Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
• • 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 invention relates to a method for converting liquid to pasty preparation forms of washable and cleaning-active surfactant compounds into storage-stable and dust-free granules with increased bulk density.
• Surfactant granules can be produced, for example, by conventional drying technology of surfactant-containing solutions and pastes, especially in the spray tower.
• European Patent Application 319 819 discloses a process for the production of surfactant granules by spray drying, a sulfonic acid and a highly concentrated aqueous sodium hydroxide solution being separately charged with a gaseous medium, then combined in stoichiometric amounts and neutralized in a multi-substance nozzle and is sprayed at a high propellant pressure in the drying tower.
• the products obtained are solid or pasty, solid products mostly being relatively dusty, having a relatively high water content and a low bulk density.
• Granulation is an alternative to spray drying of surfactant pastes.
• European patent application EP 403 148 describes a process for producing fatty alcohol sulfate granules which are dispersible in cold water.
• a highly concentrated aqueous fatty alcohol sulfate paste which contains less than 14% by weight of water and less than 20% by weight of further additives, is mechanically processed at temperatures between 10 and 45 ° C. until granules form.
• fatty alcohol sulfate granules are obtained which are already dispersed at washing temperatures between 4 and 30 ° C .;
• the process temperature to be observed and the relatively low maximum water content of the surfactant paste are critical process parameters.
• European patent application EP 402 112 discloses a process for producing fatty alcohol sulfate and / or alkylbenzenesulfonate granules, the neutralization of the anionic surfactants in acid form to give a paste with a maximum of 12% by weight of water with the addition of auxiliaries such as poly ethylene glycols, ethoxylated alcohols or alkylphenols, which have a melting point above 48 ° C, and the granulation in one high-speed mixer takes place. Again, the amount of water to be maintained represents a critical process parameter. It is also not disclosed what bulk densities the surfactant granules obtained by this process have.
• a process for the production of detergent-active and granular surfactants with a bulk density above 450 g / 1 and in particular between 500 and 1200 g / 1 is known, wherein a surfactant preparation form as Contains liquid component water and can additionally contain organic polymers and builder substances, mixed with a finely divided solid and granulated in a high-speed mixer.
• the water content of the surfactant paste is a critical process parameter. If the water content of the surfactant paste is too high, the solid is dispersed so that it can no longer act as a deagglomeration agent. On the other hand, if the solids content exceeds a certain value, the mass does not have the consistency necessary for the granulation.
• the surfactant preparation form used also contains a non-surfactant liquid component, which is preferably water or an aqueous solution.
• a non-surfactant liquid component in contrast to the prior art mentioned, the content of a non-surfactant liquid component in this process is not a critical process parameter.
• anionic surfactant preparation forms are usually prepared by neutralizing the anionic side in its acid form with concentrated aqueous alkaline solutions. So that such a form of preparation at 20 to 40 ° C. In liquid to pasty form, the mixture must generally be diluted with water. However, the high energy consumption required to remove the water is to be regarded as disadvantageous.
• the object of the invention was to further develop the mentioned method of granulation and simultaneous drying in such a way that the energy required for drying can be reduced.
• the invention accordingly relates to a process for the production of detergent-active granules with a bulk density above 450 g / l by granulation of a surfactant preparation form which has a non-surfactant liquid component, the anionic surfactant preparation form being produced in such a way that the anionic surfactant in its acid form or a mixture which contains one or more anionic surfactants in their acid form, and an aqueous alkaline solution is charged separately with a gaseous medium, then separated in almost stoichiometric amounts or combined into the granulation at a high propellant gas pressure and drying room are sprayed and the subsequent granulation is optionally carried out with the addition of one or more inorganic or organic solids and with simultaneous drying.
• the anionic surfactant preparation form can be prepared either directly after the introduction of the individual reactant streams into the granulation and drying room or even beforehand.
• the distance from the point at which the gas-charged reactant streams are brought together from the spray device depends on the process conditions and the material systems used, but is preferably kept as small as possible in order to clog the nozzle due to to avoid early onset of neutralization reactions.
