JPH07502963A - Method for stabilizing aqueous zeolite suspensions - Google Patents

Abstract

The method proposed enables aqueous zeolite suspensions to be stabilized by adding to the suspension at least one non-ionic surfactant selected from the group consisting: a) guerbet-alcohol/poly(ethyleneglycol) ethers of the formula (I): R?10-(CH2?CH2?0)m?H in which R?1 is a branched-chain alkyl group with 16 to 20 carbon atoms and m is a number from 3 to 15; b) fatty-alcohol/poly(ethyleneglycol) ethers of the formula (II): R?20-(CH2?CH2?0)n?H in which R?2 is an aliphatic hydrocarbon group with 12 to 22 carbon atoms and 1, 2 or 3 double bonds and n is a number from 1 to 10; c) fatty-alcohol/polyglycol ethers of the formula (III) in which R?3 is an alkyl group with 6 to 10 carbon atoms, p is a number from 1 to 5 and q is a number from 3 to 15; d) alkyl and/or alkenyl glycosides of the formula (IV): R?40-(G)x? in which R?4 is an alkyl and/or alkenyl group with 6 to 22 carbon atoms, G is a glycose unit derived from a sugar with 5 or 6 carbon atoms and x is a number between 1 and 10.

Description

[Detailed description of the invention] Method for stabilizing aqueous zeolite suspensions The present invention provides a method for stabilizing an aqueous zeolite suspension by adding a nonionic surfactant. Regarding the law.

Zeolites, especially zeolite type A, have recently been used as building blocks in detergents. is of particular importance and is largely replacing polyphosphoric acid, which has been used for decades. Ru. These advantages are due not only to its high calcium binding capacity, but also, above all, to its high bioavailability. Systemic toxicological compatibility [Tenund surfactants detergent ( Tens, 5urf, Det.), No. 24, p. 322, 1987].

In its manufacturing process, zeolite is obtained in the form of an aqueous suspension and kept in that state. It may be commercially available or may be subjected to spray drying. The water solubility of zeolite is extremely low (so that the zeolite suspension settles easily; the most preferred case is During storage, a significant amount of the solid usually settles to the bottom of the container and solidifies, resulting in phase separation. It then has to be moved, comminuted and resuspended, which is labor-intensive. Also other , the viscosity of the suspension may be such that it becomes difficult to transfer it to another container or circulate it with a pump. If transfer to another container or circulation with a pump were not possible, However, this can lead to significant product loss.

In the past, we have shown that it remains stable long enough during storage to allow the vibrator to pass through without occluding it. There have been many attempts to stabilize aqueous zeolite suspensions so that they can be It was conducted.

For example, in German Patent Publication No. 330 220 A1, fatty alcohol ethoxylates and fatty alcohol sulfates or fatty alcohol ether sulfates It is proposed to add a mixture of 0.5% to 5% by weight to the suspension.

German Patent Publication No. 3 408 040 A1 describes a suspension of 65% by weight of zeolite A at 0° 01 to 0.25% by weight of xanthan gum and having carboxyl or hydroxyl groups describes a method of stabilization with polymers that

According to the teaching of German Patent Publication No. 34 23 351 A1, poly glycol ether, fatty alcohol ether sulfate, fatty acid alkano Zeolite suspensions are also stabilized by the addition of polyamides or fatty acid monoglycerides. can be converted into

Furthermore, the use of many other stabilizers is known from the literature, e.g. Polycarboxylate, phosphonic acid, phosphoric acid ester, alkylbenzene sulfonate, layered silicate ``German Patent Publication No. 27388'', alkylphenol polyglycol ether [German patent publication 3401861A1], it Rizonolpolyglycol ether [German Patent Publication 3444311A1] and Oxoalcohol ethylene oxide adduct (German patent publication 3719042A1 ].

However, known methods provide adequate stability over a relatively wide temperature range, and disadvantages with respect to the viscosity of the suspension and its residue-free flowability.

