CS254036B1 - defoamer - Google Patents

Abstract

The defoamer consists of a mixture of at least two components, with 2 to 98% being a blend of petroleum (kerosene, light gas oil, heavy gas oil) and / or synthetic hydrocarbons (oligomers of C3 to C5 alkanes) of mol. weighing 130 to 1000 g. mol-1 and the remainder to 100% form byproducts recovered from the hydrolysis column of the cyclohexanol and / or cyclohexanone production process by oxidation of cyclohexane with a maximum water content of 15% by weight. This by-product has an acid number of 180 to 360 mg KOH / g, a saponification number of 200 to 550 mg KOH / g and a bromine number of 2 to 40 g Br / 100 g. Optionally, this by-product is divided into fractions. The deodorizer is used in the pulp and paper industry, in the chemical, metallurgical and food industries, as well as in other industries.

Description

The invention relates to a defoamer, including a formulation from available, predominantly petrochemical raw materials and using organic oxygen by-products.

Chemical methods of foam suppression, or defoamers, have gained considerable importance not only in the paper and pulp industry, but also in the production of torula, yeast, pharmaceuticals, sucrose, in the distillation of organic liquids and in other operations in the chemical industry, in the finishing industry, in the leather industry and in other industrial sectors.

Defoamers based on oxygenated organic compounds are known, such as partially esterified polyols, especially partially esterified glycerol, sorbitol and pentaerythritol (US Pat. 3,235,498), and also defoamers based on stearic and methacrylic acid (US Pat. 3,458,567). Also known are lower and especially higher aliphatic alcohols, oxidized paraffin, mixtures of unsaponifiable and saponified fats, tall oil, higher fatty acids (oleic, stearic acids), dibutyl phthalate, amyl acetate, tributyl phosphate, tricresyl phosphate, aluminum stearate. Even boric acid, bentonite and calcium hydroxide (Tichomirov V. K.: Foam theory and practice of their preparation and decomposition "Chimiya", Moscow 1983). The above-mentioned defoamers, or defoamer components, are technically easily available, but relatively ineffective. The technically available ones include products of oxyethylation of abietic and oleic acids, or oxyethylation of tall oil, as well as products of oxyethylation or propoxylation of acids with 4 to 25 carbon atoms with 1 to 25 moles of alkylene oxide alone or more often in combination with organosilicon compounds (US patents 2,991,248, 3,235,501 and 3,235,502). Defoamers based on polycomponent mixtures (US patents 2,923,687, 3,180,836 and Czechoslovak author's certificate 183,982), in which the important components are higher fatty acids, vegetable and mineral oils and products of polyaddition of alkylene oxides to higher fatty acids or alcohols, are relatively widespread. The defoaming effect is known (US Pat. 3,697,438) also for other polyglycols with oleic acid and in mixtures with C16 to C18 alcohols, propylene glycol, isopropyl alcohol, and mineral oil. Their advantage is non-toxicity, but their disadvantage is relatively lower defoaming effect. In contrast, defoamers based on organosilicon compounds, such as silicone oils, are highly effective but expensive. In addition, in some cases, the increase in ash content of defoamers based on organosilicon compounds is also undesirable.

A raw material and technically readily available defoamer or mixture of defoamers according to Czechoslovak author's certificate 236 099 based on the distillation residue from the crude product from the production of cyclohexanol and/or cyclohexanone by oxidation of cyclohexane also has sufficient defoaming efficiency for some types of foams. However, it is not very effective for some types of foams.

However, according to the present invention, it is a defoamer based on organic compounds, optionally with the addition of auxiliary substances, which consists of a mixture of at least two components; wherein 2 to 98% is a mixture of petroleum hydrocarbons and/or synthetic hydrocarbons with a molar mass of 130 to 1000 g. mol ^-1 and the remainder up to 100% is by-products taken as a distillation residue from the hydrolysis column of the cyclohexanol and/or cyclohexanone production process by cyclohexane oxidation, dewatered to a maximum water content of 15% by weight, with an acid number of 180 to 360 mg KOH/g, a saponification number of 200 to 550 mg KOH/g, a bromine number of 2 to 40 g Br/100 g and/or at least one fraction of this residue.

