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WO1997009269A1 - Melanges solides de plusieurs composants contenant du peroxyde d'hydrogene fixe, stable au stockage, procede de production desdits melanges et leur utilisation - Google Patents

Melanges solides de plusieurs composants contenant du peroxyde d'hydrogene fixe, stable au stockage, procede de production desdits melanges et leur utilisation Download PDF

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Publication number
WO1997009269A1
WO1997009269A1 PCT/EP1996/003725 EP9603725W WO9709269A1 WO 1997009269 A1 WO1997009269 A1 WO 1997009269A1 EP 9603725 W EP9603725 W EP 9603725W WO 9709269 A1 WO9709269 A1 WO 9709269A1
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Prior art keywords
component
compound according
weight
water
drying
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Ceased
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PCT/EP1996/003725
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German (de)
English (en)
Inventor
Kathleen Paatz
Wilfried Rähse
Horst Upadek
Johann-Friedrich Fues
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of WO1997009269A1 publication Critical patent/WO1997009269A1/fr
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic 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
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds

Definitions

  • the teaching according to the invention is based on the old idea of converting the highly effective hydrogen peroxide as a blending and / or disinfectant as a mixing component into a solid form, which provides sufficient storage stability even under difficult operating conditions with the release of the desired oxidation effect.
  • Access of water and, in particular, in aqueous liquors is also connected in the region of room temperature or only slightly elevated temperatures of, for example, 40 ° C.
  • Adequate storage stability should be ensured, in particular, under difficult conditions, such as are present in practice, for example, when mixed with liquid and / or solid ingredients of detergents and cleaning agents.
  • the teaching according to the invention is described below with reference to this last-mentioned application area of solid detergent and cleaning agent mixtures, but it is not restricted to this.
  • Hydrogen peroxide or peroxo compounds obtained therefrom which release the H2O2 as an active ingredient when water enters, are an important raw material in the large-scale sector.
  • the sodium perborate is of outstanding importance today as a detergent component with a bleaching effect. The reason for this is the sufficient storage stability of this per-compound under the difficult conditions of mixing with the other ingredients of detergents and cleaning agents.
  • a disadvantage of this form of supply is the comparatively high temperature stability of the perborate, which, in practical use, necessitates comparatively elevated temperatures of the wash liquor and / or the use of bleach activators. For today's low-temperature washing, not inconsiderable amounts of bleach activators in the detergent mixture are necessary. Their content is, for example, between 3 and 10% by weight.
  • the coating of the percarbonate particle does not provide an answer to the following problem:
  • the decomposition of the H2O2 once triggered provides water as the reaction product, which is now included in the coated particle.
  • the decomposition itself is an exothermic reaction, so that the decomposition mechanism builds up quickly by increasing the temperature.
  • stabilizers against undesired decomposition to the sodium percarbonate In particular, two triggering factors are taken into account in the relevant prior art: heavy metal compounds which can occur in several valence levels, in particular iron, act as decomposition catalysts in the ppm range. A maximum upper limit for the permissibility of such heavy metals is usually seen at about 5 ppm.
  • the most important stabilizers in practice are silicates on the one hand and alkaline earth metals, in particular magnesium, on the other hand, wherein the silicates can be used as alkali silicates but also as alkaline earth silicate compounds.
  • Magnesium is usually added in the form of water-soluble magnesium salts and, in particular, to the aqueous H2O2 solutions used for the reaction with soda.
  • concentration of these stabilizers is in the range up to about 1% by weight, based on the sodium percarbonate to be stabilized.
  • the production of sodium percarbonate is possible by 2 basic processes, namely in the so-called dry process and in the wet process.
  • caicinated soda is sprayed with concentrated hydrogen peroxide solution, the hydrogen peroxide being able to be added batchwise.
  • drying is carried out using a hot or cold air stream.
  • the teaching according to the invention uses a working principle of drying aqueous aqueous preparations, which is distinguished by the use of superheated steam as the drying gas stream.
  • the solid recyclables are produced in a form that is characterized by a multitude of advantages.
  • the applicant's parallel German patent applications according to P 4406591.4 and P 4406592.2 the content of which is hereby also made the subject of the disclosure of the invention.
  • (K2) at least one further, preferably at least partially water-soluble, inorganic and / or organic solid component, which is in particular capable of binding H2O2 and optionally H2O.
  • the invention is characterized in that the proportions (K1) in the multi-component compound are at least 3-5% by weight and the amounts (K2) are at least 5-10% by weight - based on weight to the sum (Kl) + (K2) - that the multicomponent compound is further formed as an agglomerate of a large number of fine particles of component (K2) bonded to one another and, if appropriate, (Kl) whose fine particulate material is at least partially as a corresponding one Solid material has been introduced into the agglomeration, and that the introduction of H2O2 has been carried out during and / or preferably at least in part after the formation of the agglomerated multicompound compound.
