DK161976B - PHOSPHATER STATEMENTS FOR DETERGENTS AND CLEANERS - Google Patents
PHOSPHATER STATEMENTS FOR DETERGENTS AND CLEANERS Download PDFInfo
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- DK161976B DK161976B DK036691A DK36691A DK161976B DK 161976 B DK161976 B DK 161976B DK 036691 A DK036691 A DK 036691A DK 36691 A DK36691 A DK 36691A DK 161976 B DK161976 B DK 161976B
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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
- 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
- C11D3/1286—Stabilised aqueous aluminosilicate suspensions
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- Silicates, Zeolites, And Molecular Sieves (AREA)
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Description
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Opfindelsen angår phosphaterstatninger for vaske-og rengøringsmidler.The invention relates to phosphate replacements for detergents.
Der er tidligere foreslået fremgangsmåder til vask og rengøring af faste materialer, navnlig tekstiler, samt til fremgangsmådernes gennemførelse eg-5 nede vaske- og rengøringsmidler, ved hvilke de calcium-kompleksbindende phosphaters rolle helt eller delvis er overtaget af til binding af calcium egnede, findelte, i almindelighed bundet vand indeholdende, vanduopløse-lige aluminiumsilicater (jvf. tysk offentliggørelses-10 skrift nr. DE-OS 24 12 837).Methods have previously been proposed for the washing and cleaning of solid materials, in particular textiles, and for the methods of cleaning and cleaning agents, in which the role of calcium complex-binding phosphates has been taken over, in whole or in part, for the binding of calcium, finely divided , generally bonded water containing water-insoluble aluminum silicates (cf. German Publication 10 DE-OS 24 12 837).
Det drejer sig ved nævnte teknik om forbindelser med den almene formel I: ‘ A12°3 · (Si02>y «> 15 hvor Kat er en med calcium udvekslelig kation med va-lensen m, x er et tal fra 0,7 til 1,5 og y er et tal fra 0,8 til 6, fortrinsvis 1,3 til 4.The aforementioned technique involves compounds of the general formula I: 'A12 ° 3 · (SiO 2> y'> 15 where Kat is a calcium-exchangeable cation with the valence m, x is a number from 0.7 to 1 , 5 and γ are a number from 0.8 to 6, preferably 1.3 to 4.
Som kation kommer navnlig natrium i betragtning, men det kan også erstattes med lithium, kalium, ammonium eller magnesium.Sodium in particular is considered cation, but it can also be replaced with lithium, potassium, ammonium or magnesium.
De ovenfor definerede, til binding af calcium egnede forbindelser betegnes i det følgende for simpelhedsThe compounds suitable for calcium binding as defined above are hereinafter referred to as simplicity
skyld som "aluminiumsilicater". Dette gælder navnlig og-? Sguilt like "aluminum silicates". This is especially true of- and? S
så for de fortrinsvis anvendte natriumaluminiumsilikater,so for the preferably used aluminum aluminum silicates,
Alle angivelser vedrørende disses opfinderiske anvendelse og samtlige angivelser vedrørende deres fremstilling og egenskaber gælder tilsvarende for samtlige ovenfor definerede forbindelser,All information relating to their inventive use and all information regarding their preparation and properties shall apply mutatis mutandis to all of the compounds defined above,
De til anvendelse i vaske- og rengøringsmidler særligt egnede aluminiumsilicater har en calciumbindingsevne på fortrinsvis 50 til 200 mg CaO/g af det vandfrie aluminiumsilicat. Når der i det følgende tales om vandfrit aluminiumsilicat, menes dermed den tilstand for alu-35 miniumsilicaterne, der nås efter en times tørring ved 800°C. Ved denne tørring bliver det vedhæftende og det bundne vand fjernet praktisk taget fuldstændigt.The aluminum silicates particularly suitable for use in detergents and detergents have a calcium binding capacity of preferably 50 to 200 mg CaO / g of the anhydrous aluminum silicate. In the following, anhydrous aluminum silicate is referred to as the state of the aluminum silicates reached after drying at 800 ° C for one hour. In this drying, the adhesive and the bound water are removed virtually completely.
