WO1994007840A1

WO1994007840A1 - Internally stable mixed hydroxyethers

Info

Publication number: WO1994007840A1
Application number: PCT/EP1993/002601
Authority: WO
Inventors: Rita Köster; Peter Daute; Gerhard Stoll
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-10-02
Filing date: 1993-09-24
Publication date: 1994-04-14
Also published as: FI951552A; FI951552A0; DE4233219A1; ZA937314B; EP0662947A1; CA2146236A1

Abstract

Described is a method of producing internally stable mixed hydroxyethers by subjecting epoxides of unsaturated fatty-acid esters to a ring-opening reaction with fatty-alcohol polyglycol ethers of formula (I), in which R1 is a straight-chain or branched-chain aliphatic hydrocarbon group with 4 to 22 carbon atoms and R2 is hydrogen or a methyl group. The products are suitable for use as auxiliaries in the removal of water from solid materials and have good biodegradability, low foaming power and a low solidification point.

Description

Internal hydroxy mixed ethers

Field of the Invention

The invention relates to internal hydroxy mixed ethers which are obtained by ring opening epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers, a process for their preparation and their use as auxiliaries in solids dewatering.

State of the art

In numerous branches of industry, for example in mining or sewage treatment plants, large amounts of highly water-containing, fine-particle solids are produced, which have to be dewatered before further processing or landfilling. For example, the drainage of hard coal or coke is a central process in the processing of coal-based fuels. The upper limit values for the water content of these materials required by the market can often be adhered to only with difficulty since, for example, mined coal is very fine-grained due to the extensive mechanization of underground coal mining. Around 38% of the raw material currently consists of fine coal with a particle diameter in the range from 0.5 to 10 mm; a further 14% consist of fine coal with an underlying particle diameter.

It is known that some surfactants are suitable as auxiliaries for dewatering finely divided solid suspensions containing water, in particular iron ore concentrates or hard coal, by means of which the residual moisture can be reduced. Dialkyl sulfosuccinates [US Pat. No. 2,266,954] and nonionic surfactants of the fatty alcohol polyglycol ether type [Erzmetall 30, 292 (1977)] have been described, for example, as surfactant dewatering aids of the type mentioned above. However, these surfactants have the disadvantage of considerable foam formation, which leads to considerable problems in the treatment plants, in particular when water is circulated in the treatment plants.

From German published patent application DE-Al-39 18 274 (Hen¬ kel), alkyl-end group-capped β-hydroxyalkyl ethers, so-called hydroxy mixed ethers, are known, which are produced by ring opening of alpha-olefin epoxides with fatty alcohol ethoxylates and as low-foam auxiliaries in the dewatering of solid suspensions be used. Although good results are achieved in the dewatering of solids with these agents, they have the disadvantage of unsatisfactory cold behavior. Particularly when stored outdoors, crystals can form even at temperatures of 10 to 15 ° C., as a result of which the pumping and flow behavior of these products and thus their intended use is considerably impaired. The object of the invention was therefore to provide novel hydroxy mixed ethers which, with the same application performance, have improved cold behavior.

Description of the invention

The invention relates to internal hydroxy mixed ethers which are obtained by epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers of the formula (I),

R ² SI -3i r

I.

R ¹ 0- (CH ₂ CHO) _n H _- (I)

in which R ^ represents a linear or branched, aliphatic hydrocarbon radical having 4 to 22 carbon atoms and R- ~ represents hydrogen or a methyl group, is subjected to a ring opening.

Surprisingly, it was found that the internal hydroxy mixed ethers according to the invention have significantly better cold behavior, in particular lower pour points, compared to the known terminal hydroxy mixed ethers of DE-A-39 18 274, with comparatively good, e.g. T. even have slightly improved application engineering properties.

Another object of the invention relates to a process for the preparation of internal hydroxy mixed ethers, in which Epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers of the formula (I),

R2

IR ¹ 0- (CH ₂ CHO) _n H (I)

in which R 1 is a linear or branched, aliphatic hydrocarbon radical having 4 to 22 carbon atoms and R ^{2 is} hydrogen or a methyl group, is subjected to a ring opening.

Epoxides of unsaturated fatty acid esters are, for example, addition products of oxygen to the double bonds of mono- or polyunsaturated fatty acid lower alkyl esters of the formula (II),

R ³ CO-OR ⁴ (II)

in which R ^ CO stands for an unsaturated acyl radical with 16 to 22 carbon atoms and R ^ stands for a linear or branched alkyl radical with 1 to 4 carbon atoms. Typical examples are epoxidized methyl, ethyl, propyl or butyl esters of palmoleic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, gadoleic acid and erucic acid and their technical mixtures. The epoxides used can be completely epoxidized, but they can also contain double bonds; the degree of epoxidation, based on the double bonds available, is preferably 50 to 100% and in particular 70 to 95%. Because to manufacture the epoxidized Fatty acid esters, usually technical sections of unsaturated lower fatty acid alkyl esters that still contain saturated portions, can consequently also contain small amounts of saturated fatty acid lower alkyl esters. The preferred feed is oleic acid methyl ester epoxide with an epoxy oxygen content of 4.5 to 5.1% by weight.