The advantage of the defoamer according to this invention is not only the new effect of a relatively diverse mixture of oxygenated organic compounds, so far technically utilized only as a fuel component, but also the positive synergism of the distillation residue, or narrower fractions thereof, together with petroleum fractions or synthetic hydrocarbons, showing high defoaming efficiency. Then the possibility of using a wide range of hydrocarbons for its formulation, long shelf life, good storage life. At the same time, the advantage of its obtaining is technical simplicity, flexibility of isolation of components, whether according to their formation or needs and last but not least, allowing comprehensive and effective utilization not only of the main, but also of by-products from the catalytic oxidation of cyclohexane. The defoamer according to this invention can also be a component of other defoamers.

A by-product from the oxidation process of cyclohexane to cyclohexanol and cyclohexanone isolated as a distillation residue known as MEK, stripped of some water from the hydrolysis column of the cyclohexanol or cyclohexanone production process, has an acid number in the range of 100 to 350 mg KOH/g, most often 250 +30 mg KOH/g; saponification number 250 to 480 mg KOH/g, most often 400 +30 mg KOH/g; water 4 to 10 wt. %, bromine number 5 to 30 g Br/100 g and hydroxyl number 2 to 8 wt. % OH. It usually contains below 0.02 wt. % cobalt in the form of cobalt compounds, which can be removed by conventional physicochemical methods, such as adsorption on ion exchangers, adsorbents, washing with dilute acid solutions, or possibly also in the presence of an oxygen-containing gas.

This by-product can be distilled or rectified, preferably under reduced pressure. The more effective component of the defoamer are the fractions with a higher boiling point, so the most effective is the remaining portion (distillation residue), for example the fraction with a boiling point above 150 °C/2.67 kPa.

The mixture of petroleum hydrocarbons consists of either individual hydrocarbons, mainly n-alkanes, isoalkanes, cycloparaffins, and possibly also alkylaromatics. Most often, however, petroleum fractions, and of these, mainly the kerosene fraction, or the fraction of light but also heavy gas oil, then refined oils, etc. Then synthetic hydrocarbons, mainly oligomers, co-oligomers, or low-molecular polymers and copolymers of propylene, alkenes and dienes C4 and C5, as well as products of their hydrogenation.

Furthermore, products formed by thermal cleavage of macromolecular substances, as well as hydrogenolysis of macromolecular substances and higher hydrocarbons, e.g. vacuum petroleum distillates, etc. In addition, hydrogenated oligomers of the above alkenes and dienes C3 to C5 can also be used.

Auxiliary additives are surfactants, fragrances, anticorrosive additives, optical brighteners, etc. The method of obtaining the organic oxygen component of the defoamer or component mainly uses the existing production equipment for the production of cyclohexanone from cyclohexane, while mainly the residue from the so-called hydrolysis column, also known as MEK, is utilized. This residue can be used without any further treatment as a component of the defoamer, but it is more suitable to remove the more volatile components, e.g. by distillation under reduced pressure. The defoamer according to the present invention can also be formulated together with other defoamers, including known combinations, i.e. it can also be a component of a more technically and economically demanding component of a defoamer, especially if it replaces or achieves synergism. Further details of the formulation of the defoamer or its component, as well as the method of its preparation, as well as other advantages, are apparent from the examples.

Example 1

As defoamers or components of defoamers, by-products from the oxidation of cyclohexane to cyclohexanol-cyclohexanone, isolated as a distillation residue freed from part of the water from the hydrolysis column of the cyclohexanol and cyclohexanone production, hereinafter referred to as "MEK", then the organic phase of the fraction with a boiling point of 20 to 150 °C/ /2.67 kPa from this residue, hereinafter referred to as the "MEK fraction" and the fraction above 150 °C/ /2.67 kPa, i.e. the remaining portion from the distillation of MEK, hereinafter referred to as the "MEK residue", are tested.

Analyses of MEK taken at different times were carried out, designated MEK-1 and MEK-2. In brackets are the results of MEK-2. Thus, water content = 6.9 (6.1) % by weight; acid number = 256.3 (253.8) mg KOH/g; saponification number = 412.8 (403.7) mg KOH/g; OH = — 4.7 (4.3) % by weight; bromine number = 23.1 (21.8) g Br/100 g; density at 20 °C (d4 ²⁰ ) = = 1104 (1090) kg . m ³ , at 30 °C (dl°) = = 1 100 (1086) kg . m ³ , at 40 °C (dl°) = = 1087 (1078) kg . m ³ ; density at 50 °C (gives ⁵⁰ ) = 1079 (1 070) kg . m~ ³ ; dynamic viscosity at 20 C = 268.9 (233.2) mPa . s; at 30 °C = 124.4 (126.4) mPa . s; at 40 “C = 64.8 (71.4) mPa . s at 50 ^C C is equal to 38.7 (43.1) mPa . s; cobalt content (in the form of compounds) = 0.01 (0.01) % by weight; ash = 0.05 (0.004) % by weight.

Differential distillation of MEK-1 under reduced pressure yields 13.44 wt. % of the organic phase of the fraction 20 to 150°C/2.67 kPa (acid number = 225.6 mg KOH/g; saponification number = 320.9 mg KOH/g; OH = 6.44 wt. %; CHO = 0%; H2O = 20.2 wt. %; acetic acid = 4.66 wt. % ^; propionic acid = 1.16 wt. %; butyric acid = 1.78 wt. %; valeric acid = 20.11 wt. %; caproic acid equals 10.45 wt. %; ash = 0.000 wt. %), i.e. “MEK fraction”; 8.12 wt. % of the aqueous phase (acid number = 95.6 mg KOH per gram) and the remaining portion, i.e. the fraction with a boiling point above 150°C/2.67 kPa, hereinafter referred to as the "residue" of MEK, constitutes (with losses of 1.24% by weight) 77.2% by weight (acid number = 153.0 milligrams KOH/g; saponification number = = 449.8 mg KOH/g; OH = 6.41% by weight; H2O = 1.14% by weight; ash — 0.22% by weight).

A possible component of the defoamer is kerosene or propylene oligomers (products of cation-catalyzed propylene oligomerization), so-called polypropylene oil K-100 (Propyloil K 1 000} with an average molar mass of 469 g . mol ¹ , with a density at 20 °C = 847 kg . m ³ ; freezing point = -25 °C; with an average of 1.5-1.6 double bonds per molecule._

Further hydrogenated (on a nickel catalyst) polypropylene oil K 1000.

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 g .

. dm ³ ] or polyethoxylated primary alcohols C12 to C14 with 9 moles of ethylene oxide (nonionic surfactant] of 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° and back 50 times for 1 minute at a temperature of 20 +2°C. The height of the foam and the height of the unfoamed solution are measured after 1 minute from the end of the foaming. Then the foaming of the standard Pš (%) is calculated from the relationship Pš — _; - . 100, in which b

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 drop (0.02 g) of defoamer is added to 100 cm ³ of the standard solution and Po (foaming capacity of the mixture of standard solution and defoamer) is determined. Finally, the defoaming efficiency is calculated from the graph of the dependence of foaming capacity {®/o) on defoaming efficiency, with the defoaming efficiency (%) from 100 to 0 plotted on the x-axis and the foaming capacity (%) 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.

The composition of individual defoamers and their defoaming efficiency for both nonionic (nonionic) and anionic surfactants is shown in Table 1.

Table 1' k a 1

Composition of defoamer components

Defoaming efficiency' (%) on:

quantity nonionic surfactant anionic surfactant (% wt.) 1 drop 3 drops 1 drop 3 drops

MEK-1 100 46, 59 58 60.5 MEK-1 fraction 100 49 51.5 18 7 MEK-1 residue 100 72 78 37.5 42.5 MEK-1 residue 50 polypropylene oil 72.5 87 44.5 60 To 1000 50 MEK-1 fraction 50 polypropylene oil 89 92.5 61 81.5 To 1000 50 MEK-1 50 polypropylene oil 82 85.5 85 95 To 1000 50 MEK-1 10 92.5 92 65 87 polypropylene oil 90 MEK-1 5 87 94.5 50 81 polypropylene oil 95 MEK-1 residue 10 polypropylene oil 83.5 83.5 81.5 91 To 1000 90 MEK-1 fraction 10 polypropylene oil 71 86 85 91 To 1000 90 residue MEK 1 10 kerosene 10 83 84 80 91 polypropylene oil To 1000 80 MEK-1 residue 10 hydrogenated 82 84 82 90 polypropylene oil 90

£ Λ Π » ¢5

-.1 ί» -λ ΰ

Example 2

The procedure is similar to that in Example 1, except that instead of MEK-1, MEK-2, also specified in Example 1, is examined. The results obtained are summarized in Table 2.

Table 2

Defoamer composition

Defoaming efficiency (%) for:

component quantity nonionic surfactant anionic surfactant (% wt.) 1 drop 3 drops 1 drop 3 drops MEK-2 100 63 71 38 39 MEK-2 20 polypropylene oil 33.5 51 69 83 To 1,000 80 MEK-2 10 polypropylene oil 80 89 66 76 To 1000 90 MEK-2 residue 10 polypropylene oil 74.5 82 48 68 To 1000 90 MEK-2 residue 20 mineral "white" oil 40 65 78 70 79 polypropylene oil To 1,000 40 The procedure is similar to in example 1, nium bromide. The results achieved are summarized in only the defoaming efficiency is being investigated in addition those in table 3. on a cationic surfactant, who is lauryl alcohol- Composition of defoamer Defoaming efficiency (%) for: Component Quantity i nonionic surfactant anionic surfactant cationic surfactant (% wt.) 1 drop 2 drops 1 drop 2 drops 1 drop 2 drops 1 2 3 4 5 6 7 8 MEK-1 residue 10 polypropylene 51 51 61 64 50 55 remaining K 1,000 90 MEK-1 fraction 10 polypropylene 19 30 66 67 10 12 oil K 1 000 90 MEK-1 10 polypropylene 8 10 85 90 52 55 oil K 1 000 90 MEK-1 50 polypropylene 42 59 90 90 77 94 oil K 1 000 50 MEK-1 49 polypropylene 50 oil K 1 000 38 49 84 91 74 91 dodecyldeca- ethoxamer 1 MEK-1 49 polypropylene 50 45 63 88 90 76 96 oil K 1 000 phenylethanol 1 MEK-1 45 polypropylene 50 61 74 81 92 76 94

oil Κ 1 000 triethanolamine

524036

Quantity non-ionic surfactant anionic surfactant cationic surfactant (% wt.) 1 drop 2 drops 1 drop 2 drops 1 drop 2 drops

2 3 4 5 6 7 8 MEK-1 7.5 polypropylene oil K 1 000 90 22 35 49 81 57 59 alkyl polyglycol (alkyl == C10—C16, 2.5 polyadated 4 moles ethylene oxide per 1 mole of mixture aliphatic alcohols C10—C14) MEK-1 49.5 polypropylene oil K 1000 50 44 61 87 92 74 92 fragrant composition "sherik" 0.5 MEK-1 49.5 polypropylene oil K 1000 50 55 73 82 89 77 94 product of addition monoethanolamine 0.5 with formaldehyde MEK-1 98 polypropylene 58 71 69 78 8 11 oil K 1 000 2 MEK-1 45 polypropylene oil K 1000 50 44 55 51 56 57 58 alkyl polyglycol (C16 alkyl, 5 polyaded 20 moles ethylene oxide per 1 m ethylene oxide per 1 mole aliphatic alcohol Cie MEK-1 7.5 polypropylene oil K 1000 · 90 25 39 50 66 23 31 alkyl polyglycol (C16 alkyl, polyaded 20 moles ethylene oxide per 1 mole of alcohol

524036

Claims (5)

11 12 524036 SUBJECT An organic compound based desiccant, optionally with the addition of excipients, characterized in that it comprises a mixture of at least two components, wherein 2 to 98 are. it consists of a mixture of petroleum hydrocarbons and / or synthetic hydrocarbons having a molecular weight of 130 to 1 000 g. mole-1 and the rest to 100% form byproducts taken as a distillation residue from the hydrolysis column of the cyclohexanol and / or cyclohexanone production process by oxidation of cyclohexane, dewatered to a maximum water content of 15% by weight, with an acid number of 180 to 360 mg KOH gram, saponification number 200 to 550 mgKOH / g, bromine number 2 to 40 g Br / 100 g and / or at least one fraction from this residue. 2. Deodorizer according to claim 1, characterized in that the petroleum hydrocarbon mixture is a petroleum fraction, preferably a petroleum fraction, a light gas oil. 3. A desiccant according to claim 1, wherein the synthetic hydrocarbons are oligomers or co-oligomers of C3 to C5 alkenes, preferably oligomers of propylene and oligomers of C4-alkenes, optionally after their hydrogenation and / or cracking or hydrocracking of higher hydrocarbons, preferably the cracking or hydrocracking products of the vacuum distillates of petroleum or polyolefins. 4. A deodorizer according to any one of claims 1 to 3, characterized in that the excipient additive is a surfactant, preferably a non-ionic surfactant and / or fragrance. 5. A desiccant according to any one of claims 1 to 4, characterized in that the excipient additive is a fragrance and / or optical brightener.