Therefore, the problem to be solved by the present invention is to provide an aqueous zeolite that does not have the above-mentioned disadvantages. An object of the present invention is to provide an improved method for stabilizing a suspension of nitrate.

The present invention a) General formula 11 %formula%() [wherein R1 is a branched alkyl group having 16 to 20 carbon atoms, m is 3 to The number is 15. Ko Guerbet alcohol polyethylene glycol ether b) represented by the general formula ■, R20-(CH2CH20), H(n) [wherein R2 is 12 to 22 carbon atoms or and 1.2 or 3 double bonds, and n is 1 to 10 is the number of Fatty alcohol polyethylene glycol ether indicated by C) General formula■, CH3 R30-(CH2CH2), (CH2CH20)@H(Ill) [wherein R3 is an alkyl group having 6 to 10 carbon atoms, p is a number from 1 to 5 and q is a number from 3 to 15 It is a number. Ko and d) a fatty alcohol polyglycol ether represented by the general formula ■ , R40-(G), (IV) [wherein R4 is alkyl and/or alkenyl having 6 to 22 carbon atoms] G is a glycose unit derived from a sugar having 5 or 6 carbon atoms and X is a number from 1 to 10. Ko from the group consisting of alkyl and/or alkenyl glycosides represented by characterized in that at least one selected nonionic surfactant is added to the suspension. The present invention relates to a method for stabilizing an aqueous zeolite suspension by adding a surfactant.

By using selected nonionic surfactants or mixtures of them with each other, a wide range of Reliable stability of zeolite suspensions over a temperature range, especially from 10 to 60°C It was a surprising discovery that it was possible to This suspension is also suitable for long-term It exhibits high stability even when stored for a long time, and can be transported by pipe, allowing for extremely small product rolls. It can be dispensed at

Zeolite has the general formula (V), M2. ,．． 0-Al□03-xsio2・yH20(V) [wherein M is the bond valence 2 or an alkali metal or alkaline earth metal with a number of from 1.8 to 12 Yes, and y is a number from 0 to 8 [Chem, i, u, Zt, No. 20, 1 17 pages, 1986 Ko. ] an alkali metal or alkaline earth metal, optionally containing water, denoted by It is understood that it belongs to the genus alumosilicate.

Typical examples of zeolites used in aqueous dispersions stabilized by the method of the invention include: Natural mineral clinoptilolith, Eri Onite (erionite) or chabasite (chabasite) Ru. However, synthetic zeolites, e.g. Zeolite X Naas[(A10z)sa(SiOz)+oal・264 HzO zeolite Y Na5s [(A10z)ss(SiO2)+ssco・32 5HzO Zeolite L Ks [(A102)*(SiO2)2 Fuco・22HzO Mordenite Naa, t[(A102)s, t(SiO2)ss, s] + 24 R20 is preferred, Zeolite A　Na+2[(A10□)+z(Si02)+zco・27H20 is Particularly preferred.

The aqueous dispersion contains zeolite in an amount of 20 to 60% by weight, preferably 25 to 50% by weight. It may be contained in an amount of %.

Guerbet alcohol or fatty alcohols with ethylene oxide and/or Pyrene oxide adducts are known nonionic surfactants, themselves known They may be produced on an industrial scale by alkoxylation methods.

Guerbet alcohol polyethylene glycol ether used in the method of the invention (group a) consists of 1 mole of Guerbet-type branched primary alcohol and ethylene oxy It is an adduct with an average of 3 to 15 moles. Regarding the structure and production of Guerbet alcohol For more information, please visit Soap Cosmetics Chemical Specialties (Soa p, Co5m, Chew, 5pec, ) page 52, 1987. There is. Guerbet alcohol polyethylene glycol ether used according to the invention Typical examples of It is a 3-5 mole adduct of ren oxide. In the formula, R1 is 16 or 20 carbon atoms and m is a number from 3 to 10, the compound of general formula I is a branched alkyl group having preferable.

