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
  • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

• the invention relates to a process for the preparation of concentrated, free-flowing anionic surfactant Granules with active substance contents above 50% by weight from the corresponding Anionic surfactant acids.
• anionic surfactants fall in the course of Manufacturing process in their acid form and must be used with suitable neutralizing agents be converted into their alkali or alkaline earth metal salts.
• This neutralization step can be carried out with solutions of alkali metal hydroxides or with solid ones alkaline substances, especially sodium carbonate, are carried out.
• aqueous alkalis precipitates the surfactant salts in the form of aqueous preparation forms at, water contents in the range of about 10 to 80 wt .-% and in particular can be set in the range from about 35 to 60% by weight.
• water contents in the range of about 10 to 80 wt .-% and in particular can be set in the range from about 35 to 60% by weight.
• Have products of this type pasty to room temperature at room temperature, the flow and The pumpability of such pastes is already limited in the range of approximately 50% by weight of active substance is or is even lost, so that in the processing of such pastes, in particular when incorporated into solid mixtures, for example in solid washing and Detergents, considerable problems arise.
• Free-flowing, non-hygroscopic and clumping anionic surfactant granules can with suitable carrier materials, for example zeolites and / or silicates and / or Alkali carbonates or by surface treatment, for example with finely divided solids, be preserved.
• suitable carrier materials for example zeolites and / or silicates and / or Alkali carbonates or by surface treatment, for example with finely divided solids.
• European patent application EP-A-0 678 573 (Procter & Gamble) describes a process for producing free-flowing surfactant granules with bulk densities above 600 g / l, in which anionic surfactant acids are converted to a paste with at least 40% by weight surfactant with an excess of neutralizing agent and this paste is mixed with one or more powder (s), at least one of which must be spray-dried and which contains anionic polymer and cationic surfactant, the resulting granules optionally being able to be dried.
• anionic surfactant acids are converted to a paste with at least 40% by weight surfactant with an excess of neutralizing agent and this paste is mixed with one or more powder (s), at least one of which must be spray-dried and which contains anionic polymer and cationic surfactant, the resulting granules optionally being able to be dried.
• European patent application EP-A-0 438 320 discloses a batch process for the production of surfactant granules with bulk densities above 650 g / l.
• Anionic surfactant acid is added to a solution of an alkaline inorganic substance in water, possibly with the addition of other solids, and granulated in a high-speed mixer / granulator with a liquid binder. Neutralization and granulation take place in the same apparatus, but in separate process steps, so that the process can only be operated in batches.
• ABS acid contains at least 62% NaOH is neutralized and then granulated with the addition of auxiliaries, for example ethoxylated alcohols or alkylphenols or a polyethylene glycol melting above 48.9 ° C. with a molecular weight between 4000 and 50,000.
• auxiliaries for example ethoxylated alcohols or alkylphenols or a polyethylene glycol melting above 48.9 ° C. with a molecular weight between 4000 and 50,000.
• zeolite and / or sodium carbonate is not described in this document.
• EP-A-0 508 543 (Procter & Gamble) mentions a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40% by weight surfactant paste, which is then conditioned and granulated. A continuous process which avoids the decomposition of acid-labile ingredients when using ABS acid is not disclosed here.
• German laid - open specification DE-A-42 32 874 (Henkel KGaA) discloses a process for producing washable and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their acid form. However, only solid, powdery substances are disclosed as neutralizing agents. The granules obtained have surfactant contents of around 30% by weight and bulk densities of less than 550 g / l.
• the object of the invention was to provide a simple and comparatively inexpensive method for the production of concentrated anionic surfactant granules, starting from the acid form of the surfactant and with the addition of granulation-promoting solids, for example zeolite to develop, the granules obtained active substance contents of at least 50% by weight.
• the procedure according to the invention ensures that sufficient alkalinity is present to avoid acidic decomposition of the zeolites.