Ved fremstilling af vaske- og rengøringsmidler, 2In the manufacture of detergents, 2
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hvori der foruden sædvanlige bestanddele for sådanne midler foreligger de ovenfor definerede aluminiumsili-cater, går man fortrinsvis ud fra aluminiumsilicater, der er fugtige, for eksempel endnu fugtige efter deres fremstilling. De fugtige forbindelser blandes med mindst 5 en del af de øvrige bestanddele for det middel, der skal fremstilles, og blandingen omdannes ved hjælp af kendte metoder, såsom sprøjtetørring, til det færdige vaskeeller rengøringsmiddel som slutprodukt, for eksempel et drysbart produkt.in which, in addition to usual constituents for such agents, there are the aluminum silicates defined above, preferably aluminum silicates which are moist, for example, are still moist after their preparation. The moist compounds are mixed with at least a portion of the other ingredients of the agent to be prepared, and the mixture is converted by the known methods, such as spray drying, to the finished detergent or detergent as a final product, for example a sprayable product.
10 Inden for rammerne af den ovenfor skitserede frem stillingsmetode for vaske- og rengøringsmidler tilføres eller benyttes aluminiumsilicaterne for eksempel som vandig suspension.Within the framework of the above-described method of preparation for detergents, the aluminum silicates are added or used, for example, as an aqueous suspension.
Det er kendt til dannelse af aluminiumsilicat-sus-15 pensioner at anvende alkylphenolethylenaddukter. Der anvendes fortrinsvis addukter med 6 til 7 mol ethylenoxid (tysk offentliggørelsesskrift nr. DE-OS 26 15 698).The use of alkylphenolethylene adducts is known to form aluminum silicate suspensions. Preferably, adducts containing 6 to 7 moles of ethylene oxide are used (German Publication No. DE-OS 26 15 698).
Fra tysk offentliggørelsesskrift DE-OS 30 21 295 kendes vandige natriumaluminiumsilicat-suspensioner, der 20 indeholder en i vandfasen opløst andel, beregnet på suspensionen, på 15 til 50 vægt% af trinatriumsaltet af ni-trilotrieddikesyre.German publication specification DE-OS 30 21 295 discloses aqueous sodium aluminum silicate suspensions containing 20 a water-dissolved proportion, calculated on the suspension, of 15 to 50% by weight of the trisodium salt of nitrilotriacetic acid.
Fra den ældre ansøgning ifølge tysk offentliggørelsesskrift DE-OS 32 09 631 kendes vandige suspensioner af 25 et vanduopløseligt silicat, der som dispergerende virkende bestanddel indeholder 0,5 til 6 vægt% af en blanding af mindst to forskellige alkylphenolethylater med form-From the earlier application according to German publication DE-OS 32 09 631 aqueous suspensions of 25 are known as a water-insoluble silicate which contains as dispersing active ingredient 0.5 to 6% by weight of a mixture of at least two different alkyl phenolethylates of the formulation.
7 0-CH2-CH2 -- 0 ” CH2 CH2 ~ 0H7-CH2-CH2 - 0 ”CH2 CH2 ~ OH
30 \=J L J n_L30 \ = J L J n_L
hvori R er en nærmere specificeret alkylgruppe.wherein R is a specified alkyl group.
Dansk patentansøgning nr. 4238/84, der er stam-ansøgning for denne ansøgning, beskriver vandige, pumpelige, stabile suspensioner af et vanduopløseligt, til 35 binding af calciumioner egnet aluminiumsilicat, der yderligere omfatter en blanding af mindst to forskellige al-kylphenolethoxylater som dispergerende bestanddel og en i vandfasen opløst andel af trinatriumnitrilotriacetat, 3Danish Patent Application No. 4238/84, which is the parent application for this application, discloses aqueous, pumpable, stable suspensions of a water-insoluble, for the binding of calcium ions suitable aluminum silicate, further comprising a mixture of at least two different alkyl phenol ethoxylates as dispersants. component and a proportion of dissolved in the aqueous phase of trisodium nitrilotriacetate, 3
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samt anvendelse af en sådan suspension til fremstilling ved sprøjtetørring af pulverformede eller granulerede phosphaterstatninger for vaske- og rengøringsmidler.and the use of such a suspension for preparing by spray drying powdered or granulated phosphate replacements for detergents.
Det har nu vist sig, at granulatformede phosphat-5 erstatninger for vaske- og rengøringsmidler, der har en sammensætning svarende til, at de er fremstillet ud fra ovennævnte suspensioner, er meget støvfri produkter med en lav rystevægtfylde, endvidere udviser de en høj calciumbindingsevne og er godt befugtelige.It has now been found that granular phosphate substitutes for detergents having a composition similar to those prepared from the above suspensions are very dust-free products with a low shake density, furthermore, they exhibit a high calcium binding capacity and are well wettable.
