CS254210B1 - Defoamer or mixture of antifoams - Google Patents

Abstract

The defoamer or mixture of defoamers is based on organic oxygenates or mixtures of oxygenates and hydrocarbon compounds, with a content of organic oxygenates in them of 2 to 100 %, formed by the main alcoholic by-product of cyclohexane oxidation, isolated by rectification of a predominantly cyclohexanol-cyclohexanone mixture (b.p. 92 to 142 °C; saponification number - = 10 to 60 mg KOH/g; wt. % OH = 8 to 22). Another by-product is the distillation residue from the stage of separation of residual cyclohexanol from the cyclohexanol-cyclohexanone oxidation mixture (% wt. OH = 2 to 10; % wt. CO = 3.5 to 14; bromine number = 100 to 280 g Br/100 gj. Hydrocarbon compounds consist of petroleum fractions (kerosene, light gas oil, heavy gas oil), oligomers of C3 to C5 alkenes (polypropylene oil) as well as their hydrogenates. Defoamers are used mainly in the pulp and paper and chemical industries, in the finishing industry, in the leather industry and in other sectors.

Description

The invention relates to a defoamer or a mixture of defoamers mainly based on readily available organic oxygen and hydrocarbon compounds, which are easy to formulate and are effective for suppressing foam formation or defoaming both aqueous and non-aqueous media.

The use of oxygenated organic compounds, such as higher fatty acids and alcohols, but especially organosilicon compounds, as effective defoamers is known (US Pat. No. 3,458,567, 2,923,687 and Czech Patent Certificate No. 183,982 j.

Many aqueous systems that normally foam can be defoamed with small amounts of ethoxylated castor oil and its hydrogenate and also with propoxylated oils (US Pat. No. 3,180,836). For paper wastewater, defoamers consisting of ethoxylated fatty acids and ethoxylated alkylphenols in a mixture with low molecular weight alcohols are known (US Pat. No. 3,215,635; Tichomirov V. K.: Foams. Theory and practice of their preparation and decomposition. "Chimiya", Moscow /1983/). Defoaming activity is also known (US Pat. No. 3,697,438) for esters of polyglycols with oleic acid and in a mixture with alcohols C16 to C18, propylene glycol, isopropyl alcohol and mineral oil.

Their advantage is hygienic properties, but the disadvantage is relatively low defoaming efficiency on foams formed by the action of nonionic surfactants. In the case of organosilicon compounds, such as silicone oils, the high defoaming efficiency is remarkable, but the disadvantage is mainly their raw material and energy requirements. In some cases, there is also an undesirable increase in the ash content of defoamed products due to the action of organosilicon defoamers. At least a partial solution to the above problems and a further expansion of the range of readily available technical defoamers is possible by applying this invention.

The subject of the invention is a defoamer or a mixture of defoamers based on oxygenated organic compounds or a mixture of oxygenated and hydrocarbon organic compounds. In the defoamer or in the mixture of defoamers 2 to 100% by weight. forms the leading alcoholic by-product from the oxidation of cyclohexane, isolated by rectification of predominantly a cyclohexanol-cyclohexanone mixture, with a density at 20 °C in the range of 840 to 865 kg. m ^-3 , distilling 93 + 5% in the boiling range of 92 to 142 °C, with a saponification number of 10 to 60 mg KOH/g, with a hydroxyl group content of 8 to 23% by weight. and/or a distillation residue from the stage of separation of residual cyclohexanol of the oxidation mixture of cyclohexanol-cyclohexanone with a density at 20 °C in the range of 960 to 980 kg. m ^-3 with a hydroxyl group content of 2 to 10% by weight, carboxyl groups

3.5 to 14% by weight, bromine number 100 to 280 g Br/100 g.

In the case of a mixture of oxygenated organic compounds with hydrocarbon organic compounds, the content of hydrocarbon compounds is up to 98% by weight with a molar mass of 100 to 1,000 g mol ¹ .

The advantage of the defoamer or defoamer mixture according to the present invention is the expansion of the range of defoamers, the availability of raw materials, allowing even similar, as the main product, technical and economic evaluation of by-products from the production of cyclohexanone by oxidation of cyclohexane. Then the high stability of the defoamers, reproducible efficiency, good storage stability and easy handling with them.

