EP0098187A1 - Zeolite as a detergent aid - Google Patents

Zeolite as a detergent aid Download PDF

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EP0098187A1
EP0098187A1 EP83401175A EP83401175A EP0098187A1 EP 0098187 A1 EP0098187 A1 EP 0098187A1 EP 83401175 A EP83401175 A EP 83401175A EP 83401175 A EP83401175 A EP 83401175A EP 0098187 A1 EP0098187 A1 EP 0098187A1
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Prior art keywords
zeolite
zeolites
calcium
primary particles
incrustation
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German (de)
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EP0098187B1 (en
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Robert Gresser
Max Michel
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
Rhone Poulenc Chimie de Base SA
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    • 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
    • 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

  • the present invention relates to a zeolite as a detergency aid in laundry formulas.
  • Detergency aid in detergency, in particular for its qualities of dispersant, of sequestering alkaline earth ions and its solubility, which allowed s '' get rid of it after use without leaving traces.
  • the object of the present invention is a zeolite as a detergency aid, which, with equal particle sizes, has improved detergency efficiency compared to the zeolites used to date.
  • the present invention constitutes a departure from this concept.
  • the primary particles can be agglomerated together.
  • the zeolite can also be agglomerated with another component of the laundry.
  • the "initial calcium exchange" reaction with a 4 A zeolite that is to say in a field where the concentration of exchanged calcium does not exceed 30 to 40% of the zeolite exchange capacity, can be described by a law of speed of the first order compared to calcium and of the first order compared to zeolite.
  • the measurement of the initial rate of exchange of calcium by a zeolite is done by means of a "forced circulation cell" (AM GARY and JP SCHWING, BULL. SOC. CHIM. 9 (1972), 3654 - AM GARY, E. PIEMONT, M. ROYNETTE and JP SCHWING, Anal. Chem. 44, (1972), 198 - AM GARY, THESE 3ème CYCLE STRASBOURG (1970)), for sufficiently high half-reaction times and by stopped flow spectrophotometry for shorter half-reaction times.
  • These two devices make it possible to obtain sufficiently short mixing times so as not to disturb the kinetic measurement.
  • the variation in calcium concentration over time is followed, during the exchange reaction, by spectrophotometry in a heterogeneous medium using a calcium indicator: the murexide (length 495 nm).
  • the specific surfaces and the diameter of the particles of the zeolite samples are determined by calculation, by statistical analysis of the images of these zeolites obtained with a scanning electron microscope (M.E.B).
  • the crystallinity levels of each of the three zeolite 4 A samples used are greater than 90%.
  • the theoretical exchange capacities of these three zeolites are 352 mg CaCO 3 / g anhydrous and the calcium exchange power indicated in Table 1 was determined after 15 minutes, in NaCl 3 g / l medium, using '' a specific calcium electrode (ORION 93-20-00).
  • the initial calcium concentration used here is 5.10 -3 mol 1 -1 and the zeolite concentration 1 g (anhydrous) / liter.
  • the temperature is 25 ° C.
  • the choice of medium NaCl 3g / 1) was determined by the desire to make the measurement in a medium of ionic strength representative of that of a detergent medium.
  • the constant values ks were determined by the three samples A, B, C.
  • Figures 1 to 4 show by way of example, the variations of ln Ca2 + as a function of time thus obtained for the samples A, B (1), B (2), and C for zeolite concentrations of 143, 50 respectively. , 143.50 ppm.
  • Table 3 gives the values of the constant k of the Ion samples of zeolites used
  • the calcium concentration is determined at different times by assaying Ca2 + (atomic absorption) contained in the solution obtained by sampling and filtering as quickly as possible from a small volume of solution.
  • the difference that may exist between these three samples is within the range of the measurement error.
  • Cumulative tergotometer wash cycles were performed at 60 ° C.
  • the concentration of detergent used is 6g / l and the hardness of the water used is 32 ° HT. (NFT 90 003).
  • Each cycle includes a 20-minute washing phase and 3 hard water rinses.
  • Each pot of the tergotometer contains twelve pieces of cotton (ref. 405 Testfabric, size 10 x 12 cm). The amount of solution used in each wash and in each rinse is 1 liter per jar.

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Cosmetics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Processing Of Solid Wastes (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

Type A, especially type 4A zeolites are well adapted as detergent builders, said zeolites comprising (i) primary particles having a mean particle diameter ranging from 0.1 to 10 mu , (ii) a cation exchange capacity in excess of about 100 mg CaCO3/g of anhydrous material, and (iii) a rate constant, relative to the surface area of the zeolite per liter of wash solution, in excess of about 0.15 s-1 lm-2. The builders are prepared by first determining the value of the rate constant for a given zeolite sample. Since a higher rate constant value corresponds to a lower degree of salt incrustation on fabrics, only those zeolites having a value above the predetermined minimum will be incorporated into detergents. Thus, zeolites otherwise appearing identical can be differentiated, with only those not causing high levels of incrustation being selected.

