Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
• • 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
• • 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
  • C11D3/02—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
  • C11D3/02—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

Definitions

• An essential component of commercially available cleaners for use in machine cleaning processes - for example in the known dishwashers used in the household - are to date generally sodium metasilicate mixed with sodium tripolyphosphate (also called pentasodium triphosphate and hereinafter referred to as STP).
• STP sodium tripolyphosphate
• soda and water glass as well as further components for strengthening the granulating and / or cleaning effect are used as further components.
• the mixtures of substances exist as free-flowing agglomerates, whereby a number of requirements are placed on the product properties.
• the substance mixtures are generally strongly alkaline and therefore irritating to the respiratory tract. Accordingly, the occurrence of dust in the product, as would be expected when using powdered raw materials, must be avoided. Furthermore, products of this type with high fines in the dishwasher's washing-in box tend to clump when water enters, so that a sufficiently short washing-in time is no longer guaranteed.
• the bulk density should be above 900 g / l to enable the product quantity required for the cleaning cycle to be filled into the dispenser box without problems. Since the free-flowing agglomerates contain water, it must be ensured when processing the recipe that the water remains largely crystalline to prevent caking of the granules during storage.
• Today's commercial cleaners are manufactured according to two process variants, namely either by mixing granulation or by mixing granular dust-free raw materials.
• thermodynamically most stable composition may only be achieved when the raw material properties are not constant or the process conditions are not exactly observed when the products are stored. The migration of the water required for this is generally accompanied by a clumping of the product.
• the formulation flexibility of the mixed granulation process is also relatively low, and in particular in a very specific direction:
• the use of soda and water glass as a granulation aid is necessary without these components making a significant contribution to the effectiveness of the cleaning formulation.
• the invention is based on the object of using granular detergent formulation with good flowability, good washability and good storage stability using inexpensive raw materials while reducing the disadvantages of water-wet mixed granulation.
• the invention also intends to use finely crystalline zeolite NaA in addition to or instead of STP and to use other components, for. B. of cleaning boosters - enable.
• the solution to the problem according to the invention was found by using a preferably continuous compression of a powdery premix of the desired constituents in the nip of a pair of two oppositely running press rolls with subsequent comminution of the resulting plate-shaped compacted material.
• the invention relates in a first embodiment to a process for the production of granular, free-flowing alkaline cleaning agents based on sodium metasilicate in intimate admixture with STP and / or finely crystalline zeolite NaA as reinforcing builders and, if desired, further auxiliaries for improved granulation and / or Cleaning effect by means of a mixing process, the hallmark of the new process being that the starting components of the substance mixture are in powder form mixed with each other, this mixture of substances compacted in the nip under increased pressure and the resulting compactate crushed to the desired grain size.
• the invention relates to granular, in particular free-flowing, alkaline cleaning agents of the type mentioned, which have been produced by the process described here.
• the material to be granulated is passed under pressure under the nip of a pair of two rollers running in opposite directions at approximately the same peripheral speed, and is compressed into a plate-shaped material to be pressed.
• This plate-like or band-shaped pressed material which is also referred to as "sling belt”
• the comminution of the plate or band-shaped material can be done in a mill.
• the comminuted material is then expediently fed to a screening process. Material which is too coarse is separated off and returned to the comminution device, while material which is too fine is added to the batch of the pulverulent mixture and is fed again to the compacting in the roll gap.
• the roller compression can take place without or with a pre-compression of the premixed powdery material.
• the pair of rollers can be arranged in any spatial direction, in particular thus vertically or horizontally to one another.
