CS259271B1 - Oxygen-based organic compounds - Google Patents

Abstract

The defoamer consists of 10 to 99% propylene glycol to polypropylene glycol with a molecular weight of up to 2,000 g.mol-1 and 1 to 90% of at least one C4 to C24 carboxylic acid and/or hydrocarbons with a molecular weight of 130 to 1,000 g-mdl-1. The defoamer is particularly suitable for biotechnology, for defoaming in the paper, textile and leather industries.

Description

The invention relates to a defoamer based on oxygenated organic compounds and possibly also higher hydrocarbons and additives of auxiliary substances, which is easily formed using mainly large-tonnage produced petrochemical raw materials and intermediates.

There are basically two types of foam suppressants: foam breakers and foam inhibitors. The first type of foam suppressants 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.

However, as a rule, 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, mainly in the production of antibiotics, sucrose, yeast, cellulose, paper, lubricating oils, coatings and textiles [Tichornirov VK: Foams "Chimiya", Moscow (1983)]. Furthermore, polyfluorocarbons are used as effective defoamers for lubricating oils, because they have very low surface tension (10 mNm~ ¹ ). Then, depending on the cause of foam formation or the type of foam, different types or types of defoamers are used. Thus, in the pulp and paper industry, defoamers combined with an emulsifier and a hydrocarbon are often used (USA Pat. 3,935,121). In the defoaming of sulphite liquors, defoamers based on saponified ethylene-vinyl acetate copolymer together with animal oils and polyethylene glycol dioleate are effective (US Pat. 3,893,941). For waste water from the paper industry, defoamers consisting of ethoxylated fatty acids, ethoxylated alkyl enols in a mixture with low molecular weight alcohols are also known (US Pat. 3,215,635). Conventional foaming aqueous systems can be defoamed with a small amount of ethoxylated castor oil and its hydrogenate and also with propoxylated partially saponified oils (US Pat. 3,180,836). Defoaming efficiency is also known (US Pat. 3,697,438) for esters of polyglycols with oleic acid in a mixture with C1 _R to _C18 alcohols and mineral oil. Furthermore, mixtures of higher fatty acids, as well as ethanolamides of higher fatty acids with higher hydrocarbons, especially propylene oligomers (Czech Patent Certificate Nos. 232 390, 236 099 and 240 516).

The above and other known defoamers are often complex systems, prepared from technically difficult to obtain and therefore expensive raw materials. They are not generally applicable, or are not very effective for some types of foams. Effective and at the same time water-soluble defoamers, as well as non-toxic defoamers for biotechnology, have a particularly narrow "profile". These shortcomings are at least partially solved by the defoamer according to the present invention.

According to the present invention, it is a foaming agent based on oxygenated organic compounds and optionally also higher hydrocarbons and additives, auxiliaries, characterized in that it consists of 10 to 99% propylene glycol to polypropylene glycol with a molar mass of up to 2,000 g.mol ^-1 and 1 to 90% of at least one C ₄ to C ₂₄ carboxylic acid and/or hydrocarbons with a molar mass of 130 to 1,000 g.mol ^-1 .

The advantage of the defoamer according to this invention is low toxicity to non-toxicity, low solidification temperature, relatively significant hydrophilicity, synergism of the defoamer components and their availability. Last but not least, high stability of the defoamer and significant variability of its components depending on both the type of foam to be suppressed by the defoamer and the raw material options.

By auxiliary additives are meant the known additives of surfactants, fragrances, corrosion inhibitors, optical brighteners and the like.

Hydrocarbons _with a molar mass of 130 to 1,000 g.mol ^-1 constitute a mixture of petroleum hydrocarbons, mainly n-alkanes, isoalkanes, cycloalkanes, and possibly also alkylaromatics. However, most often petroleum fractions, including mainly kerosene fraction, or fraction of light but also heavy gas oil, then refined oils, etc.

Furthermore, synthetic hydrocarbons, especially oligomers, co-oligomers, or low-molecular polymers and copolymers of propylene, alkenes and dienes C ₄ and C ₅ , 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 distillates of petroleum, paraffinic slags, etc.

The defoamer according to the present invention may also be a component of other defoamers.

Further details of the defoamer formulation, its effectiveness depending on the presence of individual components, as well as other advantages are apparent from the examples.

Example 1

As defoamers or components of already known defoamers, propylene glycol to polypropylene glycols liquid at room temperature are tested, but mainly mixtures of propylene glycol to polypropylene glycol with aliphatic carboxylic acids and with by-products from the oxidation of cyclohexene 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 reaction from MEK with a boiling point of 20 to 150 °C/2.67 kPa and the fraction above 150 °C/2.67 kPa, hereinafter referred to as "MEK-fraction above 150 ^° C/2.67 kPa". The results of the MEK analysis are as follows: water = 6.9 per cent by weight; acid number = 256.3 mg KOH/g; saponification number = 412.8 mg KOH/g; OH — 4.7% by weight; bromine number = 23.1 g Br/100 g; density at 20 °C (d ₄ ²ⁿ ) — 1104 kg . m~ ³ ; dynamic viscosity at 20 ^°C C = = 263.9 mPa . s; cobalt content (in the form of compounds) — 0.01% by weight; ash — 0.05% by weight.