10 I overensstemmelse hermed er phosphaterstatningen ifølge opfindelsen ejendommelig ved, at den består af et vanduopløseligt, til binding af calciumioner egnet silicat i form af en findelt, bundet vand indeholdende, syntetisk fremstillet, vanduopløselig forbindelse med 15 den almene formel I: (Kat2/^>x · A1203 · (Si02>y «> hvor Kat er en med calcium udvekslelig kation med va·*· lensen m, x er et tal fra 0,7 til 1,5 og y er et tal fra 0,8 til 6, en dispergerende virkende bestanddel af en blanding af mindst to forskellige alkylphenolethoxy-later med formlen II: 25 - O - CH2 - CH2 - OH (II) hvori R er en alkylgruppe med 1-15 carbonatorner, og n for det ene alkylphenolethoxylat er 2-7 og for det andet alkylphenolethoxylat er 8-15, og trinatriumsaltet af 30 nitrilotrieddikesyre, med en sammensætning svarende til, at den er fremstillet ud fra en vandig suspension af komponenterne indeholdende 0,5-80% vægt% aluminiumsili-cat med formel (I), 0,5-6 vægt% af blandingen af mindst to forskellige alkylphenolethoxylater med formel (II) 35 og 4-25 vægt% trinatriumsalt af nitrilotrieddikesyre, idet suspensionen indeholder mindst 20 vægt% vand.Accordingly, the phosphate substitute according to the invention is characterized in that it consists of a water-insoluble, silicone-suitable silicate-suitable bond in the form of a finely divided, bound water containing synthetically prepared water-insoluble compound of the general formula I: (Cat > x · A1203 · (SiO , a dispersing active ingredient of a mixture of at least two different alkyl phenol ethoxylates of formula II: 25 - O - CH 2 - CH 2 - OH (II) wherein R is an alkyl group having 1 to 15 carbon atoms and n for one alkyl phenol ethoxylate is 2 -7 and secondly alkylphenol ethoxylate is 8-15, and the trisodium salt of 30 nitrilotriacetic acid, having a composition similar to that prepared from an aqueous suspension of the components containing 0.5-80% wt% aluminum silicate of formula ( I), 0.5-6% by weight of the mixture of at least two various alkyl phenol ethoxylates of formula (II) 35 and 4-25% by weight of trisodium salt of nitrilotriacetic acid, the suspension containing at least 20% by weight of water.
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En foretrukket sammensætning af den omhandlede phosphaterstatning er 47-90 vægt% absolut tør aluminiumsilicat med formlen I, 8-50 vægt% trinatriumsalt af nitrilotrieddikesyre 5 0,5-3/75 vægt% af alkylphenolethoxylatblandingen, og rest til 100 vægt% vand.A preferred composition of the subject phosphate replacement is 47-90% by weight of absolute dry aluminum silicate of formula I, 8-50% by weight of trisodium salt of nitrilotriacetic acid 5, 0.5-3 / 75% by weight of the alkylphenol ethoxylate mixture, and the residue to 100% by weight of water.
I formlen II kan alkylgruppen R med 1-15 C-atomer eksempelvis være -CH^, -C2H5, propyl, butyl eller pentyl, den har fortrinsvis 9 C-atomer, såsom nonyl.In the formula II, the alkyl group R having 1 to 15 C atoms may be, for example, -CH2, -C2H5, propyl, butyl or pentyl, it preferably has 9 C atoms such as nonyl.
10 Ved det ene i blandingen anvendte alkylphenol- ethoxylat kan n som nævnt være 2 til 7, fortrinsvis 4 til 6 og navnlig 5, og ved det andet alkylphenolethoxy-lat kan n som nævnt være 8 til 15, fortrinsvis 8 til 12 og navnlig 9 eller 10. Blandingsforholdet mellem de to 15 alkylphenolethoxylater er fortrinsvis 1:9-9:1.In the one alkylphenol ethoxylate used in the mixture, as mentioned, n may be 2 to 7, preferably 4 to 6, and in particular 5, and in the other alkylphenol ethoxylate, n may be 8 to 15, preferably 8 to 12 and especially 9. or 10. The mixing ratio of the two alkyl phenol ethoxylates is preferably 1: 9-9: 1.
I den omhandlede phosphaterstatning kan komponenten med formel (I) være krystallinsk, og i forbindelse med denne formel kan y være et tal fra 1,3 til 4.In the present phosphate replacement, the component of formula (I) may be crystalline, and for this formula, y may be a number from 1.3 to 4.