Description

La présente invention a trait à une zéolite comme auxiliaire de détergence dans les formules lessivielles.The present invention relates to a zeolite as a detergency aid in laundry formulas.

On sait que pendant de longues années le tripolyphosphate de sodium a été considéré comme le meilleur builder .(auxiliaire de détergence) en détergence, notamment pour ses qualités de dispersant, de séquestrant des ions alcalino-terreux et sa solubilité, ce qui permettait de s'en débarrasser après usage sans qu'il laisse de traces.We know that for many years sodium tripolyphosphate has been considered the best builder. (Detergency aid) in detergency, in particular for its qualities of dispersant, of sequestering alkaline earth ions and its solubility, which allowed s '' get rid of it after use without leaving traces.

Malheureusement on a eu à lui reprocher ses "qualités" d'eutrophisation et il est apparu comme un perturbateur de l'ordre écologique.Unfortunately we had to criticize him for his "qualities" of eutrophication and he appeared as a disturber of the ecological order.

Aussi on a cherché à lui trouver un produit de substitution qui présentât les mêmes avantages tout en étant dépourvu de ses défauts.So we tried to find a substitute product that had the same advantages while being free from its faults.

C'est ainsi que naturellement l'on s'est tourné vers des produits minéraux, faciles à obtenir, bon marché, et en particulier vers les silico-aluminates bien connus pour leur pouvoir échangeur de cations et qui furent déjà utilisés en détergence dans le passé.This is how naturally we turned to mineral products, easy to obtain, inexpensive, and in particular to the silico-aluminates well known for their cation exchange power and which were already used in detergency in the past.

L'apparition dans l'intervalle de zéolites synthétiques notamment de type A les a désignés pour remplir cette fonction essentiellement en raison de leur pouvoir d'échange de cations plus élevé et de leur plus grande pureté. Sachant d'autre part que la dispersion des bentonites par exemple était favorisée par la faible taille des particules, il devint tout naturel de se diriger vers de faibles granulométries de l'ordre de 0,1 à 10p.The appearance in the meantime of synthetic zeolites, in particular of type A, has designated them to fulfill this function essentially because of their higher cation exchange power and their greater purity. Knowing on the other hand that the dispersion of bentonites for example was favored by the small size of the particles, it became quite natural to move towards small particle sizes of the order of 0.1 to 10p.

Toutefois en dépit de toutes ces précautions, il s'est avéré que les zéolites n'étaient pas en mesure de remplacer complètement le tripolyphosphate de sodium.However, despite all these precautions, it turned out that the zeolites were not able to completely replace the sodium tripolyphosphate.

En particulier, la logique de l'art antérieur incite à aller toujours vers de plus faibles granulométries en dépit des inconvénients en résultant notamment sur le plan de la facilité de manipulation.In particular, the logic of the prior art encourages us to always go towards smaller particle sizes in spite of the drawbacks resulting therefrom in particular in terms of ease of handling.

L'objet de la présente invention est une zéolite comme auxiliaire de détergence, qui, à granulométries égales, présente une efficacité améliorée en détergence par rapport aux zéolites utilisées à ce jour.The object of the present invention is a zeolite as a detergency aid, which, with equal particle sizes, has improved detergency efficiency compared to the zeolites used to date.

On sait qu'en particulier, l'on a lié la vitesse d'échange des ions Ca++ à la granulométrie et le tout à l'action en détergence des zéolites.We know that in particular, the rate of exchange of Ca ++ ions has been linked to the particle size and the whole to the detergency action of the zeolites.

La présente invention constitue une rupture de démarche avec ce concept.The present invention constitutes a departure from this concept.

La zéolite comme auxiliaire de détergence selon l'invention, est constituée par une zéolite de type A, notamment 4 A, caractérisée par le fait qu'elle présente :

  • - un diamètre moyen des particules primaires compris entre 0,1 et 10p et avantageusement entre 0,5 et 5p.
  • - un pouvoir d'échange théorique de cations supérieur à 100 mg de CaC03/g de produit anhydre, et de préférence supérieur à 200 mg,
  • - une constante de vitesse rapportée à la surface de zéolite par litre de solution supérieure à 0,15 de préférence supérieure à 0,25 et avantageusement comprise entre 0,4 et 4 seconde 1 litre mètre-2 (s-1 1m-2), ci-après désignée par k .
The zeolite as detergency aid according to the invention consists of a type A zeolite, in particular 4 A, characterized in that it has:
  • - An average diameter of the primary particles between 0.1 and 10p and advantageously between 0.5 and 5p.
  • a theoretical cation exchange power greater than 100 mg of CaC0 3 / g of anhydrous product, and preferably greater than 200 mg,
  • - a speed constant related to the zeolite surface per liter of solution greater than 0.15, preferably greater than 0.25 and advantageously between 0.4 and 4 seconds 1 liter meter -2 (s -1 1m -2 ) , hereinafter referred to as k.