Differential distillation of MEK at reduced pressure yields 13.4 wt. % of the organic phase of the fraction 20 to 150 °C/2.67 Pa (acid number — 225.6 mg KOH/g; OH -- 6.44 wt. %; CHO — O; H ₂ O = 20.2 wt. %; acetic acid — 4.66 wt. %; propionic acid = 1.16 wt. %; butyric acid = 1.78 wt. %; caproic acid =-= 10.45 %) and the remaining portion, i.e. the fraction with a b.p. above 150 °C/2.67 kPa, forms 77.2 wt. % with losses of 1.24 wt. %. (acid number = 153.0 mg KOH/g; saponification number — — 449.8 mg KOH/g; OH ~ 6.41 % by weight; H ₂ O = 1.14 % by weight; ash = 0.22 % by weight).

The defoamer component may also be aliphatic carboxylic saturated and unsaturated acids C ₆ to C ₂₄ .

The defoaming efficiency of individual defoamer samples is determined by comparing the foaming capacity of a standard sample with the foaming capacity of a standard sample with the added defoamer.

Thus, 100 cm ³ of an aqueous solution of sodium lauryl sulfate (anionic surfactant) with a concentration of 0.1% by weight (1 g.dm ^-3 ) or polyethoxylated primary alcohols C ₁₂ to C ₁₄ with 9 moles of ethylene oxide (nonionic surfactant) or lauryl ammonium bromide (cationic surfactant) of similar concentration is carefully poured into a 500 cm ³ graduated cylinder and closed with a ground-glass stopper. The standard solution is foamed by inverting the cylinder through 180° and repeating fifty 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 from the end of foaming.

Then the foaming capacity of the standard Pš (%) is calculated from the relation Pš — —— 100 in which a — foam height (cm); b — height of unfoamed solution (cm). The defoaming efficiency is determined by the same procedure as the standard, but to 100 cm ³ of the standard solution is added 1 drop (0.02 g), or 2 drops (0.04 g) of defoamer and Po (foaming capacity of the mixture of the standard solution and defoamer) is determined.

Finally, the defoaming efficiency is calculated from the graph of the dependence of foaming (%) on the defoaming efficiency, with the defoaming efficiency (%) from 100 to 0 plotted on the x-axis and the foaming (%) of the standard solution plotted on the y-axis. The % defoaming efficiency is read at the intersection of the diagonal, with the arithmetic mean of the three measurements taken as the final result.

The composition of individual defoamer samples and their defoaming efficiency on non-ionic (non-ionic), anionic and possibly also cationic surfactants is shown in Table 1.

Table 1

Defoamer composition Defoaming efficiency (%) on:

Component 1 Quantity (% wt. j 2 nonionic surfactant anionic surfactant cationic surfactant 1 drop 3 2 drops 4 1 drop 5 2 drops 6 1 drop 7 2 drops 8 Polypropylene glycol 900 100 1 23 75 81 — — Dipropylene glycol 100 16 26 40 52 — — Dipropylene glycol 97.5 35 53 4 8 — — stearic acid 2.5 Dipropylene glycol 95 34 39 76 78 — — stearic acid 5 Dipropylene glycol 90 24 40 76 82 — — stearic acid 10 Dipropylene glycol 80 10 14 62 70 — — stearic acid 20 Propylene glycol 95 12 39 1 9 — stearic acid 5 Propylene glycol 70 23 31 13 21 —- .— stearic acid 30

I

Composition of defoamer Defoamer efficiency (%) on:

Component 1 Quantity (% by weight) 2 . nonionic surfactant anionic surfactant cationic surfactant 1 drop 3 2 drops 4 1 drop 5 2 drops 6 1 drop 7 2 drops 8 Polypropylene oil K 1000 87.8 94 96 86 89 stearic acid polypropylene glycol 2.2 900 10.0 Polypropylene oil K 1000 78 stearic acid polypropylene glycol 2 87 94 85 88 — — 900 20 Dipropylene glycol MEK, fraction above 80 21 29 10 24 — — 150°C/2.67 kPa 20 Propylene glycol 90 23 28 10 16 — —. MEK 10 Polypropylene oil K 1000 87.8 stearic acid 2.2 91 96 73 85 — — dipropylene glycol Polypropylene oil 10 To 1000 87.6 stearic acid 2.4 90 94 74 80 — — dipropylene glycol polypropylene glycol 10 1000 97.5 76 81 94 96 78 80 stearic acid 2.5 Polypropylene glycol 1000 90 59 60 93 95 81 90 stearic acid 10 Polypropylene glycol 1000 80 19 19 72 75 25 65 stearic acid 20 Polypropylene glycol 1000 97.5 48 52 72 74 23 35 MEK 2.5 Polypropylene glycol 1000 90 52 53 65 69 56 60 MEK 10 Polypropylene glycol 1000 80 44 46 70 73 39 42 MEK 20 Polypropylene glycol 1000 mixture of carboxylic 90 58 62 79 80 64 71 C ₇ —C ₉ acids 10 Dipropylene glycol mixture of carboxylic 90 57 60 79 80 58 60 C ₇ —C ₉ acids 10