• the anionic surfactant in its acid form or the mixture which contains one or more anionic surfactants in its acidic form is acted upon by a gaseous medium and is passed through a multi-component nozzle, for example via a 2-component nozzle sprayed the granulating and drying room.
• a gaseous medium acted upon and at the same time sprayed with the anionic surfactant in its acid form or the mixture which contains one or more anionic surfactants in their acid form in almost stoichiometric amounts via a further multi-substance nozzle into the granulation and drying room.
• almost stoichiometric amounts mean that the ratio of the number of acidic groups to alkaline groups is preferably in the range from 1.1: 1 to 0.8: 1 and in particular from 1: 1 to 0.9: 1.
• the invention provides that the acidic and alkaline reactant streams separately charged with a gaseous medium are brought together via a single multi-component nozzle, for example via a 3-component nozzle, and sprayed into the granulating and drying room become.
• the neutralization takes place essentially in the nozzle or directly when it emerges from the nozzle.
• the combined acidic and alkaline reactant streams to be sprayed into the granulating and drying room via a plurality of multi-component nozzles. This is particularly preferred when products are to be made from different types of anionic surfactants and thus different types of combined acidic and alkaline reactant streams are to be sprayed.
• the starting materials are introduced, for example using piston pumps, in almost stoichiometric metered amounts into one or two non-modified commercial nozzle (s) or one or two spray tube (s).
• the gaseous medium (propellant gas) is mixed in directly in front of the nozzle. In the case of spraying the combined reactant streams, this means that the gaseous medium is mixed into the reactant streams before they meet in front of or in the nozzle.
• Further technical details for carrying out the process for example with regard to the control of the reaction temperature, the flow rate of the reactant streams or the pressure at which the reaction mixture is sprayed into the granulating and drying room, can be found in European patent application 319819.
• the anionic surfactants in their acid form can be carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably fatty acids, alkylarylsulfonic acids, sulfo fatty acid esters and the sulfuric acid semiesters of optionally alkoxylated, especially ethoxylated fatty alcohols and / or sulfosuccinic acid.
• fatty acid esters in particular fatty acid methyl esters, can also be used, in which case the ester group is not saponified, but instead is saponified.
• Suitable anionic surfactants in their acid form are therefore in particular either an anionic surfactant in its acid form or a mixture from the group of anionic surfactants in their acid form, if appropriate in combination with nonionic, amphoteric and / or cationic surfactants.
• Preferred anionic surfactants in their acid form are C8-C22 ⁇ alkyl sulfonic acids, Cg-Ci3-alkylbenzenesulfonic acids, usually called dodecylbenzenesulfonic acid, and methyl ⁇ -sulfofatty acid in their acid form.
• alkyl sulfonic acids are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, pal ityl or stearyl alcohol, or the C ⁇ o-C2 ⁇ _ 0xoalcohols, and those secondary alcohols this chain length.
• the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
• esters of ⁇ -sulfofatty acids which, by sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 10 to 20 C atoms in the fatty acid molecule, for example the sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and the ⁇ -sulfofatty acids (diacids) obtainable by ester cleavage.
• ester cleavage for example the sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids
• diacids obtainable by ester cleavage.
• alkanesulfonic acids which can be obtained from Ci2 _ Ci8 "" alkanes by sulfochlorination or sulfoxidation.
• Preferred nonionic surfactants are derived from liquid alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol residue is linear or methyl in the 2-position may be branched, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• linear residues of alcohols of native origin with 12 to 18 carbon atoms such as, for example, coconut oil, tallow fat or oleyl alcohol, are particularly preferred.
• the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, nre).
• alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
• the preferred ethoxylated alcohols include, for example, Cg-Cn-oxo alcohol with 7 EO, Ci3-Ci5-0xo alcohol with 3 EO, 5 EO or 7 EO and in particular Ci2-Ci4 alcohol with 3 EO or 4 EO, Ci2-Ci8 alcohols 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2 ⁇ i4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
• G as a nonionic surfactant can be alkylglycosides of the general formula R-0- (G) x , in which R is a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position Is symbol that stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligo erization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4.