Eventuellement les particules primaires peuvent être agglomérées entre elles. La zéolite peut aussi être agglomérée avec un autre constituant de la lessive.Optionally, the primary particles can be agglomerated together. The zeolite can also be agglomerated with another component of the laundry.

Les travaux de la demanderesse ont en effet montré que dans les conditions d'utilisation en détergence, on pouvait relier l'effet en détergence représenté par l'incrustation à la constante ks à granulométrie et à surface données.The work of the Applicant has in fact shown that under the conditions of use in detergency, it was possible to relate the effect in detergency represented by the incrustation to the constant ks with grain size and given surface.

De manière surprenante, on a observé, que pour des granulométries et surfaces égales, pour des pouvoirs d'échange égaux après 15 Linutes et pour des temps égaux nécessaires à la réalisation du quart de l'échange (t 1/4), l'on avàit des comportements différents en détergence notamment vis-à-vis de l'incrustation, et que ces comportements étaient fonction de la valeur de ladite constante.Surprisingly, it has been observed that for equal particle sizes and surfaces, for equal exchange powers after 15 Linutes and for equal times necessary for carrying out a quarter of the exchange (t 1/4), the we had different behaviors in detergency, in particular with regard to incrustation, and that these behaviors were a function of the value of said constant.

La réaction "d'échange initial du calcium" par une zéolite 4 A, c'est-à-dire dans un domaine où la concentration en calcium échangé ne dépasse pas 30 à 40 % de la capacité d'échange de la zéolite, peut être décrite par une loi de vitesse du premier ordre par rapport au calcium et du premier ordre par rapport à la zéolite.The "initial calcium exchange" reaction with a 4 A zeolite, that is to say in a field where the concentration of exchanged calcium does not exceed 30 to 40% of the zeolite exchange capacity, can be described by a law of speed of the first order compared to calcium and of the first order compared to zeolite.

La vitesse d'échange initial V a pour expression :

Figure imgb0001

  • avec : (Zéol.) : concentration en zéolite exprimée en ppm de zéolite anhydre.
  • k : constante de vitesse du second ordre, exprimée en -1 -1 s ppm .
  • S : surface de zéolite mise en jeu par litre de solution, mesurée au microscope à balayage, exprimée en m 1 -1.
  • k : constante de vitesse rapportée à la surface de
  • zéolite , par litre de solution, exprimée en s-1 1 m-2.
The initial exchange speed V has the expression:
Figure imgb0001
  • with: (Zeol.): zeolite concentration expressed in ppm of anhydrous zeolite.
  • k: second order speed constant, expressed in -1 -1 s ppm.
  • S: zeolite surface used per liter of solution, measured using a scanning microscope, expressed in m 1 -1 .
  • k: speed constant related to the surface of
  • zeolite, per liter of solution, expressed in s -1 1 m -2 .

La mesura de la vitesse d'échange initial du calcium par une zéolite se fait au moyen d'une "cellule à circulation forcée" (A.M. GARY et J.P. SCHWING, BULL. SOC. CHIM. 9 (1972), 3654 - A.M. GARY, E. PIEMONT, M. ROYNETTE et J.P. SCHWING, Anal. Chem. 44, (1972), 198 - A.M. GARY, THESE 3ème CYCLE STRASBOURG (1970)), pour des temps de demi-réaction suffisamment élevés et par spectrophotométrie à flux stoppé pour des temps de demi-réaction plus faibles. Ces deux dispositifs permettent d'obtenir des temps de mélange suffisamment faibles pour ne pas perturber la mesure cinétique. On suit ainsi, après mélange très rapide des réactifs, la variation de concentration en calcium avec le temps, au cours de la réaction d'échange, par spectrophotométrie en milieu hétérogène à l'aide d'un indicateur de calcium : la murexide (longueur d'onde 495 nm).The measurement of the initial rate of exchange of calcium by a zeolite is done by means of a "forced circulation cell" (AM GARY and JP SCHWING, BULL. SOC. CHIM. 9 (1972), 3654 - AM GARY, E. PIEMONT, M. ROYNETTE and JP SCHWING, Anal. Chem. 44, (1972), 198 - AM GARY, THESE 3ème CYCLE STRASBOURG (1970)), for sufficiently high half-reaction times and by stopped flow spectrophotometry for shorter half-reaction times. These two devices make it possible to obtain sufficiently short mixing times so as not to disturb the kinetic measurement. Thus, after very rapid mixing of the reactants, the variation in calcium concentration over time is followed, during the exchange reaction, by spectrophotometry in a heterogeneous medium using a calcium indicator: the murexide (length 495 nm).