The fatty alcohol polyethylene glycol ethers forming group b) are from 12 to Technical fatty alcohol with 22 carbon atoms and 1.2 or 3 double bonds It is an ethylene oxide adduct with an average of 1 to 10 moles of ethylene oxide. A typical example is palmitrail Alcohol, oleyl alcohol, elaidyl alcohol, betroserinyl alcohol kohl, linolyl alcohol, lilunyl alcohol, gadleyl alcohol or is an ethylene oxide adduct of erucyl alcohol. In the formula, R2 is self, -3 8 alkenyl group, and n is a number from 4 to 9, especially a number from 4 to 5. Fatty alcohol polyglycol ethers are preferred. fatty alcohol polyethylene Glycol ethers have both traditional and narrow homolog distributions. You may do so.

In addition, fatty alcohols derived from industrial distillates rather than pure alcohols Based on lyethylene glycol ether, e.g. vegetable or animal raw materials Those obtained in selective hydrogenation of fatty acid methyl ester fractions may also be used. . The industrial fraction is defined as having an iodine value of at least 10 in the fatty alcohol fraction used. may contain saturated fatty alcohols with the number of carbon atoms in the above range. . Fats based on fatty alcohols with an iodine value of 10 to 125, especially 55 to 110 Alcohol polyethylene glycol ethers are preferably used. such fat Examples of fatty alcohol polyethylene glycol ethers are peanut oil, cottonseed oil, and coconut oil. Leander oil, soybean oil, beef tallow, rapeseed oil (oleic acid content > 80% by weight), sunflower based on soybean oil (oleic acid content > 80% by weight) and especially yano oil. Ru. Industrial oleyl alcohol based on oleyl alcohol with an iodine value of 10 to 20 Particularly preferred is a 6 to 8 mole ethylene oxide adduct of alcohol.

Fatty alcohol polyglycol ethers (group C) have 8 to 10 carbon atoms On average 1 to 5 moles of propylene oxide and ethylene oxide of fatty alcohol with It is an adduct of 3 to 15 moles of oxide. Propylene oxide and ethylene oxide may be added statistically (random distribution). However, the product is initially alcohol using typical alkoxylation catalysts such as sodium methylate or hydroxide. Reaction with brobylene oxide in the presence of dorotalcite and optionally propylene oxide. The lurate is separated from the lower boiling point impurities by distillation and then converted into ethylene oxide. It is preferable to obtain it by reacting with (block distribution). In the formula, R3 is It is an octyl group, p is a number of 1, and q is a number of 1 to 10, according to the general formula The use of fatty alcohol polyglycol ethers is preferred.

The alkyl and/or alkenyl glycosides (glucosides) used according to the invention Pd) is also a known substance. Its production method includes, for example, glucose or starch As a starting material, react with alcohol directly or via an intermediate step of butyl glyconde. [U.S. Pat. No. 3,547,828, U.S. Pat. No. 3,839,318, German Pat. Publication No. 3723826].

The alkyl group R4 of general formula (2) has 6 to 22, preferably 12 to 18 carbon atoms. may be derived from saturated or monounsaturated primary alcohols with A typical example is Prone alcohol, caprylic alcohol, cabri alcohol, lauryl alcohol alcohol, myristyl alcohol, cetyl alcohol, palmityl alcohol, Thearyl alcohol, elaidyl alcohol, oleyl alcohol, petroleum Nyl alcohol, behenyl alcohol or erucyl alcohol and these It is an industrial mixture.

Alkyl or alkenyl glycoside corresponding to the general formula ■, with aqueous zeolite content Particularly suitable for stabilizing dispersants may be derived from aldoses or ketoses. . Glyconodos of reduced satucaroids, especially glucose, are known for their high reactivity and absorption. It is particularly suitable due to its ease of handling. Therefore, preferably used alkyl and /or alkenylgluconide is alkyl and/or alkenylgluconide It is de.