  • the invention relates to a multifunctional multi-substance compound in solid form for use in detergents and / or cleaning agents, containing at least 15% by weight of alkali silicates in the module range from 1 to 4, preferably from 1.2 to 3 , in a homogeneous mixture with at least 10% by weight of finely divided inorganic and / or organic water-soluble and / or water-dispersible salts, in particular from the field of builder or cobuilder components and / or builders for detergents and cleaning agents, by drying aqueous mixtures the components forming the multicompound compound have been produced to a preferably giant-capable product.
  • this multifunctional multicompound compound additionally contains H2O2 bound.
  • the invention relates to the process for the preparation of the multicomponent compounds described above, which process is characterized in that the finely divided component (s) to (K2) and, if appropriate, also components present as a solid to (K1) agglomerate and dry using a preferably aqueous liquid phase to give a pourable and free-flowing material and at the same time with / or after this drying Introduces H2O2 into the multi-substance material.
  • a particularly important embodiment is that one works in at least one process step with superheated steam as the drying gas, the drying preferably being carried out in a spray and / or fluidized bed treatment.
  • the invention relates to detergents and cleaning agents in solid preparation form, in particular textile detergents based on a mixture of surfactants, builder components, bleaching agents and other customary valuable and / or auxiliary substances, which are characterized in that they are multifunctional builder and bleaching agent components Multi-component compounds according to the previous definition included.
  • the agglomeration stage using the components to (K1) and (K2) is preferably carried out with the intermediate participation of an aqueous phase which, in the preferred embodiments of the invention, has been discharged again at least in part from the solid material.
  • the H2O2 is also introduced in a manner known per se in technically important embodiments in such a way that aqueous preparations of the H2O2 are introduced into the multicomponent compound.
  • the water portion entered here is likewise at least partially discharged again by drying.
  • An essential core of the action according to the invention lies in the previously described concept of giving the solid alkali silicate compounds known as effective H2O2 or peroxo stabilizers an even stronger and in particular multifunctional meaning that the proportion of the solid alkali silicates in the water-soluble compound -Compounds is raised substantially.
  • the stabilizing alkali silicate simultaneously becomes "solid thinner" in the multi-substance mixture and thus leads to a spatial distancing of the solid components with peroxo structure, which are at risk of decay.
  • the multifunctionality of this stabilizer component based on alkali silicates is not limited to this increased stabilizing effect.
  • the alkali silicate compounds now present in increased concentrations can have an independent function, which can be seen in the solid multicompound compound completely independently of their stabilizing effect. So this alkali silicate can function in particular in the field of detergents and cleaning agents Active ingredient component for setting the desired alkaline areas in the wash liquor.
  • the function of the alkali silicates as detergent builders and / or cobuilders for developing and strengthening the detergency in admixture with the surfactant compounds and the further components of a conventional detergent or cleaning agent formulation comes into consideration here.
  • sodium silicate is to be reacted with module 2 with aqueous carbonic acid in the presence of hydrogen peroxide.
  • a mixture of the sodium percarbonate formed with the sodium silicate portion modified in the module is obtained.
  • the teaching of the invention is free from such a constraint regarding the change in the chemical nature of component (K1).
  • the selection of suitable alkali silicate compounds by type and amount in the multi-substance coumpounds according to the invention can be determined by technical considerations for the intended use, in particular for the use of the alkali silicates as detergent builders and / or co-builders. In this regard, reference is made to the general specialist knowledge, only a number of important aspects being particularly emphasized in the following.
  • Corresponding compounds of sodium and / or potassium are particularly suitable alkali silicates.
  • Compounds of sodium can be of particular importance, especially in the field of detergents and cleaning agents which are commercially available today.
  • the module - i.e. the molar ratio of SiO 2 to M2O, where M here denotes alkali metal, in particular therefore sodium and / or potassium, can be chosen within a very wide range from the point of view of stabilization.
  • M denotes alkali metal
  • This fact is derived from the fact that not only alkali metal silicates have been described as stabilizers for, for example, percarbonate, the prior art also provides for the use of highly disperse silica as such for stabilizing sodium percarbonate, see, for example, DE-A 2748783.
  • sodium silicate is formed on the surface of the percarbonate particles and thus has a stabilizing effect.
  • Alkali silicates suitable according to the invention thus correspond, for example, to the modulus range from about 0.8 to 10. If the stabilizing effect of the alkali silicate is not only taken into account, the technical teaching also places particular emphasis on the secondary effect of these stabilizers in the aqueous solution used Fleet, then additional considerations are appropriate here. It is known, for example, that alkali silicates with a module range of approximately 1 to 4 are of particular importance, so that these compounds become the preferred stabilizers if the multicomponent compounds are to be used in the specified field. Within this range, module values from approximately 1.2 to 3.8 and preferably from approximately 1.5 to 3.0 can be of particular importance, with module values in the range from 1.7 to 2.7 large in detergents and cleaning agents is of practical importance. It applies to the teaching according to the invention that these secondary requirements for the functionality of the alkali silicate can generally be met without hesitation in the ultimately required use without endangering the advantages of the improved stabilization of the peroxo compounds threatened by decomposition.
  • This first objective of the action according to the invention of stabilizing the multicomponent compounds against the undesired decomposition of the peroxo compounds influences the minimum amounts of alkali silicates in the multicomponent compound.