La présente invention sera plus aisément comprise à l'aide de l'exemple suivant donné à titre illustratif mais nullement limitatif.The present invention will be more easily understood with the aid of the following example given by way of illustration but in no way limiting.

Les caractéristiques des échantillons de zéolite 4 A utilisés sont rassemblées au tableau 1 suivant :

Figure imgb0002
The characteristics of the 4 A zeolite samples used are collated in Table 1 below:
Figure imgb0002

Les surfaces spécifiques et le diamètre des particules des échantillons de zéolite sont déterminées par le calcul, par analyse statistique des clichés de ces zéolites obtenus au microscope électronique à balayage (M.E.B).The specific surfaces and the diameter of the particles of the zeolite samples are determined by calculation, by statistical analysis of the images of these zeolites obtained with a scanning electron microscope (M.E.B).

Les taux de cristallinité de chacun des trois échantillons de zéolite 4 A utilisés sont supérieurs à 90 %.The crystallinity levels of each of the three zeolite 4 A samples used are greater than 90%.

Les capacités d'échange théoriques de ces trois zéolites sont de 352 mg CaC03/g anhydre et le pouvoir d'échange du calcium indiqué au tableau 1 a été déterminé au bout de 15 minutes, en milieu NaCl 3g/l, au moyen d'une électrode spécifique au calcium (ORION 93-20-00). La concentration initiale en calcium utilisée est ici de 5. 10-3 mol 1-1 et la concentration en zéolite de 1 g (anhydre)/litre. La température est de 25°C. Le choix du milieu (NaCl 3g/1) a été déterminé par la volonté de faire la mesure dans un milieu de force ionique représentative de celle d'un milieu lessiviel.The theoretical exchange capacities of these three zeolites are 352 mg CaCO 3 / g anhydrous and the calcium exchange power indicated in Table 1 was determined after 15 minutes, in NaCl 3 g / l medium, using '' a specific calcium electrode (ORION 93-20-00). The initial calcium concentration used here is 5.10 -3 mol 1 -1 and the zeolite concentration 1 g (anhydrous) / liter. The temperature is 25 ° C. The choice of medium (NaCl 3g / 1) was determined by the desire to make the measurement in a medium of ionic strength representative of that of a detergent medium.

Selon la méthode décrite ci-dessus, on a déterminé les valeurs constantes ks par les trois échantillons A, B, C.According to the method described above, the constant values ks were determined by the three samples A, B, C.

Les mesures cinétiques ont été effectuées à 25°C.Kinetic measurements were made at 25 ° C.

Les concentrations des réactifs mis en jeu dans les mesures cinétiques sont données au tableau 2 ci-après :

Figure imgb0003
The concentrations of the reagents involved in the kinetic measurements are given in Table 2 below:
Figure imgb0003

Les quantités de zéolite mises en jeu dans les mesures cinétiques ―sont choisies de façon à ce que la concentration initiale en calcium ne dépasse pas 30 à 40 % de la capacité d'échange de la zéolite.The quantities of zeolite involved in the kinetic measurements ―are chosen so that the initial calcium concentration does not exceed 30 to 40% of the exchange capacity of the zeolite.

Les figures 1 à 4 représentent à titre d'exemple, les variations de ln Ca2+ en fonction du temps ainsi obtenues pour les échantillons A, B(1), B(2), et C pour des concentrations en zéolite respectivement de 143, 50, 143, 50 ppm.Figures 1 to 4 show by way of example, the variations of ln Ca2 + as a function of time thus obtained for the samples A, B (1), B (2), and C for zeolite concentrations of 143, 50 respectively. , 143.50 ppm.

Ces variations sont linéaires, ce qui vérifie l'hypothèse d'une réaction du premier ordre par rapport au calcium avec une constante de vitesse apparente k app donnée par les pentes des droites ln (Ca2+) = f (t). Cette loi du premier ordre est également vérifiée quand la concentration en zéolite varie dans le domaine considéré et la variation de k avec la concentration en zéolite est une droite app passant par l'origine, ce qui montre que la réaction d'échange initial peut être décrite par une loi de vitesse du premier ordre par rapport au calcium et du premier ordre par rapport à l'a zéolite.These variations are linear, which verifies the hypothesis of a first order reaction with respect to calcium with an apparent speed constant k a pp given by the slopes of the lines ln (Ca2 +) = f (t). This first order law is also verified when the zeolite concentration varies in the domain considered and the variation of k with the zeolite concentration is a straight line passing through the origin, which shows that the initial exchange reaction can be described by a law of speed of the first order compared to calcium and of the first order compared to a zeolite.