Ved samtlige angivelser vedrørende aluminiumsili-20 cat er der regnet med den tilstand for aluminiumsilicatet, der opnås efter en times tørring ved 800°C. Ved denne tørring fjernes det vedhæftende og det bundne vand praktisk taget fuldstændigt.For all aluminum silicate data, the state of the aluminum silicate is obtained after drying at 800 ° C for one hour. In this drying, the adhesive and the bound water are virtually completely removed.
For de til komponenten med formel (I) anvendte 25 aluminiumsilicater kan der være tale om amorfe eller om krystallinske produkter, blandinger af amorfe og krystallinske produkter og også delkrystallinske produkter. Aluminiumsil icaterne kan forekomme naturligt, eller de kan være syntetisk fremstillede produkter, idet de synte-30 tisk fremstillede produkter foretrækkes. Fremstillingen kan for eksempel foregå ved omsætning af vandopløselige silicater med vandopløselige aluminater i nærværelse af vand. Til dette formål kan vandige opløsninger af udgangsmaterialerne sammenblandes, eller en i fast til-35 stand foreliggende komponent kan omsættes med den anden, som vandig opløsning foreliggende komponent. Også ved sammenblanding af begge, i fast tilstand foreliggende 5For the aluminum silicates used for the component of formula (I), these may be amorphous or crystalline products, mixtures of amorphous and crystalline products and also semi-crystalline products. The aluminum silicates may occur naturally or they may be synthetically produced products, with the synthetically produced products being preferred. The preparation can be carried out, for example, by reacting water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials may be mixed or one solid state component may be reacted with the other component as aqueous solution. Also by mixing both, in the solid state 5
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komponenter fås ved tilstedeværelse af vand det ønskede aluminiumsilicat. Også ud fra A1(0H)2, A1203 eller Si02 kan der ved omsætning med alkalisilicat- eller -aluminab-opløsninger fremstilles aluminiumsilicater. Fremstillin-5 gen kan også foregå efter andre kendte metoder. Der er til den foreliggende opfindelse navnlig tale om aluminiumsilicater, der udviser en tredimensional rumgitterstruktur .components are obtained by the presence of water the desired aluminum silicate. Aluminum silicates can also be prepared by reaction with alkali silicate or aluminab solutions from Al (OH) 2, Al2 O3 or SiO2. The preparation can also be carried out by other known methods. In particular, the present invention is concerned with aluminum silicates exhibiting a three-dimensional space lattice structure.
Den foretrukne, omtrent inden for området fra 100 10 til 200 mg CaO/g AS, navnlig fra 100 til 180 mg CaO/g AS beliggende calciumbindeevne, forekommer navnlig hos forbindelser med sammensætningeni 0,7-1,1 Na20 · A1203 · 1,3-3,3 SiC>2.The preferred, approximately in the range of from 100 to 200 mg of CaO / g AS, in particular from 100 to 180 mg of CaO / g AS located in calcium, is particularly found in compounds having the composition of 0.7-1.1 Na 2 O · Al 2 O 3 · 1, 3-3.3 SiC> 2.
Denne sumformel omfatter to typer med forskellige 15 krystalstrukturer (henholdsvis deres ikke-krystallinske forprodukter), der også afviger fra hinanden ved deres sumformler. Disse er: a) 0,7-1,1 Na20 · Al2C>3 · 1,3-2,4 SiC>2 b) 0,7-1,1 Na20 · Al203 · 2,4-3,3 Si02.This sum formula comprises two types with different 15 crystal structures (respectively, their non-crystalline precursors), which also differ from each other by their sum formulas. These are: a) 0.7-1.1 Na 2 O · Al 2 C> 3 · 1.3–2.4 SiC> 2 b) 0.7–1.1 Na 2 O · Al 2 O 3 · 2.4–3.3 SiO 2.
20 De forskellige krystalstrukturer viser sig i rønt genstrålingsdiagrammet .20 The various crystal structures are shown in the X-ray diffraction diagram.
Det i vandig suspension foreliggende amorfe eller krystallinske aluminiumsilicat kan ved filtrering skilles fra den tilbageværende vandige opløsning og tørres 25 ved temperaturer fra f.eks. 50 til 400°C og højere.The amorphous or crystalline aluminum silicate present in aqueous suspension can be separated by filtration from the remaining aqueous solution and dried at temperatures of e.g. 50 to 400 ° C and higher.
Alt efter tørringsbetingelserne indeholder produktet mere eller mindre bundet vand.Depending on the drying conditions, the product contains more or less bound water.
