EP0061600B1 - Process for the preparation of mixed granules of condensed phosphates and builders - Google Patents
Process for the preparation of mixed granules of condensed phosphates and builders Download PDFInfo
- Publication number
- EP0061600B1 EP0061600B1 EP82101656A EP82101656A EP0061600B1 EP 0061600 B1 EP0061600 B1 EP 0061600B1 EP 82101656 A EP82101656 A EP 82101656A EP 82101656 A EP82101656 A EP 82101656A EP 0061600 B1 EP0061600 B1 EP 0061600B1
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- European Patent Office
- Prior art keywords
- weight
- water
- mixture
- ammonium polyphosphate
- proportion
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
- C11D3/062—Special methods concerning phosphates
Definitions
- the invention relates to a process for the production of mixed granules from water-soluble condensed phosphates of the general formula M 2 0 (MP0 3 ) 1 , in which M is sodium, potassium or ammonium and n is a number between 4 and about 100 and builder salts.
- M is sodium, potassium or ammonium
- n is a number between 4 and about 100 and builder salts.
- the P 2 0 s content of the condensed phosphates ranges from 60.4 to 69.6%.
- Na 2 CO 3 is used as the anhydrous component
- the mixture is given a high level of alkalinity, which severely limits the range of use of the mixture in the detergent sector.
- the total phosphate content is increased to an undesirable extent, so that such mixtures are not suitable for use as a component of detergent formulations with a reduced phosphate content.
- the object of the present invention is to produce mixed granules from condensed phosphates and organic builder salts, which are also known to have hygroscopic properties, using the smallest possible amounts of granulation aids which do not adversely affect the washing properties of the condensed phosphate.
- the granules produced should be free-flowing, storable and abrasion-resistant, so that they can be admixed as a detergent component to a base product produced by the hot spray process.
- alkali metal salts of nitrilotriacetic acid and / or of poly-a-hydroxyacrylic acid and / or polyacrylic acid are preferably used as builder salts, the latter having a molecular weight of about 2,000 to 30,000.
- n represents an integer average value from 3 to 1,000, in particular from 10-1000
- m denotes an integer up to a maximum of n + 2
- m / n a value from 1.0 to 1.67, in particular 1 , corresponds.
- the amount is 5 to 50% by weight of the builder salt, the amount of ammonium polyphosphate 0.04-0.4% by weight and the amount of water 2-9%, in each case based on the amount of the condensed phosphate.
- a variant of the method according to the invention consists in that the spraying of the water or the aqueous ammonium polyphosphate solution onto the mixture provided is carried out intermittently, the interruptions taking about 2 minutes. After each spray phase, the resulting granules can optionally be powdered on the surface with powdered pentasodium triphosphate.
- abrasion-resistant, storable and non-baking mixed granules with a considerable proportion of condensed phosphates are obtained, which is surprising in so far as it was previously assumed that water would not be suitable for the granulation of melt phosphates or their mixtures with other substances and in use of water as a granulating aid, there would always be caking of the melt phosphate particles to form undesired larger aggregates, unless hydrated water-free salts which prevent water absorption of the melt phosphate are added to the melt phosphate.
- the present invention is not tied to such a restriction, since the degree of hydration of the other granulate components is insignificant due to the presence of the ammonium polyphosphate as a binder.
- a powdery, highly hygroscopic mixture of 12.5 kg of commercially available melting phosphate with a P z 0 5 content of 68% and 12.5 kg of sodium nitrilotriacetate was intermittently, for a total of 10 minutes, with a 4% by weight aqueous ammonium polyphosphate solution sprayed.
- the P 2 0 5 content of the ammonium polyphosphate was 72.5% by weight and the amount of the phosphate was 0.6% by weight, based on the amount of melt phosphate used.
- a hard granulate was obtained, the particles of which were 93.4% coarser than 150 ⁇ m.
- the particle fraction> 150 ⁇ m had an abrasion resistance according to the drum method of 85%.
- the bulk density of the granules was 650 g / l. After storage for one week in a thin-walled plastic bag that was permeable to air humidity, only a few agglomerates had formed, which disintegrated into the individual granules due to little mechanical action.
- Example 2 25 kg of a mixture corresponding to Example 1 were placed on a rotating turntable and the mixture was again intermittently sprayed with a 4% by weight solution of ammonium polyphosphate.
