EP0424403A1 - Adsorbant granulaire a facilite amelioree de rincage - Google Patents

Adsorbant granulaire a facilite amelioree de rincage

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Publication number
EP0424403A1
EP0424403A1 EP89906072A EP89906072A EP0424403A1 EP 0424403 A1 EP0424403 A1 EP 0424403A1 EP 89906072 A EP89906072 A EP 89906072A EP 89906072 A EP89906072 A EP 89906072A EP 0424403 A1 EP0424403 A1 EP 0424403A1
Authority
EP
European Patent Office
Prior art keywords
weight
water
adsorbent
composition according
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP89906072A
Other languages
German (de)
English (en)
Inventor
Elmar Wilms
Lothar Pioch
Günther VOGT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0424403A1 publication Critical patent/EP0424403A1/fr
Pending legal-status Critical Current

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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
    • C11D3/12—Water-insoluble compounds
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • 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
    • C11D3/2079—Monocarboxylic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention relates to a granular adsorbent with a high absorption capacity for liquid to pasty detergent and cleaning agent components, in particular liquid or, when heated, nonionic surfactants that melt, which is particularly suitable for use in phosphate-free or low-phosphate detergents and cleaning agents. It has a significantly improved washing-in behavior, i. H . it does not form undissolved residues in the washing-in devices of washing machines and moreover improves the washing-in behavior of detergent mixtures in such devices.
  • nonionic surfactants have a very high cleaning capacity, which makes them particularly suitable for use in cold detergents or. Makes 60 ° C detergents suitable. However, their proportion cannot be increased significantly beyond 8 to 10% by weight in the generally customary production of detergents by means of spray drying, since otherwise there is excessive smoke formation in the exhaust air from the spray towers and inadequate pouring properties of the spray powder. Processes have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance.
  • Loose in particular spray-dried phosphates, borates or perborate, sodium aluminosilicate (zeolite), silicon dioxide (Aerosil) or salt mixtures previously prepared in a certain manner, eg. B. proposed from sodium carbonate and sodium bicarbonate, but all known agents have know disadvantages.
  • Phosphates are often undesirable because of their eutrophic properties.
  • Borates or perborates have only a limited absorption capacity for liquid substances, which also applies to finely powdered zeolites, while special adsorbents, such as diatomaceous earth and aerosil, do not contribute to the washing action as inert components.
  • Absorbent carrier granules which consist of several components and are usually produced by spray drying, are e.g. B. from US 3 849 327, US 3 886 098 and US 3 838 027 and US 4 269 722 (DE 27 42 683) known.
  • these carrier grains which have been developed especially for the adsorption of nonionic surfactants, contain considerable amounts of phosphates, which limits their possible uses.
  • Phosphate-free carrier grains are known from DE 32 06 265. They consist of 25 to 52% sodium carbonate or bicarbonate, 10 to 50% zeolite, 0 to 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate.
  • a granular adsorbent is known from EP 184 794 (US Pat. No. 4,707,290) which can absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight zeolite, 0 , 1 to 8% by weight of sodium silicate, 3 to 15% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight contains nonionic surfactants and can be obtained by spray drying.
  • nonionic surfactants based on anhydrous substance
  • the invention accordingly relates to a granular adsorbent with a high absorption capacity for liquid to pasty detergents and cleaning agents and improved washing-up behavior, consisting essentially of
  • soap 1 to 6% by weight of soap, derived from essentially saturated fatty acids with 12 to 24 carbon atoms in the form of the sodium and / or potassium soap,
  • Suitable zeolites have no particles with a size of more than 30 ⁇ m and consist of at least 80% of particles with a size of less than 10 ⁇ m. Their average particle size (volume distribution, measuring method: Coulter Counter) is in the range from 1 to 10 ⁇ m. Your calcium binding capacity, which is determined according to the information in DE 24 12 837, lies in the range from 100 to 200 mg CaO / g. The zeolites can still contain excess alkali from their production.
  • the component (b) consists of a water-soluble soap, preferably a sodium soap, which is derived from saturated fatty acids with 12 to 24, preferably 14 to 22, carbon atoms, and their mixtures with oleic acid, the proportion of saturated fatty acids should be at least 50% by weight, preferably at least 75% by weight.
  • a water-soluble soap preferably a sodium soap, which is derived from saturated fatty acids with 12 to 24, preferably 14 to 22, carbon atoms, and their mixtures with oleic acid, the proportion of saturated fatty acids should be at least 50% by weight, preferably at least 75% by weight.
  • Examples are soaps made from coconut oil, tallow oil and hardened rapeseed oil fatty acids, hardened fish oil fatty acids and their mixtures. Their proportion is 1.0 to 6, preferably 1.5 to 5 and in particular 2 to 4% by weight.
  • the component (c) consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts being preferred.
  • Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid.