Sådanne høje tørringstemperaturer er i almindelighed ikke at anbefale. Der anvendes hensigtsmæssigt ikke 30 højere temperaturer end 200°C, når aluminiumsilicatet skal anvendes i vaske- og rengøringsmidler. Til fremstilling af suspensionen, hvorfra phosphaterstatninger ifølge opfindelsen fremstilles, behøver aluminiumsilica-terne imidlertid slet ikke tørres efter deres fremstil-35 ling. Der kan, hvilket er særligt fordelagtigt, anvendes et efter fremstilling endnu fugtigt aluminiumsilicat. Der kan imidlertid også til fremstilling af sådanne suspen- 6Such high drying temperatures are generally not recommended. Conveniently, no higher temperatures than 200 ° C are used when the aluminum silicate is to be used in detergents. However, for the preparation of the suspension from which phosphate replacements according to the invention are made, the aluminum silicates need not be dried at all after their preparation. Particularly advantageous, a still-moistened aluminum silicate can be used after manufacture. However, for the preparation of such suspensions 6 can also be used
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sioner anvendes aluminiumsilicater, der ved middeltemperaturer, f.eks. ved fra 80 til 200°C, er tørret indtil fjernelse af det vedhæftende flydende vand.sions are used aluminum silicates which at medium temperatures, e.g. at 80 to 200 ° C, is dried until removal of the adherent liquid water.
Middel-partikelstørrelsen for de enkelte alumini-5 umsilicatpartikler kan være forskellig og ligger for eksempel i området mellem 0,1 ym og 0,1 mm. Denne angivelse angår primærpartikelstørrelsen, d.v.s. størrelsen af de ved fældning og eventuelt efterfølgende krystallisation dannede partikler. Der anvendes med særlig for-10 del aluminiumsilicater, der for mindst 80 vægt%’s vedkommende består af partikler med en størrelse på fra 10 til 0,01 ym, navnlig fra 8 til 0,1· ym.The average particle size of the individual alumina silicate particles may be different, for example in the range of 0.1 µm to 0.1 mm. This indication relates to the primary particle size, i.e. the size of the particles formed by precipitation and possibly subsequent crystallization. Particular advantage of aluminum silicates is used, which for at least 80% by weight consists of particles having a size of from 10 to 0.01 µm, in particular from 8 to 0.1 µm.
Disse aluminiumsilicater indeholder fortrinsvis næsten ingen primær- eller sekundær-partikler med dia-15 metre over 45 ym. Som sekundærpartikler betegnes sådanne partikler, der er opstået ved agglomerering af primær-partiklerne til større formationer.These aluminum silicates preferably contain almost no primary or secondary particles with diameters over 45 microns. As secondary particles, such particles that are formed by agglomeration of the primary particles are referred to as larger formations.
Vedrørende agglomereringen af primær-partiklerne til større formationer har det til fremstilling af de 20 nævnte suspensioner vist sig bedst at anvende de efter deres fremstilling endnu fugtige aluminiumsilicater, da det har vist sig, at en dannelse af sekundærpartikler praktisk taget helt forhindres ved anvendelse af disse endnu fugtige produkter.Regarding the agglomeration of the primary particles into larger formations, it has been found best to use the still-moistened aluminum silicates after their preparation, since it has been found that the formation of secondary particles is practically completely prevented by the use of these suspensions. yet moisturizing products.
25 Ved en særligt foretrukket udførelsesform for phosphaterstatninger ifølge opfindelsen anvendes som komponent med formel (I) pulverformet Zeolith af type A med særligt defineret partikelspektrum.In a particularly preferred embodiment of phosphate replacements according to the invention, a component of the formula (I) type A powdered zeolith of a particularly defined particle spectrum is used.
Sådanne zeolithpulvere kan fremstilles ifølge de 30 tyske fremlæggelsesskrifter nr. DE-AS 24 47 021 og 25 17 218 og de tyske offentliggørelsesskrifter nr. DE-OS 26 52 419, 26 51 420, 26 51 436, 26 51 437, 26 51 445 og 26 51 485.Such zeolite powders can be prepared in accordance with the 30 German disclosures DE-AS 24 47 021 and 25 17 218 and the German disclosures DE-OS 26 52 419, 26 51 420, 26 51 436, 26 51 437, 26 51 445 and 26 51 485.
De udviser da de deri angivne partikelfordelingskurver.They then exhibit the particle distribution curves specified therein.
Ifølge en særligt foretrukket udførelsesform kan 35 der anvendes et pulverformet Zeolith af type A, der udviser den i tysk offentliggørelsesskrift nr. DE-OS 26 51 485 beskrevne partikelstørrelsesfordeling.According to a particularly preferred embodiment, a powder type Zeolith of type A can be used which exhibits the particle size distribution described in German Publication No. DE-OS 26 51 485.
