US5565422A (en) * 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility
US5573697A (en) * 1995-05-31 1996-11-12 Riddick; Eric F. Process for making high active, high density detergent granules
US5614485A (en) * 1990-07-10 1997-03-25 The Procter & Gamble Company Process for making a granular dishwashing composition by agglomerating ingredients and admixing solid alkali metal silicate
US5703037A (en) * 1994-04-20 1997-12-30 The Procter & Gamble Company Process for the manufacture of free-flowing detergent granules
US5929021A (en) * 1995-12-20 1999-07-27 Lever Brothers, Division Of Conopco, Inc. Process for preparing a granular detergent
US6051545A (en) * 1997-06-06 2000-04-18 Lever Brothers Company Division Of Conopco, Inc. Cleaning compositions
US6066615A (en) * 1998-02-10 2000-05-23 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions
US6191095B1 (en) * 1997-05-30 2001-02-20 Lever Brothers Company, A Division Of Conopco, Inc. Detergent compositions
US6576605B1 (en) * 1998-10-28 2003-06-10 The Procter & Gamble Company Process for making a free flowing detergent composition

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GB8818613D0 (en) * 1988-08-05 1988-09-07 Paterson Zochonis Uk Ltd Detergents
DE4216629A1 (de) * 1992-05-20 1993-11-25 Henkel Kgaa Verfahren zur Herstellung aniontensidhaltiger Wasch- und Reinigungsmittel
DE4232874A1 (de) * 1992-09-30 1994-03-31 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
WO1997017422A1 (en) * 1995-11-06 1997-05-15 Kao Corporation Method for producing crystalline alkali metal silicate granules and granular high density detergent
DE19600466A1 (de) * 1996-01-09 1997-07-10 Henkel Kgaa Verfahren zur Herstellung von granularen Wasch- oder Reinigungsmitteln bzw. Komponenten hierfür
TW397862B (en) * 1996-09-06 2000-07-11 Kao Corp Detergent granules and method for producing the same, and high-bulk density detergent composition
DE19700776A1 (de) * 1997-01-13 1998-07-16 Henkel Kgaa Granulares Waschmittel mit verbessertem Fettauswaschvermögen
DE19758811B4 (de) 1997-03-11 2008-12-18 Henkel Ag & Co. Kgaa Waschmittelpressling
DE19710254A1 (de) 1997-03-13 1998-09-17 Henkel Kgaa Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt
DE69817811T2 (de) 1997-05-30 2004-04-01 Unilever N.V. Rieselfähige körnige waschmittelzusammensetzungen
GB9711829D0 (en) 1997-06-06 1997-08-06 Unilever Plc Detergent compositions
DE60016428T2 (de) * 1999-08-20 2005-11-24 Kao Corp. Verfahren zur herstellung von waschmitteln mit hoher schüttdichte
DE10232304B4 (de) * 2002-07-17 2005-10-27 Henkel Kgaa Neutralisation im Mischer
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US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
TR27438A (tr) * 1990-01-19 1995-05-24 Unilever Nv Granül yapisinda deterjan terkipleri ve bunlari hazirlamaya mahsus yöntem.
EP0438320A3 (en) * 1990-01-19 1992-02-19 Unilever Plc Detergent compositions and process for preparing them
EP0438320A2 (de) * 1990-01-19 1991-07-24 Unilever Plc Reinigungsmittel und Verfahren zu deren Herstellung
US5298183A (en) * 1990-06-06 1994-03-29 Lever Brothers Company, Division Of Conopco, Inc. Soap powder compositions
US5614485A (en) * 1990-07-10 1997-03-25 The Procter & Gamble Company Process for making a granular dishwashing composition by agglomerating ingredients and admixing solid alkali metal silicate
US5527489A (en) * 1990-10-03 1996-06-18 The Procter & Gamble Company Process for preparing high density detergent compositions containing particulate pH sensitive surfactant
WO1992006170A1 (en) * 1990-10-03 1992-04-16 The Procter & Gamble Company Process for preparing high density detergent compositions containing particulate ph sensitive surfactant
EP0506184A1 (de) * 1991-03-28 1992-09-30 Unilever N.V. Waschmittel und Verfahren zu ihrer Herstellung
US5282996A (en) * 1991-03-28 1994-02-01 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions and process for preparing them
EP0555622A1 (de) * 1992-02-14 1993-08-18 The Procter & Gamble Company Verfahren zur Herstellung von Detergenskörnchen durch Neutralisation von Sulfonsäuren
TR26854A (tr) * 1992-02-14 1994-08-19 Procter & Gamble Sülfonik asitlerin nötralizasyonuyla deterjan zerrelerinin yapilmasi icin islem.
EP0578872A1 (de) * 1992-07-15 1994-01-19 The Procter & Gamble Company Waschmittelzusammensetzungen
TR28449A (tr) * 1992-07-15 1996-07-04 Procter & Gamble Mükemmel bir beyaz görünüme sahip yüksek aktiviteli deterjan terkipleri.
WO1995029215A1 (en) * 1994-04-20 1995-11-02 The Procter & Gamble Company Process for the manufacture of free-flowing detergent granules
US5703037A (en) * 1994-04-20 1997-12-30 The Procter & Gamble Company Process for the manufacture of free-flowing detergent granules
US5573697A (en) * 1995-05-31 1996-11-12 Riddick; Eric F. Process for making high active, high density detergent granules
US5565422A (en) * 1995-06-23 1996-10-15 The Procter & Gamble Company Process for preparing a free-flowing particulate detergent composition having improved solubility
US5929021A (en) * 1995-12-20 1999-07-27 Lever Brothers, Division Of Conopco, Inc. Process for preparing a granular detergent
US6191095B1 (en) * 1997-05-30 2001-02-20 Lever Brothers Company, A Division Of Conopco, Inc. Detergent compositions
US6051545A (en) * 1997-06-06 2000-04-18 Lever Brothers Company Division Of Conopco, Inc. Cleaning compositions
US6066615A (en) * 1998-02-10 2000-05-23 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions
US6576605B1 (en) * 1998-10-28 2003-06-10 The Procter & Gamble Company Process for making a free flowing detergent composition

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EP0352135A1 (de) 1990-01-24
DE68918522D1 (de) 1994-11-03
HK142995A (en) 1995-09-15
TR27078A (tr) 1994-10-18
DE68918522T2 (de) 1995-03-09
IN170991B (de) 1992-06-27
JPH0333199A (ja) 1991-02-13
ES2063826T3 (es) 1995-01-16
JPH0678558B2 (ja) 1994-10-05
BR8903627A (pt) 1990-03-13
PH26671A (en) 1992-09-15

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