In the defoamer or defoamer mixture according to the invention, the organic oxygen compounds constitute 2 to 100 %, and this amount may additionally include known components of defoamers, such as stearic acid, ethanolamide, acids, aliphatic alcohols C10 to C18, etc. However, the main substance is the alcoholic by-product of the oxidation of cyclohexane, usually catalyzed oxidation mainly to cyclohexanol-cyclohexanone, isolated by rectification of a predominantly cyclohexanol-cyclohexanone mixture on a column (FK-102). It is essentially a colorless liquid, from which 93 + 5 % is distilled in the temperature range of 92 to 142 °C/101 kPa; its density is in the range of 840 to 865 kg. m+ acid number ranges from 0.01 to 5 mg KOH/g, saponification number from 10 to 60 mg KOH per gram, hydroxyl groups from 8 to 23% by weight; carboxyl groups from 2 to 8% by weight. It usually contains:

up to 53% amyl alcohol;

up to 5% isoamyl alcohol, up to 10% n-butanol, up to 7% isobutanol, up to 2 °/o sec.butyl alcohol, up to 20% cyclohexanone, up to 10% cyclopentanol, up to 6% cyclopentanone, about 2% water.

Furthermore, impurities of cyclohexane, cyclohexene and cyclohexanol constitute about 1%.

Other oxygenated organic compounds which, as such or together with hydrocarbons, form the defoamer according to the invention are also a by-product of cyclohexane oxidation, isolated as a distillation residue from the stage of separation of residual cyclohexanol from the oxidation mixture cyclohexanol--cyclohexanone (heavy fraction from column FK-105). This heavy fraction (from column FK-105) is usually dark in color, has a density at 20 degrees Celsius in the range of 960 to 980 kg. m" ³ and in the temperature range of 150 to 263 ° C/101 'kPa distils 93 + 5%; the acid number is usually in the range of 0.3 to 3 mg KOH/g; the bromine number is 100 to 280 g Br/100 g; the content of hydroxyl groups is 2 to 10% by weight and carboxyl groups is 3.5 to 14% by weight.

Hydrocarbon compounds include individually saturated or unsaturated mainly aliphatic hydrocarbons, possibly containing naphthenic hydrocarbons and aromatic admixtures, most often petroleum fractions and of these mainly kerosene fraction, or fraction of light but also heavy gas oil. Then synthetic hydrocarbons, mainly oligomers, co-oligomers, or low molecular weight polymers and copolymers of propylene, alkenes and dienes Ci and Cs, further products formed by thermal cleavage of macromolecular substances, as well as hydrogenolysis of macromolecular substances and higher hydrocarbons, e.g. hydrocarbons from vacuum distillates of petroleum, etc. In addition, hydrogenated oligomers of the above alkenes and dienes Cs to Cs can also be used.

The defoamer or defoamer mixtures according to the present invention may be refined, colored, or perfumed. Further details of the formulation of the defoamer or defoamer mixture according to the present invention, as well as the defoaming efficiency and other advantages are apparent from the examples.

Example 1

From the production of cyclohexanone via the intermediate mixture cyclohexanol-cyclohexanone by catalytic oxidation of cyclohexane, the leading alcoholic by-product is obtained, isolated by rectification of predominantly cyclohexanol-cyclohexanone mixture in a column (FK-102). The density of this colorless liquid (hereinafter referred to as by-product FK-102) at a temperature of 20 °C = 855 kg.m ^-3 and in the range of 92 to 142 ^° C/101 kPa it distils 95 %/o; acid number = 0.95 mg KOH/g; saponification number = 21.0 mg KOH/g, bromine number = 27.8 mg KOH/g; hydroxyl groups 14.3 % by weight; carboxyl groups = = 4.6 % by weight; contains (in % by weight):

51.9% amyl alcohol,

3.7% isoamyl alcohol,

9.5% n-butanol,

5.6% isobutanol,

1.1% sec.butyl alcohol,

19.7% cyclohexanone,

8.0% cyclopentanol,

5.0% cyclopentanone and

3.6% water.