• the powdery material is then either by gravity filling or by means of a suitable device, for. B. fed to the nip by means of a stuffing screw.
• the pressure in the nip and the dwell time of the material in the area of the pressure are to be set so high that a well-formed, high-density, hard cuff band is produced.
• the high degree of compaction is to be striven for in order to set the desired bulk densities of the free-flowing material ultimately obtained, which should be above 900 g / l.
• the abrasion stability of the granules is also influenced by the degree of compaction; high degrees of compaction lead to abrasion-stable granules, which in turn are desirable.
• excessive pressures impair the process reliability, since when they are used the material is plasticized on the rollers and leads to sticking. This undesirable effect occurs when an increase in the pressing pressure no longer causes further compression of the material and the additional force that is now added predominantly causes the heating and plasticization of the material - for example by partial melting of water-containing constituents, in particular water-containing metasilicate.
• the optimum pressing force to be used depends on the recipe. Usually, according to the invention, a specific pressing force in the range from approximately 15 to 30 kN / cm roller length is used in the nip, the range from approximately 20 to 25 kN / cm roller length being particularly preferred.
• the solid densities set in the compactate are preferably at least about 1.7 g / cm 3. Corresponding solid densities of at least about 1.8 to over 2 g / cm 3 are particularly suitable.
• the optimal density value to be set depends to a certain extent on the recipe.
• the ability of the granules to be flushed in - determined as the flushing time of a predetermined amount of material in a test apparatus - is favored by higher compression pressures and thus by higher solids densities, and not deteriorated.
• fillings made of harder particles are less prone to Clump and form less fines even during the induction process, so that an unimpeded water flow through the bed is promoted here.
• the setting of the thickness of the plate-like or band-shaped compact is important in order to achieve the desired high bulk densities of the finally granulated free-flowing cleaning agents. If the selected bowl thickness is significantly smaller than the desired upper grain limit of the granulated product to be produced, platelet-shaped particles are obtained during the comminution of the plate-shaped compactate which initially results, which lead to beds with a high void volume and therefore a comparatively low bulk weight. At higher compactate thicknesses, however, particles are obtained in the subsequent comminution, the dimensions of which can approach the desired ratio of 1: 1: 1. Such a grain shape leads to denser fillings, the void volume of which is a maximum of about 50%.
• the chip granulate obtained in the method according to the invention after the shredded ribbon has been comminuted is subjected to a surface abrasion of corners and edges and, in particular, the bulk density of the granular material is increased again, or that Empty space volume reduced accordingly.
• the primary granulate chips can be rolled on rotating disks which have a corrugation on their upper side. If necessary, an undesired fine fraction is then separated off again and again fed to the compacting in the roll gap.
• the desired upper grain limit in the free-flowing agglomerate is in the range from about 1.6 to 2 mm, while on the other hand fine fractions below about 0.2 mm are undesirable.
• the preferred free-flowing agglomerates accordingly show a broad grain size range in the range from about 0.2 to 2 mm.
• the void volume should not make up significantly more than about 50%, but can be less than 50%.
• the layer thickness here is preferably at least about 2 mm. Layer thicknesses of the compactate in the range of approximately 4 to 8 mm and in particular in the range of approximately 5 to 6 mm can be particularly preferred.
• the essential components of the cleaner mixtures produced in the process according to the invention contain sodium metasilicate in intimate admixture with the framework-forming STP and / or zeolite NaA.
• the mixture of substances has a certain water content, which is predominantly or exclusively in the form of hydrate or Water of crystallization can be present.
• additives such as soda and / or water glass or cleaning-enhancing additives can be present in a mixture.
• Metasilicate is generally present in amounts from 20 to 75% by weight and preferably from about 35 to 65% by weight of the total mixture. Amounts of metasilicate in the range from about 40 to 60% by weight can be particularly suitable.
• the metasilicate can be used in the powdered feed material as an anhydrous product and / or in the form of hydrated phases with certain predetermined and / or changing amounts of hydrated water contents. Suitable metasilicate phases containing water of hydration are known to be corresponding products with 5 or 9 water of crystallization, with particular importance being attached to the corresponding metasilicate with 5 water of crystallization.