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Den dispergerende virkende bestanddel er som nævnt en blanding af mindst to alkylphenolethoxylater med formlen Ils 5 -€> O-CHj-CHjj -- 0-CH2-CH2-OH (II) hvori R er som defineret ovenfor.The dispersing active ingredient is, as mentioned, a mixture of at least two alkyl phenol ethoxylates of the formula II 5 -> O-CH 2 -CH 2 - O-CH 2 -CH 2 -OH (II) wherein R is as defined above.
Disse alkylphenolethoxylater kan anvendes i vilkår- lig blanding, fortrinsvis i et forhold på fra 1:9 til 9:1, navnlig fra 2:3 til 3:2 og især fra 0,9:1,1 til 1,1:0,9. Alkylphenolethoxylaterne svarer da navnlig til formlen II, hvor R - nonyl og n = 5 henholdsvis 9.These alkyl phenol ethoxylates can be used in any mixture, preferably in a ratio of from 1: 9 to 9: 1, in particular from 2: 3 to 3: 2 and especially from 0.9: 1.1 to 1.1: 0, 9th The alkyl phenol ethoxylates then correspond in particular to formula II, where R - nonyl and n = 5 and 9 respectively.
^ Koncentrationen af disse blandinger i den oven for nævnte vandige suspension kan fortrinsvis andrage fra 1 til 2 vægt%.The concentration of these mixtures in the above aqueous suspension may preferably be from 1 to 2% by weight.
Suspensionerne til fremstilling af phosphater-statningerne ifølge opfindelsen kan fremstilles ved sim-2g pel sammenblanding af deres bestanddele, idet aluminium-silicaterne eksempelvis kan anvendes som sådanne eller -eventuelt fra deres fremstilling - endnu fugtige eller foreliggende i vandig suspension.The suspensions for preparing the phosphate substitutions of the invention can be prepared by simulation of 2 g of their constituents, for example, the aluminum silicates can be used as such or, optionally, from their preparation - still moist or present in aqueous suspension.
Der kan imidlertid også anvendes allerede tørrede, d.v.s. for vedhæftende vand befriede, eventuelt endnu 25 bundet vand indeholdende, aluminiumsilicater.However, already dried may also be used, i.e. for adherent water liberated, optionally still 25 bonded water containing aluminum silicates.
Sådanne suspensioner kan opbevares ved stuetemperatur eller ved højere temperaturer, og de kan transporteres gennem rørledninger, pumper eller på anden måde.Such suspensions may be stored at room temperature or at higher temperatures and may be transported through pipelines, pumps or otherwise.
For det meste foregår håndteringen af suspensionen ved temperaturer mellem stuetemperatur, der er den mest foretrukne, og ca. 60°C.Mostly, the suspension is handled at temperatures between the most preferred room temperature and approx. 60 ° C.
Ved fremstillingen af phosphaterstatningerne ifølge opfindelsen går man navnlig frem på den måde, at en suspension som ovenfor nævnt, for eksempel fra en 35 forrådsbeholder, ved en hvilken som helst fremgangsmåde omdannes til det pulverformede produkt. Suspensionerne 8In the preparation of the phosphate replacements according to the invention, in particular, it is stated that a suspension as mentioned above, for example from a storage container, is converted into the powdered product by any process. The suspensions 8
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bliver imidlertid, fortrinsvis i en tilstand som "grød", underkastet forstøvningstørring. Det har nemlig vist sig, at der ud fra sådanne suspensioner ved forstøvningstørring kan vindes meget støvfattige produkter. De ved for-5 støvningstørring vundne produkter udviser en høj calciumbindingsevne og er godt befugtelige.however, preferably in a state such as "porridge", is subjected to spray drying. Namely, it has been found that very dust-poor products can be obtained from such suspensions by spray drying. The products obtained by dust-drying show a high calcium binding capacity and are well wettable.
Der opnås fortrinsvis herved tilsyneladende tørre, drysbare eller udhaeldelige granulatformede eller pulverformede produkter. Ved fremstillingen af sådanne phos-10 phaterstatninger til vaske- og rengøringsmidler optræder der ingen besværlige rester ved tilførslen af de vandige suspensioner til tørringsapparaturet, og man opnår meget støvfrie produkter, der udviser en lav rystevægtfylde.Preferably dry, extensible or pourable granular or powdery products are thus obtained. In the preparation of such phosphate substitutes for detergents, no troublesome residues occur in the application of the aqueous suspensions to the drying apparatus and very dust-free products exhibiting a low shake density are obtained.