  • the amount to be used is clearly above the maximum values of about 1% by weight recommended in the prior art and is preferably at lower limit values of at least 3-5% by weight and in particular at least about 10% by weight of alkali silicate on the sum of the proportions of (K1) - the alkali silicate compound (s) - and the components (K2) to be discussed in detail below - the other solid components used in a mixture with (K1).
  • Further preferred lower limit values for the amount of (Kl) - again based on the sum (Kl) + (K2) - are at least about 15% by weight and in particular at least 25% by weight.
  • the invention provides for the use of one or more further finely divided solid component (s) which are designated (K2) in the definition according to the invention.
  • solid component (s) which are designated (K2) in the definition according to the invention.
  • Representative of this (K2) components can be inorganic and / or organic compounds and in particular corresponding water-soluble salts.
  • Particularly suitable compounds are those which are capable of binding H2O2 and, if appropriate, H2O.
  • a decisive element here for the action according to the invention is that these (K2) representatives in turn do not have to be able to form H2O2 complex compounds of increased stability. The mere ability to add H2O2 even without special stability requirements determines the selection of preferred components of the class (K2).
  • the components (K2) are present in a very fine distribution in the alkali silicate - the component (C1) - serving as stabilizer and diluent. If hydrogen peroxide is introduced into the mixed product in the manner to be described below, these (K2) components can to a certain extent serve as catchers for the H2O2 and, under normal conditions, fix them to the liquid component per se in situ and thus ensure the solid properties. It is known that numerous representatives of inorganic and / or organic salts are not only capable of such fixation, for example of water of crystallization, but can also fix the H2O2 molecule in a structural structure. In this respect, the definition of the (K2) components is very broad.
  • the carbonates, bicarbonates, sulfates, halides, borates, phosphates and / or polyphosphates may be mentioned from the range of inorganic salts without claiming to be complete.
  • These salts are expediently also incorporated as alkali salts and in particular as sodium and / or potassium salts as component (K2) in the multi-compound compounds according to the invention.
  • K2 sodium and / or potassium salts
  • the alkali silicates for (K1) should - especially under the conditions for their condition described in detail below - be able to incorporate H2O2 components into their solid structure.
  • this should apply to over-dried but nevertheless water-soluble forms of the alkali silicates in chain or band structure and / or surface structure, which are known in the technical field as so-called Q2 or Q3 forms.
  • Q2 or Q3 forms It is therefore entirely within the scope of the invention that at least portions of the hydrogen peroxide to be incorporated in the multi-component compound are also incorporated in the alkali silicate (C1) component. Nonetheless, the use of the (K2) mixture components is of essential importance to the invention. In preferred embodiments described below, they form the basis for a physical configuration of the dried material with a microporous structure and, accordingly, a comparatively large BET surface area and large cumulative volume.
  • organic (K2) components mixed with the alkali silicate can be used.
  • the organic scavenger components should preferably be water-soluble and, in particular, should be able to incorporate the H2O2 molecule.
  • Suitable representatives for such organic (K2) compounds are, in particular, alkali metal salts of lower carboxylic acids, with corresponding alkali metal salts of lower polyfunctional carboxylic acids being particularly preferred.
  • the preferred alkali salts are corresponding compounds of sodium and / or potassium.
  • polyfunctional carboxylic acids examples include citric acid, succinic acid, adipic acid, glutaric acid, tartaric acid, sugar acids, amino carboxylic acids and / or nitrilotriacetic acid.
  • oligomeric and / or polymeric polycarboxylates can also be present, as are used to a large extent as so-called cobuilder components in today's detergent formulations.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid can be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • biodegradable terpolymers for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers.
  • K2 component (s) mixtures of several “scavenger substances” of the type specified are used as (K2) component (s).
  • (K2) component (s) mixtures of several “scavenger substances” of the type specified.
  • general specialist knowledge of the conditions for the practical use of multi-component compounds, for example in detergents and cleaning agents, can again be decisive for the special selection of such (K2) mixtures.
  • the (Kl) component based on alkali silicate can have the main builder function in the finished detergent, but this usually requires the co-use of a cobuilder component in order to achieve the desired detergency.
  • cobuilders are organic polyfunctional carboxylate compounds, be it in the form of low molecular weight polyfunctional carboxylic acid salts, in particular citrates, or in the form of the previously described oligo- or polycarboxylates.
  • the invention enables any combination as ultimately required by experts without departing from the principle according to the invention.
  • the inorganic and organic (K2) components present in a mixture then serve as “catcher substances” for at least a portion of the H2O2 in the multicomponent compound.
  • the alkali silicate used as the (K1) component acts as a stabilizer and at the same time as a solid thinner for the (K2) carrier substances.
  • each mixture component has the functionality intended for it, or is then filled out by it.
  • the total of the (K2) components are preferably present in amounts of at least about 5% by weight and in particular of at least about 10% by weight. It may be expedient for the proportion of (K2) component (s) to be at least 15% by weight and preferably at least 20% by weight, in each case based on the sum of (Kl) + (K2) .