• Anhydrous metasilicate (KO) and metasilicate containing water of crystallization, in particular corresponding product with 5 water of crystallization (K5), can be used in preferred embodiments of the invention in the feed material in mixing ratios of 5: 1 to 1: 5 and in particular in mixing ratios of 3: 1 to 1: 3 .
• STP and / or zeolite NaA are present as intimate mixes with the metasilicate.
• the amount of these builder substances (anhydrous) is usually in the range from about 20 to 50% by weight, preferably in the range from about 35 to 40% by weight, based on the total mixture.
• STP can only - d. H. in the absence of zeolite NaA - find use, but it is also possible to replace the STP portion in any mixing ratio by using finely crystalline zeolite NaA - in particular corresponding detergent grade material - in one embodiment of the invention the complete replacement of STP provided by NaA zeolite.
• the water content of the finished granules is generally 8 to 25% by weight and is in particular in the range of approximately 10 to 20% by weight.
• the total water can be added as bound water from the outset as part of the premixing However, it is also possible to add aqueous phase to the powdery starting mixture or to individual components of this starting mixture in order to adjust the overall desired final water contents in the product.
• Soda and / or water glass can be used in particular as agglomeration aids and / or as additional alkalizing agents.
• the amount of soda is generally not more than 20% by weight and in particular not more than 15% by weight, based on the total mixture.
• the amount of water glass used is usually not more than 10% by weight.
• the use of water glass N with a Na2O / SiO2 ratio of 1: 3.35 or water glass A with a corresponding ratio of 1: 2 comes into consideration here.
• auxiliaries that can be used in particular for the purpose of cleaning enhancement are, for example, solubility-improving substances such as sodium acetate or sodium citrate, foam inhibitors, e.g. B. the paraffin foam brakes known from detergent or cleaning agent chemistry, surfactants with washing or cleaning activity, chlorine carriers such as trichloroisocyanuric acid, cleaning enhancers, e.g. B. n-octanol components with complex binding ability such as phosphonobutane tricarboxylic acid and the like.
• foam inhibitors e.g. B. the paraffin foam brakes known from detergent or cleaning agent chemistry
• surfactants with washing or cleaning activity e.g. B. the paraffin foam brakes known from detergent or cleaning agent chemistry
• chlorine carriers such as trichloroisocyanuric acid
• cleaning enhancers e.g. B. n-octanol components with complex binding ability such as phosphonobutane tricarboxylic acid and the
• the STP portion of the recipe can be used as an STP prehydrate with different water contents or as a non-hydrated STP. Surprisingly, products show at for which non-hydrated STP was used, compared to granules based on STP prehydrates with comparable total water contents of the recipe, better flushability. Cleaners previously available contain STP as partial hydrate or as hexahydrate.
• this finely crystalline material is added as part of an STP prehydrate which has been obtained by hydrating STP with an aqueous suspension containing zeolite NaA.
• Fine crystalline zeolite NaA can also be used as such or as a spray-dried material.
• Comparatively higher levels of zeolite NaA can impair the flushability of the agglomerate according to the invention.
• the induction behavior can be improved again by using water-containing metasilicates.
• the process according to the invention is thus superior to the previously known water-moist granulation, in which water-containing metasilicates cannot readily be used. In the stated manner, products with satisfactory wash-in properties can be obtained even with high zeolite contents.

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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)
• Detergent Compositions (AREA)

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• 1986
  • 1986-07-18 DE DE19863624336 patent/DE3624336A1/de not_active Ceased
• 1987
  • 1987-03-23 DE DE19873709488 patent/DE3709488A1/de not_active Withdrawn
  • 1987-07-10 ES ES87109974T patent/ES2021641B3/es not_active Expired - Lifetime
  • 1987-07-10 EP EP87109974A patent/EP0253323B2/fr not_active Expired - Lifetime
  • 1987-07-17 JP JP62179870A patent/JPS6333500A/ja active Pending
• 1988
  • 1988-03-14 EP EP88103981A patent/EP0283885B1/fr not_active Revoked
  • 1988-03-14 ES ES198888103981T patent/ES2030780T3/es not_active Expired - Lifetime
  • 1988-03-22 US US07/171,609 patent/US4834902A/en not_active Expired - Fee Related

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