The method of obtaining the oxidized vegetable oils
(57) Abstract:The invention relates to a method for producing an oxidized vegetable oils, which are used in paint, printing, light industry, binders in the construction industry and other sectors of the economy. The production of oxidized vegetable oils involves the oxidation semidrying oils with oxygen in the presence of biopolymeric phtalocyanine or melamine-formaldehyde complexes of metals of variable valence of Co, Mn, Ni, Fe deposited on a solid inert carriers, in the temperature range 130-160oWith purging air 40 h-1to achieve the viscosity 960-1340 C. Proposed method are the light of the oxidized oil when using recyclable heterogeneous catalysts for reuse. 6 table. The invention relates to a method for producing an oxidized vegetable oils, which are used as film-forming paints and lacquers, printing, light industry, binders in the construction industry and other sectors of the economy [Grinberg A. I. Technology of film-forming substances. - L.: Goskomizdat, 1955, 651 S.].Iza at a temperature of 150-160oIn the presence of catalysts (desiccant - linoleate manganese-lead or manganese-lead-cobalt), after purging the oxidized oil is supplied to the heat treatment without blowing air at a temperature 260-265oWith or 280oWith under vacuum.The disadvantage of this method is the high temperature heat treatment and the high duration of the process that leads to the loss of vegetable oil during its oxidation, increase harmful emissions into the atmosphere, worsening the quality of oxidate (darkening), and the need to use lead driers [Grinberg A. I. Technology of film-forming substances. - L.: Goskomizdat, 1955, 651 S.].A method of obtaining polymerized oils, comprising the following operations: blowing air at a temperature of 138oWith, then mixing at a temperature of 60oC with the addition of 0.4% diluted sulfuric acid, and upon reaching the desired viscosity neutralization with triethanolamine. The disadvantages of this method include a multi-stage process, the need for neutralization of sulfuric acid [U.S. Pat. USA 2838551. Polymerized vegetable oil and the way they are received / Kantor M, VI is no oxidation semidrying vegetable oils oxygen at a temperature of 130-150oIn the presence of aluminum-organic compounds (AOC): diethylaluminium (DEAH), triethylaluminium (tea), triisobutylaluminum (CHIBA) [RF patent 2162479 Way to obtain oxidized vegetable oils / Prikhodko, S. I. and others, 2001]. The disadvantage of this method is the necessity of using expensive initiators of the process.The objective of the invention is to remedy these disadvantages: the process under mild conditions, the use of recyclable heterogeneous catalysts for reuse, eliminating mnogostadiinost process and, as a consequence, obtaining light oxidized oils.This object is achieved by carrying out the oxidation semidrying vegetable oils oxygen (air flow 40 h-1) at a temperature of 130-160oIn the presence of heterogeneous catalysts: pyropolymer phthalocyanine complexes of metals of variable valence of Co, Mn, Ni, Fe or biopolymeric melamine-formaldehyde complexes of these metals deposited on solid media (aluminum oxide, aluminosilicates, zeolites, glass, glass ceramics, metal-ceramics). The method of producing catalyst is impregnated with an inert carrier Rast is termoobrabotki substances at 600-1000oC in an atmosphere of inert gas prior to the occurrence of cross-linked polymer systems. For example, the media-Al2O3with particle sizes of 1.0-1.5 mm was soaked with a solution of tetrachlorosilane cobalt with a concentration of 2 g/l within 24 hours, the Sample was dried at room temperature for 6 h and at 100oC for 3 hours Then a sample of the catalyst was subjected to heat treatment at 1000oWith in argon for 1 h, the Occurrence of cross-linked polymer system was controlled using IR spectroscopy [EN 93052319/04, B 12, 27.04.1996].The use of these compounds allows you to:
1. avoid the use of expensive consumable toxic lead-cobalt-manganese driers,
2. avoid the use of expensive aluminum-organic catalysts,
3. get oxidized oil with low chromaticity, as the process is carried out in mild conditions, as well as in the present invention do not require the use of painted catalysts (siccatives),
4. to regenerate and reuse the oxidation catalyst, thereby to reduce the cost of production of oxidized oil.The choice of temperature range is explained by the following: reduction rate is ikenaga oil; the temperature increases above 160oWith impractical because the inputs to the process are achieved far exceed the effects of the viscosity at the process temperature of equal to 180oWith is 1280 S.The proposed method is confirmed by the following examples.Example 4, PL.1.In a metal reactor column type with the lower perforated plate (air distribution) and a stainless steel mesh (for holding grains of catalyst) is loaded catalyst - penopolimery phthalocyanine cobalt (Fcso) deposited on alumina-Al2O3with a particle size of 3-5 mm in the amount of 30% of the working volume of the reactor. Then the reactor is loaded pre-dehydrated sunflower oil to fill the reactor to 70% of