WO1993002171A1 - Procede de stabilisation de suspensions aqueuses de zeolites - Google Patents

Procede de stabilisation de suspensions aqueuses de zeolites Download PDF

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Publication number
WO1993002171A1
WO1993002171A1 PCT/EP1992/001590 EP9201590W WO9302171A1 WO 1993002171 A1 WO1993002171 A1 WO 1993002171A1 EP 9201590 W EP9201590 W EP 9201590W WO 9302171 A1 WO9302171 A1 WO 9302171A1
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WO
WIPO (PCT)
Prior art keywords
carbon atoms
formula
alkyl
alcohol
radical
Prior art date
Application number
PCT/EP1992/001590
Other languages
German (de)
English (en)
Inventor
Karl-Heinz Schmid
Andreas Syldath
Ditmar Kischkel
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59206964T priority Critical patent/DE59206964D1/de
Priority to EP92915813A priority patent/EP0595919B1/fr
Priority to JP5502572A priority patent/JPH07502963A/ja
Publication of WO1993002171A1 publication Critical patent/WO1993002171A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the invention relates to a method for stabilizing aqueous zeolite suspensions by adding selected nonionic surfactants.
  • Zeolites in particular of the zeolite A type, are of particular importance as builders of modern detergents and have largely replaced the polyphosphates that have been used for decades. Their advantages lie not only in their high calcium binding capacity, but also in their high ecotoxicological compatibility [Tens.Surf. Det., 24, 322 (1987)].
  • the zeolites are obtained in the form of aqueous suspensions, which can either be stored as such and placed on the market, or can be subjected to spray drying.
  • Zeolites have an extremely low solubility in water, so that suspensions of these substances are easy sediment. In the most favorable case, this leads to a phase separation, but usually considerable amounts of the solid separate out on the bottom of the vessels during storage, harden and then have to be separated, comminuted and resuspended with great technical effort. In other cases, the viscosity of the suspension increases so much that decanting or pumping over becomes difficult, if not impossible, and in any case involves considerable product losses.
  • German patent application DE 33 30 220 AI proposes adding 0.5 to 5% by weight of a mixture of fatty alcohol ethoxylates and fatty alcohol sulfates or fatty alcohol ether sulfates to the suspensions.
  • German patent application DE 34 08 040 A1 describes a process for stabilizing 65% by weight zeolite A suspensions with the aid of 0.01 to 0.25% by weight xanthan gum and carboxyl- or hydroxyl-containing polymers.
  • zeolite suspensions can also be stabilized at pH 9 to 10 by adding polyglycol ethers, fatty alcohol ether sulfates, fatty acid alkanolamides or fatty acid monoglycerides.
  • the literature also describes the use of numerous other stabilizers, for example polycarboxylates with molecular weights above 1500, phosphonic acids, phosphoric acid esters, alkylbenzenesulfonates, layered silicates [DE-OS 27 388], alkylphenol polyglycol ethers [DE 34 01 861 AI], isotridecyl polyglycol ethers [DE 34 44 311 AI] and addition products of ethylene oxide onto oxo alcohols [DE 37 19 042 AI] are known.
  • polycarboxylates with molecular weights above 1500 phosphonic acids, phosphoric acid esters, alkylbenzenesulfonates, layered silicates [DE-OS 27 388], alkylphenol polyglycol ethers [DE 34 01 861 AI], isotridecyl polyglycol ethers [DE 34 44 311 AI] and addition products of ethylene oxide onto oxo alcohols [DE 37 19 042 AI] are known.
  • the object of the invention was therefore to develop an improved method for stabilizing aqueous zeolite suspensions which is free from the disadvantages described.
  • the invention relates to a process for stabilizing aqueous zeolite suspensions by adding surfactants, which is characterized in that the suspensions are selected from at least one nonionic surfactant from the group consisting of a) Guerbet alcohol polyethylene glycol ethers of the formula (I), R- 1 -O - (CH 2 CH 2 O) m H (l) in which R 1 is a branched alkyl radical having 16 to 20 carbon atoms and m is a number from 3 to 15, b) fatty alcohol polyethylene glycol ethers of the formula (II),
  • R 3 O- (CH 2 CHO) p (CH 2 CH 2 O) q H (III) in R 3 for an alkyl radical with 6 to 10 carbon atoms, p for numbers from 1 to 5 and q for numbers of 3 to 15, and d) alkyl and / or alkenyl glycosides of the formula (IV),
  • Zeolites are optionally to be understood as meaning water-containing alkali or alkaline earth aluminosilicates of the general formula (V)
  • zeolites the aqueous dispersions of which can be stabilized in the process according to the invention, are the naturally occurring minerals clinoptilolite, erionite or chabasite.
  • synthetic zeolites are preferred, for example
  • the aqueous suspensions can contain the zeolites in amounts of 20 to 60, preferably 25 to 50% by weight.
  • Addition products of ethylene oxide and / or propylene oxide with Guerbet or fatty alcohols are known nonionic surfactants which are produced on an industrial scale by the known process of alkoxylation.
  • Guerbet alcohol polyethylene glycol ethers (group a) which can be used for the purposes of the process according to the invention are addition products of an average of 3 to 15 mol of ethylene oxide to 1 mol of a branched primary alcohol of the Guerbet type; regarding structure and production of Guerbet alcohols, see Soap, Cosm.Chem. Spec, 52 (1987).