• the inventive method has the advantage of a simplified equipment (only one mixer required) and the more convenient Execution of the process on the one hand because of problems that are usually encountered in neutralization occur (acidic nests) and on the other hand moving or pumping around highly viscous anionic surfactant pastes are not required.
• the Heat of neutralization is intercepted by the heat capacity of the powder. Local overheating and discoloration of the anionic surfactant is drastically reduced in this way or completely prevented.
• the neutralization on the powder The amount of water introduced is reduced, resulting in granules with an increased anionic surfactant content can be produced.
• the fine crystalline, synthetic and bound used Zeolite containing water can be, for example, A and / or P.
• Zeolite P Zeolite MAP® (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures are also preferred in the context of the present invention from A, X and / or P.
• the zeolite can be spray-dried powder or as an undried stabilized suspension, still moist from its manufacture come.
• the zeolites to be mixed with the sodium hydroxide solution in step a) have the general formula M 2 / n O.Al 2 O 3 .x SiO 2 .y H 2 O, in which M is a cation of valence n, x stands for values that are greater than or equal to 2 and y can have values between 0 and 20.
• the zeolite structures are formed by linking AlO 4 tetrahedra with SiO 4 tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees.
• the intercrystalline "zeolitic" water can be released continuously and reversibly depending on the type of zeolite, while for some types of zeolite structural changes are also associated with the release or absorption of water.
• the "primary binding units” AlO 4 tetrahedra and SiO 4 tetrahedra
• secondary binding units which have the form of one or more rings.
• 4-, 6- and 8-membered rings appear in various zeolites (referred to as S4R, S6R and S8R), other types are connected via four- and six-membered double ring prisms (most common types: D4R as a square prism or D6R as a hexagonal prism ).
• S4R, S6R and S8R zeolites
• D4R most common types: D4R as a square prism or D6R as a hexagonal prism
• These "secondary subunits" connect different polyhedra, which are denoted by Greek letters.
• ⁇ The most common is a polygon that consists of six squares and eight equilateral Hexagons is built and which is referred to as " ⁇ ". With these units various different zeolites can be realized. So far, 34 are natural Zeolite minerals and about 100 synthetic zeolites are known.
• the best known zeolite, zeolite 4 A is a cubic assembly of ⁇ -cages linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 ⁇ and 4.2 ⁇ in size, the formula unit in the unit cell can be determined with Na 12 [(AlO 2 ) 12 (SiO) 12 ] ⁇ 27 Describe H 2 O.
• Faujasite type zeolites are particularly preferably used in the method according to the invention Faujasite type zeolites.
• the mineral belongs together with the zeolites X and Y. Faujasite to the faujasite types within the zeolite structure group 4 by the double six-ring subunit D6R is marked (compare Donald W. Breck: “Zeolite Molecular Sieves ", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92).
• zeolite structure group 4 also includes Minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), p (Gmelinite type), L and ZK-5. The latter two synthetic zeolites have none mineral analogues.
• Faujasite-type zeolites are composed of ⁇ -cages, which are linked tetrahedrally via D6R subunits, the ⁇ -cages being arranged in the diamond in a manner similar to the carbon atoms.
• the three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities with a diameter of approx. 13 ⁇ and can be determined using the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] ⁇ 264 H 2 O.
• the network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).
• zeolite of the faujasite type denotes all three zeolites that form the faujasite subgroup of zeolite structure group 4.
• zeolite Y and faujasite as well as mixtures are therefore also according to the invention of these compounds can be used according to the invention, the pure zeolite X is preferred.
• Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which do not necessarily have to belong to the zeolite structure group 4 are according to the invention can be used, it being advantageous if at least 50% by weight of the zeolite consist of a zeolite of the faujasite type.
• the aluminum silicates used in the process according to the invention are commercially available, and the methods for their presentation are in standard monographs described.
• Examples of commercially available X-type zeolites can be described by the following formulas: Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, K 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, Ca 40 Na 6 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, Sr 21 Ba 22 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, in which x can have values between 0 and 276 and the pore sizes range from 8.0 to 8.4 ⁇ .