Admixtures of cyclohexane, cyclohexene and cyclohexanol make up around 1 °/o.

Distillation residue from the stage of separation of residual cyclohexanol from the cyclohexanol-cyclohexanone oxidation mixture (heavy fraction from column FK-105). This heavy fraction from column FK-105 (hereinafter referred to as the residue from FK-105) has a density of 970 kg m ^-3 at 20 °C and distills 95% by weight in the temperature range 150 to 263 °C/101 kPa; acid number = 0.9 milligrams KOH/g; bromine number 229.7 g Br/100 g; hydroxyl group content — = 4.51 % by weight; carboxyl groups 8.3 percent by weight.

Both the by-product FK-102 and the residue from FK-105 in particular are tested as defoamers. Furthermore, mixtures with propylene oligomers, so-called polypropylene oil (Propyloil K 300) with an average molecular weight of 449 g. mol" ¹ , density at 20 "C = 840 kilograms. m ^-3 ; refractive index n _D ²⁰ = 1.465, freezing point = -35 °C and bromine number = 53.5 g Br/100 g sample are tested. Also with propylene oligomers with a higher average molecular weight (propyloil K-1000), which reaches 560 g. mol ^-1 , with a density at 20 degrees Celsius = 847 kg. m ^-3 and a freezing point = -25 °C; There are an average of 1.5 double bonds per molecule of polypropylene oil K-1000.

The defoaming efficiency is determined by comparing the foaming of the standard sample with the foaming of the standard sample to which the defoamer is added. The procedure is as follows: 100 cm ³ of a standard solution of sodium alkyl sulfate (as an anionic surfactant or polyethoxylated primary alcohols C12 to C14 with 9 moles of ethylene oxide (as a nonionic surfactant) with a concentration of 1 g dm ^-3 is carefully poured into a measuring cylinder with a volume of 500 cm ³ and closed with a ground glass stopper. The standard solution is foamed by inverting the cylinder through 180° and back 50 times for 1 min. at a temperature of 20 + + 2 ³ C. The height of the foam and the height of the unfoamed solution are measured after 1 min. from the end of foaming. Then the foaming of the standard Pš (%) is calculated from the relationship:

Pš = 100, where a — foam height in cm and b = height of unfoamed solution in cm.

The defoaming efficiency is determined by the same procedure as for the standard solution, but 1 drop of defoamer (0.02 g) is added to 100 cm ³ of the standard solution and Po (foaming capacity of the mixture of the standard solution with defoamer) is determined. The defoaming efficiency is calculated from a graph of the dependence of foaming (%) on the defoaming efficiency, with the defoaming efficiency (in °/o) from 100 to 0 plotted on the x-axis and the foaming capacity of the standard solution on the y-axis. The °/o of the defoaming efficiency is read at the intersection of the diagonal, with the arithmetic mean of 3 measurements taken as the final result.

The achieved defoaming efficiency results of individual defoamers are summarized in Table 1.

Example 2

The procedure is similar to that in Example 1, except that the amount of polypropylene oil (K-1000) in the defoamer is 50% and the distillation residue from the stage of separation of residual cyclohexanol from the cyclohexanol-cyclohexanone oxidation mixture (heavy, portion from column FK-105) is the remaining 50% by weight. The defoaming efficiency for nonionic surfactant is 28% and for anionic surfactant 40%.

In another variant, a defoamer Table 1 is prepared consisting of 30% by weight of the heavy fraction from the FK-105 column, 35% polypropylene oil (K-1000) and 35% kerosene. The defoaming efficiency for the nonionic surfactant is 35% and for the anionic surfactant 47%.

Number Defoamer composition Defoaming efficiency (%) on:

attempt component (% by weight) nonionic surfactant anionic surfactant 1 drop 2 drops 1 drop 2 drops 1 product FK-102 100 63 77 35 43 2 product FK-105 100 63 76 52 48 3 polypropylene oil (K-1000) stearic acid 80 2.5 100 97 100 98.5 4 FK-105 polypropylene oil (K-300) stearic acid 17.5 87.5 2.5 96 98.5 57 43.5 5 product FK-102 polypropylene oil (K-1000) FK-105 10.0 48.7 48.7 91.5 100 63 88 Θ stearic acid monoethanolamide polypropylene oil (K-1000) FK-105 2.5 87.5 10.5 97 99.5 33 89.5

stearic acid monoethanolamide 2.5

Example 3

Defoamers or potential defoamers are prepared as in Example 1, and the extreme limits of the components for defoaming efficiency are examined. The achieved results of defoaming efficiency for nonionic and anionic surfactants depending on the composition of the defoamer are given in Table 2.