• the surfactant preparation form can contain additives, which are preferably ingredients of detergents and cleaning agents, as further constituents.
• additives which are preferably ingredients of detergents and cleaning agents, as further constituents.
• surfactant preparations which contain additives in amounts of 0.001 to 15% by weight, based on the surfactant preparation form, are used in the process according to the invention.
• Particularly preferred additives are dyes, foam inhibitors, bleaches and / or constituents which improve solubility.
• Suitable dyes are temperature-stable dyes, preferably pigment dyes, which are advantageously used in amounts of 0.001 to 0.5% by weight, based on the surfactant preparation form.
• Suitable foam inhibitors are, for example, soaps of natural and synthetic origin, which have a high proportion of Ci8 "C24 fatty acids.
• Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide.
• Bisacyla ide derived from Ci2-C20- A ⁇ - alkylamines and C2-C5-dicarboxylic acids are also usable.
• foam inhibitors are also advantageously used, for example those made of silicones and paraffins or
• the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance, and the foam inhibitor content of the surfactant preparation form is preferably 0.01 to 0.5% by weight.
• bleaching agents that can be used are, for example, peroxy carbonate, peroxypyrophosphates, citrate perhydrates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
• hydrogen peroxide as a bleaching agent in surfactant preparation forms which are used according to the invention.
• the content of bleach in the surfactant preparation form is preferably 0.5 to 15% by weight, in particular the content of hydrogen peroxide is 0.5 to 5% by weight.
• the constituents which improve the solubility include liquid, pasty and solid compounds which are soluble or dispersible in the other constituents of the Ten ⁇ preparation form.
• Preferred solubility-improving constituents are polyethylene glycols with a relative molecular weight between 200 and 20,000 and highly ethoxylated fatty alcohols with 14 to 80 ethylene oxide groups per mole of alcohol, in particular Ci2-Ci8 fatty alcohols with 20 to 60 ethylene oxide groups, for example Taig fatty alcohol with 30 EO or 40 EO used.
• the use of polyethylene glycols with a relative molecular weight between 200 and 600 is particularly preferred.
• These polyethylene glycols are advantageously used as a separate constituent of the non-surfactant liquid component.
• the content of the surfactant preparation form in these constituents which improve the solubility of the finished granules is preferably 1 to 15% by weight and in particular 2 to 10% by weight.
• the neutralization or saponification reaction is preferably carried out with concentrated aqueous alkaline solutions, for example solutions of hydroxides, carbonates or hypochlorites of sodium or potassium, in particular with a concentrated aqueous sodium hydroxide solution and / or potassium hydroxide solution, concentrations around 45 to 55% by weight are particularly preferred.
• concentrated aqueous alkaline solutions for example solutions of hydroxides, carbonates or hypochlorites of sodium or potassium
• concentrations around 45 to 55% by weight are particularly preferred.
• a further dilution of the reactant streams with water is not necessary, so that the process according to the invention has the advantage over the process described in the earlier German patent application P 41 27 323.0 that smaller amounts of water have to be removed in the granulating and drying room and thus the energy consumption can be reduced.
• Suitable gaseous media are, in particular, gases such as air or nitrogen which are inert to the starting and end materials.
• gases such as air or nitrogen which are inert to the starting and end materials.
• water vapor is also suitable here, in particular if one of the reactant streams or the reactant streams is to be heated before the merging.
• the sprayed reactant streams are now granulated and dried simultaneously.
• "Drying” is understood to mean the partial or complete removal of the non-surfactant liquid component. If desired, there may be residual values of free, ie unbound water and residual amounts of alcohol, as long as the finished granules are free-flowing and non-sticky. However, a free water content of 10% by weight and in particular 0.1 to 7% by weight, based in each case on the finished granules, is preferably not exceeded.