- the mixture on the turntable was powdered with a total of 5 kg of a finely divided sodium tripolyphosphate after each spray phase.
- a hard granulate had formed, the particles of which were 85.6% coarser than 150 ⁇ m.
- the ammonium polyphosphate content of the granules was 0.1% by weight, based on the amount of melt phosphate, and the bulk density was 630 g / l.
- the abrasion resistance of the granules determined by the drum method gave a value of 69%. After storage for one week under the same conditions as in Example 1, there was still a slight tendency to form agglomerates.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Glanulating (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Mischgranulaten aus wasserlöslichen kondensierten Phosphaten der allgemeinen Formel M20(MP03)1, in welcher M Natrium, Kalium oder Ammonium bedeutet und n eine Zahl zwischen 4 und etwa 100 ist und Gerüststoffsalzen. Der P20s-Gehalt der kondensierten Phosphate umfaßt den Bereich von 60,4 bis 69,6 %.The invention relates to a process for the production of mixed granules from water-soluble condensed phosphates of the general formula M 2 0 (MP0 3 ) 1 , in which M is sodium, potassium or ammonium and n is a number between 4 and about 100 and builder salts. The P 2 0 s content of the condensed phosphates ranges from 60.4 to 69.6%.
Es ist bekannt, wasserlösliche kondensierte Phosphate vorstehender allgemeinen Formel - auch Schmelzphosphate genannt - als Bestandteil von Wasch- und Reinigungsmitteln zu verwenden. Entsprechende Reinigungsmittelformulierungen sind z. B. in den Europäischen Patentanmeldungen Nr. 79 302 058.7 und 79 302 059.5 offenbart. Der Einsatz von beispielsweise kondensierten Alkaliphosphaten in Waschmittelformulierungen ist insofern vorteilhaft, als sie ein gutes Kalkbindevermögen sowie gute Schmutztrage- bzw. Peptisier- und Emulgiereigenschaften besitzen. Nachteilig ist dagegen die Hygroskopizität dieser Verbindungen, so daß Waschmittel mit einem Gehalt an Schmelzphosphaten beim Lagern durch Aufnahme von Feuchtigkeit der Luft zum Zusammenbacken tendieren. Diesem Nachteil versucht man gemäß der Europäischen Patentanmeldung Nr. 79302058.7 damit zu begegnen, daß man die Waschmittel in feuchtigkeitsundurchlässige Verpackungen einbringt.It is known to use water-soluble condensed phosphates of the above general formula - also called melt phosphates - as a constituent of washing and cleaning agents. Corresponding detergent formulations are e.g. B. disclosed in European Patent Applications Nos. 79 302 058.7 and 79 302 059.5. The use of, for example, condensed alkali metal phosphates in detergent formulations is advantageous in that they have good lime-binding capacity and good dirt-carrying or peptizing and emulsifying properties. On the other hand, the hygroscopicity of these compounds is disadvantageous, so that detergents containing melt phosphates tend to cake when stored by absorbing moisture in the air. According to European Patent Application No. 79302058.7, one tries to counter this disadvantage by introducing the detergents into moisture-impermeable packaging.