In addition to the epoxides of unsaturated fatty acid lower alkyl esters, epoxidized unsaturated fatty acid glycerol esters of the formula (III) are also suitable as starting materials,

CH2O-COR ⁴

I CH-O-COR ⁵ (III)

I CH2O-COR ⁶

in which R ^ CO, R ^ CO and R ^ CO independently of one another represent unsaturated acyl radicals having 16 to 24 carbon atoms.

Typical examples are epoxides of unsaturated triglycerides of plant or animal origin, such as soybean oil, rape oil, olive oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, beef tallow or fish oil. These feedstocks can also contain saturated portions; Usually, however, epoxides of such fatty acid glycerol esters are used which have an iodine number in the range from 50 to 150, preferably up to 115. As already described, both completely and partially epoxidized esters can be used as starting materials. The preferred feedstock is epoxidized Soybean oil with an epoxy content of 4.5 to 6.5% by weight.

Fatty alcohol polyglycol ethers of the formula (I) are suitable as the nucleophile for the ring opening of the insert epoxides mentioned. Typical examples are adducts of 1 to 30, preferably 2 to 10, moles of ethylene and / or propylene oxide with butanol, pentanol, capro alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, isotridecyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostyl alcohol , Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, and their technical mixtures, such as those obtained in the hydrogenation of Fettsron fatty acid methyl ester fractions or aldehydes from Roelen's oxosynthesis. Addition products of 2 to 8 moles of ethylene oxide with butanol as well as technical C12 14 or Ci2 / ιg coconut fatty alcohol cuts are preferably used.

The epoxides and the fatty alcohol polyglycol ethers can usually be used in a molar ratio of 1: 0.5 to 1: 1.5, preferably 1: 0.9 to 1: 1.1, based on the epoxy content.

In view of the shortest possible reaction time, it is advisable to carry out the ring opening reaction in the presence of basic catalysts, such as, for example, sodium methylate, which can be used in amounts of 0.1 to 5% by weight, based on the epoxide. In the same way it is advantageous to carry out the ring opening reaction at temperatures of 80 to 150, preferably 100 to 130 ° C.

Industrial applicability

The internal hydroxy mixed ethers to be used according to the invention support the dewatering of solid suspensions, are readily biodegradable and are characterized by low pour points.

Another object of the invention therefore relates to their use as auxiliaries for the dewatering of finely divided solid suspensions, such as iron ore concentrates, quartz sand, hard coal or coke. Another important area of application is the use of the internal hydroxy mixed ethers to be used according to the invention as auxiliaries in the dewatering of solid suspensions which are used in waste paper processing, e.g. B. in the de-inking process or filler flotation.

The internal hydroxy mixed ethers according to the invention can be used individually; for the dewatering of certain solids, however, it can be advantageous to combine products of different chain lengths or different degrees of alkoxylation with one another in order to exploit synergies in their physicochemical properties. In the same way, it can be advantageous to use combinations of the internal hydroxy mixed ethers with other already known ionic or nonionic drainage aids. According to an advantageous embodiment of the process according to the invention, the internal hydroxy mixed ethers are used in amounts of 10 to 500, preferably 50 to 300 and in particular 150 to 250 g, based on solids content, per ton of solid.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

I. Manufacturing examples

A) Hydroxy mixed ether based on oleic acid methyl ester epoxy.

374 g (1 mol) of butyl diglycol 5 EO ether and 5 g of sodium methylate (30% solution in methanol) were heated to 60 ° C. in vacuo in order to remove the methanol introduced with the catalyst. After adding 312 g (1 mol) of oleic acid methyl ester epoxy (Edenor ( ^R ) MeTiOs epoxy, from Henkel KGaA, Düsseldorf / FRG), the mixture was heated to 160 ° C. for 130 minutes. The hydroxy mixed ether was obtained as a clear liquid in practically quantitative yield.

Product characteristics;

Pour point 9 ° C

Viscosity (according to Höppler) 60 mPa.s hydroxyl number 81

Saponification number 88

Iodine number 15.2

Acid number 1.1

Residual epoxy acid content 0.1% by weight

Hydroxy mixed ether based on soybean oil epoxide.

Analogously to Example A), 748 g (2 mol) of butyl diglycol-5 EO ether and 5 g of sodium methylate (30% solution in methanol) were heated to 60 ° C. in vacuo in order to remove the methanol introduced with the catalyst. After the addition of 929 g (1 mol) of soybean oil epoxide (Edenor ( ^R ) D81, epoxy acid content 6.5% by weight, from Henkel KGaA, Düsseldorf / FRG), the mixture was heated to 160 ° C. for 130 minutes. The hydroxy mixed ether was obtained in practically quantitative yield as a clear liquid.