  • the preferred upper limits for the amount of (K1) are approximately 95% by weight and preferably 90% by weight. Amounts of the (K1) component in the range from about 25 to 80% by weight can be particularly expedient.
  • the numerical value of about 75% by weight is derived for the preferred upper limit for the amount (K2).
  • amounts of (K2) component (s) in the range from about 15 to 60% by weight will be particularly expedient. It is further preferred that the (K2) components are at least largely dried in an anhydrous manner and are freed of water components which are bound, for example, as water of crystallization.
  • the amount (K1) in the multi-component compound is at most about 50% by weight and preferably not more than about 35-40% by weight, with a simultaneously increased amount of H2O2 binders (K2).
  • This proportion (K2) can then be up to 75-80% by weight, for example.
  • comparatively large amounts of H2O2 can be stored in the multicompound compound and - due to the intimate mixing with the components - effectively stabilized.
  • This component (s) (C1) is still present in a concentration which is significantly higher than in the prior art and can, for example, effectively correspond to its own function in the context of textile washing.
  • the amount (K1) is above 50% by weight.
  • Multi-component components of the type according to the invention are capable of absorbing and fixing possibly considerable amounts of H2O2. It will be described in detail below that this peroxide can be introduced into the multicomponent compound either during the agglomeration and drying of the multicomponent mixture and / or subsequently.
  • the content of fixed H2O2 and / or its subsequent products, which arise in particular in situ is at least about 0.2 to 0.3% by weight and preferably at least about 0.5% by weight.
  • H2O2 contents are important, which are then, for example, at least about 1% by weight and in particular at least about 3% by weight.
  • H2O2 can be stored in the goods in a storage-stable manner, so that preferred lower limits for the H2O2 content, for example at least 5% by weight, also remain at least 7 or 8% by weight, or at least 10% by weight, but possibly also significantly higher, for example 15 or 20% by weight.
  • preferred lower limits for the H2O2 content for example at least 5% by weight, also remain at least 7 or 8% by weight, or at least 10% by weight, but possibly also significantly higher, for example 15 or 20% by weight.
  • the following further considerations apply, which show a further considerable degree of freedom for the action according to the invention:
  • the (K2) components used as “scavenger substances” are introduced into the mixture of substances free of H2O2 components.
  • the hydrogen peroxide is added as a separate component in the course of drying and / or subsequently and incorporated into the multi-component compound.
  • the (K2) scavenger substances are not only capable of fixing H2O2, they are in particular able to bind water - be it in complex form, be it as water of crystallization or as a mere additive compound.
  • important advantages for the invention can be derived from this:
  • the total free-standing capacity of the (K2) substances for fixing can be used for fixing H2O2 molecules in part, but also for fixing if necessary of water molecules are used. There is thus the possibility of these two components coexisting in the multicompound compound, with the ability of the alkali silicate - the (K1) component - to take water into its molecular structure and to take it into account fix.
  • this (K1) component in the form of an over-dried and accordingly greatly reduced residual water content, the possibility opens up in the practical entry of the hydrogen peroxide with commercially available aqueous per ⁇ oxide solutions to work without thereby endangering the storage stability of the finished peroxide-containing multi-component compound.
  • the amount of water introduced as part of this peroxide entry can, if desired, be at least largely discharged again by drying, but it may well be tolerable to leave not inconsiderable amounts of water in addition to the hydrogen peroxide in the material, without necessarily triggering instability with regard to the peroxide portion.
  • use can be made of the specialist knowledge for optimizing the peroxide stabilization in the field concerned here. Without claiming completeness, a few important points are highlighted:
  • catalytically active residues in particular corresponding traces of heavy metal
  • additional complexing or masking in such a way that they lose their catalytic activity.
  • Suitable organic stabilizers are, in particular, complexing agents, examples of which are only: salts of polyphoshonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid (EDTMP). Further examples are: ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) or the stabilizers specified in detail in DE 2234135, DE 3125638 and EP 0442549.
  • the amount of these known stabilizer components is in the usual range, ie with comparatively very small amounts based on the valuable substances of the multi-component compound according to the invention.
  • the stabilizers used in the prior art are at most about 1 to 3% by weight, based on the weight of the multi-component compound.
  • Further information on complexing agents for heavy metals that are also suitable according to the invention can be found in the relevant specialist literature, for example Dr. L. Hartinger "Pocket Book of Wastewater Treatment for the Metalworking Industry", Vol. 1: Chemistry, Chapter 3.7.5 “Metal Precipitation” and Chapter 4.5 "Metal Complex Compounds", Carl Hanser Verlag Kunststoff Vienna 1976 as well as “Teaching and Handbook of WASTEWATER TECHNOLOGY” , 3rd edition, vol.VII, chapter 8.2.2 “Neutralization and metal precipitation", Ernst & Sohn publishing house for architecture and technical sciences Berlin.
