CS264732B1 - defoamer - Google Patents

Abstract

The defoamer consists of 90 to 99.8% by weight of at least one polyaddition product of a C£ to C^ alkylene oxide to a monohydric aliphatic alcohol C4 to C^ or a dihydric to tetrahydric aliphatic alcohol (C12 diols, trimethylolpropane, glycerol, pentaerythritol and 0.2 to 10% by weight of at least one ethanolamide of a C16 to C20 carboxylic acid (stearic acid ethanolamide, palmitic acid ethanolamide). Another component may be a mixture of hydrocarbons with a molecular weight of 130 to 1,000 as well as at least one Cg to C^4 aliphatic alcohol and auxiliaries. The defoamer can be emulsified in water or dispersed in other media. It is used primarily for foams formed by the interaction of anionic and cationic surfactants, but also nonionic ones, primarily in the pulp and paper industry.

Description

264732 2

BACKGROUND OF THE INVENTION The present invention relates to an antifoam based on a mixture of technically available organic oxygenated nitrogen compounds, optionally also hydrocarbons and auxiliaries, particularly suitable for defoaming or preventing foaming in the pulp and paper industry.

Antifoams based on oxygenated organic compounds containing carboxylic or hydroxyl groups in the molecule are known. Such are at least partially esterified polysols, 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. 3,458,567). Also technically available are the polyaddition products of ethylene oxide with oleic acid, abietic acid, and tall oil acids, often combined with organosilicon compounds (U.S. Pat. Nos. 2,991,248, 3,235,501 and 3,235,502). However, their disadvantage is the relatively low antifoaming efficiency and reactivity of some components with the components of the defoam systems. Significant but technically difficult to obtain are antifoams based on organosilicon compounds such as polymethylsiloxane, polyethylsiloxanes and others (Tichomir V.K., Foams, "Chimia", Moscow (1983)). However, ashless types of defoamers are required for several applications.

Antifoaming agents based on poly-component mixtures are relatively widespread (U.S. Pat. Nos. 2,923,687, 3,180,836, 3,697,438 and U.S. Pat. No. 183,982), in which higher fatty acids, vegetable and mineral oils and fatty oily polyaddition products are important ingredients. acid. Saline esters of polyglycols with oleic acid and in admixture with alcohols C g gg to Cgg. Otherwise, however, the need for a wide range of substances is a drawback, but less effective. In contrast, the relatively high defoaming efficiency of foams produced mainly by nonionic and anionic surfactants, and especially in hydrophobic systems, has a defoamer of 50 to 99% by weight. % hydrocarbons and 1 to 20 wt. aliphatic acids (esp. author certificate 232 390) or alkanolamides of carboxylic acids (MS Authorization No. 240 516). However, they are viscous under normal application conditions and have a lower foam efficiency due to cationic surfactants, as well as the disposal of foams in hydrophilic systems.

In addition, we need to expand the range of antifoaming antifoam products, technically easy to use intermediates, and also effective in defoaming aqueous solutions in the oil and pulp industry.

According to the invention, the defoamer based on a mixture of organic oxygen and nitrogen organic compounds consists of 90 to 99.8 wt. at least one product of the C2 to C4 alkylene oxide polyaddition to a monovalent aliphatic alcohol to C1g and / or to a divalent aliphatic alcohol and 0.2 to 10 wt. at least one carboxylic acid monoethanolamide; The advantage of the defoamer is the synergistic effect of its components, high antifoaming efficiency not only on foams formed with the interaction of anionic and cationic surfactants, but also nonionic. Thereafter, the defoaming effect in the wider temperature limits, inerting with the vaccine materials and, generally, the components of the defoamer systems. Then the possibility of emulsifying in water and raw material availability.

By the composition of the defoamer according to the present invention is meant only the content of organic components and powder to colloidal inorganic materials. In fact, the defoamer may be emulsified or dispersed in water and other media and then applied to defoaming.