its working volume. After the download is heating the reactor to 160oAnd begins the oxidation by air oxygen. The air flow rate is set to 40 cm3/cm3oil per hour (40 h-1). The monitoring process is carried out in viscosity of the oxidized oil on the OT-4. The reaction is finished when reaching a viscosity of 1200 C. the duration of the process while SOS is equal to 250.After completion of the oxidation air supply is stopped, the oil through the nozzle bottom drain of the reactor into the receiving container for the finished product. Next, the reactor with the catalyst washed once with hot white spirit supplied through the fitting bottom drain, then blown technical nitrogen and then air. After washing, the catalyst can be reused at least 250 times.The following examples of synthesis are given in the tables:
table. 1, 4 examples, confirming the influence of the conditions of the oxidation process on the properties of the obtained product;
table. 2, 5 examples, showing the influence of metal ion catalyst at the conditions of the oxidation process and properties of oxidized oil;
table. 3, 6 examples, confirming the impact of semidrying oils on the process conditions and properties of the obtained product;
Thus, the results indicate that the oxidation of vegetable oils oxygen (40-1) at a temperature of 130-160oC in the presence of pyropolymer phthalocyanine complexes of metals of variable valency and pyropolymer melamine-formaldehyde complexes of these metals are obtained light oxidized who ate oxygen, characterized in that the process is carried out in the presence of biopolymeric phtalocyanine or melamine-formaldehyde complexes of metals of variable valence of Co, Mn, Ni, Fe deposited on a solid inert carriers, in the temperature range 130-160oWith purging air 40 h-1to achieve the viscosity 960-1340 C.
FIELD: production of vegetable oils and fats acid polyvalent metal salts useful as catalysts and siccatives in tannery, paint-vehicle industry, etc.
SUBSTANCE: claimed salts are obtained by reaction of alkali salts of fatty acids with aqueous solution of water soluble polyvalent metal salt or mixture thereof. Alkali or ammonia salts are obtained by qualitative alkali hydrolysis of respective vegetable oil, fats, low viscous oxidates or mixture thereof under strenuous stirring and gradual temperature rising from 20-30°C to 60-100°C with equivalent amount alkali or ammonium in form of 3,26-48,46 % aqueous solution for 3-10 min in presence of initial additive of sodium stearate or oleate in amount of 0.5-1.0 % based on mass of hydrolyzed substance up to residual alkali content in system not more than 2-3 % based on starting value, followed by stirring for 10-15 min. In obtained reaction mixture under stirring and at mentioned above elevated temperature previously prepared and heated up to 60-98°C aqueous solution of water soluble polyvalent metal salt or mixture thereof for 10-20 min is introduced in amount of 1 g-eq/mol of alkali used for hydrolysis followed by stirring for 15-20 min. Then obtained salt composition is separated from aqueous phase by filtration, centrifugation or extraction with organic solvent.
EFFECT: polyvalent metal salts with anion composition fully (quantitatively and qualitatively) corresponding to acid composition of respective oil or fat.
5 cl, 3 tbl, 21 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to greasing and emulsifying substances used in fur, leather and other branches of industry. Invention describes a method for deep sulfonation of oxidized vegetable oils, fats and their mixtures, and oxidized mixtures with the nominal viscosity value in the range 33-75 by viscosimeter VZ-4 at 20°C in their treatment with sodium sulfite. The process is carried out in system consisting of oxidized component or mixture of oxidized components, sodium sulfite, water and soap additives, carboxylic acid, phenol and copper (II) salt as a catalyst in bead mill of vertical type at temperature of environment up to practically complete ceasing or quantitative consumption of sodium sulfite and charge of the latter is calculated by the following formula: mNA2SO3 = 0.006 x mOX x (I.N.)OX wherein mOX and (I.N.)OX mean mass and iodine number of oxidized component or mixture of oxidized components, respectively. The mass ratio of oxidized component and water varies in the range from 1:4 to 1:2.5. Dosing additives with respect to oxidized component are following: soap, 2%; carboxylic acid, 4%; phenol, 2.5%. Oxidized flax, sunflower, soybean and cotton oils, oxidized fish oil and mixtures of vegetable oils with fish oil or pig fat are subjected for sulfonation reaction with air in regimen of intensive bubble bubbling at 105 ± 5°. Soaps in indicated system are represented by sodium stearate and sodium oleate and by reaction mixtures of practically quantitative alkaline hydrolysis of fats and vegetable oils also. Benzoic, oxalic, malonic and citric acids are used as acid, and sulfate, acetate and other water-soluble salts of copper (II) are sued as a catalyst dosed in the amount (2-7.5) x 10-4 mole/kg of the parent charge. The sulfonation reaction degree is 33-40%.