Le tableau 3 donne les valeurs de la constante k des échantil- s Ions de zéolites utilisées

Figure imgb0004
Table 3 gives the values of the constant k of the Ion samples of zeolites used
Figure imgb0004

On remarque, que pour l'échantillon B, les deux méthodes C.C.F. et S.F.S. donnent des valeurs voisines et on retiendra la valeur de 0,7.Note that for sample B, the two methods C.C.F. and S.F.S. give neighboring values and the value of 0.7 will be retained.

Ces trois échantillons ont été testés en détergence.These three samples were tested in detergency.

Sur les trois échantillons A,B et C, on a également déterminé les -valeurs du t(1/4). Rappelons que selon la DE-AS 2 422 655, il s'agit du temps nécessaire pour échanger le 1/4 des ions représentant la dureté de l'eau (col. 22 - p. 42-43)..On the three samples A, B and C, the -values of t (1/4) were also determined. Recall that according to DE-AS 2 422 655, this is the time required to exchange 1/4 of the ions representing the hardness of the water (col. 22 - p. 42-43).

Selon la demande précitée, on mesure ce paramètre au moyen d'une électrode spécifique à ions divalents en suivant la concentration en calcium au cours de la réaction d'échange, en présence d'une concentration en magnésium égale à la moitié de la concentration initiale en calcium (conditions de dureté des eaux américaines). L'utilisation d'une électrode spécifique présente l'inconvénient de perturber fortement la mesure cinétique dans les premières secondes de la réaction à cause du temps de réponse de l'électrode, c'est pourquoi la demanderesse a jugé préférable d'utiliser la méthode suivante :

  • Dans une cellule thermostatée à 25°C contenant 100ml d'une suspension de zéolite (0,03 %), on injecte un mélange de calcium et de magnésium de telle sorte que les concentrations initiales en calcium et en magnésium soient respectivement égales à 1,37.10 -3 et 0,685.10 -3 mol 1 (concentrations mises en jeu dans le test selon la DE-AS 2 422 655).
According to the above-mentioned application, this parameter is measured by means of a specific electrode with divalent ions by following the calcium concentration during the exchange reaction, in the presence of a magnesium concentration equal to half of the initial concentration. in calcium (hardness conditions of American waters). The use of a specific electrode has the disadvantage of strongly disturbing the kinetic measurement in the first seconds of the reaction because of the response time of the electrode, this is why the Applicant considered it preferable to use the method next :
  • In a cell thermostatically controlled at 25 ° C. containing 100 ml of a suspension of zeolite (0.03%), a mixture of calcium and magnesium is injected so that the initial concentrations of calcium and magnesium are respectively equal to 1, 37. 10 -3 and 0 , 685. 10 -3 m ol 1 (concentrations involved in the test according to DE-AS 2 422 655).

On détermine la concentration en calcium à différents instants par dosage de Ca2+ (absorption atomique) contenu dans la solution obtenue par prélèvement et filtration la plus rapide possible d'un petit volume de solution.The calcium concentration is determined at different times by assaying Ca2 + (atomic absorption) contained in the solution obtained by sampling and filtering as quickly as possible from a small volume of solution.

Les temps nécessaires à l'obtention du quart de l'équilibre d'échange ainsi obtenus pour les échantillons A,B et C sont indiquées au tableau 4.

Figure imgb0005
The times required to obtain a quarter of the exchange equilibrium thus obtained for samples A, B and C are indicated in Table 4.
Figure imgb0005

La différence susceptible d'exister entre ces trois échantillons est à l'intérieur du domaine de l'erreur de mesure.The difference that may exist between these three samples is within the range of the measurement error.

L'on doit donc considérer que cette mesure, pas plus que celle du pouvoir d'échange, n'est représentative de l'effet en détergence des échantillons A, B et C.We must therefore consider that this measure, no more than that of the exchange power, is representative of the detergency effect of samples A, B and C.