The polyaddition products for the monovalent aliphatic alcohol are individual alcohols C 1 to C 10, but more often they are mixtures of at least two aliphatic alcohols, optionally with admixtures under the conditions of virtually inert substances such as acetals and esters. In the case of polyaddition, the most common single alkylene oxides, more rarely mixtures of alkylene oxides, are applied. Indeed, when two alkylene oxides are also polyaddition, the polyaddition is most often carried out first with one alkylene oxide, e.g. ethylene oxide (oxirane) and then with propylene oxide (methyloxime 264732), optionally with another alkylene oxide or with ethylene oxide and the like. The combination of polyaddition of several alkylene oxides is most often applied to polyaddition to polyhydric alcohols. The hydrocarbons of the present invention include saturated or unsaturated, especially aliphatic and naphthenic hydrocarbons, optionally with aromatic admixtures. Most often, however, petroleum fractions and petroleum fractions, light and heavy gas oil fractions, especially refined oils. Then synthetic hydrocarbons, especially oligomers and co-oligomers, or low molecular weight polymers and copolymers of ethylene, propylene, alkenes and dienes and Cg, further products resulting from thermal cleavage of macromolecular substances, as well as hydrogenolysis of macromolecular and higher hydrocarbons such as vacuum petroleum distillates and the like. In addition, the hydrogenated oligomers of said alkenes and dienes C8 to C18 can be utilized.

Suitable components are aliphatic alcohols C8 to C14, as well as alcoholic alcohols from the production of pure higher aliphatic alcohols, such as " ancestor " fractions and distillation residue. This can be the anterior portion and the distillation residue from the rectification of crude 2-ethylhexanol, but the 2-EHTP distillation is a more efficient component. It does not harm the presence of acetates, admixtures of aldehydes and ketones.

Thus, the distillation residue from the rectification of crude 2-ethylhexanol contains mostly 26 to 46% by weight. 2-ethylhexanol, 35 to 50 wt. monovalent and divalent alcohols Cg2, divalent alcohols Cg, then acetals, aldehydes and other non-identified oxygenated organic compounds. Furthermore, it is a leading part of the rectification of 2-ethylhexanol containing a mixture of isobutanol with n-butanol in a total amount of usually 40 to 85% by weight, isoamyl alcohol of 3 to 7%, 2-ethylhexanol 5 to 20, further addition of ketones and others. unspecified oxygen-organic compounds.

The ethanolamides of the carboxylic acids C16 to C2Q are both components of much more effective and unsaturated acids, but also lower carboxylic acids. The carboxylic acid ethanolamide additives in the above combinations with the other antifoam components have a synergistic effect.

Suitable excipients are emulsifiers, fungicides, bactericides, corrosion inhibitors, pigments, dyes, optical brighteners and fragrances. Further details of the antifoam formulation of the present invention, their efficacy as well as other advantages are apparent from the examples. Přikladl

The defoaming efficacy of the individual antifoam samples is determined by comparing the foaming power of the standard sample to that of a standard sample with an added defoamer. Thus, 100 cm 3 of an aqueous solution of standard sodium lauryl sulphate (anionic surfactant) at a concentration of 0.1 wt% ~ 3 (1 g.dm) or polyethoxylated primary alcohols Cg 2 to C 8 with 9 moles of ethylene oxide (nonionic surfactant) of similar concentration and finally a similar laurylammonium bromide solution (cationic surfactant) is carefully poured into metering cylinders of 500 tin each and sealed with a stopper plug. The standard solution is foamed by 180 ° and slept fifty times over 1 min at 23 ± 2 ° C. The foam height and the height of the unpulled solution are measured after 1 min after the end of the foaming process.

Thereafter, the Standard Pš (%) foaming is calculated from the PŠ = a / b relationship. 100, a = foam height (CM); b = height of the unpopulated solution (cm). The de-oiling efficiency is determined by the same procedure as the standard solution, but 1 (0.02 g) or 2 drops (0.04 g) of antifoam is added to 100 cm 3 of the standard solution and Ρθ (foaming of the standard solution / defoamer mixture) is determined .