  • Typical examples of Guerbet alcohol polyethylene glycol ethers which can be used according to the invention are addition products of 3 to 15 mol of ethylene oxide with 2-hexyldecanol or 2-octyldodecanol.
  • Compounds of the formula (I) in which R 1 is a branched alkyl radical having 16 or 20 carbon atoms and m is a number from 3 to 10 are preferred.
  • fatty alcohol polyethylene glycol ethers which form group b
  • adducts of an average of 1 to 10 moles of ethylene oxide with technical fatty alcohols with 12 to 22 carbon atoms and 1, 2 or 3 double bonds are suitable.
  • Typical examples are ethylene oxide adducts with palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, gadoleyl alcohol or erucyl alcohol.
  • the fatty alcohol polyethylene glycol ethers can have both a conventional and a narrow homolog distribution.
  • fatty alcohol polyethylene glycol ethers can also be used, which are not derived from pure alcohols but from technical cuts, such as those obtained in the selective hydrogenation of fatty acid methyl ester fractions based on vegetable or animal raw materials.
  • the technical cuts can also contain saturated fatty alcohols of the C number range mentioned, provided that the iodine number of the fatty alcohol fraction used is at least 10.
  • Fatty alcohol polyethylene glycol ethers based on fatty alcohols which have an iodine number of 10 to 125, in particular 55 to 110, are preferably used.
  • fatty alcohol polyglycol ethers based on peanut oil, cottonseed oil, coriander oil, soybean oil, beef tallow, rapeseed oil (oleic acid content> 80% by weight), sunflower oil (oleic acid content> 80% by weight) and in particular coconut oil.
  • An adduct of 6 to 8 mol of ethylene oxide with a technical oleyl alcohol based on coconut alcohol with an iodine number of 10 to 20 is particularly preferred.
  • Fatty alcohol polyglycol ethers are addition products of on average 1 to 5 moles of propylene oxide and 3 to 15 moles of ethylene oxide with fatty alcohols having 8 to 10 carbon atoms.
  • the addition of propylene oxide and ethylene oxide can take place statistically (Random distribution).
  • the preferred procedure for the preparation of the products is that the fatty alcohols are first reacted with propylene oxide in the presence of typical alkoxylation catalysts, for example sodium methylate or hydrotalcite, the propoxylate is freed from low-boiling impurities, if appropriate by distillation, and then reacted with ethylene oxide (block distribution ).
  • typical alkoxylation catalysts for example sodium methylate or hydrotalcite
  • the propoxylate is freed from low-boiling impurities, if appropriate by distillation, and then reacted with ethylene oxide (block distribution ).
  • alkyl and / or alkenyl glycosides (group d) to be used according to the invention are also known substances. Processes for their preparation are based, for example, on glucose or starch which are reacted with alcohols either directly or via the intermediate stage of the butyl glycosides [US 3,547,828, US 3,839,318 , DE-A-37 23 826].
  • the alkyl radical R 4 in formula (IV) can be derived from primary saturated or monounsaturated alcohols having 6 to 22, preferably 12 to 18, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, elaidyl alcohol, oleyl alcohol, petroselinyl alcohol, behenyl alcohol or erucyl alcohol and their technical mixtures.
  • Alkyl or alkenyl glycosides of the formula (IV) which are particularly suitable for the stabilization of aqueous zeolite suspensions can be derived from aldoses or ketoses. Because of the higher reactivity and the technical availability, primarily the glycosides of the reducing saccharides and especially glucose come into consideration. The preferred alkyl and / or alkenyl glycosides are therefore the alkyl and / or alkenyl glucosides.
  • the stabilizers used are alkyl glycosides of the formula (IV) in which R 4 is a linear alkyl radical having 12 to 18 carbon atoms, G is a glucose unit and x is a number from 1 to 3 .
  • the stabilizers of groups a) to d) can be used individually or in mixtures. It is also possible to combine several stabilizers within groups a) to d). Mixtures of addition products with an average of 7 and 9 moles of ethylene oxide on technical have proven particularly effective Oleyl alcohol in a weight ratio of 20:80 to 80:20 has been proven.
  • a mixture comprising i) 10 to 25% by weight of a fatty alcohol polyethylene glycol ether of the formula (11) / in which R2 is an alkenyl radical having 12 to 18 carbon atoms and n is a number from 5 to 10, and ii) 75 to 90% by weight of an alkyl glycoside of the formula (IV) in which R 4 is an alkyl radical having 12 to 18 carbon atoms, G is a glucose unit and x is a number from 1.1 to 1.4 .
  • Mixtures of this type are obtained, for example, as an intermediate in the production of alkyl glucosides and can be used without further purification to stabilize aqueous zeolite suspensions [DE 36 03 581 AI].
  • the introduction of the stabilizers into the suspension is not critical and can, for. B. mechanically by stirring, optionally at elevated temperatures of 50 ° C. There is no chemical reaction.
  • the nonionic surfactants can be added to the suspensions in amounts of 0.1 to 5, preferably 1 to 3% by weight, based on the suspension.
  • the stability of the suspensions was assessed over a period of 1 to 6 days according to the following criteria:
  • the height of the liquid phase above the suspension was determined in mm.
  • Residue in the beaker after decanting Specification in% by weight based on the suspension.
  • Ratio weight ratio of the used

