CS236099B1

CS236099B1 - Defoamer or mixture of antifoaming agents

Info

Publication number: CS236099B1
Application number: CS398783A
Authority: CS
Inventors: Vendelin Macho; Jan Ilavsky; Milan Paulovic; Milan Polievka; Ludovit Jurecek; Ladislav Komora
Original assignee: Vendelin Macho; Jan Ilavsky; Milan Paulovic; Milan Polievka; Ludovit Jurecek; Ladislav Komora
Priority date: 1983-06-02
Filing date: 1983-06-02
Publication date: 1985-05-15

Abstract

Odpeňovač alebo zmes odpeňovačov na báze organických zlúčenin pozostáva z destilačného zvyáku zo surového produktu výroby cyklohexanolu a/alebo cyklohexanonu oxidáciou cyklohexánu s číslom kyselosti 150 až 350 mg ΚθΗ/g a číslom zmydelnia 350 až 600 mg KGH/g a/alebo vedťajáích vyášievrúcich kyslíketých organických produktov z hydroformylócie propylénu oxidom uhoínatým s vodíkom, pozostávajúce z 50 až 100 % zo zmesi kyslíketých organických zlúčenín s teplotou varu 110 až 210 °C/2 kPa, pričom priemerné číslo ich zmydelnenia je v rozsehu 30 až 100 mg KOH/gDefoamer or mixture of defoamers based on organic compounds consisting of a distillation residue from the crude product of the production of cyclohexanol and/or cyclohexanone by oxidation of cyclohexane with an acid number of 150 to 350 mg KθΗ/g and a saponification number of 350 to 600 mg KGH/g and/or secondary high-boiling oxygenated organic products from the hydroformylation of propylene with carbon monoxide and hydrogen, consisting of 50 to 100% of a mixture of oxygenated organic compounds with a boiling point of 110 to 210 °C/2 kPa, with their average saponification number in the range of 30 to 100 mg KOH/g

Description

BACKGROUND OF THE INVENTION The present invention relates to an antifoam or antifoam mixture on basic petrochemical products.

Antifoaming agents based on oxygenated organic compounds containing carboxyl or hydroxyl functional groups in the molecule are known. Such are at least partially esterified polyols, e.g. partially esterified glycerol, sorbitol and pentaerythritol (U.S. Pat. No. 3,235,498), stearic and methacrylic acid based defoamers (U.S. Pat. No. 3,458,587). Especially important are the organosilicon compounds. Among the technically available are the oxyethylation products of abietic acid and oily acid, respectively. tall oil oxyethylation as well as oxyethylation or propoxylation products of 4 to 25 carbon atoms with 1 to 25 moles of alkylene oxide alone or more frequently in combination with organosilicon compounds (U.S. Pat. Nos. 2,991,248, 3,235,501 and 3,335,502). Polycompatible antifoam defoamers (U.S. Pat. Nos. 2,923,687, 3,180,836 and U.S. Pat. No. 183,982) are relatively widespread, with the major ingredients being fatty acids, vegetable and mineral oils and alkylene oxide polystyrene products to higher fatty Acids or alcohols, The efficacy is known (U.S. Pat. No. 3,697,438) as well as esters of polyglycols with oleic acid and in admixture with alcohols C1g to C14, propylene glycol, isopropyl alcohol and mineral oil. The advantages are non-toxic, but the lack of proportionality reduces the efficacy of defoaming. In contrast, a high antifoaming effect on foams mainly formed by nonionic and anionic surfactants has an antifoam based on 50 to 99 wt. % hydrogen and 1 to 20 wt. Oxygen Organic Compounds - 3 - 238 099 [MS. however, components require relatively high purity. However, there is a need to extend the range of antifoams based on raw materials and technically available products.

According to the present invention, the antifoam or antifoam mixture comprises organic compounds consisting of a distillation residue of a cross-linked product of cyclohexanol production and / or cyclohexanone oxidation of cyclohexane with an acid number of 150 to 350 mg KOH / g> saponification number of 350 to 600 mg KOH / g and / or secondary oxygen scavenging organic products from hydroformylation propylene with carbon monoxide with hydrogen. The advantage of the antifoam or antifoam mixture according to the invention is the availability of raw materials since it is technically only low-valued by-products from the production of cyclohexanone oxidation cyclohexane, as well as non-hydrogenated higher boiling byproducts from the production of n-butyraldehyde and isobutyraldehyde by hydroformylation of propylene with carbon monoxide with hydrogen Another advantage is the possibility of separating, from these by-products, less volatile fractions, such as with a temperature of up to 100 ° C / 2 kPa, without sacrificing defoaming efficiency. This gives the lower vapor pressure, the characteristic odor of the vapor, the darkness of the flame, the flame, and the flame, so that the hazard class IV is applicable and can be applied to a higher technical and safety risk.

The byproducts of cyclohexanol production and cyclohexanone-catalytic oxidation of cyclohexane should not contain, in general, more remarkable amounts of cyclohexanone or cyclohexanol, since the latter is not only lost. a valuable main product, the alloys are almost or ineffective in terms of defoaming (e.g., cyclohexanol has a defoaming efficiency of 0%).

Similarly, the higher-grade, non-hydrogenated byproducts of the propylene hydroformylation * of the synthesis gas of the synthesis gas of the oxosynthesis of the synthesis gas are to be free of n-butyraldehyde, isobutyraldehyde and substantially also butanol and isobutanol. Their presence would not only be the loss of the intermediate product (2-ethylhexanol, n-butanol, isobutanol) of the oxoprocess, but they would significantly reduce the possibility of defoamer application by any unpleasant odor.