  • Suitable copolymers are those of acrylic acid with methacrylic acid or. Copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers such as vinyl methyl ether or. Vinyl ethyl ether, further with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
  • copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 70 mole percent, preferably less than 50 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as described in more detail in EP 25 551 -B1, have proven to be particularly suitable. These are copolymers that contain 40 to 90% by weight of acrylic acid or. Methacrylic acid and 60 to 10 wt. -% contain maleic acid. Such copolymers are particularly preferred in which 45 to 85 percent by weight of acrylic acid and 55 to 15 percent by weight of malic acid are present.
  • the molecular weight of the homo- or. Copolymers are generally 2,000 to 150,000, preferably 5,000 to 100,000.
  • Their proportion of the adsorbent is 1 to 12% by weight, preferably 1.5 to 8% by weight. % and in particular 2 to 5% by weight, calculated as the sodium salt.
  • the resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. With a share of 1.5 wt. -% sufficient abrasion resistance is already achieved for many cases. Mixtures with 2 to 5% by weight of sodium salt of polyacid have optimal abrasion properties.
  • the weight ratio of soap (b) to polymeric acid sodium salt (c) is in the range from 2.5: 1 to 1: 5, in particular in the range from 1.5: 1 to 1: 4 . These areas are characterized by good flushing results. Stronger Deviations, especially higher soap contents at the expense of the polymer acid content, lead to less favorable values.
  • the sodium sulfate (component d), calculated as an anhydrous substance, is present in proportions of 0 to 25% by weight, preferably 0, 5 to 22 and in particular 3 to 20% by weight.
  • the sodium suifate can contribute to a considerable improvement in the grain structure and the flushing-in behavior of the agents and at the same time increases their bulk density, which results in the possibility of saving packaging and transport volume.
  • the adsorbent can contain nonionic surfactants in proportions of up to 5% by weight, preferably 0 to 4% by weight, and in particular 0.3 to 3% by weight.
  • Suitable nonionic surfactants are, in particular, ethoxylation products of linear or methyl-branched (oxo radical) alcohols with 12 to 18 carbon atoms and 3 to 10 ethylene glycol ether groups. Also useful are ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides, which correspond to the fatty alcohol ethoxyates described in terms of the number of carbon atoms in the hydrophobic radical and the glycol ether groups.
  • Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups are also useful.
  • block polymers of ethylene oxide and propylene oxide, which are commercially available under the Pluronics name, are also suitable.
  • the nonionic surfactants can be present if, in the production of the granular adsorbents, aqueous zeolite dispersions are used, in which these surfactants act as dispersion stabilizers. In individual cases, the nonionic surfactants can also be completely or partially replaced by other dispersion stabilizers, as described in DE 25 27 388 (US Pat. No. 4,072,622).
  • the difference of up to 100% by weight is due to water, which is present in a bound form and as moisture, the major amount being bound to the zeolite.
  • a proportion of the water which is about 8 to 18 wt .-% (based on the agent) can be removed at a drying temperature of 145 ° C.
  • Another portion which is between 4 and 8% by weight depending on the zeolite content, is released at the annealing temperature (800 ° C.) and corresponds to the water stored in the crystal lattice of the zeolite.
  • the average grain size of the adsorbent is 0.2 to 1.2 mm, the proportion of the grains below 0.05 mm less than 1% by weight, preferably less than 0.5% by weight and above 2 mm not more than Is 5% by weight.
  • at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.1 to 1.2 mm, the proportion of the grains preferably no longer being between 0.1 and 0.05 mm than 3% by weight, in particular less than 1% by weight, the proportion of the grains between 0.1 and 0.2% by less than 20% by weight, in particular less than 10% by weight, and the proportion the grain between 1.2 and 2 mm is not more than 10% by weight, in particular not more than 5% by weight.
  • the bulk density of the adsorbent is 350 to 680 g / l, preferably 400 to 650 g / l.
  • the agent consists essentially of rounded grains, which have a very good flow behavior. This very good flow behavior is also given when the grains are impregnated with large proportions of liquid or semi-liquid detergent components, in particular nonionic surfactants.
  • the proportion of these adsorbed components can be 10 to 35% by weight, preferably 15 to 30% by weight, based on the adsorbate.
  • the invention further relates to a process for the production of the granular adsorbent according to the invention.
  • This The process is characterized in that an aqueous batch containing the components (a) to (c) and, if appropriate, the components (d), (e) and additional alkali metal hydroxide, with a total of 40 to 55% by weight of anhydrous components Ingredients sprayed into a drop room by means of nozzles and dried to a moisture content of 8 to T8% by weight that can be removed at 145 ° C. by means of drying gases which have an inlet temperature of 150 to 280 ° C. and an outlet temperature of 50 to 120 ° C. .
  • the aqueous batch can be prepared by mixing the dry or water-containing constituents with the addition of the water required for liquefaction.
  • the zeolite can be used as a spray-dried powder or granulate or as a water-containing filter cake or as an aqueous dispersion. If spray dried zeolite granules are used as the starting material, they can already contain polymers and / or the sodium sulfate or. contain a portion of it. Instead of the soap or the salts of the polymeric carboxylic acids, the corresponding free acids can also be incorporated and the alkali required for salt formation can be added separately. An addition of alkali hydroxide, in particular NaOH, is also recommended in order to reduce the aqueous zeolite suspension or.
  • the slurry alkaline ie to a pH of at least 8 and provide a sufficient alkali excess so that the pH does not drop to less than 8 during spray drying.
  • a lowering of the pH value which would lead to a loss of activity of the zeolite, can be brought about by CO_ in the dry gas.
  • the addition of NaOH which ensures a sufficient alkali reserve, can be, for example, up to 3% by weight. In general, 0.2 to 1% by weight is sufficient.
  • the content of water-free ingredients in the aqueous mixture is preferably 43 to 50% by weight. Its temperature is advantageously 50 to 100 ° C and its viscosity 2,000 to 20,000 mPa's, usually from 8,000 to 14,000 mPa's.
  • the atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar.
  • the drying gas which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent.
  • the inlet temperature measured in the ring channel (i.e. immediately before entering the lower part of the tower), is preferably 150 to 280 ° C. 170 to 250 ° C.
  • the exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 130 ° C., preferably 55 to 115 ° C.
  • the spray drying is conducted so that the grain size of the spray product has the distribution specified above. Existing fine and coarse grains are screened before further processing. It has been shown that the rinsing behavior of the adsorbent impregnated with nonionic surfactants deteriorates with increasing proportion of fine grain.
  • the adsorbent is to be impregnated with nonionic surfactants, these can be sprayed onto the spray product which is still warm or onto the spray product which has already cooled or has been warmed up again after cooling. Heating the nonionic surfactant to temperatures between 35 and 60 ° C, preferably 40 to 50 ° C, accelerates the adsorption process.
  • the abrasion resistance and shape consistency of the grains is in compliance with the specified proportions or. Production conditions so high that the freshly prepared, but especially the cooled and, if necessary, reheated, ripened grains are treated, mixed and conveyed with the liquid additives under the usual spray mixing conditions can be made without the formation of fine fractions or coarser aggiomerates.
  • Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be present in proportions of 0.03 to 3, preferably 0.05 to 2% by weight, based on the adsorbent loaded with additive. For example, B.
  • finely powdered zeolites silica airgel (Aerosil), colorless or colored pigments, such as titanium dioxide, and other powder materials already proposed for powdering granules or detergent pellets, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxyimethylcellulose.
  • a treatment is generally not necessary, especially since the dispensability is not improved thereby.
  • the additives to be adsorbed can consist of known non-ionic surfactants, as are usually used in washing and cleaning agents.
  • suitable additives are organic solvents, with which the cleaning ability of detergents and cleaning agents is improved, in particular with respect to greasy soiling, and which can in this way be incorporated into a granular cleaning agent without problems.
  • sensitive substances such as enzymes, bioeides, fragrances, bleach activators, softening agents, optical brighteners and anionic or cationic surfactants can also be mixed with the adsorbents after prior dissolution or dispersion in organic solvents or the liquid or melted nonionic surfactants. These substances come together with the solvent or dispersant in the porous grain and are thus protected against interactions with other powder components.
  • Preferred detergent constituents which are bound to the adsorbent and are present together with this as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of the polyglycol ethers, derived from alcohols having 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
  • EO ethylene oxide
  • PO propylene oxide
  • They reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation. The number of EO or. For technical alkoxylates, PO groups correspond to the statistical mean.
  • ethoxylated fatty alcohols examples include C 2-18 ⁇ coconut alcohols with 3 to 12 EO, C., g- tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and corresponding ethoxylation products obtainable from other native fatty alcohol mixtures Chain and EO distribution. From the series of ethoxylated oxo alcohols are, for example, those of the composition
  • nonionic surfactants additionally contain a compound which is difficult or not soluble in water, but does have a dispersible polar, hydrophobic radical. Examples of this are free, soap-forming fatty acids.
  • Partial esters of polyhydric alcohols such as partial glycerides and fatty acid glycol ester, fatty acid amides, fatty acid partial amides of alkylene diamines and hydroxyalkyl alkylene diamines, fatty amines, quaternary
  • the number of carbon atoms in the hydrophobic radicals should be at least 10, usually 12 to 1 8.
  • the quantitative ratio of nonionic surfactant to sparingly soluble additional compound is 99: 1 to 70:30. It is essential for the success that the nonionic surfactant and additive are mixed together beforehand. A successive application of the individual substances to the adsorbent does not lead to an improvement in the solubility and flushing behavior.
  • Preferred examples of this group are coconut, tallow and rapeseed fatty acids, which can also be hardened, mixtures of tallow fatty acid partial glyceride and the tallow acid partial diamide of hydroxyethyl-ethylenediamine, dr-taigalkyl-dimethyl-ammonium chloride and the disodium salt of alpha sulfo fatty acids, derived from hardened C .. _. "Fatty acids.
  • the granular adsorbents impregnated with the nonionic surfactants or with the mixtures of nonionic surfactant and additive can be combined with further powdery to granular detergents or detergent components, such as those, for example are obtainable by spray drying or granulation, or can also be mixed with bleaching agents or with a known composition containing bleaching agents in any ratio.
  • granular detergents or detergent components such as those, for example are obtainable by spray drying or granulation
  • bleaching agents or with a known composition containing bleaching agents in any ratio are of great advantage, since an undesirable formation of abrasion and dust is avoided.
  • the powder mixtures are stable in storage and do not tend to scale or exude the nonionic surfactant. When used, they are particularly easy to flush in compared to known agents.
  • the zeolite used had a calcium binding capacity of 165 mg CaO / g and an average particle size of 3 ⁇ m, with no proportions above 20 ⁇ m. It was used as an aqueous dispersion containing 48% by weight of anhydrous zeolite, 1.5% by weight of component (s) and 53.1% by weight of water.
  • the polycarboxylic acid is a copolymer of acrylic acid and maleic acid with an r ⁇ »M Moolleekkuullaarrggeewwiicchhtt was ooff 7700 0000 (Sokalan) in the form of Natriumsal- zes used accommodated.
  • the slurry which had a temperature of 85 ° C. and a viscosity of 10 200 mPa.s, was sprayed with a pressure of 40 AT in a tower in which combustion gases at a temperature of 226 ° C. (measured in the ring channel) were directed towards the spray product were.
  • the outlet temperature of the dry gas was 60 ° C.
  • the granular adsorbent leaving the spray tower contained
  • the liter weight was 563 g / l.
  • the grains were sprayed in a spray mixing apparatus consisting of a horizontally arranged cylindrical drum equipped with mixing and conveying elements and spray nozzles (L ⁇ DIGE mixer) with nonionic surfactants or surfactant mixtures heated to approx. 50 ° C.
  • the temperature of the adsorbent was 20 ° C.
  • the surfactant melt consisted of (based on the final weight of the impregnated granulate):
  • Dry sea sand with the following grain spectrum was chosen as the reference substance.
  • the run-off time of the dry sand after opening the outflow opening was set at 100%.
  • the pourability of the products according to the invention is given in%, based on this 100% value. Values above 75% are considered very good.
  • washing-in behavior was investigated, conditions being simulated which correspond to a washing-in device of a household washing machine operated under critical conditions.
  • 100 g of product were introduced into the test device (ZANUSSI induction channel) and, after a rest period of 1 minute, 10 liters of tap water were fed in within 90 seconds. After flushing in 10 liters, the remaining residues were weighed back in the wet state and 30% of the weight was calculated as water. The following ratings were awarded for induction washing:
  • C more than 10 g of residue (stating the residue in g).
  • a and B values are very good to satisfactory in practice.
  • C values indicate inadequate induction washing.
  • the adsorbent had a flushing grade of A 5.
  • 2 series of tests were carried out, namely with the impregnated adsorbent without the addition of a detergent and a mixture of 25 parts of the impregnated adsorbent and 75 parts of a detergent, consisting of 50 parts of tower spray powder, 20 parts of sodium perborate and 5 parts of further granular constituents, containing defoamers, enzymes, fragrances and bleach activators (designation "with W").
  • the tower spray penver had the following composition (in
  • Granules of the following composition produced (in% by weight):
  • the liter weight was 590 g / l.
  • the sieve analysis showed the following grain distribution:
  • Example 2 As described in Example 1, 84 pbw of the adsorbent were impregnated in a spray-mixing apparatus with 16 pbw of a molten surfactant mixture according to Example 2.
  • the bulk weight of the product was 710 g / l, the flow behavior 80% and the wash-in test A8.
  • a mixture of 20 pbw of these granules, 80 pbw of the spray-dried detergent used in Examples 1-4, 15 pbw of sodium perborate and 5 pbw of other granular constituents gave the wash-in test value A6 under the same test conditions.
  • a granular adsorbent prepared as described in Example 1 had the following composition (in% by weight):
  • the product After screening fine and coarse fractions, the product had a bulk density of 580 g / l with the following particle size distribution:
  • aqueous slurry was prepared using a spray-dried zeolite granulate. These granules consisted of a mixture of zeolite (with a water content of 20% by weight) and from anhydrous sodium sulfate. Na polyacrylate (MW 32,000), coconut tallow soap and sodium hydroxide were also added to the slurry. The water content of the slurry was 52.5% by weight (including the water bound to the zeolite). The slurry, which had a temperature of 88 ° C., was spray-dried in the spray tower by the countercurrent method, the drying gases having an inlet temperature of 130 ° C. and an outlet temperature of 67 ° C. The granules had the following composition (in% by weight): 59.0% zeolite (anhydrous) 0.6% NaOH