Finally, the effervescence efficiency is plotted from a graph of foaming versus defoaming efficiency (%), with an antifoaming efficiency (%) of 100 to 0 and a foaming ratio (%) of the standard solution on the x-axis. In the intersection of the diagonal, the% defoaming efficiency is subtracted, taking the arithmetic mean of the three measurements as the final result. The defoamer formulation from the individual components is made at a temperature of 30 ± 5 ° C,

The components of the antifoam products are tested for the propylene oxide polyaddition products to C4 to C18 aliphatic alcohols, in particular the 15 mole propylene oxide polyaddition product for the distillation residue of the crude 2-ethylhexanol. This distillation residue (by distillation 86% as a fraction in the range of 184 to 285 ° C / 101 kPa), shortly referred to as 2-EHTP, has the following characteristics: OH = 12.9; bromine number = 4.7 g Br / 100 g; acid number = 0.9 mg KOH / g; saponification number = 22.1 mg KOH / g; 2-ethylhexanol = 36.3%; alcohols, including diols C12 = 44.1 wt%; butyraldehyde diisobutyl acetal = 0.7% and 7 other oxygenated organic substances at a concentration of 1 to 6% by weight; average molecular weight = = 190; density at 20 ° C = 901.9 kg / m 3; n30 = 1.4530.

Then the product of the polyaddition of 15 moles of propylene oxide per mole of alcohols Cg and C ^ 2 in 2-EHTP, SalI is referred to as EHTP-15. Furthermore, the copolyadition of propylene oxide and ethylene oxide to trimethylolpropane by the addition of ethylene oxide to alkali catalyzed addition of ethylene oxide to trimethylolpropane, and polyaddition of propylene oxide is continued until virtually all propylene oxide is reacted. The polyether thus obtained has a hydroxyl number of 47.34 mgKOH / g; acid value = 0.153 mg KOH / g; sodium content 5.2.10 3 wt. and potassium 1.6.10 4% by weight, with a molecular weight of 2700 ± 400, Sallow referred to as Polyether-48. The tentopolyether is also suitable as a component for producing mainly soft polyurethane foams.

The components of the hydrocarbons are the kerosene fraction, referred to as kerosene, then the refined alkanickonaphthenic oil, the so-called white oil and the propylene oligomers, the so-called poly-propylene oil K-1000 having an average molecular weight of 469 g / mol; freezing point = -25 ° C, with an average of 1.6 double bonds per molecule. Then, lower average molecular weight oligomers, referred to as K-300 polypropylene oil. Furthermore, aliphatic alcohols Cg are pure but more frequent than mixtures. Such a defined heavy fraction from the rectification of crude 2-ethylhexanol, referred to as 2-EHTP, and a light weight fraction (2-EHLP) from the rectification of crude 2-ethylhexanol; a fraction of from 109 to 182.5 ° C / 101 kPa, d30 = 812.2 kg / m 3 and refractive index = 1.4088; % wt. OH = 19.4; CHO = 0.24 wt%; CHO bound = 0.25 wt%; bromine number = 1.3 g Br / 100 g; H 2 O = 0.45 wt%; acid value = 1.26 mg KOH / g; saponification number = 2.5 mg KOH / g; isobutanol content = 20.3% by weight; n-butanol with a saline unknown component = 51.7% by weight; isoamyl alcohol = 4.1%; 3-heptanone = 4.1%; 2-ethylhexanol = 15.3%; 2-ethylhexanol = 1.95%; Oxygen organic compounds not more specifically identified = 2.1% by weight.

Then, stearic acid ethanolamide CH3 (CH2) 16 CONHCH2 CH2 OH (2-hydroxyethyl stearic acid).

Finally, micrograin to colloidal silicon dioxide (SiO2) and magnesium oxide (MgO).