The defoamer or antifoam mixture according to the invention can also be applied in combination with other antifoams, possibly with their diluents, such as higher petroleum fractions. In addition, the antifoam or the antifoam mixture of the present invention can be clarified, discolored, colored or perfumed. Further details regarding the composition of the antifoam or the antifoam mixture of the present invention as well as the antifoaming efficacy and other advantages will be apparent from the examples. Example 1

As the defoamer, distillation residues from the crude catalyzed oxidation product of cyclohexanone to cyclohexanol cyclohexanone (MEK) of the following physicochemical properties are used: density at 20 ° C = 1137.4 kg · m 3, at 30 ° C «1131.2 kg .m “3 and at 50 ° C = 1117.7 kg.m” 3} dynamic viscosity at 30 ° C «0.6268 Pa.sa at 50 ° C 0.1209 Pa.s} temperature -26 to -29 ° Cj number of saponification = 416.2 mg KOH / g} ester number = 153? 3 mg KOH / g} bromine number = 20.9 g Br2 / 1Og g) wt. OH = 5.72} water content «6.4 wt.% Ash = 0.27 wt.%, Mainly consisting of Co, Cr, Sn, K, Na, Pe, Ca, Mg.

These distillation residues (MEK) are further distilled under reduced pressure to obtain a fraction of tv 30 to 100 ° C / 2 kpa (MEK fr. 30 to 100 ° C / 2 kPa) and a residue with tv above 100 ° C / 2 kPa (MEK above 100 ° C / 2 kPa) having the following physico-chemical parameters: temperature (point) of ignition = 204 ° C} temperature (point) of burning 226 ° C, ignition temperature (point) «384 ° C bromine number = 21.8 g Br2 / 100 g} CHO = 1.31 wt% OI-I with 0.0 wt% acid number 197.0 mgKOH / g saponification number = 430.3 mg EOH /G·

The detersive efficacy of all three samples shall be set at. \ T

The solution of the surfactant is carefully poured into a 500 cm @ 2 -cylinder cylinder, and closed with a ground-glass stopper. The standard solution is spun at a temperature of 20 + 2 ° C by inverting the cylinder by 180 ° with a frequency of 50 times / min. Measure the height of the foam and the unfilled solution after 1 min after the end of foaming. The penivost of the standard P- (v $) is calculated from the relation P ~ «100, in which the foam height (cm), b = the height of the unpopulated solution (cm). De-potentiating the efficacy of the antifoam agent is similar, but the difference is that a 100 cm 2 standard solution is added from a foaming agent in a quantity of 0.05 g (1 drop) and the PQ (in $) standard penivose together with with a blower. This post-foaming efficiency of the distillation residues (MEK) is 59.5 $} of the fraction 30 to 100 ° C / 2 KPa (MEK fr. 30 to 100 ° C / 2 KPa) is 0 $, but the remainder with tv above 100 ° 0 / 2 kPa (MEK over 100 ° C / 2 kPa) is 74.4 $. Example 2

Heavy fractions of aldehyde distillation, respectively, are used as defoamer. crude oxo product produced by hydroformylation of propylene with carbon monoxide and hydrogen, i.e., by distilling off n-butyraldehyde (which is for aldolization and hydrogenation to produce 2-ethylhexanol as the main product, as well as hydrogenation of n-butyraldehyde to n-butyraldehyde). butanol) and isobutyraldehyde (which is used for hydrogenation), the distillation residue of the oxygenated organic products, especially after their hydrolysis with sodium hydroxide and regeneration of the cobalt catalyst, respectively. also the acid recovery of Οθ, consisting of oxygenated organic compounds, also referred to as ωO-TP (oxo-heavy after hydrolysis by lye). Their average molecular weight = 199.4 g.mol} bromine number = 21.59 gBr 2/100 gj CHO free = 5.36 $ mass} CHO bound = 5.38 $ mass} acidity number = Oj68 mgK0H / G. Recovery Effect OKO-TP is $ 51. In Lower Saxony, the lower lower fractions are distilled out of OKO-TP, distilling 29% by weight at a boiling point of 25 to 100 ° C / 2 KPa. This fraction (OKO-TP 25 to 100 ° C / 2 kPa) has a defoaming efficiency of $ 50.3, with the remainder (OKO-TP over 100 ° C / 2 KPa) having a 51.3 $ · efficiency of this residue. has a flame temperature of 116 ° C and a flash point of 102 ° C, a fire point of 195 ° C, a bromine number of 22.7 g of Brg / 100 g of OH of 1.0 wt. CHO = 1.29% w / w acidity = 1.41 mgKI / g and saponification value = 74.3 mg KOH / g.

Claims

P E E D Μ E T EXPLOSION

238 098

1 · A defoamer or mixture of antifoams based on organic compounds, characterized in that it consists of a distillation residue from a crude product of the manufacture of cyclohexanol and / or cyclohexanone by oxidation of cyclohexane with an acid number of 150 to 350 mg KOH / g, saponification number 350 to 60O mg KOH (g) or byproducts of oxygen-containing organic products from the hydroformylation of propylene with carbon monoxide with hydrogen.

2. A defoamer or antifoam mixture as claimed in claim 1, characterized in that the by - products of the high - oxygen oxygen - containing organic products resulting from the hydroformylation of propylene with carbon monoxide and. vb consists of 50 to 100% of a mixture of oxygenated organic compounds boiling at 110 to 210 ° C / 2 kPa, with an average saponification value in the range of 30 to 100 mg KOH / g.