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Example 2

The procedure is similar to that in example 1, only the defoamer consists of 2.5 wt. % stearic acid, 7.5 wt. % dipropylene glycol and 90 wt. % propylene oligomers, so-called polypropylene oil Κ 1000 with an average molecular weight of 469 g.mol· ¹ , while the density at 20 ^P C = 847 g . m - ^! , solidification temperature = -25 °C; there are on average 1.5-1.6 double bonds per m lecule.

The defoaming efficiency of the mentioned defoamer for an anionic surfactant is 74, respectively. 75%, for nonionic surfactant 58, or 82% and for cationic surfactant 22, respectively. 38%.

Example 3

The procedure is similar to that in example i, except that the defoamer consists of 50% by weight of polypropylene glycol with an average molecular weight of 900 and 50% by weight of a mixture of aliphatic C _{7 -C 8} carboxylic acids.

The defoaming efficiency of the anionic surfactant is 86, respectively. 88 °/o; to nonionic surfactant 76, or 80% and for cationic surfactant 82, resp. 84%.

Example 4

The procedure is similar to that in Example 1, except that the defoamer consists of 45% by weight of polypropylene glycol (900), 45% by weight of polypropylene oil (K 1,000) and 10% by weight of a mixture of C ₅ —C ₅ carboxylic acids. The mixture of C ₅ —C 5 carboxylic acids _(; has the following composition: acetic acid = traces; propionic acid — 16.8% by weight; n-valeric acid = 66.5% by weight; caproic acid = 7.2% by weight; acid number == 553.5 milligrams KOH/g; saponification number — — 578.87 mg KOH/g; water 0.64% by weight.

The defoaming efficiency of the mentioned defoamer for an anionic surfactant is 54, respectively. 59 °/o, to nonionic 13, or 15% and for cationic surfactant 44, respectively. 45 °/o.

Claims (3)

EXAMPLE 2 The procedure is similar to Example 1, with only the defoamer remaining at 2.5% by weight. % stearic acid, 7.5 wt. % dipropylene glycol and 90 wt. of propylene oligomers, so-called polypropylene oil, to 1000o average molecular weight of 469g.mol -1, with a density at 20pc of 847g. m-3, pour point = -25 ° C; an average of 1.5-1.6 doubles in one tube. The defoaming efficiency of said antifoam to an anionic surfactant is 74, respectively. 75%, to non-ionic surfactant 58, respectively. 82% and to the cationic surfactant 22, respectively. 38%. Example 3 The procedure is similar to that of Example 1, with only a defoamer consisting of 50 wt. of polypropylene glycol having an average molecular weight of 900 and 50% by weight; mixtures of aliphatic C7-C8 carboxylic acids. The anionic surfactant detersive activity is 86, respectively. 88 ° / o; to non-ionic surfactant 76, respectively. And 80% and 82% and 84%, respectively. EXAMPLE 4 The procedure is similar to that of Example 1, except that the antifoam consists of 45% by weight of polypropylene glycol (900), 45% by weight. % polypropylene oil (K 1000) and 10 wt. a mixture of carboxylic acids C5-C5. A mixture of carboxylic acids C5-C (having the composition: acetic acid = traces; propionic acid - 16.8% by weight; acid valeric = 66.5% by weight; Caps. = 7,2% by weight, acid value = 553,5 milligrams KOH / g, saponification number - 578,87 mg KOH / g, water 0,64% by weight Dehydration efficiency of said defoamer to anionic surfactant is 54 and 59 °, respectively, to non-ionic 13 and 15%, respectively, and to cationic surfactant 44 and 45 °, respectively. What is claimed is: 1. A scavenger based on oxygenated organic compounds and optionally also higher hydrocarbons, additives and auxiliaries, characterized in that it consists of 10 to 99% propylene glycol to polypropylene glycol having a pitch weight of up to 2000 g / mol and 1 to 1 g / mol. 90% of at least one carboxylic acid C4 to C24 and / or hydrocarbons having a molecular weight of 130 to 1000 g.mol -1. 2. Deodorizer according to claim 1, characterized in that the hydrocarbons form mixtures of petroleum hydrocarbons, preferably a kerosene fraction and a mixture of n-alkanes C10 to C18. 3. A desiccant according to claim 1, wherein 2, wherein the hydrocarbons having a molecular weight of 130 to 1000 g.mol-1 form synthetic hydrocarbons, such as the oligomers of the alkenes C3 to C- " after their hydrogenation, preferably the propylene oligomers and / or cracking and hydrocracking products of higher hydrocarbons, preferably hydrocracking products of vacuum petroleum distillates.