• a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX®, is also commercially available and can preferably be used in the process according to the invention and through the formula n Na 2 O (1-n) K 2 O Al 2 O 3 (2 - 2.5) SiO 2 (3.5 - 5.5) H 2 O can be described.
• Y-type zeolites are also commercially available and can be expressed, for example, by the formulas Na 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] x H 2 O, K 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] x H 2 O, in which x stands for numbers between 0 and 276 and have a pore size of 8.0 ⁇ .
• the particle sizes of the zeolites of the faujasite type used in the process according to the invention lies in the range from 0.1 to 100 ⁇ m, preferably between 0.5 and 50 ⁇ m and especially between 1 and 30 ⁇ m, each with standard particle size determination methods measured.
• the amount of zeolite used in the invention Process is usually 5 to 50 wt .-%, preferably 10 to 45 wt .-% and in particular 15 to 40 wt .-%, based on finished Granules.
• the sodium hydroxide solution used to neutralize the ABSS can be any Concentration, with higher concentrations because of the correspondingly lower Water content and reduced water evaporation are preferred.
• the sodium hydroxide solution used is at least 30% by weight, preferably at least 40% by weight and in particular at least 50 Wt .-% NaOH contains.
• the main anionic surfactants used in the context of the present invention Alkylbenzenesulfonic acids (ABSS), alkylsulfonic acids or alkylsulfuric acids into consideration.
• ABSS alkylbenzenesulfonic acids
• the amount of anionic surfactant acid in the The method according to the invention is used so that the resulting granulate is ⁇ Contains 50% by weight of anionic surfactant (s).
• the amount of anionic surfactant acid is which is introduced into the mixer, 35 to 75% by weight, preferably 45 to 65% by weight and in particular 50 to 60 wt .-%, based on the total amount in the mixer Fabrics.
• the ABSS in the process according to the invention are preferably C 9-13- alkylbenzenesulfonic acids, olefin sulfonic acids, that is to say mixtures of alkene and hydroxyalkanesulfonic acids and disulfonic acids, of the kind obtained, for example, from C 12-18 monoolefins having a terminal or internal double bond by sulfonating with gaseous or liquid Sulfur trioxide is considered.
• the alkanesulfonic acids which can be obtained from C 12 -C 18 alkanes by sulfochlorination and sulfoxidation and by subsequent hydrolysis or by bisulfite addition to olefins.
• alkyl sulfuric acids which are obtained, for example, by reacting fatty alcohols with H 2 SO 4 , can also be used as anionic surfactant acid.
• Suitable alkyl sulfuric acids are, for example, the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, e.g. B. coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
• the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable.
• ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide
• saturated and unsaturated fatty acids with C 8 -C 18 chain lengths in the form of their mixtures and / or the ⁇ -sulfofatty acids of saturated C 8 -C 18 fatty acids is also possible in the process according to the invention.
• Mixtures of the fatty acids and .alpha.-sulfofatty acids mentioned with other sulfonic acids and alkylsulfuric acids, for example alkylbenzenesulfonic acids and fatty alkylsulfuric acids, can also be used with particular advantage.
• anionic surfactant acid is used an alkylbenzenesulfonic acid (ABSS) used.
• ABSS alkylbenzenesulfonic acid
• the concentration of the anionic surfactant acids can vary due to the production process.
• the surfactant acids contain the end products of the sulfonation, sulfation or Sulfoxidation usually water and minor amounts of impurities such as Salts, for example sodium sulfate.
• the anionic surfactant acid has an active substance content of at least 60% by weight, preferably of at least 75% by weight and in particular of at least 85% by weight, having.
• anionic surfactant acids can also be mixed with others Use substances, for example non-ionic surfactants. It is according to the invention but also possible to mix other non-surfactant components with the anionic surfactant acid and bring it into the process. Here it is particularly preferred to use aqueous solutions use of polycarboxylates.