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Des suspensions aqueuses de zéolites sont stabilisées si on leur ajoute au moins un agent tensioactif non ionique choisi dans le groupe formé par a) des alcool-polyéthylèneglycol-éthers de Guerbet de formule (I): R10-(CH2CH20)mH où R1 désigne un reste alkyle ramifié de 16 à 20 atomes de carbone et m est compris entre 3 et 15, b) des polyéthylèneglycol-éthers d'alcools gras de formule (II): R20-(CH2CH20)nH où R2 désigne un reste hydrocarbure aliphatique de 12 à 22 atomes de carbone et à 1, 2 ou 3 doubles liaisons et n est compris entre 1 et 10, c) des polyglycol-éthers d'alcools gras de formule (III) où R3 désigne un reste alkyle de 6 à 10 atomes de carbone, p est compris entre 1 et 5 et q, entre 3 et 15, et d) des alkyl- et/ou alkénylglucosides de formule (IV): R40-(G)x où R4 désigne un reste alkyle et/ou alkényle de 6 à 22 atomes de carbone, G est un motif glucose dérivé d'un sucre à 5 ou 6 atomes de carbone, et x est compris entre 1 et 10.
PCT/EP1992/001590 1991-07-22 1992-07-13 Procede de stabilisation de suspensions aqueuses de zeolites WO1993002171A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE59206964T DE59206964D1 (de) 1991-07-22 1992-07-13 Verfahren zur stabilisierung von wässrigen zeolith-suspensionen
EP92915813A EP0595919B1 (fr) 1991-07-22 1992-07-13 Procede de stabilisation de suspensions aqueuses de zeolites
JP5502572A JPH07502963A (ja) 1991-07-22 1992-07-13 水性ゼオライト懸濁物の安定化方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4124247.5 1991-07-22
DE4124247A DE4124247A1 (de) 1991-07-22 1991-07-22 Verfahren zur stabilisierung von waessrigen zeolith-suspensionen