Product characteristics;

Pour point -7 ° C

Residual epoxy oxygen content 0.1% by weight viscosity (Höppler) 33 mPa.s hydroxyl number 131

C) Hydroxy mixed ether based on alpha-tetradecene epoxide.

Analogously to Example A), 374 g (1 mol) of butyl diglycol-5 EO ether and 5 g of sodium methylate (30% solution in methanol) were heated to 60 ° C. in vacuo in order to remove the methanol introduced with the catalyst. After addition of 212 g (1 mol) of alpha-tetradecene epoxide, the mixture was heated to 160 ° C. for 130 minutes. The hydroxy mixed ether was obtained in virtually quantitative yield as a cloudy liquid.

Product characteristics;

Pour point

Viscosity (according to Höppler)

Hydroxy1zah1

Residual epoxy oxygen content

Products A) and B) are inventive, product C) is used for comparison.

II. Drainage of Ouarzsand

Quartz sand of the following grain size was used for the drainage tests:

<125 µm: 2.8% by weight

125 to 200 µm: 26.4% by weight

200 to 315 µm: 60.1% by weight

> 315 µm: 10.7% by weight

The tests were carried out in a cup centrifuge, with which centrifuge parameters from 15 to 2000 can be achieved. Perforated plates with sieve openings of 0.1 x 2 mm were used as the sieve covering. The drainage aids were used in aqueous solutions; all concentration data are based on the solid.

After the quartz sand had been weighed into the centrifuge beaker, the aqueous solutions of the drainage aids were poured over the bed. After a draining time of 1 min, the solid was dewatered over a period of 30 s at a speed of 500 rpm. The moist solids were then weighed out, dried to constant weight at 100 ° C. and the residual moisture and the residual moisture reduction in% rel. certainly. All test results represent means of duplicate determinations. The results are summarized in Tab. 1. Tab. 1; Drainage of quartz sand

Legend; HM = aids

El - Weight 150 g auxiliary / t solids

E2 = initial weight 250 g auxiliary / t solids

E3 = initial weight 350 g auxiliary / t solids

III. Drainage of iron ore concentrate

The operational filter application of an iron ore concentrate was used for the drainage tests. The tests were carried out in a pressure filter (60 cm ² ) at a pressure difference of 2 bar. The filter feed had a solids content of 65% by weight and the sample amount was 120 ml. The drainage aids were again used in aqueous solutions; all concentration data are based on the solid. After dewatering, the moist solids were weighed out, dried to constant weight at 100 ° C and the residual moisture in% rel. certainly. All test results represent means of duplicate determinations. The results are summarized in Table 2.

Tab. 2; Drainage of iron ore concentrate

Legend; HM = aids

El = weight 100 g auxiliary / t solids

E2 = initial weight 150 g auxiliary / t solids

E3 = initial weight 200 g auxiliary / t solids

Claims

1. Internal hydroxy mixed ethers, obtainable by epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers of the formula (I),

R ²

IR! Θ- (CH2CHO) _n H (I)

in which R represents a linear or branched, aliphatic hydrocarbon radical having 4 to 22 carbon atoms and R ^{2 represents} hydrogen or a methyl group, is subjected to a ring opening.

2. Process for the preparation of internal hydroxy mixed ethers, in which epoxides of unsaturated fatty acid esters are used with fatty alcohol polyglycol ethers of the formula (I),

R ²

IR! 0- (CH ₂ CHO) _n H (I)

3. The method according to claim 2, characterized in that one uses epoxides of unsaturated fatty acid lower alkyl esters of the formula (II). R3CO-OR ⁴ (II)

in which R ^ CO stands for an unsaturated acyl radical with 16 to 22 carbon atoms and R ⁴ for a linear or branched alkyl radical with 1 to 4 carbon atoms.

4. The method according to claim 2, characterized in that epoxides of ungc attested fatty acid glycerol esters of the formula (III) are used,

CH2O-COR ⁵

I.

CH-O-COR ⁶ (III)

I.

CH ₂ 0-COR ⁷

in which R ^ CO, R - *> CO and R cθ independently of one another represent unsaturated acyl radicals having 16 to 24 carbon atoms.

5. The method according to claim 2, characterized in that one uses the epoxides and the fatty alcohol polyglycol ether in a molar ratio of 1: 0.5 to 1: 1.5 - based on the epoxy content.

6. The method according to claim 2, characterized in that one carries out the ring opening reaction in the presence of basic catalysts.

7. The method according to claim 2, characterized in that one uses the catalysts in amounts of 0.1 to 5 wt .-% - based on the epoxy.

8. The method according to claim 2, characterized in that one carries out the ring opening reaction at temperatures of 80 to 150 ° C.

9. Use of internal hydroxy mixed ethers according to claim 1 as an aid for dewatering fine-particle solid suspensions, in particular in the treatment of waste paper.