EFFECT: improved preparing method.
5 cl, 1 tbl, 16 ex
SUBSTANCE: method includes preliminary heating of oils at a temperature of 40-90°C with simultaneous air blowing and following oxidation of oils by air with heating. Oxidation is carried out until oxidate, viscosity of the solution of which in white spirit constitutes 19-25 s. At the stage of preliminary heating air with the content of ozone of 1.5-2.5 mg/l is blown through oil with the consumption of not more than 4 l/min·kg, and oil heating is realised by a heater from a temperature 40°C to 90°C at a rate of 2.5 degree/min. Sulphonic acids in an amount of 0.05-0.15% of oil weight and manganese (II) stearate in an amount of 0.8-1.5% of oil weight are added to oil, and the temperature mode of oxidation is supported by heating of oil to a temperature of 175°C at a rate of 3-5 degree/min with the following periodical cooling to a temperature of 100°C. The quantity of heating and cooling cycles of oil constitutes not fewer than two, and air consumption is supported at the level not higher than 4 l/min·kg.
EFFECT: reduction of the vegetable oil oxidation time, with obtaining a film-forming substance with required quality parameters, simplification of the technological process.
2 dwg, 1 tbl, 1 ex
SUBSTANCE: self-oxidizing polymer composition includes a drying agent obtained by mixing 1,4,7-trialkyl-1,4,7-triazacyclononane (L) and a manganese salt having the general formula Mn2+[X]n, in which, as the anion X, PF6-, SbF6-, AsF6-, BF4-, B(C6F5)4-, Cl-, Br-, I-, NO3- or R2COO-, and in this case n=2, or the anion X is SO42-, and in this case n=1, where R2 is C1-C20-alkyl. The 1,4,7-trialkyl-1,4,7-triazacyclononane (L) is present in the mixture in such an amount that the molar ratio of L:Mn is at least 1.25:1 and preferably at least 1.5:1. A coating composition consisting of a self-oxidizing polymer composition, a method for coating a substrate, a substrate, and applying the composition to paints, compositions, varnishes, inks and glazes and using a mixture of L and Mn as a drying agent for an air-drying self-oxidizing polymer composition are also disclosed.
EFFECT: provision of cobalt-free catalysts that can provide rapid drying and at the same time contribute to reducing the yellowness of the coating compositions.
14 cl, 12 tbl, 15 ex
SUBSTANCE: composition includes a dehumidifier for self-oxidizing resin composition, drying in air, and a polymer comprising unsaturated aliphatic groups. Mentioned dehydrator is prepared by mixing the manganese salt with 1, 4, 7-trisubstituted-1, 4 ,7-triazacyclononane (L). The manganese salt has the general formula Mn2+[X]n, in which the anion X is selected from PF6-, SbF6-, AsF6-, BF4-, B(C6F5)4-, Cl-, Br-, I-, NO3- or R2COO-, in this case n=2, or the anion X is SO42-, where n=1, and where R2=C1-C20 Alkyl. In this case, 1,4,7-trialkyl-1,4,7-triazacyclononane (L) is present in the mixture in such an amount that the molar ratio of Mn:L is at least 1.25:1, preferably at least 1.5:1 and less than 20:1. The coating composition, the method for coating the substrate, the substrate coated with the composition, the use of the composition in paints, glues, varnishes, inks and varnishes and the use of a mixture of 1,4,7-trialkyl-1,4,7-triazacyclononan (L) and manganese salt as a dehumidifier for self-oxidizing resin composition, drying in air.
EFFECT: providing non-cobalt catalysts for coating formulations containing them, and which simultaneously provide quick-drying coatings that have significant hardness and gloss properties.
14 cl, 9 tbl, 3 ex
SUBSTANCE: method is described for oxidating vegetable oil in an oxidation column, consisting in the fact that to begin the oxidation process the column is filled with oil preheated to the temperature of 115-120°C, and air bubbling starts, initiating the oxidation process, in which, after the oxidation process in the column begins and the oil temperature inside the column rises to 145-150°C, oil is supplied to the bottom of the column from the additional tank, into which, before feeding it to the column, a certain amount of desiccant catalyst initiating the oil oxidation is added, oil heated by the reaction heat is oxidized, and a part of the oxidized oil is withdrawn from the top of the column and returned into the tank, circulating until the viscosity of the oxidized oil reaches the set value.
EFFECT: energy saving, the possibility of oxidizing a large amount of oil in an oxidizing column of small dimensions by circulating oil through an oxidation column.
2 cl, 1 dwg