Weitere Bemühungen, die Feuchtigkeitsempfindlichkeit wasserlöslicher Schmelzphosphate zu vermindern gehen gemäß der USA-Patentschrift 2568110 dahin, das Schmelzphosphat in Granulatform zu bringen, indem eine wässerige, etwa 20-65 gew.%ige Lösung des Schmelzphosphates mit einer wasserfreien, hydratisierbaren Substanz, wie z. B. Natriumcarbonat, Dinatriumhydrogenphosphat oder Pentanatriumtriphosphat intensiv gemischt wird. Das Gemisch enthält etwa 5 bis 45 % Schmelzphosphat, 20 bis 90 % der wasserfreien Substanz, Rest Wasser, wobei die Wassermenge jedoch so zu bemessen ist, daß das fertige Gemisch ein festes Produkt darstellt. Aus vorstehenden Mischungsverhältnissen geht hervor, daß der Schmelzphosphatanteil im Gemisch relativ niedrig bzw. der Anteil der wasserfreien Komponente hoch ist. Im Falle des Einsatzes von Na2C03 als wasserfreie Komponente wird dem Gemisch eine hohe Alkalität verliehen, die den Anwendungsbereich des Gemisches auf dem Waschmittelsektor stark begrenzt. Beim Ersatz des Na2C03 durch beispielsweise Pentanatriumtriphosphat wird der Gesamtphosphatgehalt in einem unerwünschten Maße erhöht, so daß derartige Gemische nicht geeignet sind, als Bestandteil von Waschmittelformulierungen mit reduziertem Phosphatgehalt eingesetzt zu werden.Further efforts to reduce the moisture sensitivity of water-soluble melt phosphates go according to the US patent 2568110 to bring the melt phosphate in granular form by an aqueous, about 20-65% by weight solution of the melt phosphate with an anhydrous, hydratable substance such as e.g. B. sodium carbonate, disodium hydrogen phosphate or pentasodium triphosphate is mixed intensively. The mixture contains about 5 to 45% melt phosphate, 20 to 90% of the anhydrous substance, the rest water, but the amount of water must be such that the finished mixture is a solid product. The above mixing ratios show that the proportion of melt phosphate in the mixture is relatively low or that the proportion of the anhydrous component is high. If Na 2 CO 3 is used as the anhydrous component, the mixture is given a high level of alkalinity, which severely limits the range of use of the mixture in the detergent sector. When replacing the Na 2 CO 3 with, for example, pentasodium triphosphate, the total phosphate content is increased to an undesirable extent, so that such mixtures are not suitable for use as a component of detergent formulations with a reduced phosphate content.
Vorliegender Erfindung liegt die Aufgabe zugrunde, Mischgranulate aus kondensierten Phosphaten und organischen Gerüststoffsalzen, welche bekanntlich ebenfalls hygroskopische Eigenschaften besitzen, herzustellen unter Verwendung möglichst geringer Mengen von Granulierhilfsmitteln, die die waschaktiven Eigenschaften des kondensierten Phosphates nicht negativ beeinflussen. Das hergestellte Granulat soll riesel- und lagerfähig sowie abriebfest sein, so daß es einem nach dem Heißsprühverfahren hergestellten Basisprodukt als Waschmittelkomponente beigemischt werden kann.The object of the present invention is to produce mixed granules from condensed phosphates and organic builder salts, which are also known to have hygroscopic properties, using the smallest possible amounts of granulation aids which do not adversely affect the washing properties of the condensed phosphate. The granules produced should be free-flowing, storable and abrasion-resistant, so that they can be admixed as a detergent component to a base product produced by the hot spray process.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Mischgranulaten aus wasserlöslichen kondensierten Phosphaten der allgemeinen Formel (I)
- a) ein Gemisch aus dem kondensierten Phosphat mit einem P20g-Gehalt von 60,4 bis 69,6 Gew.%, einem organischen Gerüststoffsalz und einem Ammoniumpolyphosphat als Bindemittel mit Wasser besprüht und das Gemisch granuliert, oder daß man
- b) ein Gemisch aus dem kondensierten Phosphat mit einem P205-Gehait von 60,4 bis 69,6 Gew.%, und einem organischen Gerüststoffsalz mit einer wäßrigen Lösung oder Suspension von Ammoniumpolyphosphat besprüht und das Gemisch granuliert,
wobei das Ammoniumpolyphosphat der allgemeinen Formel 11, die Menge des organischen Gerüststoffsalzes etwa 5 bis 100 Gew.%, die Menge des Ammoniumpolyphosphätes etwa 0,003-1 Gew.% und die eingesetzte Wassermenge etwa 0,5-10 Gew.% beträgt, jeweils bezogen auf die Menge des kondensierten Phosphates.The invention relates to a process for the production of mixed granules from water-soluble condensed phosphates of the general formula (I)
- a) a mixture of the condensed phosphate with a P 2 0g content of 60.4 to 69.6% by weight, an organic builder salt and an ammonium polyphosphate as a binder are sprayed with water and the mixture is granulated, or that one
- b) a mixture of the condensed phosphate with a P 2 0 5 content of 60.4 to 69.6% by weight and an organic builder salt is sprayed with an aqueous solution or suspension of ammonium polyphosphate and the mixture is granulated,
wherein the ammonium polyphosphate of the general formula 11, the amount of the organic builder salt is about 5 to 100% by weight, the amount of the ammonium polyphosphate is about 0.003-1% by weight and the amount of water used is about 0.5-10% by weight, based in each case the amount of the condensed phosphate.