  • the heavy metal masking agents when used, it may be expedient to incorporate these stabilizers into the components or multicomponent mixtures loaded with excessive levels of heavy metals before the multicomponent mixture is loaded with the aqueous H2O2. In this way it can be ensured that excessive levels of heavy metal residues are inactivated to such an extent that undesired catalysis of the H2O2 decomposition is prevented.
  • aqueous H 2 O 2 solutions which are incorporated into the multicomponent compound as part of its drying or as part of a separate subsequent loading ⁇ step to be incorporated.
  • the mixture component is particularly important (Kl) to be seen as a problem component.
  • Kl the mixture component
  • the large-scale production of water glass generally leads to heavy metal contamination in areas which are significantly above the limit values previously given for reasons of stability.
  • C1 the content of undesired iron in the range above 50 ppm and in particular in the range from 100-250 ppm, based on solid alkali silicate, can already be present.
  • the alkali metal silicate component (C1) contaminated with heavy metal components is mixed in the form of an aqueous solution in a preliminary stage with the stabilizer or stabilizer mixture selected in each case, mixed intensively and at room temperature or else elevated temperatures for a period of at least about 10-15 minutes brought to abreaction.
  • the reaction of the heavy metal impurities in the alkali metal silicate solution with the added stabilizers can be particularly suitable in the range of the room temperature with reaction times in the hour range.
  • Particularly suitable stabilizers are the aforementioned compounds of the type of HEDP and the related substances mentioned in connection therewith which are capable of forming complexes with the heavy metal components.
  • the agglomeration of the capture components added in finely divided form to (K2) can take place using the pretreated and stabilized aqueous alkali silicate solution as the binding medium.
  • the carrier compound which can be loaded with H2O2 in a subsequent working step, is then formed from the agglomerate formed in this way by at least partial drying. Details will be given below.
  • the production of the preparation forms of the solid mixtures according to the invention and their loading with the hydrogen peroxide is controlled by the overarching idea of bringing the (K1) and (K2) components into the most intimate mixture possible.
  • the free choice of the components for (Kl) and (K2) in terms of type and quantity allows the functions in the finished product to be optimally coordinated.
  • the agglomeration can take place in a manner known per se; reference is made, for example, to the relevant specialist literature.
  • the finely divided solid material - in particular the components of (K2) - can be used with average particle sizes in the range from, for example, 0.1 to 1.5 mm and in particular with average particle sizes in the range from 0.2 to 0.8 mm.
  • a special one A suitable range for average particle sizes of these solid components can be 0.2 to 0.5 mm and in particular approximately 0.2 to 0.4 mm.
  • Corresponding numerical ranges apply in the event that the components of (K1) are at least partly fed to the agglomeration process as solids.
  • the multicompound compound is formed in a first process stage by wet agglomeration of the components used in finely divided solid form to (K2), with a particularly aqueous preparation as the liquid phase - Solution and optionally dispersion - of (Kl) components is used.
  • K2 finely divided solid form
  • Kl liquid phase - Solution
  • the mixing ratios of (K2) to (Kl) also determine the respective offer forms.
  • their proportionate use as solid particles in the wet agglomeration process can be useful.
  • the primary wet agglomerate is subjected to a drying process before the introduction of hydrogen peroxide.
  • all drying techniques are suitable here, in particular corresponding processes using a hot gas phase as the drying medium.
  • the use of hot air and / or hot inert gases can be particularly expedient here in order to exclude undesired reactions of the component ⁇ ) to (K1) with CO 2 portions of the drying gas.
  • Preferred multi-component compounds of the invention lie the (Kl) component (alkali silicate) with a residual water content that is significantly lower than the equilibrium water content of the respective material.
  • the water content of a typical water glass with module values in the range from about 2 to 3.7 is in the usual drying process in the range from about 18 to 20% by weight. According to the invention, it may be desirable to lower this water content below the limit of 18% by weight and in particular to a limit of at most 15% by weight. A further lowering of the residual water into the area of significantly over-dried water glasses may be desirable.
  • the residual water content of the (Kl) component is in the range from about 3 to 12% by weight and in particular in the range from about 5 to 10% by weight, based in each case on the (Kl )-Component.
  • the alkali silicate is particularly X-ray amorphous. Methods for producing such over-dried sodium disilicate are described, for example, in EP-A-0444415. It describes the production of an amorphous sodium disilicate to be used as a builder in detergents and has a water content of 0.3 to 6% by weight.
  • These highly dehydrated amorphous disilicates are produced in a multi-stage process which initially involves the production of a powdery amorphous material with a water content of 15 to 23% by weight. This material is subsequently treated with flue gas in countercurrent at temperatures of 250 to 500 ° C. The processed material is then shredded.
  • drying mechanisms can also be considered within the framework of the teaching according to the invention. It has been shown, however, that particularly useful results are obtained if a very specific working aid, namely superheated steam, is used as drying gas and / or protective gas in certain work steps described below.
  • This very use of superheated steam as a drying and / or protective gas for drying up the multicomponent mixtures composed according to the invention has many advantages. First, only the most important elements are referred to:
  • a crucial core idea lies in the application of the principle of drying, in particular spray and / or fluidized bed drying, aqueous preparations of valuable materials and mixed materials with superheated steam as a hot gas stream for supplying the vaporization energy into the material to be dried and the simultaneous absorption of the evaporated water portion in the stream of superheated water vapor and removal of this evaporated water portion together with the superheated steam stream withdrawn from the drying zone.