X in general formula (IV) represents the degree of polymerization, that is, monoglycoside and oligoglycoside. It is a number from 1 to 10. For a particular compound, X is always natural A number from 1 to 6 can be assumed, but if a certain alkyl or alkenyl glycosylation X is a calculated value that is analytically measured, and is generally a fraction. Average degree of polymerization of 1 to 3 Alkyl and/or alkenyl glycosides with X are preferably used.

Alkyl and/or alkyl having a degree of polymerization X of 1.5 or less, especially 1.1 to 1.4 Kenyl glycosides are particularly preferred.

Particularly stable zeolite dispersions are those in which R4 is a linear C+Z-+a alkyl group, G an alkyl group represented by the general formula ■, where is a glucose unit and X is a number from 1 to 3 Obtained when Ricondo is used as a stabilizer.

The stabilizers of groups a) to d) may be used alone or in mixtures. Guru Several stabilizers belonging to groups a) to d) may be mixed with each other. For example, Weight ratio of ethylene oxide average 7 and 9 molar adducts of industrial oleyl alcohol A mixture of 20:80 to 80:20 is particularly effective. Another preference of the invention The aspect is, 1) In the formula, R2 is a Cl2-+8 alkenyl group and n is a number from 5 to 10. Fatty alcohol polyethylene glycol ether represented by general formula H 10~ 25% by weight, and 11) In the formula, R4 is a 01□-18 alkyl group, and G is a glucose unit. , an alkyl glyconode 7 represented by the general formula ■, where X is a number from 1°1 to 14 5-90% by weight characterized by the use of a mixture containing. Mixtures of this type can be used, for example, in alkyl gels. Formed as an intermediate step in the production of lukosto, it is directly aqueous gel without further purification. May be used for stabilizing olite dispersions [German Patent Publication No. 3603581A1] .

Stabilizers can be introduced into the dispersion mechanically, for example by stirring, without limitation, as desired. The temperature may be raised to 50°C. There is no scientific reaction here.

The nonionic surfactant is preferably present in an amount of 0.1 to 5% by weight relative to the suspension. It may be added to the suspension in an amount of 0.1 to 3% by weight.

The following examples serve to illustrate the invention without limiting it to the same extent.

Example Zeolite a [Sash(TM), 49.6% solids by weight, free alkaline Aqueous suspension with potash content of 0.32% by weight, manufactured by Henkel KGaA was introduced into a 500 ml glass beaker and then 1.5% by weight relative to the suspension of stabilizer or stabilizer mixture (expressed as solids) was added.

Stabilizer used: Example corresponding to the present invention - (30% by weight aqueous paste) A Octatool has an average of 1 mole of propylene oxide and an average of 5 moles of ethylene oxide. le adduct B Industrial oleyl alcohol based on rapeseed oil (iodine value = 108) Ren oxide average 7.2 mole adduct Etile, an industrial oleyl alcohol based on C rapeseed oil (iodine value = 108) average 9 mol adduct of carbon oxide D　C,6 Guerbet alcohol adduct with 3 moles of ethylene oxide on average E　Hydrogenated coconut C I 2/+ 4 alkyl gelcond based on oil alcohol, polymerization degree XG 　Isotridecyl alcohol adduct with ethylene oxide on average of 5 moles H isotride Adduct of ethylene oxide on average of 5 moles of sil alcohol ■ Itztrizonolalco Average 9 mol ethylene oxide adduct J industrial CI2/l coconut oil fat Ethylene oxide average 7 mol adduct of alcohol (iodine value <0.3) The stability of the suspension was evaluated for 1-6 days based on the following criteria.

1) Sedimentation The height of the liquid phase above the suspension was measured in mIl.