Opfindelsen beskrives nærmere gennem følgende 15 eksempler.The invention is further described by the following 15 examples.
Eksemplerexamples
Der anvendtes hver gang 250 g udgangsprodukt af en 42%'s grød af HAB A 40 (Zeolith A) i vand med i for-20 hold til tørstof NTA Na^-pulver samt som stabilisator Marlophen 85/89, idet dette er en 1:1 blanding af to nonylphenolethoxylater med formel (II), idet for det ene n=5 og for det andet n=9. Der blev taget hensyn til, at NTA Na^-pulveret udviser et indhold af aktivt stof på 25 98%. Det samme blev gentaget med 44%'s og 46%'s grød. Prøverne blev dispergeret med dissolver'en 5 minutter ved 1000 o/m.Each time 250 g of starting product of a 42% porridge of HAB A 40 (Zeolith A) was used in water in proportion to dry matter NTA Na 2 powder and as a stabilizer Marlophen 85/89, this being a 1 : 1 mixture of two nonylphenol ethoxylates of formula (II), one n = 5 and the other n = 9. It was taken into account that the NTA Na 2 powder exhibited an active substance content of 25 98%. The same was repeated with 44% and 46% porridge. The samples were dispersed with the dissolver for 5 minutes at 1000 rpm.
Sprøjtetørringen af suspensionen foregik under følgende betingelser: 30 ___________ __________ Varmlufttemperatur: 400°C (elektrisk opvarmet)The spray drying of the suspension was carried out under the following conditions: 30 ___________ __________ Hot air temperature: 400 ° C (electrically heated)
Afgangstemperatur : 110 - 120°C Sprøjtetryk : 2 bar 9Discharge temperature: 110 - 120 ° C Injection pressure: 2 bar 9
DK 161976 BDK 161976 B
_10% ΝΤΑ_20% ΝΤΑ_10% ΝΤΑ_20% ΝΤΑ
Rystekeglehøjde (cm) 6,3 4,8Shaking cone height (cm) 6.3 4.8
Glødetab (%) 22,1 23,9Glow loss (%) 22.1 23.9
Rystevægtfylde (g/1) 435 430 5 Ca-bindeevne 162,8 168,2Shake density (g / l) 435 430 5 Ca binding capacity 162.8 168.2
Vandoptagning efter 7 2,0 1,2 dage (%)Water uptake after 7 2.0 1.2 days (%)
Sammensætning af vundet granulatformet 10 phosphaterstatning ifølge opfindelsen:Composition of won granular phosphate replacement according to the invention:
Zeolith A (absolut tør) 75 vægt% 68 v*gti NTA 8,3 vægt% 17 vægt%Zeolith A (Absolutely Dry) 75% by weight 68% by weight NTA 8.3% by weight 17% by weight
Marlophen 1,5 vægt% 1,5 vægt% 15 vand Rest RestMarlophen 1.5 wt% 1.5 wt% 15 water Rest Rest
Claims (2)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3332078 | 1983-09-06 | ||
| DE3332078 | 1983-09-06 | ||
| DE19843401861 DE3401861A1 (en) | 1983-09-06 | 1984-01-20 | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES ENABLED TO CALCIUMIONS, THEIR USE FOR THE PRODUCTION OF PHOSPHATE SUBSTITUTES FOR WASHING AND CLEANING AGENTS AND PHOSPHATE SUBSTITUTES |
| DE3401861 | 1984-01-20 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK36691A DK36691A (en) | 1991-03-01 |
| DK36691D0 DK36691D0 (en) | 1991-03-01 |
| DK161976B true DK161976B (en) | 1991-09-02 |
| DK161976C DK161976C (en) | 1992-02-03 |
Family
ID=25813766
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK423884A DK423884A (en) | 1983-09-06 | 1984-09-05 | HIGH STABLE SUSPENSIONS OF WATER-SOLUBLE, FOR THE BINDING OF CALCIUMIONS SUITABLE SILICATES, THEIR USE FOR THE PREPARATION OF PHOSPHATER STATEMENTS FOR WASHING AND CLEANING AGENTS, AND PHOSPHATER STATEMENTS |