• the surfactant granules can be produced in all devices in which granulation can be carried out with simultaneous drying.
• the invention provides that the combination of these two process steps is carried out in a batch or continuous fluidized bed. It is particularly preferred to carry out the process continuously in the fluidized bed. It is also possible to add a component of the non-surfactant liquid component which has not been incorporated into the surfactant preparation form simultaneously and separately.
• the nozzle or the nozzles and the direction of spraying of the products to be sprayed can be arranged as desired.
• Fluidized bed apparatuses which are preferably used have base plates with dimensions of at least 0.4 m.
• fluidized bed apparatuses are preferred which have a base plate with a diameter between 0.4 and 5 m, for example 1.5 m or 2.6 m.
• fluidized bed apparatuses are also suitable which have a base plate with a diameter greater than 5 m.
• a perforated base plate or a Conidur plate (commercial product from Hein & Lehmann, Federal Republic of Germany) is preferably used as the base plate.
• the process according to the invention is preferably carried out at swirl air speeds between 0.5 and 8 m / s and in particular between 1 and 5.5 m / s.
• the granules are discharged from the fluidized bed advantageously by means of a size classification of the granules.
• This classification can take place, for example, by means of a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
• the inflowing air is thus composed of the classifier air and the ground air, both of which can either be heated or unheated or one can be heated and the other unheated.
• cooled soil air can also be used.
• the soil air temperature is generally between - 20 and 400 ° C, preferably between 35 and 350 ° C and in particular between 35 and 120 ° C.
• the Temperature of the vortex air about 5 cm above the base plate 10 to 120 ° C, preferably 20 to 90 ° C and in particular 30 to 85 ° C.
• the air outlet temperature inevitably results from the reaction conditions.
• a starting mass is particularly suitable as starting mass, in particular those which can also be used as solids in the process according to the invention and which have a particle size distribution which corresponds approximately to the particle size distribution of the finished granules.
• surfactant granules as starting mass which have already been obtained in a previous process sequence.
• the components of the non-surfactant liquid component evaporate partially or completely in the fluidized bed. Dried to dried germs are formed, which are coated with further quantities of the surfactant preparation form, granulated and in turn dried at the same time.
• the surfactant preparation form is granulated with the admixture of one or more inorganic or organic solids and dried at the same time, the solid (s) being able to be dusted pneumatically via blow lines.
• This solid which serves as a carrier for the surfactant preparation form, preferably consists of ingredients from washing and cleaning agents.
• Suitable solids are, for example, also surfactants or surfactant mixtures which have been prepared by granulation, by spray drying or by the process according to the invention and are recycled.
• the use of spray-dried and / or surfactant granules obtained by the process according to the invention is preferred.
• non-surfactant ingredients of detergents and cleaning agents preferably one or more constituents from the group of the alkali carbonates, alkali sulfates, crystalline and amorphous alkali silicates and sheet silicates, and zeolite, in particular zeolite NaA in detergent quality, salts of the solids Citric acid or other polycarboxylic acids, solid peroxy bleaching agents and optionally bleach activators and solid polyethylene glycols with a relative molecular weight greater than or equal to 2,000, in particular between 4,000 and 20,000, are used.
• Preferred solids have, for example, no more than 5% by weight of particles with a diameter above 2 mm and preferably no more than 5% by weight of particles with a diameter above 1.6 mm.
• solids are preferred which consist of at least 90% by weight of particles with a diameter below 1.0 mm. Examples of these are alkali carbonates with more than 90% by weight of particles with a diameter of less than or equal to 0.5 mm and zeolite NaA powder in detergent quality, which contains at least 90% by weight of particles with a diameter below 0 , 03 mm contains.
• the added solids are used with particular advantage in amounts of 10 to 50% by weight and in particular 20 to 45% by weight, based in each case on the sum of the surfactant preparation form and the solid.
• the surfactant granules which can be produced by the process according to the invention are claimed.