Afin de mettre en évidence l'effet de la zéolite selon l'invention, on a réalisé les essais d'incrustation suivants :

  • Pour comparer les performances en incrustation des zéolites A, B et C, on a entrepris une série de cycles de lavage à l'aide d'une formulation détergente à builder mixte TPP/zéolite de composition suivante :
    Figure imgb0006
In order to demonstrate the effect of the zeolite according to the invention, the following inlay tests were carried out:
  • To compare the inlay performance of zeolites A, B and C, a series of washing cycles was undertaken using a TPP / zeolite mixed builder detergent formulation of the following composition:
    Figure imgb0006

On a effectué des cycles cumulés de lavage en tergotomètre à 60°C. La concentration en lessive mise en jeu est de 6g/l et la dureté de l'eau utilisée est de 32°H.T. (NFT 90 003). Chaque cycle comprend une phase de lavage de 20 min et 3 rinçages en eau dure. Chaque pot du tergotomètre contient douze pièces de coton (réf. 405 Testfabric, dimension 10 x 12 cm). La quantité de solution mise en jeu dans chaque lavage et dans chaque rinçage est de 1 litre par pot.Cumulative tergotometer wash cycles were performed at 60 ° C. The concentration of detergent used is 6g / l and the hardness of the water used is 32 ° HT. (NFT 90 003). Each cycle includes a 20-minute washing phase and 3 hard water rinses. Each pot of the tergotometer contains twelve pieces of cotton (ref. 405 Testfabric, size 10 x 12 cm). The amount of solution used in each wash and in each rinse is 1 liter per jar.

L'incrustation est ensuite évaluée au bout de 5, 10, 20 et 30 cycles de lavage de la façon suivante :

  • L'analyse des cendres (par fluorescence X) obtenues par calcination des échantillons de tissu montre que l'incrustation est essentiellement constituée par du phosphate pentacalcique Ca5(P3O10)2 et des sels calciques insolubles. Une évaluation de l'incrustation peut donc être donnée par le taux de calcium et le taux de Ca5(P3O10)2 (déterminés par dosage du calcium et du phosphore dans les çendres).
The inlay is then evaluated after 5, 10, 20 and 30 washing cycles as follows:
  • Analysis of the ash (by X-ray fluorescence) obtained by calcination of the tissue samples shows that the incrustation is essentially constituted by pentacalcium phosphate Ca 5 (P 3 O 10 ) 2 and insoluble calcium salts. An assessment of the incrustation can therefore be given by the calcium level and the Ca 5 (P 3 O 10 ) 2 level (determined by dosing the calcium and phosphorus in the ashes).

Les masses de calcium et de Cs5(P3O10)2 ainsi déterminées pour 100 g de tissu sont données au tableau suivant :

Figure imgb0007
The masses of calcium and Cs 5 (P 3 O 10 ) 2 thus determined per 100 g of tissue are given in the following table:
Figure imgb0007

Les résultats mettent en évidence une réduction significative de l'incrustation quand on passe de 'la zéolite A à la zéolite B et à l'échantillon C : au bout de 30 cycles de lavages cumulés, les taux de calcium et de Ca5(P3010)2 sont respectivement abaissés de 14 % et de 18 % quand on passe de la zéolite A à la zéolite B. Dans le cas de l'échantillonThe results show a significant reduction in the incrustation when going from 'zeolite A to zeolite B and to sample C: after 30 cumulative washing cycles, the calcium and Ca5 levels (P3010) 2 are lowered by 14% and 18% respectively when switching from zeolite A to zeolite B. In the case of the sample

C, ces taux sont respectivement réduits de 30 à 35 % si on compare à la zéolite A et de 18 et 20 % par rapport à l'échantillon B.C, these rates are respectively reduced by 30 to 35% if compared to zeolite A and by 18 and 20% compared to sample B.

Claims (12)