The composition of the individual antifoams, as well as their antifoaming efficacy on the foams produced by the combination of nonionic, anionic and cationic surfactants, is shown in the results summarized in Tab. 1, 5, 264732

Table 1

Defoamer composition Deoxidizing efficacy (%} for foam formed by surfactant action)

Component Content (% by weight) nonionic anionic cationic 1 drop 2 drops 1 drop 2 drops 1 drop 2 drops 1 2 3 4 5 6 7 8 Polyéter-48 100 39 46 42 46 45 47 2-EHTP 100 58 65 81 89 80 84 EHTP-15 100 56 65 90 92 71 79 EHTP-15 Monoethanolamide 99,8 83 89 97 100 87 88 Stearic acid 0,2 EHTP-15 Monoethanolamide 99,0 84 89 98 100 85 87 Stearic acid 1,0 EHTP-15 Monoethanolamide 98,0 80 84 95 99 84 86 Stearic acid 2,0 EHTP-15 47,5 Kerosene Monoethanolamide 50 68 74 100 100 100 100 Stearic acid 2,5 EHTP-15 47,5 2-EHTP 50,0 57 66 98 100 88 90 Stearic acid monoethanolamide 2,5 2-EHTP-15 49,5 Kerosene Monoethanolamide 50,0 81 86 93 95 97 100 stearic acid 0,5 EHTP-15 49,9 Kerosene Ethanolamide 50,0 53 56 86 88 100 100 stearic acid 0,1 EHTP-15 19,9 Polypropylene oil K 1000Etanolamide acid 80,0 100 100 69 90 100 100 stearic 0,1 EHTP-15 20,0 Polypropylene oil K 1000 80,0 83 93 59 70 94 97 EHTP-15 91 , 9 Stearic acid ethanolamide 7.4 38 47 90 93 93 99 sio2 0,7 EHTP-15 50 Kerosene Ethanolamide 47,5 76 89 85 91 98 100 stearic acid 2,5 EHTP-15 40 Kerosene 57,5 71 85 84 89 98 100

Stearic Acid Ethanolamide 2.5 264732 6

Tab. 1 1 2 3 4 5 6 7 8 EHTP-15 40 Kerosene Ethanolamide 55 Stearic acid 3.5 95 100 92 95 91 95 Si ° 2 1.5 EHTP-15 8 Kerosene Ethanolamide Acid 90 98 100 94 98 99 100 Stearic 2 EHTP -15 8 Polypropylene Oil K 300Etanolamide Acid 90 100 100 97 98 100 100 Stearic 2 EHTP-15 7.5 2-EHTP 90.0 78 80 79 82 99 100 Stearic Ethanolamide 2.5 EHTP-15 7.5 Kerosene Ethanolamide Acid 90 , 0 79 82 96 98 100 100 stearic 2.5 EHTP-15 20.0 Kerosene Ethanolamide acid 77.5 96 100 91 100 100 100 stearic 2.5 EHTP-15 50.0 2-ethylhexanol Ethanolamide acid 48.5 54 63 90 96 82 87 stearic 1.5 EHTP-15 25.4 White oil Ethanolamide acid 72.4 82 85 97 99 100 100 stearic 2.2 EHTP-15 7.5 Polypropylene oil K 1000 70.0 Petroleum Ethanolamide acid 20.0 78 80 79 82 99 100 stearic 2.5 Polyether - 48 Ethanolamide acid 97.0 50 53 94 97 94 96 stearic 3.0 EHTP-15 25.4 Kerosene Ethanolamide acid 72.4 98 100 100 100 100 100 stearic 2.2 The product of the polyaddition of 6 mol butene oxide per mole 6 0 dodecanol 2-EHTP 38,5 57 69 92 98 87 93 Stearic Acid Ethanolamide 1,5 7 264732

Tab. 1 1 2 3 4 5 6 7 8 EHTP-15 50 2-Ethylhexanol 37,5 56 64 90 95 83 88 2-Propanol 10 Stearic Ethanolamide 2,5 Polyether - 48 50,0 2-Ethylhexanol 49,0 41 48 83 92 81 87 Stearic ethanolamide 1.0 Polyether - 48 50.0 2-EHTP 46.0 Ethanolamide acid 49 90 84 92 80 94 stearic 1.0 Si ° 2 3.0 Polyether - 48 50 Polypropylene oil K 1000 50 67 68 95 9.8 86 90 Polvere - 48 24.9 Kerosene 70.9 Ethanolamide Acid 90 96 100 100 100 100 Stearic 2.1 MgO 2.1 EHTP-15 91.9 • Acid ethanolamide 46 60 90 100 97 100 Stear 0.7 Example 2