Als Gerüststoffsalze werden bevorzugt die Alkalisalze der Nitrilotriessigsäure und/oder der Poly-a-hydroxi-acrylsäure und/oder Polyacrylsäure verwendet, wobei letztere ein Molekulargewicht von etwa 2 000 bis 30 000 besitzen.
Nach einer weiteren bevorzugten Ausführungsform des Verfahrens der Erfindung beträgt die Menge des Gerüststoffsalzes 5 bis 50 Gew.%, die Menge des Ammoniumpolyphosphates 0,04-0,4 Gew.% und die Wassermenge 2-9 %, jeweils bezogen auf die Menge des kondensierten Phosphates.According to a further preferred embodiment of the method of the invention, the amount is 5 to 50% by weight of the builder salt, the amount of ammonium polyphosphate 0.04-0.4% by weight and the amount of water 2-9%, in each case based on the amount of the condensed phosphate.
Schließlich besteht eine Variante des erfindungsgemäßen Verfahrens darin, daß man das Aufsprühen des Wassers bzw. der wäßrigen Ammoniumpolyphosphatlösung auf das vorgelegte Gemisch intermittierend durchführt, wobei die Unterbrechungen etwa 2 Min dauern. Nach jeder Sprühphase kann das entstehende Granulat gegebenenfalls mit pulverförmigem Pentanatriumtriphosphat oberflächlich bepudert werden.Finally, a variant of the method according to the invention consists in that the spraying of the water or the aqueous ammonium polyphosphate solution onto the mixture provided is carried out intermittently, the interruptions taking about 2 minutes. After each spray phase, the resulting granules can optionally be powdered on the surface with powdered pentasodium triphosphate.
Gemäß Erfindung werden abriebfeste, lagerfähige und nichtbackende Mischgranulate mit einem erheblichen Anteil an kondensierten Phosphaten erhalten, was insofern überraschend ist, als man bisher grundsätzlich davon ausging, daß sich Wasser für die Granulierung von Schmelzphosphaten oder deren Gemische mit anderen Substanzen nicht eignen würde und in Anwendung von Wasser als Granulierhilfsmittel stets ein Zusammenbacken der Schmelzphosphatteilchen zu unerwünschten größeren Aggregaten eintreten würde, es sei denn, daß man dem Schmelphosphat hydratisierbare wasserfreie Salze zumischt, die eine Wasseraufnahme des Schmelzphosphates verhindern. An eine derartige Einschränkung ist die vorliegende Erfindung nicht gebunden, da durch die Gegenwart des Ammoniumpolyphosphates als Bindemittel der Hydratationsgrad der übrigen Granulatkomponenten unerheblich ist.According to the invention, abrasion-resistant, storable and non-baking mixed granules with a considerable proportion of condensed phosphates are obtained, which is surprising in so far as it was previously assumed that water would not be suitable for the granulation of melt phosphates or their mixtures with other substances and in use of water as a granulating aid, there would always be caking of the melt phosphate particles to form undesired larger aggregates, unless hydrated water-free salts which prevent water absorption of the melt phosphate are added to the melt phosphate. The present invention is not tied to such a restriction, since the degree of hydration of the other granulate components is insignificant due to the presence of the ammonium polyphosphate as a binder.