1) Zéolite comme auxiliaire de détergence de type A, notamment 4 A caractérisée par le fait qu'elle présente : - un diamètre moyen des particules primaires compris entre 0,1 et 10µ, - un pouvoir d'échange de cations supérieur à 100 mg CaCO3/g de produit anhydre, - une constante de vitesse, rapportée à la surface de la zéolite par litre de solution supérieure à 0,15 s-1 lm-2 et de préférence supérieure à 0,25-1 s -1 1m-2. 1) Zeolite as a type A detergency aid, in particular 4 A, characterized in that it has: - an average diameter of the primary particles of between 0.1 and 10 μ, - a cation exchange power greater than 100 mg CaCO 3 / g of anhydrous product, - a speed constant, related to the surface of the zeolite per liter of solution greater than 0.15 s -1 lm-2 and preferably greater than 0.25 -1 s -1 1m -2 . 2) Zéolite selon la revendication 1, caractérisée par le fait qu'elle présente une constante ks comprise entre 0,4 et 4 s -1 1 -2 m .2) Zeolite according to claim 1, characterized in that it has a constant ks between 0.4 and 4 s -1 1 -2 m. 3) Zéolite selon l'une des revendications 1 et 2, caractérisée par le fait qu'elle présente un pouvoir d'échange de cations supérieur à 200 mg CaCO3/g de produit anhydre.3) Zeolite according to one of claims 1 and 2, characterized in that it has a cation exchange power greater than 200 mg CaCO 3 / g of anhydrous product. 4) Zéolite selon l'une des revendications 1 à 3, caractérisée par le fait qu'elle présente un diamètre moyen des particules primaires compris entre 0,5 et 5µ.4) Zeolite according to one of claims 1 to 3, characterized in that it has an average diameter of the primary particles of between 0.5 and 5 µ. 5) Zéolite selon l'une des revendications 1 à 4, caractérisée par le fait que les particules primaires sont agglomérées entre elles.5) Zeolite according to one of claims 1 to 4, characterized in that the primary particles are agglomerated together. 6) Zéolite selon l'une des revendications 1 à 5, caractérisée par le fait qu'elle est agglomérée avec un autre constituant de la lessive..6) Zeolite according to one of claims 1 to 5, characterized in that it is agglomerated with another constituent of the detergent. 1) Procédé de nettoyage à l'aide de compositions lessivielles renfermant une zéolite de type A, notamment 4A, caractérisé par le fait ladite zéolite présente : - un diamètre moyen des particules primaires compris entre 0,1 et 10 µ, - un pouvoir d'échange de cations supérieur à 100 mg CaC03/g de produit anhydre, - une constante de vitesse, rapportée à la surface de la zéolite par litre de solution supérieure à 0,15 s-1 lm-2 et de préférence supérieure à 0,25 s-1 1m-2. 1) Method of cleaning using detergent compositions containing a type A zeolite, in particular 4A, characterized in that said zeolite has: - an average diameter of the primary particles of between 0.1 and 10 μ, - a cation exchange power greater than 100 mg CaC0 3 / g of anhydrous product, - a speed constant, related to the surface of the zeolite per liter of solution greater than 0.15 s -1 lm -2 and preferably greater than 0.25 s -1 1m -2 . 2) Procédé selon la revendication 1, caractérisé par le fait que ladite présente une constante ks comprise entre 0,4 et 4 s-1 1m-2.2) Method according to claim 1, characterized in that said has a constant ks between 0.4 and 4 s -1 1m -2 . 3) Procédé selon l'une des revendications 1 et 2, caractérisé par le fait que ladite zéolite présente un pouvoir d'échange de cations supérieur à 200 mg CaC03/g de produit anhydre.3) Method according to one of claims 1 and 2, characterized in that said zeolite has a cation exchange power greater than 200 mg CaCO 3 / g of anhydrous product. 4) Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que ladite zéolite présente un diamètre moyen des particules primaires compris entre 0,5 et 5 p.4) Method according to one of claims 1 to 3, characterized in that said zeolite has an average diameter of the primary particles between 0.5 and 5 p. 5) Procédé selon l'une des revendications 1 à 4, caractérisé par le fait que les particules primaires sont agglomérées entre elles.5) Method according to one of claims 1 to 4, characterized in that the primary particles are agglomerated together. 6) Procédé selon l'une des revendications 1 à 5, caractérisé par le fait que la zéolite est agglomérée avec un autre constituant de la lessive.6) Method according to one of claims 1 to 5, characterized in that the zeolite is agglomerated with another constituent of the detergent.
EP83401175A 1982-06-18 1983-06-09 Zeolite as a detergent aid Expired EP0098187B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83401175T ATE21704T1 (en) 1982-06-18 1983-06-09 ZEOLITE AS A CLEANING AID.

Applications Claiming Priority (2)

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FR8210638 1982-06-18
FR8210638A FR2528722A1 (en) 1982-06-18 1982-06-18 ZEOLITE AS AUXILIARY OF DETERGENCE

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FR2552070B1 (en) * 1983-09-21 1987-09-11 Rhone Poulenc Chim Base PROCESS FOR OBTAINING ZEOLITE BY CONTINUOUSLY FEEDING AN AQUEOUS SODIUM SILICATE SOLUTION AND AN AQUEOUS SODIUM ALUMINATE SOLUTION, PRODUCT OBTAINED AND APPLICATION OF THE PRODUCT TO THE DETERGENCE
EP0287514A1 (en) * 1987-04-15 1988-10-19 Ciba-Geigy Ag Detergent for the after treatment of fiber reactive dyeings, process for its preparation and its use
DE3715051A1 (en) * 1987-05-06 1988-11-17 Degussa PHOSPHATE-FREE DETERGENT BUILDER
EP1215277B2 (en) † 2000-12-18 2009-11-25 Kao Corporation Base particles and detergent particles
JP6464203B2 (en) 2017-01-10 2019-02-06 ファナック株式会社 Machine learning device for machine tool and thermal displacement correction device