2) Precipitate: 1 = Slight precipitation, no solidification 2 = Slight precipitation, slight solidification 3- Slight precipitation, large amount of solidification 4-Thick precipitate, no solidification 5=Thick precipitate, slight solidification 6=Thick sediment, large solidification 3) Viscosity.

■=Low liquid-like ~ ■=Paste-like, high viscosity 4) Run-off property Results expressed as % by weight based on the dispersion remaining in the glass beaker after decanting. The results are summarized in Tables 1 and 2. Examples 1 to 11 correspond to the present invention, and C1 to C4 are for comparison. This is an example. All percentages are by weight.

Table 1 Stabilization of zeolite A suspension Table 1 - Continued Stability ratio of zeolite A suspension Table 2 - Stabilization of zeolite A suspension ( Comparative example) Legend S = stabilizer (nonionic surfactant) ratio; weight of stabilizer used quantity ratio 1 degree = concentration of stabilizer used Continuation of front page (51) Int, C1, 6 identification code Internal reference number ClID 3:22) (72) Inventor Kishkel, Ditmar Federal Republic of Germany Day-4019 Monheim, Schwanenstraße 20l.

Claims (8)

[Claims] 1. a) general formula I; R1O-(CH2CH2O)mH(I) [wherein R1 represents 16 to 20 carbon atoms] and m is a number from 3 to 15. ] Guerbet alcohol polyethylene glycol ether b) represented by the general formula II, R2O-(CH2CH2O)nH(II) [wherein R2 is 12 to 22 carbon atoms and an aliphatic hydrocarbon group having 1, 2 or 3 double bonds, and n is 1 to 1 It is the number of 0. ] Fatty alcohol polyethylene glycol ether c) general formula III; ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, R3 is 6 to 10 carbon atoms an alkyl group having children, p is a number from 1 to 5 and q is a number from 3 to 15; ] and d) a fatty alcohol polyglycol ether represented by general formula I V, R4O-(G)x(IV) [wherein R4 is alkyl and/or alkenyl having 6 to 22 carbon atoms] and G is a glycose unit derived from a sugar having 5 to 6 carbon atoms. and x is a number from 1 to 10. ] from the group consisting of alkyl and/or alkenyl glycosides represented by characterized in that at least one selected nonionic surfactant is added to the suspension. A method for stabilizing an aqueous zeolite suspension by adding a surfactant. 2. A nonionic surfactant is suspended in aqueous zeolite A with a solid content of 20 to 60% by weight. The method according to claim 1, characterized in that the method is added to a product. 3. In the formula, R1 is a branched C16 or C20 alkyl group, and m is a number from 3 to 10. Guerbet alcohol polyethylene glycol ether represented by general formula I 3. The method according to claim 1 or 2, characterized in that tel is used. 4. In the formula, R2 is a C16-18 alkenyl group, and n is a number from 4 to 9. Using a fatty alcohol polyglycol ether represented by formula II The method according to any one of claims 1 to 3, characterized in that: 5. In the formula, R3 is an octyl group, p is a number of 1, and q is a number of 1 to 10. using a fatty alcohol polyglycol ether represented by the general formula III The method according to any one of claims 1 to 4, characterized in that: 6. In the formula, R4 is a linear C12-18 alkyl group, and G is a glucose unit. using an alkyl glycoside represented by the general formula IV, where x is a number from 1 to 3. The method according to any one of claims 1 to 5, characterized in that: 7. i) In the formula, R2 is a C12-18 alkenyl group and n is a number from 5 to 10. Fatty alcohol polyethylene glycol ether represented by general formula II 10-25% by weight, and ii) In the formula, R4 is a C12-18 alkyl group and G is a glucose unit; , x is a number from 1.1 to 1.4, 75-90% by weight according to claims 1 to 6, characterized in that a mixture (% by weight relative to the mixture) of Any method described. 8. A nonionic surfactant is added to the suspension in an amount of 0.1 to 5% by weight based on the suspension. 8. The method according to any one of claims 1 to 7, characterized in that: