CS253000B1 - defoamer - Google Patents

Abstract

The defoamer based on synthetic oxygenated organic compounds or their mixture with hydrocarbons consists of 0.5 to 100% of at least one aliphatic alcohol C1 to C10 from 30 to 100% of the esterified and/or transesterified by-product from the oxidation process of cyclohexane to cyclohexanol and cyclohexanone. Its acid number is 0.1 to 15 mg KOH/g, saponification number 100 to 500 mg KOH. In a mixture of oxygenated organic compounds with hydrocarbons, these (hydrocarbons with a molar mass of 140 to 1,000 grams mol"1 form petroleum fractions, such as kerosene, light gas oil and oligomers of C3 to C5 alkenes) in the defoamer can constitute up to 99%. It is mainly used in the chemical and pulp and paper industries as well as in biotechnological processes.

Description

The invention relates to a defoamer based on synthetic oxygenated organic compounds or their mixtures with hydrocarbons, effective for foam suppression or defoaming of both aqueous and non-aqueous environments, as well as a method of its production using a by-product from petrochemical production.

There are basically two types of foam suppressants: foam breakers and foam inhibitors. The first type of agents include diethyl ether, alcohols and water vapor. Some weak surfactants that foam only in dilute solutions (amyl alcohol) act as foam breakers when applied to soap foams and foams from their own dilute solutions. A foam inhibitor is, for example, methanol. It does not foam itself and also inhibits the foaming of a dilute surfactant solution. The surface of the liquid is flooded with a high concentration of rapidly diffusing molecules and any increase in surface tension is quickly nullified.

It is also known that more effective and versatile than soluble defoamers are materials based on silicone oils, which are insoluble in water and have low surface tension. Their emulsion or solution is most often used to inhibit foaming. Furthermore, polyfluorocarbons are used as valuable defoamers for lubricating oils, because they have a very low surface tension (10 mNm' ¹ ). Depending on the cause of foam formation or the type of foam, different types of defoamers are used.

Thus, in the pulp and paper industry, defoamers combined with emulsifiers and hydrocarbons are often used (US Pat. 3,935,121). Defoamers based on saponified ethylene-vinyl acetate copolymers together with animal oils and polyethylene glycol dioleate are effective in defoaming sulfite liquors (US Pat. 3,893,941). For waste water from the paper industry, defoamers consisting of ethoxylated fatty acids, ethoxylated alkylphenols in a mixture with low molecular weight alcohols are also known (US Pat. 3,215,35). Many aqueous systems that commonly foam can be defoamed with small amounts of ethoxylated castor oil and its hydrogenate and also with propoxylated partially saponified oils (US Pat. 3,180,836). Defoaming activity is known (US Pat. 3,697,438) also for esters of polyglycols with oleic acid and in mixtures with alcohols C16 to C18, propylene glycol, isopropyl alcohol and mineral oil [Tichomirov V. K.: Foams, Theory and Practice of Their Formation and Defoaming, "Chemistry", Moscow (1980)].

The above and other known defoamers are often complex systems, prepared from technically difficult to obtain and thus expensive raw materials. They are not generally applicable, or are not very effective for some types of foams. These shortcomings are partly eliminated by the solution according to the present invention.

According to the present invention, it is a defoamer based on synthetic oxygenated organic compounds or their mixtures together with hydrocarbons, formed by at least one aliphatic alcohol C1 to C10 from 30 to 100% of the esterified and/or transesterified by-product isolated as a distillation residue from the hydrolysis stage of the oxidation process of cyclohexane to cyclohexanol and cyclohexanone, wherein the acid number is in the range of 0.1 to 15 mg KOH/g, the saponification number is 200 to 500 mg KOH/g and the boiling point above 90 °C/l01 kPa and the saponification number is 200 to 500 mg KOH/g and the remainder up to 100% is formed by at least one hydrocarbon with a molar mass of 140 to 1000 g mol" ¹ , optionally with the addition of a known defoamer.

The defoamer according to the present invention can be prepared in particular by esterifying and/or transesterifying 0.3 to 2 wt. parts of a by-product from the oxidation process of cyclohexane to cyclohexanol and cyclohexanone, usually isolated as a distillation residue from the hydrolysis stage, freed from part of the water and, if necessary, also from metal salts, with an acid number of 100 to 350 mg KOH/g and a saponification number of 250 to 480 mg KOH/g. parts of at least one aliphatic alcohol C1 to C10, whereby after separation of 30 to 100% of the reaction water and unconverted alcohol or alcohols and low-boiling fractions, preferably with a boiling point of 90 to 170 °C, the crude product of the defoamer is or only after further separation into fractions, the individual fractions, preferably the fraction with a boiling point above 400 °C, are calculated at atmospheric pressure, or are formulated together with hydrocarbons and optionally with other components.

The advantage of the defoamer or defoamer component according to the invention is the complete defoaming efficiency, especially the significant synergistic defoaming effect of the organic oxygen component in combination with hydrocarbons, mainly propylene oligomers, and the availability of raw materials. The method of its production can be carried out: on a conventional esterification plant by non-catalytic or catalytic esterification and transesterification.

A by-product from the oxidation process of cyclohexane to cyclohexanol and cyclohexanone, isolated as a distillation residue (MEK) freed from water particles from the hydrolysis column of the cyclohexanol or cyclohexanone production plant, has an acid number in the range: 100 to 350 mg KOH/g, most often 250 +30 mg KOH per gram; saponification number 250 to 480 mg KOH/g, most often 400 +30 mg KOH per gram; water 4 to 10% by weight; bromine number 10 to 30 g Br/100 g hydroxyl number 5 + 2% by weight OH. It usually contains less than 0.02% by weight cobalt in the form of cobalt salts, which can be removed by conventional physicochemical methods.

Esterification or transesterification is carried out with at least one aliphatic alcohol of C1 to C2. Aliphatic alcohols of C5 to C6 are preferred, although mixtures of C4-C5 alcohols can also be used, which are also produced as a by-product in the production process of cyclohexanol and cyclohexadiol (product from column FK 102). Furthermore, individual alcohols and mixtures of alcohols from the oxo process.

Esterification can be carried out non-catalytically or catalytically using conventional esterification and transesterification catalysts. It is appropriate to use "ansolvoic acids" or solid suspended catalysts, not only from the point of view of their efficiency, but also from the point of view of their easy removal from the crude product of esterification and transesterification. For non-catalytic esterification, higher temperature and pressure are usually required. To remove the esterification water, it is appropriate to use additives of substances, so-called water removers, with which water forms an azeotrope (mixtures of xylenes, etc.

It is also advisable to remove all unconverted aliphatic alcohol, as well as other primary fractions, and possibly also cyclohexanol admixtures, which are obtained by transesterification. The crude product itself has a defoaming effect, especially in combination with hydrocarbons. Higher efficiency is generally achieved by higher-heating fractions, especially the distillation residue and especially in combination with propylene oligomers with an average molecular weight of 450 to ⁸⁰⁰ g mol.

The hydrocarbons according to the invention include individually saturated or unsaturated, mainly aliphatic and naphthenic hydrocarbons, optionally also with admixtures of aromatics. However, most often, petroleum fractions and of these, in particular, kerosene fractions, or fractions of light, but also heavy gas oil. Then synthetic hydrocarbons, in particular, oligomers, co-oligomers, or low-molecular polymers and copolymers of propylene, alkenes and dienes C1 and C5, further products formed by thermal cleavage of macromolecular substances, as well as hydrogenation of macromolecular substances and higher hydrocarbons, e.g. vacuum distillates of petroleum and p. In addition, hydrogenated oligomers of the above alkenes and dienes C1. to C5 can also be used.

The defoamer or defoamer component according to the invention can also be combined with known defoamers, added with emulsifiers, further refined, colored, or perfumed. It is most conveniently produced discontinuously, but the method of its production can also be carried out semi-continuously and continuously. Further details of the defoamer formulation, effectiveness, and its production are apparent from the examples.

Example 1

Into a three-necked flask equipped with a stirrer, esterification attachment and thermometer are weighed 675 g of 2-ethylhexanol and 1,000 g of a by-product from the oxidation of cyclohexane to cyclohexanol and cyclohexanone, isolated as a distillation residue freed from part of the water from the hydrolysis column of the production of cyclohexanol or cyclohexanone, usually referred to as MEK with the following parameters: acid number = 253.8 mg KOH/g; saponification number = 403.7 mg KOH/g; bromine number = 21.8 g Br/100 g; water = 6.1% by weight; OH30 = 4.32% by weight; Co — 0.01% by weight; density at 30 °C (d4j = 1,086 kg . . m“ ³ ; dynamic viscosity at 30 °C. = 124.4 mPa . s. Next, 5 g of catalyst (tetrabutoxytitanate or antimony trioxide), while esterification and transesterification are carried out for 10 h. 149 g of water, 133 g of organic layer and 1,345 g of crude product are formed, from which 344 g of 2-ethylhexanol fraction are distilled off, while the mass of the crude ester obtained is 993 g (SE). Then 900 g of this crude ester is distilled on a molecular distillation or molecular evaporator at a pressure of 6 Pa and a temperature of 250 to 300 °C, 15% by weight is distilled off as the 1st oil fraction (SE 1st fraction).

