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
  • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D11/02—Preparation in the form of powder by spray drying
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • 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 high absorption capacity for liquid to pasty detergent and cleaning agent components, in particular liquid or non-ionic surfactants melting at temperatures below 40 C, which is particularly suitable for use in phosphate-free or low-phosphate detergents and cleaning agents.
• nonionic surfactants have a very high cleaning ability, which makes them particularly suitable for use in cold detergents or 60 C detergents.
• their proportion cannot be increased significantly beyond 8 to 10 percent 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 poor 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 prepared beforehand in a certain manner have been proposed as the carrier substance, but all known agents have certain disadvantages.
• Phosphates are often undesirable because of their eutrophic properties.
• Borates and perborates have only beschr like nktes absorption capacity for liquids, which also applies to finely powdered zeolites, while special adsorbent such as diatomaceous earth and aerosil, increase the ash content in the detergent or on the material to be cleaned and do not contribute to the wash action.
• the component (a), which is present in proportions of 60 to 80, preferably 65 to 75 percent by weight, consists of synthetic, bound water-containing sodium aluminosilicate, preferably of the zeolite A type. It is also possible to use zeolite NaX and its mixtures with zeolite NaA, the proportion of zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%. Suitable zeolites have no particles larger than 30 microns and consist of at least 80% particles smaller than 10 microns. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg Ca0 / g.
• the proportion of sodium silicate is 0.1 to 5 percent by weight, preferably 0.2 to 3 percent 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, furthermore 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 60 mole percent.
• Copolymers of acrylic acid or methacrylic acid with maleic acid as are characterized, for example, in EP 25 551-B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90 percent by weight of acrylic acid or methacrylic acid and 60 to 10 percent by weight of maleic acid. Particularly preferred are those copolymers in which 45 to 85 percent by weight acrylic acid and 55 to 15 percent by weight maleic acid are present.
• the molecular weight of the homo- or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000.
• Their proportion of the adsorbent is 3 to 15 percent by weight and preferably 4 to 12 percent by weight.
• the resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. With a proportion of 4 to 5 percent by weight, sufficient abrasion resistance is already achieved. Mixtures with 8 to 12 percent by weight polyacid or its salts have optimal abrasion properties.
• the moisture content which can be removed at a drying temperature of 145 ° C. is 8 to 18 percent by weight, preferably 10 to 16 percent by weight. Other amounts of water bound by the zeolite that are released at higher temperatures are not included in this amount.
• the adsorbent can contain nonionic surfactants in proportions of up to 5 percent by weight, preferably 0.5 to 4 percent 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.
• ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides which correspond to the fatty alcohol ethoxylates described with regard to 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 can also be used.
• block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics® are also suitable.
• the nonionic surfactants are usually present when aqueous zeolite dispersions in which the surfactants function as dispersion stabilizers are used as the starting point for the production of the granular adsorbents. In individual cases, the nonionic surfactants can also be replaced in whole or in part by other dispersion stabilizers, as described in DE 25 27 388.
• the average grain size of the adsorbent is 0.2 to 1.2 mm, the proportion of the grains being below 0.05 mm not more than 2 percent by weight and above 2 mm not more than 5 percent by weight.
• at least 80 percent by weight, in particular at least 90 percent by weight, of the grains have a size of 0.1 to 1.2 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 10 percent by weight, in particular not more than 5 Weight percent, and the proportion of grains between 1.2 and 2 mm is also not more than 10 weight percent, in particular not more than 5 weight percent.
• the bulk density of the adsorbent is 400 to 700 g / l, preferably 500 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, which can amount to up to 40 percent by weight, based on the adsorbate, of liquid or semi-liquid detergent components, in particular nonionic surfactants. With regard to these properties, they are superior to the carrier grain materials which have been disclosed hitherto and have been proposed as useful for detergents and cleaning agents.
• the invention further relates to a method for producing the granular adsorbent according to the invention.
• This process is characterized in that an aqueous batch of constituents (a) to (c) and optionally (e), which contains 50 to 65 percent by weight of water, is sprayed into a falling space by means of nozzles and by means of drying gases which have an inlet temperature of 150 to 280 C and have an outlet temperature of 50 to 120 ° C, to a removable moisture content of 145 C from 8 to 18 weight percent.
• the water content of the aqueous batch is preferably 55 to 62 percent by weight. Its temperature is advantageously 50 to 100 ° C and its viscosity 5,000 to 20,000 mPa ⁇ s.
• the atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar. It is expedient to use two-component nozzles into which compressed air can also be introduced in addition to the batch to be sprayed.
• 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 (ie immediately before entering the lower part of the tower), is 150 to 280 ° C., preferably 180 to 250 ° C. and especially 190 to 230 ° C.
• the exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 120 ° C., preferably 55 to 105 ° C.
• 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.
• the abrasion resistance and constancy of shape of the grains is so high if the specified proportions or production conditions are observed that even the freshly prepared, but especially the cooled and, if necessary, reheated, mature grains can be treated, mixed and conveyed with the liquid additives under the usual spray mixing conditions without the formation of fine fractions or coarser agglomerates.
• 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 used in proportions of 0.03 to 3, preferably 0.05 to 2 percent by weight, based on the adsorbent loaded with additive will.
• pulverulent zeolites for example pulverulent zeolites, silica airgel (AerosilUR), colorless or colored pigments such as titanium dioxide and other, previously proposed for powders of grains or powder detergent materials such as finely powdered Natriumtripoly p HOS phosphate, sodium sulfate, magnesium silicate and carboxymethyl cellulose.