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FR2237839A1 (en) * 1973-07-16 1975-02-14 Procter & Gamble
FR2283220A1 (en) * 1973-05-11 1976-03-26 Procter & Gamble DETERGENT COMPOSITIONS
FR2291268A1 (en) * 1974-11-13 1976-06-11 Procter & Gamble DETERGENT COMPOSITIONS CONTAINING INSOLUBLE MATALLOSILICATES AND A WATER SOLUBLE VINYL COPOLYMER
EP0000215A1 (en) * 1977-06-21 1979-01-10 Procter & Gamble European Technical Center Low-phosphate detergent composition for fabric washing
FR2396086A1 (en) * 1977-06-27 1979-01-26 Henkel Kgaa USE OF WATER-INSOLUBLE ALKALINE ALUMINOSILICATES FINE PARTICLES FOR WASHING AND CLEANING ROUGH SKINS AND SHOVELS
EP0038591A1 (en) * 1980-04-17 1981-10-28 THE PROCTER & GAMBLE COMPANY Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap

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US4126574A (en) * 1973-09-07 1978-11-21 Henkel Kommanditgesellschaft Auf Aktien Surfactant-containing aluminosilicates and process
US4184975A (en) * 1974-10-03 1980-01-22 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Pourable agglomerated aluminosilicate builder compositions for washing and cleansing agents
DE2517218B2 (en) * 1975-04-18 1977-05-05 Henkel & Cie GmbH, 4000 Düsseldorf; Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, 6000 Frankfurt TYPE A CRYSTALLINE ZEOLITE POWDER
US4096081A (en) * 1976-02-06 1978-06-20 The Procter & Gamble Company Detergent compositions containing aluminosilicate agglomerates
NO152746C (en) * 1976-12-30 1985-11-13 Rhone Poulenc Ind SYNTHETIC CRYSTALLINIC ALUMINUM SILICATE AND USE THEREOF IN DETERGENT MIXTURES
DE2714604C3 (en) * 1977-04-01 1985-04-25 Joh. A. Benckiser Gmbh, 6700 Ludwigshafen Granulate based on polymer phosphate and ion-exchanging alkali aluminosilicate
DE2734296A1 (en) * 1977-07-29 1979-02-08 Degussa PROCESS FOR THE PRODUCTION OF FINE PARTICULAR, WATER-INSOLUBLE SILICATES ENABLED FOR CATION EXCHANGE

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FR2283220A1 (en) * 1973-05-11 1976-03-26 Procter & Gamble DETERGENT COMPOSITIONS
FR2237839A1 (en) * 1973-07-16 1975-02-14 Procter & Gamble
FR2291268A1 (en) * 1974-11-13 1976-06-11 Procter & Gamble DETERGENT COMPOSITIONS CONTAINING INSOLUBLE MATALLOSILICATES AND A WATER SOLUBLE VINYL COPOLYMER
EP0000215A1 (en) * 1977-06-21 1979-01-10 Procter & Gamble European Technical Center Low-phosphate detergent composition for fabric washing
FR2396086A1 (en) * 1977-06-27 1979-01-26 Henkel Kgaa USE OF WATER-INSOLUBLE ALKALINE ALUMINOSILICATES FINE PARTICLES FOR WASHING AND CLEANING ROUGH SKINS AND SHOVELS
US4210416A (en) * 1977-06-27 1980-07-01 Henkel Kommanditgesellschaft Auf Aktien Fine-particulate alkali metal aluminosilicates in the process of washing and cleaning rawhides and fur skins
EP0038591A1 (en) * 1980-04-17 1981-10-28 THE PROCTER & GAMBLE COMPANY Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap

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FI832225A0 (en) 1983-06-17
FR2528722A1 (en) 1983-12-23
US4519933A (en) 1985-05-28
DE3365635D1 (en) 1986-10-02
IE831434L (en) 1983-12-18
NO160719B (en) 1989-02-13
FI73729B (en) 1987-07-31
ATE21704T1 (en) 1986-09-15
NO160719C (en) 1989-05-24
FR2528722B1 (en) 1984-12-07
KR840004939A (en) 1984-10-31
DK280283D0 (en) 1983-06-17
NO832174L (en) 1983-12-19
BR8303216A (en) 1984-01-31
FI73729C (en) 1987-11-09
PT76886A (en) 1983-07-01
KR880000857B1 (en) 1988-05-26
CA1190204A (en) 1985-07-09
EP0098187B1 (en) 1986-08-27
DK280283A (en) 1983-12-19
PT76886B (en) 1986-01-24
JPS5956497A (en) 1984-03-31
IE55459B1 (en) 1990-09-26

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