  • the discharged water is condensed and worked up, while the rest of the superheated steam in a closed circuit into the drying zone is returned after the amount of energy removed by the drying has been fed back to him.
  • the closed circulation system of the superheated steam enables the CO 2 -free drying and thus avoids undesired secondary reactions in the material to be dried.
  • the conditions of drying can be controlled as desired with regard to the residual water content.
  • the removal of water is possible with simultaneous condensation of the silica residues to form oligomer and / or polymer compounds.
  • Practically any degree of overdrying in the silicate material can be set without adversely affecting the spontaneous and easy solubility of the dried product in water. Taking into account the tendency of the silica residue to three-dimensionally crosslink and thus to form sparingly soluble to insoluble fractions in the dry material, there is a very decisive advantage for the use of the superheated steam as the drying medium.
  • the primary dry material is obtained in the form of a free-flowing granular material of considerable bulk weights, nevertheless this dry material has suitable BET surfaces for covering with other valuable and / or auxiliary substances go far beyond the outer shells of the grain structure to be calculated.
  • the primary dry material is a material with a microporous, absorbent internal structure, which can be filled with sufficiently flowable components in a subsequent work step. It is immediately understandable that a material of such a nature must be particularly well suited for subsequent implementation with aqueous peroxide solutions. This microporous inner structure is also of decisive importance for the dissolving behavior of the dry material according to the invention.
  • the first embodiment provides for all components of the finished multicompound compound to be combined with one another and dried in the course of a material pass through agglomeration.
  • the constituents can be fed to the drying zone in a mixture with one another, but also at least partly in separate streams and combined here in the course of the drying process.
  • the hydrogen peroxide component is not fed to the drying stage at all or only in part.
  • a granular material falls out of the components (C1) and (K2) and any other components that may be used.
  • the process product obtained is a granular material with the desired microporous internal structure.
  • the embodiment concerned here to only use a portion of the amount of H2O2 to be entered in this drying stage.
  • the alkali silicates of the (Kl) component are used to discharge three-dimensional space - the so-called Q4 structure - enabled, which is characterized by limited water solubility. In the phase of superheated steam, no or practically no insoluble components are formed even if the (Kl) component is overdry.
  • the alkali silicate portion of the dry material is characterized by high water solubility even at ambient temperature. Its proportion of insoluble material is usually ⁇ 3% by weight and in particular ⁇ 1% by weight. This high willingness to be water-soluble is precisely what the multi-functionality of the solid compounds aimed for according to the invention is the (Kl) component is also relevant to the decision, if, for example, the builder function is aimed at in practical use.
  • a multicomponent mixture in the sense of the combinations according to the invention can initially be agglomerated and dried in any manner in the absence of superheated steam.
  • the water solubility of this multicomponent mixture and in particular the (K1) component is then regulated by treatment with superheated steam.
  • the printed state of the art has corresponding information here, compare, for example, DE-A 2360502. For the use of such a modification of the process, it is understandable that the subsequent impregnation of a pre-formed dry multi-compound with the hydrogen peroxide is particularly useful.
  • the hydrogen peroxide can indeed be introduced during the agglomeration and drying of the aforementioned aqueous preparation of components (C1) and (K2), but the hydrogen peroxide is preferably introduced into a preformed dry material.
  • the dry material with the largest possible surface area should be offered for subsequent introduction of the hydrogen peroxide or its aqueous preparation forms.
  • work can be carried out, for example, in the fluidized bed or in other forms; reference is made to this ⁇ for example to DE-C 21 33566 and DE-A 2344017.
  • the corresponding preparation of perhydrate compounds based on sodium carbonate, sodium phosphate or mixtures thereof is described.
  • That extremely finely divided material (particle size of about 0.05 to 1.4 mm) is sprayed with an aqueous peroxide solution (concentration of 35 to 90% by weight) and for a period of, for example, 15 minutes in the range of moderately heated temperatures (20 to 60 ° C).
  • aqueous peroxide solution concentration of 35 to 90% by weight
  • Comparable method steps can be used in the embodiment of such a method which has now been modified according to the invention, but in particular the temperature can also be raised.
  • Particularly suitable for the production of the multi-component compounds according to the invention are processes, ⁇ °; to which the drying of the aqueous peroxide solution added simultaneously or subsequently is carried out using and / or in the protection of a gas phase.
  • Gas phases can be used as carrier gas for the fluidized-bed drying and / or for the application of the hydrogen peroxide solution and the subsequent drying on a pre-formed, finely divided solid material. Basically, the use of flowing hot gas phases shortens the drying time and thus the period of temperature stress.
  • the maximum desired temperature of the product can be set or controlled by suitable selection of the temperature of the hot gas phase.
  • H2O2 for example, the addition of H2O2 to selected (K2) components, for example sodium carbonate, is an exothermic reaction.