Formulation of Polyether - 48 (30% w / w), EHTP-15 (40% w / w), 2-propanol (28.5% w / w) palmitic ethanolamide (1.45% w / w) and silica (0.05%) % by weight) of the scavenger obtained is emulsified with distilled water in a ratio of 1: 1 by weight to said organic components and the antifoaming activity is tested one and two drops. The efficacy on nonionic surfactant is 39, respectively. 49 i, for anionic surfactant 67, respectively. 83 i and to cationic surfactant 68 and 76 T. Example 3

The antifoaming efficiency of the product of the polyaddition itself is investigated. ethylene oxide of polypropylene glycol of medium mol. weight 1800 (Copolymer 610), on the one hand, with an addition of 0.2 wt. stearic acid ethanolamide.

The polyaddition product itself has antifoaming activity with one and two drops on the nonionic surfactant aqueous solution 11 and 11, respectively. 18%, but containing 0.2 wt. stearic acid ethanolamide 63, respectively. 73! and with 1 S wt. already 67, respectively. 75%. The aqueous anionic surfactant-free product of the polyaddition has an antifoaming activity of 91 and 100, respectively. 96%, with 0.2 i of said ingredient 79, respectively. 87 í a s 1 S ingredients 82, resp. 93. For the cationic surfactant solution, the product of the polyaddition itself has a defoaming efficiency of 66, respectively. 71, with 0.2 wt. 89, respectively. 93 i with 1 wt. stearic acid ethanolamide 92, respectively. 97%. Example 4

The antifoaming efficiency of a new defoamer (N 222) for wastewater from a pulp mill with magnesium-sulphite technology, so-called MgBi leachate, diluted with water at 3 ° N 1:15, is studied at 50 ° C. The N 222 consists of 90 wt. % Polyether-48, 9.8 wt. EHTP-15 a3 0.2 wt. stearic acid monoethanolamide. In the case of weighing 5.8 mg of defoamer 200 cm of waste water, the foaming power is 3.03 even without foaming; at 11.3 mg / 200 cm @ 2 waste water2.3% and with 29 mg antifoam / 200 IU? foamability 1.5%.

Claims (6)

264732 8 SUBJECT OF THE INVENTION What is claimed is: 1. A scavenger based on a mixture of organic oxygen and nitrogen organic compounds, characterized in that it consists of 90 to 99.8% by weight of organic compounds. at least one polyaddienkylene oxide Cg product except for the monovalent aliphatic alcohol to Cgg and / or to the divalent toormic aliphatic alcohol and 0.2 to 10 wt. at least one monoethanolamide of carboxylic acid Cgg to Cgg. 2. Deodorizer according to claim 1, characterized in that the polyaddition product of the alkylene oxide with aliphatic alcohols forms the product of the polyaddition predominantly a mixture of 2-ethylhexanol, dodecanol adiol C12 with 3 to 20 moles of propylene oxide, preferably a polyaddition product of 15 moles propylene oxide with 1 mole distillation residue from the rectification of crude 2-ethylhexanol. 3. Deodorizer according to claim 1 or 2, characterized in that the product of the polyaddition with trivalent to tetravalent aliphatic alcohol is the product prepared by the polyaddition of propylene oxide and / or ethylene oxide to trimethylpropane and / or glycerol, preferably propylene oxide with ethylene oxide natriethylpropane, to an average molecular weight of 200 to 3500 . 4. A scavenger according to any one of claims 1 to 3, further comprising from 5 to 85% by weight of hydrocarbons having a molar mass of 130 to 1000 g.mol 1, preferably alkanic-cyclanic hydrocarbons and / or oligomers of alkenes Cg to Cg. 5. A scavenger according to any one of claims 1 to 4, further comprising 5 to 70% by weight of at least one aliphatic alcohol C8 to C8. 6. A scavenger according to any one of claims 1 to 5, further comprising from 0.05 to 5% by weight of dust to colloidal inorganic compounds, preferably silica, magnesium oxide, calcium carbonate and dicalcium phosphate. Severografia, n. P., MOST Price 2,40 Kcs