Table 2

Composition of defoamer Defoaming efficiency (%) for: Component (% by weight) nonionic surfactant anionic surfactant 1 3 1 3 drop drops drop drops 1 2 3 4 5 6

Polypropylene oil (To 1000) 97.5 0 0 35 36 FK-102 2.5 Polypropylene oil (To 1000) 80 54 45 27.5 24 FK-102 20 Polypropylene oil (To 1000) 97.5 51 73 0 49 FK-105 2.5 Polypropylene oil (To 1000) 95 45 48 26 49.5 FK-105 5 Polypropylene oil (To 1000) 80 35 48 13 34 FK-105 20 Polypropylene oil (To 1000) 80 Stearic acid 2.5 100 100 97 98.5 FK-105 17.5

Defoamer composition

Component (%wt.)

1 2 FK-102 50 FK-105 50 FK-102 80 FK-105 20 FK-102 20 FK-105 80 FK-102 10 FK-105 10 Polypropylene oil K 1000 80 FK-102 5 FK-105 5 Polypropylene oil K 1000 40 kerosene 40 Polypropylene oil K 1000 40 FK-102 10 FK-105 10 Polypropylene oil K 1000 80 FK-102 15 FK-105 5 Polypropylene oil K 1000 97.5 Stearic acid 2.5

Example 4

As hydrocarbon organic compounds, oligomers of the residual pyrolysis C4 fraction, prepared according to Czechoslovak Patent No. 193 855, are used. Their average molecular weight is 10

Defoaming efficiency (%) on:

1 drop 3 3 drops 4 1 drop 5 3 drops 6 26 31 49.5 56.6 14.5 28 48 41 22 42 65 56 3 10.5 53.5 44 0 21 16 72.5

0 0 52.5 62 11 18 61.5 57 100 100 61 61.2 weight = 507 g. mole ¹ and number = 82 g Br/100 g. The defoamer is formulated so that bromine that

It consists (in % by weight) of 80% oligomers of C4 alkenes, and 20% of the rest of FK-105. The defoaming efficiency (1 drop) for non-ionic surfactant is 59% and for anionic surfactant 41%.

P R E D M Ξ T

Claims (2)

P R E D Μ Ξ T A defoamer or mixture of defoamers based on organic oxygen compounds or a mixture of oxygen and hydrocarbon organic compounds, characterized in that 2 to 100 wt. forms a leading alcoholic by-product from the cyclohexane oxidation, isolated by rectification of a predominantly cyclohexanol-cyclohexanone mixture, with a density at 20 ^and C in the range of 840 to 865 kg. m ^-3 , distilling to 93 + 5% over a boiling range of 92 to 142 ° C, with a saponification value of 10 to 60 milligrams of KOH / g, containing. % hydroxyl groups 8 to 23 wt. and / or the distillation residue from the step of separating the residual cyclohexanol of the cyclohexanol-cyclohexanone oxidation mixture at a density at 20 ° C YNOLE in the range of 960 to 980 kg. m ^-3 with a hydroxyl group content of 2 to 10% by weight, a carboxyl group of 3.5 to 14% by weight, a bromine number of 100 to 280 g / 100 g, and in the case of a mixture of oxygenated organic compounds with hydrocarbon organic compounds 98 wt. with a molar mass of 100 to 1000 g. mol ^-1 . 2. Defoamer or antifoam mixture according to claim 1, characterized in that, in the mixture of oxygen and hydrocarbon organic compounds, the hydrocarbons form petroleum fractions, preferably light gas oil and / or alkene oligomers Cs to Cs, preferably propylene oligomers and C4-alkene oligomers. the oligomers, if any, are hydrogenated.