• Preferred surfactant granules have a surfactant content of from 10 to 100% by weight, in particular from 30 to 95% by weight and with particular advantage between 40 and 90% by weight, in each case based on the finished granules.
• Pure surfactant granules are obtained when the non-surfactant liquid component evaporates completely and the granules are thus completely dried and the optionally added solid consists of a pure surfactant material.
• surfactant granules which have been produced by the process according to the invention and now serve as a solid in the process according to the invention are optionally comminuted to the desired particle size distribution and recycled.
• the content of surfactants in the granules can be adjusted to any of the desired values.
• the surfactant granules obtained by the process according to the invention preferably have a bulk density of above 450 g / 1 to 1000 g / 1, in particular between 500 and 850 g / 1, and are dust-free, ie they contain in particular no particles with a particle size below 50 ⁇ m. Otherwise, the particle size distribution of the surfactant granules corresponds to the usual particle size distribution of a heavy detergent of the prior art.
• the surfactant granules have a particle size distribution in which a maximum of 5% by weight, preferably a maximum of 3% by weight of the particles have a diameter above 2.5 mm and a maximum of 5% by weight, with particular advantage a maximum of 3% by weight of the Particles have a diameter below 0.1 mm.
• the surfactant granules are characterized by their light color and their free-flowing properties. A further measure to prevent the surfactant granules produced according to the invention from sticking together is not necessary.
• surfactant granules being powdered in a known manner with finely divided materials, for example with zeolite NaA, soda, in order to further increase the bulk density.
• Preferred surfactant granules have such a regular, in particular approximately spherical, structure that a rounding step is generally not necessary and is therefore not preferred. Examples
• Examples 1 to 3 analogously to the disclosure of EP 319819 ABSS (Ci2 ⁇ alkylbenzenesulfonic acid; Example 1) and FASS (sulfuric acid half-ester of Ci2-Ci4 fatty alcohol; Examples 2 and 3) via a multi-component nozzle with NaOH (50 wt. % sodium hydroxide solution) spray-neutralized (propellant: nitrogen) and granulated together with a solid and dried simultaneously in a granulation drying plant (AGT) from Glatt, Federal Republic of Germany.
• a surfactant granulate which had been obtained in a previous batch (under the same process conditions) and had approximately the same composition as the finished granules of Examples 1 to 3 was used as the starting mass.
• the process conditions can be found in Table 1 become.
• Soda sodium carbonate with a bulk density of 620 g / l; commercial product from Matthes & Weber, Federal Republic of Germany was used as the solid.
• Example 4 describes the analogous preparation of surfactant granules without the addition of solids.
• Dust-free and non-sticky granules with high surfactant contents were obtained in all examples (see Table 2).
• the proportion of granules with a grain size above 2.5 mm was below 5% by weight in all examples.
• the content of the granules at 100% consists of unsulfonated components and salts that were contained in the raw material FASS.
• Examples 1-3 The content of the granules at 100% consists of soda and unsulfonated parts and salts, which were contained in the raw materials ABSS and FASS.

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Citations (3)

• 1993
  • 1993-02-11 DE DE4304062A patent/DE4304062A1/de not_active Ceased
• 1994
  • 1994-02-02 EP EP94906207A patent/EP0683814B1/de not_active Expired - Lifetime
  • 1994-02-02 DE DE59402608T patent/DE59402608D1/de not_active Expired - Fee Related
  • 1994-02-02 JP JP6517628A patent/JPH08506368A/ja active Pending
  • 1994-02-02 ES ES94906207T patent/ES2101507T3/es not_active Expired - Lifetime
  • 1994-02-02 WO PCT/EP1994/000301 patent/WO1994018303A1/de active IP Right Grant
  • 1994-02-02 AT AT94906207T patent/ATE152477T1/de not_active IP Right Cessation
  • 1994-02-02 KR KR1019950703269A patent/KR100297272B1/ko not_active IP Right Cessation
  • 1994-02-09 MY MYPI94000305A patent/MY110838A/en unknown

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