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Un mélange granulaire fabriqué par séchage par pulvérisation renferme (a) 45-75 % en poids de zéolite, (b) 1-6 % en poids d'un savon hydrosoluble composé essentiellement d'acides gras C12-18, (c) 1-12 % en poids d'homo- ou copolymères d'acide acrylique, d'acide méthacrylique ou d'acide maléique ou bien de leurs sels hydrosolubles, calculés sous forme de sel de sodium, (d) 0-25 % en poids de sulfate de sodium, (e) 0-5 % en poids de tensio-actifs du type dérivés non ioniques d'éther de polyglycol, (f) 10-22 % en poids d'eau. Ledit mélange présente une granulométrie moyenne de 0,2 à 1,2 mm et une masse volumique apparente de 350 à 680 g/l. Le produit s'utilise comme additif d'agent de lavage, est caractérisé par une capacité élevée à adsorber des constituants d'agent de lavage allant d'une consistance liquide à une consistance pâteuse, en particulier des détergents non ioniques, ainsi que par une facilité améliorée de rinçage dans des lave-linge à usage domestique.
EP89906072A 1988-06-03 1989-05-26 Adsorbant granulaire a facilite amelioree de rincage Pending EP0424403A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3818829 1988-06-03
DE3818829A DE3818829A1 (de) 1988-06-03 1988-06-03 Koerniges adsorptionsmittel mit verbessertem einspuelverhalten