The analysis of this fraction gives: acid number = 2.3 mg KOH/g; saponification number = 262.5 mg KOH/g; bromine number = = 16.7 g Br/100 g; OH = 1.6% by weight; density at 20°C (d4 ²⁰ ) = 946 kg . rn“ ³ . Average mol. weight = 264 g . mol“ ¹ . Then, at a temperature of 305 to 320 °C/6 Pa, a total of 45% of the 2nd oil fraction (from the injection) (SE 2nd fraction) of this composition is collected: acid number — 1.7 mg KOH/g; saponification number = -308.1 mg KOH/g; bromine number = — 10.4 g Br/100 g; OH = 0.9% by weight; density at 20 °C = 978 kg . m“ ³ ; average molar mass = 372.5 g . mol“ ¹ .

The distillation residue (SE residue) has an acid number of -- 2.8 mg KOH/g; saponification number = 368.8 mg KOH/g; bromine number — = 21.0 g Br/100 g; OH = 1.0 wt. %; density at 20 °C (di ²⁰ ) = 1,034.0 kg . m“ ³ and kinematic viscosity of 1,353 mm ² . s“ ¹ .

The defoaming efficiency of individual fractions alone and in combination with hydrocarbons or propylene oligomers (propylene oil K-1000) and petroleum fraction (kerosene) is tested. Propylene oil Kl 000 (pPropyloil K-1000) has an approximate molecular weight of — 469 g . mol“ ¹ ; freezing point = —25 °C; there are an average of 1.5 to 1.6 double bonds per molecule.

The defoaming efficiency of individual defoamer samples is determined by comparing the foaming of the standard sample with the foaming of the standard sample with the added defoamer. Thus, 100 cm ³ of an aqueous solution of standard sodium lauryl sulfate (anionic surfactant) with a concentration of 0.1% by weight (1 gram . dm“ ³ ) or polyethoxylated primary alcohols C12 to C14 with 9 moles of ethylene oxide (nonionic surfactant) of a similar concentration 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 by 180 °C and repeating fifty-two to five times for 1 min at a temperature of 20 +2 °C. The height of the foam and the height of the unfoamed solution are measured after 1 min has elapsed since the end of the foaming agent.

Then the foaming capacity of the standard Pš (%) is calculated from the relation Ps = —- . 100, in which a = foam height (cm) b height of unfoamed solution (cm). The defoaming efficiency is determined by the same procedure as for the standard solution, but 1 (0.02 g) or 3 drops (0.06 g) of defoamers are added to 100 cm ³ of the standard solution and Po (foaming capacity of the mixture of the standard solution and defoamer) is determined. The defoaming efficiency is finally calculated from the graph of the dependence of foaming capacity (%) on the defoaming efficiency, with the defoaming efficiency (%) from 100 to 0 plotted on the x-axis and the foaming efficiency (%) of the standard solution on the y-axis. The % defoaming efficiency is read at the intersection of the diagonal, with the arithmetic mean of three measurements taken as the final result. Defoamer formulations from the individual components are made at a temperature of 30 +5 °C.

The composition of individual defoamers, as well as their defoaming efficiency on nonionic (nonionic) and anionic surfactants, is shown in Table 1.

Composition of defoamer components Table 1 amount (% wt.) Defoaming efficiency (%) for: nonionic surfactant anionic surfactant 1 drop 3 drops 1 drop 3 drops 1 2 3 4 5 6

SE 100 10.5 18 8 14 SE 1st faction 100 28 39 33 38 SE 2nd faction 100 20 39 7 6.5 SE rest 100 93 93 59 66 SE 20 60 71 20.8 35 Polypropylene oil K 1,000 80 SE 10 42 54 36.5 32.5 Polypropylene oil K 1,000 00 SE 5 49 56 22 40 Polypropylene oil K 1000 95 SE 1st faction 20 48 53 80 77.5 Polypropylene oil K 1000 80 SE 1st faction 90 45 50 87 89 Polypropylene oil K 1,000 10 SE 1st faction 5 40 59 88.5 90.5 Polypropylene oil K 1,000 95 SE 2nd faction 20 44.5 61.5 92.5 94 Polypropylene oil K 1,000 80 SE 2nd faction 10 38 51 94.5 95 Polypropylene oil K 1,000 90 SE 2nd faction 5 36.5 42.5 95 96.5, Polypropylene oil K 1,000 95 SE 2nd faction 50 30 47 86 84.5 Kerosene 50 SE 50 39.5 55 88.5 100 Kerosene 50 SE rest 20 54 73 71 76 Polypropylene oil K 1,000 80 SE rest 5 54 72 79.5 89.5 Polypropylene oil K 1,000 95 SE rest 2.5 79.5 69 65.5 92.5 Polypropylene oil K 1,000 97.5 SE rest 50 61 67 94.8 98 Polypropylene oil K 1,000 50 SE rest 80 80 82.5 55.4 58 Kerosene 20 Example 2 40 +5 °C is they will use more additional components you. The results achieved are summarized taboo!'· The procedure is similar to that in example 1, to 2