Das Verfahren der Erfindung wird durch die nachfolgenden Beispiele näher erläutert :The process of the invention is illustrated by the following examples:
Auf einem rotierenden Drehteller wurde eine pulverförmige, stark hygroskopische Mischung aus 12,5 kg handelsüblichem Schmelzphosphat mit einem Pz05-Gehalt von 68 % und 12,5 kg Natriumnitrilotriacetat intermittierend, insgesamt 10 Minuten lang, mit einer 4 gewichtsprozentigen wäßrigen Ammoniumpolyphosphat-Lösung besprüht. Der P205-Gehalt des Ammoniumpolyphosphates betrug 72,5 Gew.% und die Menge des Phosphates 0,6 Gew.%, bezogen auf die eingesetzte Menge an Schmelzphosphat. Es wurde ein hartes Granulat erhalten, dessen Teilchen zu 93,4 % gröber als 150 µm waren. Die Teilchenfraktion > 150 µm hatte eine Abriebfestigkeit nach der Trommelmethode von 85%. Das Schüttgewicht des Granulates betrug 650 g/I. Nach einwöchiger Lagerung in einem dünnwandigen Plastikbeutel, der für Luftfeuchtigkeit durchlässig war, hatten sich nur wenige Agglomerate gebildet, die durch geringe mechanische Einwirkung in die Einzelgranulate zerfielen.On a rotating turntable, a powdery, highly hygroscopic mixture of 12.5 kg of commercially available melting phosphate with a P z 0 5 content of 68% and 12.5 kg of sodium nitrilotriacetate was intermittently, for a total of 10 minutes, with a 4% by weight aqueous ammonium polyphosphate solution sprayed. The P 2 0 5 content of the ammonium polyphosphate was 72.5% by weight and the amount of the phosphate was 0.6% by weight, based on the amount of melt phosphate used. A hard granulate was obtained, the particles of which were 93.4% coarser than 150 μm. The particle fraction> 150 µm had an abrasion resistance according to the drum method of 85%. The bulk density of the granules was 650 g / l. After storage for one week in a thin-walled plastic bag that was permeable to air humidity, only a few agglomerates had formed, which disintegrated into the individual granules due to little mechanical action.
Auf einem rotierenden Drehteller wurden 25 kg einer Mischung entsprechend Beispiel 1 vorgelegt und die Mischung wiederum intermittierend mit einer 4 gewichtsprozentigen Lösung von Ammoniumpolyphosphat besprüht. Im Unterschied zur Verfahrensweise nach Beispiel 1 wurde die auf dem Drehteller befindliche Mischung nach jeder Sprühphase mit insgesamt 5 kg eines feinteiligen Natriumtripolyphosphates bepudert. Es hatte sich ein hartes Granulat gebildet, dessen Partikel zu 85,6 % gröber als 150 µm waren. Der Ammoniumpolyphosphatgehalt des Granulates betrug 0,1 Gew.%, bezogen auf die Menge Schmelzphosphat, und das Schüttgewicht 630 g/I. Die nach der Trommelmethode ermittelte Abriebfestigkeit des Granulates ergab einen Wert von 69 %. Nach einwöchiger Lagerung unter den gleichen Bedingungen wie in Beispiel 1 war eine noch geringe Neigung zur Agglomeratbildung festzustellen.25 kg of a mixture corresponding to Example 1 were placed on a rotating turntable and the mixture was again intermittently sprayed with a 4% by weight solution of ammonium polyphosphate. In contrast to the procedure according to Example 1, the mixture on the turntable was powdered with a total of 5 kg of a finely divided sodium tripolyphosphate after each spray phase. A hard granulate had formed, the particles of which were 85.6% coarser than 150 µm. The ammonium polyphosphate content of the granules was 0.1% by weight, based on the amount of melt phosphate, and the bulk density was 630 g / l. The abrasion resistance of the granules determined by the drum method gave a value of 69%. After storage for one week under the same conditions as in Example 1, there was still a slight tendency to form agglomerates.
Auf einem rotierenden Drehteller wurde eine Mischung aus 12,5 kg handelsüblichem Schmelzphosphat mit einem P205-Gehalt von 68 %, 6,25 kg Natriumnitrilotriacetat und 6,25 kg Natriumpolyacrylat mit einem Kondensationsgrad von 17, wie in Beispiel 2 beschrieben, mit einer 4 gewichtsprozentigen Ammoniumpolyphosphat-Lösung und insgesamt 5 kg eines feinteiligen Natriumtripolyphosphates behandelt. Es hatte sich ein im Vergleich zu den Produkten nach Beispiel 1 und 2 etwas weicheres Granulat gebildet, dessen Partikel zu 95,1 % gröber als 150 µm waren. Der AmmoniumpolyphosphatGehalt betrug 0,35 Gew.