• the granular adsorbents can also be coated with a film of water-soluble polymers after the additives have been applied.
• Useful coating agents are e.g. Water-soluble cellulose ethers or the polymers mentioned as component (b) and also polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylamide.
• the additives to be adsorbed can consist of known nonionic 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, especially against greasy soiling is improved and can be easily incorporated into a granular detergent in this way.
• sensitive substances such as enzymes, biocides, fragrances, bleach activators, softening agents, optical brighteners and anionic or cationic surfactants can be added to the adsorbents after they have been dissolved or dispersed in organic solvents or the liquid or melted nonionic surfactants. These substances penetrate into the porous grain together with the solvent or dispersant and are thus protected against interactions with other powder components.
• the adhesive agents according to the invention can also be produced by build-up granulation, for example by introducing the powdered zeolite (a), an aqueous solution of sodium silicate (b) and an aqueous solution of the polymeric carboxylic acid (c) or their salt into a fluidized bed and granulated and dried in it.
• This build-up granulation can be carried out either continuously or in batches.
• the adsorbents according to the invention are distinguished by favorable grain properties, in particular by good pourability and high grain strength. With regard to their grain strength, they differ advantageously from granules which consist only of aluminosilicate and homo- or copolymeric carboxylic acids. It is particularly surprising that even small amounts of sodium silicate (component b) of 0.1 to 0.2% by weight bring about a significant improvement in the grain stability. This property is of increased importance insofar as the adsorbent is mechanically processed in the mixing devices during further processing, in particular when applying nonionic surfactants, and greater abrasion is to be prevented or restricted as far as possible.
• the zeolite used had a particle size of 1 to 8 microns, the proportion over 8 microns being 6 percent by weight. There were no portions above 20 microns.
• a copolymer of acrylic acid and maleic acid with a molecular weight of 70,000 (Sokalan®) in the form of the sodium salt was used as the polycarboxylic acid.
• the liter weight was 550 g / l.
• the grains were sprayed with a molten mixture of nonionic surfactants in a spray mixing apparatus consisting of a cylindrical drum (L ⁇ DIGE mixer) equipped with mixing elements and spray nozzles inclined to the horizontal.
• the temperature of the adsorbent was 20 ° C., that of the surfactant melt 50 ° C.
• the surfactant mixture consisted of 30.1 percent by weight tallow alcohol with 5 EO (ethylene oxide groups), 34.6 percent by weight tallow alcohol with 14 EO and 35.3 percent by weight of an oleyl alcohol-cetyl alcohol mixture (JZ 53) with EO.
• 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 sprayed amounts of nonionic surfactant, the bulk density of the treated powders and the results of the trickle test are shown in Table I. It first shows that the diffusion of the nonionic surfactant into the carrier grain takes some time, which is why the flow behavior is expediently determined only 24 hours after the material to be treated has been discharged from the spray mixer. It also shows that none of the comparative products is suitable for taking up 40 percent by weight of nonionic surfactant, while the product according to the invention has good pourability after 24 hours, which is of the order of magnitude of the pourability of a spray-dried detergent of conventional composition.
• Example 2 As described in Example 1, a slurry containing 3 wt .-% of water 5, spray-dried. The temperature of the slurry was 83.5 ° C and the viscosity at this temperature was 9200 mPa ⁇ s. The dry gas had a temperature of 230 ° C at the tower entrance and 58 ° C at the tower exit.
• the zeolite used had a particle size of 1 to 8 microns, the proportion over 8 microns being 6% by weight. There were no portions above 20 microns.
• a copolymer of acrylic acid and maleic acid with an average molecular weight of 70,000 (Sokalan CP5®) in the form of the sodium salt was used as the polycarboxylic acid.
• Sokalan CP5® a copolymer of acrylic acid and maleic acid with an average molecular weight of 70,000
• ethoxylated fatty alcohol a tallow alcohol reacted with 5 mol ethylene oxide (EO) (30% cetyl alcohol, 70% stearyl alcohol) was used.
• the liter weight was 540 g / l.
• 67.6 parts by weight of the granules were sprayed with a molten mixture of nonionic surfactants in a spray mixing apparatus consisting of a cylindrical drum (L ⁇ DIGE mixer) equipped with mixing elements and spray nozzles inclined to the horizontal.
• the temperature of the granules was 20 ° C, that of the surfactant melt 50 ° C.
• the surfactant mixture consisted of 4.1 parts by weight of tallow alcohol with 5 EO, 20 parts by weight of a lauryl alcohol-myristyl alcohol mixture (2: 1) with 5 EO, and 8.3 parts by weight of a cleyl alcohol-cetyl alcohol mixture reacted with 7 EO.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Separation Of Suspended Particles By Flocculating Agents (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Water Treatment By Sorption (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (3)

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• 1984
  • 1984-12-10 DE DE19843444960 patent/DE3444960A1/de not_active Withdrawn
• 1985
  • 1985-12-05 JP JP60272658A patent/JPH0676596B2/ja not_active Expired - Lifetime
  • 1985-12-07 AT AT85115577T patent/ATE51017T1/de not_active IP Right Cessation
  • 1985-12-07 DE DE8585115577T patent/DE3576520D1/de not_active Expired - Lifetime
  • 1985-12-07 EP EP85115577A patent/EP0184794B1/fr not_active Expired - Lifetime
  • 1985-12-09 US US06/807,065 patent/US4707290A/en not_active Expired - Lifetime
  • 1985-12-10 ES ES549771A patent/ES8608924A1/es not_active Expired

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