only for the formulation of defoamers at a temperature of £53000

Table 2

Composition of defoamer components amount (%) weight Defoaming efficiency (%J on: nonionic surfactant anionic surfactant 1 drop 3 drops 1 drop 3 drops 1 2 3 4 5 6 SE rest 10 14 28.5 39 44 Kerosene 90 SE rest 50 Polypropylene oil K 1,000 49 100 100 89 69 Stearic acid (stearin) 1’ SE rest 50 Polypropylene oil K 1000 49 96 100 100 100 Stearic acid monoethanolamide 1 SE rest 80 Polypropylene oil K 300 19 85 91 89 94.6 Stearic acid (stearin) 1 SE rest 80 Kerosene 19 52 85.5 88 95 Stearic acid (stearin) 1 SE rest 80 Kerosene 17.5 51.5 85.5 65 87 Stearic acid (stearin) 2.5

Example 3

The procedure is similar to that in Example 1, except that instead of 675 g of 2-ethylhexanol, 385 g of n-butanol are weighed out for 1,000 g of cyclohexane oxidation by-product. 823 g of crude ester are obtained, which in the amount of one drop has a defoaming efficiency of 32% for nonionic surfactant and 34% for anionic surfactant. However, a formulated defoamer containing 20% by weight of the said crude ester and 80% by weight of polypropylene oil K 1,000 has a defoaming efficiency of 53% for nonionic surfactant and 88% for anionic surfactant under comparable conditions.

Claims (2)

£ §3000 9 10 Table 2 Composition of the defoamer component (%) by weight. Efficiency (% J to: non-ionic surfactant anionic surfactant1 drop 3 drops · 1 drop 3 drops 1 2 3 4 5 6 SE rest 10 14 28,5 39 44 Kerosene 90 SE residue 50 Polypropylene oil K 1 000 49 100 100 89 69 Stearic acid (stearin) 1 'SE residue 50 Polypropylene oil K 1000 49 96 100 100 100 Stearic acid monoethanolamide 1 SE Residue 80 Polypropylene oil K 300 19 85 91 89 94,6 Stearic acid (stearin) 1 SE Residue 80 Kerosene 19 52 85,5 88 95 Stearic acid (stearin) 1 SE residue 80 Kerosene 17,5 51,5 85,5 65 87 Stearic acid (stearin) 2,5 Example 3 The procedure is similar to Example 1, only per 1 000 g of secondary 385 g of n-butanol were weighed out of the cyclohexane oxidation product instead of 675 g of 2-ethylhexanol to give 823 g of a crude ester which, in a single drop, had a non-ionic surfactant of 32% and an anionic surfactant of 34%. containing 20% by weight of said crude ester and 8 0% by weight of polypropylene olefin K 1000 has antifoaming activity under comparable conditions to nonionic resin 53% and to anionic 88%. OBJECT What is claimed is: 1. A synthetic oxygen scavenger or a mixture thereof together with hydrocarbons comprising at least one aliphatic alcohol Ct to C10 of 30 to 100% crosslinked and / or pre-esterified to a desirable product isolated as a desulphurised organic compound. a tilatory residue from the hydrolysis step of the cyclohexane to cyclohexanone cyclohexanone oxidation process wherein the acid value is in the range of 0.1 to 15 mg KOH / g, saponification number of 200 to 500 mg KOH / g and varunad temperature of 90 ° C / 101 kPa. 2. Deodorizer according to claim 1, characterized in that at least one hydrocarbon is present in the mixture of oxygenated organic compounds and hydrocarbons at a molecular weight of 140-1000 gmol-1, preferably a petroleum fraction such as pelarol. the fraction, the light gas oil and / or the oligomers of the alkenes of C3 to C5, preferably the oligomers of propylene, in an amount of up to 99.5.