| DK036691A DK161976C (en) | 1983-09-06 | 1991-03-01 | PHOSPHATER STATEMENTS FOR DETERGENTS AND CLEANERS |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK423884A DK423884A (en) | 1983-09-06 | 1984-09-05 | HIGH STABLE SUSPENSIONS OF WATER-SOLUBLE, FOR THE BINDING OF CALCIUMIONS SUITABLE SILICATES, THEIR USE FOR THE PREPARATION OF PHOSPHATER STATEMENTS FOR WASHING AND CLEANING AGENTS, AND PHOSPHATER STATEMENTS |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0144492B1 (en) |
| BR (1) | BR8404454A (en) |
| DE (2) | DE3401861A1 (en) |
| DK (2) | DK423884A (en) |
| ES (1) | ES8602086A1 (en) |
| FI (1) | FI842105A (en) |
| NO (1) | NO842130L (en) |
| PT (1) | PT79169B (en) |
| YU (1) | YU44460B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4769168A (en) * | 1985-08-05 | 1988-09-06 | Colgate-Palmolive Company | Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use |
| US5476610A (en) * | 1991-07-22 | 1995-12-19 | Henkel Kommanditgesellschaft Auf Aktien | Process for stabilizing aqueous zeolite suspensions |
| DE4203789A1 (en) * | 1992-02-10 | 1993-08-12 | Henkel Kgaa | METHOD FOR STABILIZING AQUEOUS ZEOLITE SUSPENSIONS |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT335590B (en) * | 1974-08-29 | 1977-03-25 | Henkel & Cie Gmbh | LIQUID TO PASTE DETERGENT AND CLEANING AGENT CONCENTRATE AND METHOD OF MANUFACTURING |
| DE2615698A1 (en) * | 1976-04-09 | 1977-10-20 | Henkel & Cie Gmbh | Stable, pumpable, water-insoluble silicate suspension - contg. dispersant and auxiliary stabilising, non-surfactant, water-soluble salt |
| GB2015488B (en) * | 1978-03-02 | 1982-09-22 | Unilever Ltd | Stabilised sodium aluminosilicate suspensions |
| DE3021295C2 (en) * | 1980-06-06 | 1986-10-16 | Basf Ag, 6700 Ludwigshafen | Aqueous storage-stable, flowable and pumpable sodium aluminosilicate suspensions |
| FI822428L (en) * | 1981-07-15 | 1983-01-16 | Unilever Nv | RENGOERINGSBLANDNING |
| DE3132767A1 (en) * | 1981-08-19 | 1983-03-10 | Degussa Ag, 6000 Frankfurt | Phosphate substitute for detergents |
| DE3209631A1 (en) * | 1982-03-17 | 1983-09-29 | Degussa Ag, 6000 Frankfurt | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS |
-
1984
- 1984-01-20 DE DE19843401861 patent/DE3401861A1/en not_active Ceased
- 1984-05-05 DE DE8484105075T patent/DE3469915D1/en not_active Expired
- 1984-05-05 EP EP84105075A patent/EP0144492B1/en not_active Expired
- 1984-05-25 FI FI842105A patent/FI842105A/en not_active Application Discontinuation
- 1984-05-29 NO NO842130A patent/NO842130L/en unknown
- 1984-06-25 YU YU1103/84A patent/YU44460B/en unknown
- 1984-08-08 ES ES534962A patent/ES8602086A1/en not_active Expired
- 1984-09-03 PT PT79169A patent/PT79169B/en unknown
- 1984-09-05 DK DK423884A patent/DK423884A/en not_active Application Discontinuation
- 1984-09-05 BR BR8404454A patent/BR8404454A/en unknown
-
1991
- 1991-03-01 DK DK036691A patent/DK161976C/en active
Also Published As
| Publication number | Publication date |
|---|---|
| DE3401861A1 (en) | 1985-03-21 |
| NO842130L (en) | 1985-03-07 |
| DK36691A (en) | 1991-03-01 |
| FI842105A (en) | 1985-03-07 |
| DK161976C (en) | 1992-02-03 |
| EP0144492A1 (en) | 1985-06-19 |
| FI842105A0 (en) | 1984-05-25 |
| YU44460B (en) | 1990-08-31 |
| PT79169A (en) | 1984-10-01 |
| YU110384A (en) | 1988-04-30 |
| DK423884D0 (en) | 1984-09-05 |
| BR8404454A (en) | 1985-05-21 |
| DK36691D0 (en) | 1991-03-01 |
| EP0144492B1 (en) | 1988-03-16 |
| DK423884A (en) | 1985-03-07 |
| ES534962A0 (en) | 1985-11-01 |
| ES8602086A1 (en) | 1985-11-01 |
| DE3469915D1 (en) | 1988-04-21 |
| PT79169B (en) | 1986-07-22 |
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