%, bezogen auf die Menge des Schmelzphosphates und das Schüttgewicht 625 g/I. Nach einwöchiger Lagerung unter den gleichen Bedingungen, wie in den Beispielen 1 und 2 beschrieben, war das Produkt noch einwandfrei rieselfähig.On a rotating turntable, a mixture of 12.5 kg of commercially available melt phosphate with a P 2 0 5 content of 68%, 6.25 kg of sodium nitrilotriacetate and 6.25 kg of sodium polyacrylate with a degree of condensation of 17, as described in Example 2, with treated with a 4 percent by weight ammonium polyphosphate solution and a total of 5 kg of a finely divided sodium tripolyphosphate. A slightly softer granulate was formed compared to the products according to Examples 1 and 2, the particles of which were 95.1% coarser than 150 µm. The ammonium polyphosphate content was 0.35% by weight, based on the amount of the melt phosphate and the bulk density 625 g / l. After storage for one week under the same conditions as described in Examples 1 and 2, the product was still free-flowing.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT82101656T ATE11563T1 (en) | 1981-03-25 | 1982-03-04 | PROCESS FOR THE MANUFACTURE OF MIXED GRANULES FROM CONDENSED PHOSPHATES AND BUILDER SALTS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813111617 DE3111617A1 (en) | 1981-03-25 | 1981-03-25 | METHOD FOR PRODUCING MIXED GRANULES FROM CONDENSED PHOSPHATES AND FRUIT SALTS |
| DE3111617 | 1981-03-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0061600A1 EP0061600A1 (en) | 1982-10-06 |
| EP0061600B1 true EP0061600B1 (en) | 1985-01-30 |
Family
ID=6128175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82101656A Expired EP0061600B1 (en) | 1981-03-25 | 1982-03-04 | Process for the preparation of mixed granules of condensed phosphates and builders |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4517109A (en) |
| EP (1) | EP0061600B1 (en) |
| AT (1) | ATE11563T1 (en) |
| CA (1) | CA1152844A (en) |
| DE (2) | DE3111617A1 (en) |
| DK (1) | DK134482A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995015369A1 (en) * | 1993-12-03 | 1995-06-08 | Monsanto Company | Process for producing granular alkali metal nitrilotriacetate |
| US5998663A (en) * | 1998-01-14 | 1999-12-07 | Solutia, Inc. | Granular alkali metal nitrilotriacetate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0048435A1 (en) * | 1980-09-23 | 1982-03-31 | Hoechst Aktiengesellschaft | Process for the preparation of granular condensed phopsphates |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2904513A (en) * | 1954-04-16 | 1959-09-15 | Monsanto Chemicals | Inorganic phosphate compositions, and methods for the preparation and utilization thereof |
| DE1102329B (en) * | 1959-10-01 | 1961-03-16 | Basf Ag | Washing-up liquid to prevent incrustations in textiles after washing |
| NL302725A (en) * | 1963-01-14 | |||
| US3627686A (en) * | 1968-09-30 | 1971-12-14 | Chemed Corp | Machine dishwashing compositions containing sodium polyacrylate and nta |
| DE1903831A1 (en) * | 1969-01-27 | 1970-09-03 | Miele & Cie Maschinenfabrik | Detergents for automatic dish-washing - machines |
| GB1384241A (en) * | 1971-02-23 | 1975-02-19 | Albright & Wilson | Manufacture of ammonium polyphosphate |
| US4077897A (en) * | 1976-02-13 | 1978-03-07 | The Procter & Gamble Company | Process for preparing detergent compositions |
| US4228025A (en) * | 1979-06-29 | 1980-10-14 | The Procter & Gamble Company | Agglomeration process for making granular detergents |
-
1981
- 1981-03-25 DE DE19813111617 patent/DE3111617A1/en not_active Withdrawn
-
1982
- 1982-03-04 EP EP82101656A patent/EP0061600B1/en not_active Expired
- 1982-03-04 DE DE8282101656T patent/DE3262089D1/en not_active Expired
- 1982-03-04 AT AT82101656T patent/ATE11563T1/en not_active IP Right Cessation
- 1982-03-24 DK DK134482A patent/DK134482A/en not_active Application Discontinuation
- 1982-03-24 CA CA000399296A patent/CA1152844A/en not_active Expired
-
1983
- 1983-10-14 US US06/542,075 patent/US4517109A/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0048435A1 (en) * | 1980-09-23 | 1982-03-31 | Hoechst Aktiengesellschaft | Process for the preparation of granular condensed phopsphates |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE11563T1 (en) | 1985-02-15 |
| DE3111617A1 (en) | 1982-10-07 |
| CA1152844A (en) | 1983-08-30 |
| EP0061600A1 (en) | 1982-10-06 |
| US4517109A (en) | 1985-05-14 |
| DE3262089D1 (en) | 1985-03-14 |
| DK134482A (en) | 1982-09-26 |
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