  • K2 components for example sodium carbonate
  • a further modification of the bound multicompound compounds containing H2O2 falls within the scope of the teaching according to the invention. In particular, two treatment steps that can also be combined with one another must be taken into account here.
  • Sodium percarbonate crystals make only limited sense for the reasons given.
  • This procedural measure can be expedient for the goods which are now stabilized in terms of storage according to the invention.
  • Such a final coating with inorganic and / or organic coating substances can in particular prevent undesired interaction when used in solid detergents with other components of such active ingredient mixtures.
  • the numerous materials from the proposals of the prior art come into consideration as Hü11 substances; reference is once again made to DE-A 41 09953 and the extensive secondary literature cited therein.
  • a particularly simple example of an inorganic coating is the final covering of the outside surfaces of the manor with water glass, the alkali silicate used here being identical to or different from the (Kl) components.
  • Organic coating materials can be applied as a melt, so that an additional post-drying step is not necessary here.
  • the second possibility of the aftertreatment of a multicompound compound, in particular with a microporous good structure, in the sense of the definition according to the invention makes use of the comparatively large BET surfaces and accordingly increased cumulative volumes, which are derived from the high microporosity of the goods.
  • the invention provides for additional valuable and / or auxiliary substances to be applied to the primary dry material in a form that is flowable at the application temperature and to fill the microporous internal structure of the material at least partially with it.
  • Corresponding valuable substances and / or auxiliary substances from the field of wetting agents, detergents and cleaning agents are suitable as impregnating compounds.
  • surfactants or surfactant-containing liquid preparations which are preferably water-free, for example free-flowing nonionic surfactants, but also other builders or cobuilder components, anti-foaming agents, solubilizers and any other valuable substances.
  • the bulk densities of the multicomponent material are usually at least about 150 g / 1 and preferably at least 200 g / 1. These lower numerical values already apply to the multi-component compound consisting of (K1) and (K2) components.
  • the bulk densities of the material are significantly increased by the loading with peroxide and the possibly additional final covering and / or loading of the microporous grain interior with further valuable and / or auxiliary substances. In particular, they are at least 350 g / l.
  • the bulk densities of the combined material can be varied very largely freely by suitable measures. The values aimed for in modern detergents with bulk densities of at least about 700 g / l can thus be set at any time.
  • a preformed carrier compound composed of the (K1) and (K2) components with an aqueous hydrogen peroxide solution.
  • the use of loading temperatures below 35 ° C. and in particular up to a maximum of about 30 ° C. may be expedient, preferably at the same time preferably applying aqueous H2 O 2 solutions which are as highly concentrated as possible.
  • the application in the fluidized bed has proven particularly successful here.
  • Corresponding commercially available hydrogen peroxide solutions with a content of about 70% H2O2 are suitable, for example.
  • This loading stage is generally carried out in the presence of a protective gas phase.
  • air can be used as a protective gas, in particular when working at the low temperatures mentioned.
  • Additional stabilizers can be added to the multifunctional compound together with the aqueous hydrogen peroxide solution. As a rule, however, this is in the previous one The embodiment described is not necessary, even if the relatively large traces of heavy metal, which are entered on an industrial scale, are present, but have previously been masked by separate inactivation.
  • a solid mixture of 30% by weight of the sodium water glass described above (module 2.0) and 70% soda was sprayed with a liquid mixture in a Lödige mixer.
  • the liquid mixture consisted of 70% aqueous H2O2 solution, which is necessary for the stoichiometric conversion of the soda used above to sodium percarbonate (Na2CÜ3, 1.5 H2O2), 5% by weight of an aqueous water glass solution N 2.0 and 0.03% by weight .-% HEDP.
  • the data in% by weight relate to the amount of solids mixture used.
  • the liquid mixture was sprayed on quickly and the amount of water entered evaporated to a large extent and was withdrawn from the mixer via a vacuum connection.
  • the aqueous water glass solution acted as a binder for the solids used.
  • the finished agglomerate of water glass N and sodium percarbonate had a bulk density of 600 g / 1.
  • Example 2 The procedure was as in Example 1. After completion, the granules were coated with a moisture-protecting layer of a Ci ⁇ fatty alcohol ("Lorol C 18 R ) and a nonionic surfactant with 40 EO units (" Dehydol TA 40 "), mixing ratio 80:20. The end product contained 20% of the organic components.
  • Example 2 The procedure was as in Examples 1 and 2.
  • the granules of Example 2 were mixed in a die press after intersective mixing with the organic components, in this case 80% Dehydol TA 40 and 20% Dehypon LT 104 R (fatty alcohol C12-Cis + 10 E0, n-butyl) shaped about 1 mm granules.
  • the final spherical shape was given to them in a Marumerizer.
  • the procedure was as in Examples 1 to 3.
  • the 1 mm granules (average grain diameter) were covered with a final protective layer.
  • the coating layer (15% by weight with respect to the amount of granules) consisted of 80% by weight of fatty alcohol Lorol C18 and 20% by weight of nonionic surfactant Dehydol TA 40.