• a Lödige mixer for example one Ploughshare mixers from Lödige, or a mixer from Schugi
• a mixer from Schugi are used by Circumferential speeds of the mixing elements, preferably between 1 and 6 m / s (ploughshare mixer) or 3 to 50 m / s (Eirich, Schugi), in particular between 5 and 20 m / s of the zeolite and the sodium hydroxide solution and subsequently with the addition of Anionic surfactant acid granulated.
• a predetermined one can be made in a manner known per se Grain size of the granules can be adjusted.
• the neutralization and mixing process only needs a very short period of time, for example about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) for homogenization of the mixture to form the free-flowing granules.
• a dwell time of 0.5 to 10 seconds is usually sufficient to to obtain a free-flowing granulate.
• the mixing ratios of the components and in particular the proportions of the submitted solid are so on the over ABSS and the NaOH entered water content to match that a free-flowing granulate can be trained. The more solid material is usually required, the higher the water content of ABSS and NaOH.
• the granules are immediately after the granulation a fluidized bed and dried the surface with small amounts of finely divided zeolite treated, as this further increases the surfactant content and bulk density can.
• the process according to the invention advantageously works continuously, with zeolite and NaOH can be dosed into the input area of the mixer via dosing devices.
• the Anionic surfactant acid can then be injected, the spraying also over a multi-component nozzle can take place, air as a further material through the neutralizer / mixer / granulator is blown, the heat of neutralization for water evaporation makes usable.
• the pure zeolite can be dosed as powder in a Schugi mixer become. Subsequently, taking into account the direction of rotation, the sodium hydroxide solution is used first injected and then granulated with the addition of anionic surfactant acid.
• a Lödige ploughshare mixer can be operated continuously by the mixer through adjustable Weirs are divided into different chambers.
• the zeolite is in the first chamber with the sodium hydroxide solution, in the second chamber with the addition of anionic surfactant granulated.
• the granulate can be carried along powdery substances are powdered.
• zeolite X (Wessalith® XD, Degussa) were placed in a 50 liter laboratory mixer (Lödige ploughshare mixer) and 1.26 kg of 50% sodium hydroxide solution were added. This mixture was mixed for 30 seconds, then 5.2 kg of a 97% C 9-13 alkylbenzenesulfonic acid solution were added and the mixture was granulated. After discharge from the mixer, the granules obtained were subjected to fluidized-bed drying. The granules E1 obtained by this procedure according to the invention were compared with the comparative examples V1 and V2.
• V1 was produced by simultaneously adding sodium hydroxide solution and alkylbenzenesulfonic acid to the zeolite placed in the mixer; in the preparation of V2, the alkylbenzenesulfonic acid was added to the initially placed zeolite and only then was the sodium hydroxide solution sprayed on.
• Comparative example V3 was obtained by granulating a 75% ABS paste (obtained from Alkylbenzenesulfonic acid and NaOH) obtained with zeolite.
• the calcium complexing ability was determined potentiometrically with a Ca-sensitive electrode from Orion. For this purpose, were first at 30 ° C thermostatted glass vessel 1 liter of water at 30 ° d (corresponding to 30 mg CaO / l) submitted, this solution with sodium hydroxide solution to pH 10 and with potassium chloride to simulate a for a detergent customary electrolyte content adjusted to a 0.08 molar KCl solution. 1 g each of the granules E1, V1 and V2 were added to the respectively prepared ones with stirring Solution added. The decrease in Ca hardness was recorded using a computer Function of time determined and the value of the residual hardness 10 minutes after the addition of the Substance evaluated for the solution presented. From the difference between the initial hardness and residual hardness resulted in the bound hardness per g of substance.
• the grades of the individual examiners were combined to an average, the Examiners can also assign intermediate grades.

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Citations (4)

• 1998
  • 1998-05-22 DE DE1998122942 patent/DE19822942A1/de not_active Withdrawn
• 1999
  • 1999-05-14 EP EP99109605A patent/EP0959124A1/fr not_active Withdrawn

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