Publications (1)

Publication Number Publication Date
WO1993002171A1 true WO1993002171A1 (fr) 1993-02-04

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PCT/EP1992/001590 WO1993002171A1 (fr) 1991-07-22 1992-07-13 Procede de stabilisation de suspensions aqueuses de zeolites

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EP (1) EP0595919B1 (fr)
JP (1) JPH07502963A (fr)
AT (1) ATE141640T1 (fr)
DE (2) DE4124247A1 (fr)
DK (1) DK0595919T3 (fr)
ES (1) ES2090669T3 (fr)
WO (1) WO1993002171A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4203789A1 (de) * 1992-02-10 1993-08-12 Henkel Kgaa Verfahren zur stabilisierung von waessrigen zeolith-suspensionen
US5759979A (en) * 1993-04-05 1998-06-02 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures comprising APG and fatty alcohol polyglycol ether
JP2017141311A (ja) * 2014-05-30 2017-08-17 協和化学工業株式会社 液状安定剤及び液状安定剤を含有する熱可塑性樹脂組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169075A (en) * 1974-10-10 1979-09-25 Henkel Kommanditgesellschaft Auf Aktien Process for the production of powdery washing agents by spray-drying
EP0075995A2 (fr) * 1981-09-28 1983-04-06 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant de mélanges d'alcylpolysaccharide et d'agents tensio-actifs non-ioniques
WO1985001039A1 (fr) * 1983-08-22 1985-03-14 Henkel Kommanditgesellschaft Auf Aktien Suspension aqueuse, stabilisee a base de zeolithe
EP0294694A2 (fr) * 1987-06-06 1988-12-14 Degussa Aktiengesellschaft Suspensions de silicates aqueuses stables insolubles dans l'eau capables de fixer des ions de calcium et leur utilisation pour la production d'agents de lavage et de nettoyage
WO1991014760A1 (fr) * 1990-03-24 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Melange tensio-actif non-ionique peu moussant
EP0487262A2 (fr) * 1990-11-20 1992-05-27 Unilever Plc Compositions détergentes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169075A (en) * 1974-10-10 1979-09-25 Henkel Kommanditgesellschaft Auf Aktien Process for the production of powdery washing agents by spray-drying
EP0075995A2 (fr) * 1981-09-28 1983-04-06 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant de mélanges d'alcylpolysaccharide et d'agents tensio-actifs non-ioniques
WO1985001039A1 (fr) * 1983-08-22 1985-03-14 Henkel Kommanditgesellschaft Auf Aktien Suspension aqueuse, stabilisee a base de zeolithe
EP0294694A2 (fr) * 1987-06-06 1988-12-14 Degussa Aktiengesellschaft Suspensions de silicates aqueuses stables insolubles dans l'eau capables de fixer des ions de calcium et leur utilisation pour la production d'agents de lavage et de nettoyage
WO1991014760A1 (fr) * 1990-03-24 1991-10-03 Henkel Kommanditgesellschaft Auf Aktien Melange tensio-actif non-ionique peu moussant
EP0487262A2 (fr) * 1990-11-20 1992-05-27 Unilever Plc Compositions détergentes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 006, no. 135 (C-115)1982 & JP,57 061 616 ( LION CORP. ) *

Also Published As

Publication number Publication date
ATE141640T1 (de) 1996-09-15
DK0595919T3 (da) 1996-12-23
EP0595919A1 (fr) 1994-05-11
JPH07502963A (ja) 1995-03-30
EP0595919B1 (fr) 1996-08-21
ES2090669T3 (es) 1996-10-16
DE4124247A1 (de) 1993-01-28
DE59206964D1 (de) 1996-09-26

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