Publications (1)

Publication Number Publication Date
EP0424403A1 true EP0424403A1 (fr) 1991-05-02

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP89109494A Expired - Lifetime EP0344629B1 (fr) 1988-06-03 1989-05-26 Composition adsorbente granulaire avec une capacité de dégagement ameliorée
EP89906072A Pending EP0424403A1 (fr) 1988-06-03 1989-05-26 Adsorbant granulaire a facilite amelioree de rincage

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP89109494A Expired - Lifetime EP0344629B1 (fr) 1988-06-03 1989-05-26 Composition adsorbente granulaire avec une capacité de dégagement ameliorée

Country Status (9)

Country Link
US (1) US5139693A (fr)
EP (2) EP0344629B1 (fr)
JP (1) JP2633045B2 (fr)
KR (1) KR960012274B1 (fr)
AT (1) ATE98294T1 (fr)
DE (2) DE3818829A1 (fr)
DK (1) DK272790D0 (fr)
ES (1) ES2047059T3 (fr)
WO (1) WO1989012087A1 (fr)

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3931871A1 (de) * 1989-09-23 1991-04-04 Henkel Kgaa Granulares, phosphatfreies wasserenthaertungsmittel
GB8924294D0 (en) * 1989-10-27 1989-12-13 Unilever Plc Detergent compositions
DE3936405A1 (de) * 1989-11-02 1991-05-08 Henkel Kgaa Koerniges, nichtionische tenside enthaltendes additiv fuer wasch- und reinigungsmittel mit verbessertem einspuelverhalten
IT1237749B (it) * 1989-12-29 1993-06-15 Carello Spa Proiettore orientabile per veicoli
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ATE98294T1 (de) 1993-12-15
JPH03504734A (ja) 1991-10-17
ES2047059T3 (es) 1994-02-16
KR960012274B1 (ko) 1996-09-18
DE58906340D1 (de) 1994-01-20
KR900701993A (ko) 1990-12-05
JP2633045B2 (ja) 1997-07-23
US5139693A (en) 1992-08-18
EP0344629A1 (fr) 1989-12-06
DK272790A (da) 1990-11-15
DK272790D0 (da) 1990-11-15
WO1989012087A1 (fr) 1989-12-14
EP0344629B1 (fr) 1993-12-08
DE3818829A1 (de) 1989-12-14

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