  • the procedure was as in Examples 2 to 4.
  • the solid mixture consisted of 30% sodium water glass 2.0 including complexing agent, 20% tri-Na citrate and 50% soda.
  • the solid mixture was dried in a spray tower with superheated steam. While spraying with a 70% H2 ⁇ 2 solution the slightly soluble tri-Na citrate was partially dissolved and served as a binder for the build-up granulation.
  • the H2O2 was added stoichiometrically to the soda and tri-sodium citrate in order to produce the corresponding addition compounds.
  • the yield of H2 ⁇ 2 addition compounds was 94% after drying to remove residual water.
  • the granules were then coated in a Lödige mixer with a 30% layer of 55% by weight Dehydol TA 40, 30% by weight Lorol C18 and 15% by weight Dehypon LT 104.
  • Example 5 The procedure was as in Examples 1 to 5.
  • the coating layer which closes on the outside has been applied to the granules in a fluidized bed.

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Abstract

L'invention concerne un mélange solide de plusieurs composants au moins en partie hydrosoluble, destiné notamment à être utilisé dans des nettoyants et détergents, des agents de blanchiment et/ou des agents désinfectants. Ledit mélange contient du péroxyde d'hydrogène absorbé et/ou lié ainsi que, le cas échéant, des composés per formés sous l'action de ce dernier, dans un mélange de (K1) silicates alcalins présentant un module (rapport molaire SiO2 : M2O représentant le métal alcalin) de 0,8 à 10 et (K2) au moins un autre constituant solide inorganique et/ou organique, de préférence au moins en partie hydrosoluble, pouvant absorber H2O2 et le cas échéant H2O. L'invention est caractérisée en ce que ledit mélange de plusieurs composants contient au moins 3 à 5 % en poids de (K1) et au moins 5 à 10 % en poids de (K2), par rapport à la somme (K1)+(K2); ledit mélange de plusieurs composants se présente sous forme d'agglomérat d'une pluralité de fines particules, liées entre elles de façon solide, de constituant (K2) et éventuellement (K1), incorporées au moins en partie sous une forme solide appropriée lors de l'agglomération; l'incorporation de H2O2 est effectuée pendant et/ou, de préférence, au moins en partie, après la formation du mélange de plusieurs composants aggloméré. L'invention concerne en outre des mélanges solides multifonctionnels de plusieurs composants destinés à être utilisés dans des nettoyants et détergents, ainsi qu'un procédé de production desdits mélanges et leur utilisation dans des nettoyants et détergents.
PCT/EP1996/003725 1995-09-04 1996-08-23 Melanges solides de plusieurs composants contenant du peroxyde d'hydrogene fixe, stable au stockage, procede de production desdits melanges et leur utilisation Ceased WO1997009269A1 (fr)

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DE1995132558 DE19532558A1 (de) 1995-09-04 1995-09-04 Lagerstabil fixiertes Wasserstoffperoxid enthaltende Mehrstoffgemische in Feststofform, Verfahren zu ihrer Herstellung und ihre Verwendung (II)
DE19532558.3 1995-09-04

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DE19711810A1 (de) * 1997-03-21 1998-09-24 Thomas Willuweit Verwendung von Alkalipercarbonat-Peroxyhydraten in der Fischzucht

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1299969A1 (ru) * 1984-02-20 1987-03-30 Государственный научно-исследовательский институт химии и технологии элементоорганических соединений Способ получени гранулированного перкарбоната натри
AT391121B (de) * 1985-11-15 1990-08-27 Gnii Khim T Elemento Organ Verfahren zur herstellung von granuliertem stabilisiertem natriumperkarbonat
EP0550077A1 (fr) * 1992-01-03 1993-07-07 The Procter & Gamble Company Composition de blanchiment granulaire pour le lavage du linge
WO1995025065A1 (fr) * 1994-03-14 1995-09-21 Henkel Kommanditgesellschaft Auf Aktien Melanges complexes sous forme solide contenant du peroxyde d'hydrogene fixe stable au stockage, leur procede de fabrication et leur utilisation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1299969A1 (ru) * 1984-02-20 1987-03-30 Государственный научно-исследовательский институт химии и технологии элементоорганических соединений Способ получени гранулированного перкарбоната натри
AT391121B (de) * 1985-11-15 1990-08-27 Gnii Khim T Elemento Organ Verfahren zur herstellung von granuliertem stabilisiertem natriumperkarbonat
EP0550077A1 (fr) * 1992-01-03 1993-07-07 The Procter & Gamble Company Composition de blanchiment granulaire pour le lavage du linge
WO1995025065A1 (fr) * 1994-03-14 1995-09-21 Henkel Kommanditgesellschaft Auf Aktien Melanges complexes sous forme solide contenant du peroxyde d'hydrogene fixe stable au stockage, leur procede de fabrication et leur utilisation

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* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8742, Derwent World Patents Index; Class D25, AN 87-298074, XP002021156 *
DATABASE WPI Section Ch Week 9445, Derwent World Patents Index; Class D25, AN 94-364463, XP002021155 *

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