Method for preparing sulfated oxidized vegetable oils, fats and their mixtures

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

 

The invention relates to the production of components fatliquoring agents and emulsifying formulations and can be used in fur, leather and other industries.

Known methods of making a composition for the fatliquoring of leather (and. C. the USSR No. 1723141, 1723142, 1759835, Pat. Of the Russian Federation No. 2099430) or emulsifying composition (U.S. Pat. Of the Russian Federation No. 2039087), in which the oxidation air is subjected to mixtures in different proportions of natural and synthetic fats, vegetable oils, and oil with subsequent sulfonation products obtained cookilaria aqueous solution of a bisulfite, a mixture of sulfite and bisulfite or one of sodium sulfite. However, if cookilaria there is no oil UNDER, to obtain the target composition in ways not possible. In addition, the intermediate of cookilaria with oil shall be subjected to the sulfonation immediately after receipt.

Closest to the claimed is a method of obtaining a composition for the fatliquoring of leather and fur (A.S. USSR №1460077), according to which fish, mink oil or a mixture of fish or pork fat with unsaponifiable substances in the ratio of 9:1 are oxidized by oxygen in the presence of cobalt or manganese salts of polyunsaturated20-C26acids at 45-60°under stirring and sparging air for 2-3 hours; then add the emulsifier based on ethoxylated fatty acid or p is letreguilly esters to alcohols in quantities of 0.5-4% by weight of fat, stirred for 15 min, add 20-30% from fat mass aqueous solution of sodium bisulfite (37%) and lead the process of sulforaphane at the above temperature for 3-10 hours to obtain a viscous mobile or thick pasty mass from light to dark brown color.

This method has several disadvantages.

1. In it, as in all of the above, the sulfonation is exposed to freshly prepared and not stored for any long time oxidat. From this it follows that the oxidation and sulfonation, if they are carried out in different devices have to be skorrelirovany and mass, and composition that may not meet the optimal option for any liquid-phase oxidation (cooksley), neither of sulfonation. Especially oxidation as the process is more complex, requiring a special reactor, and easier and more economical flowing in the devices column type when you download more than 1 so

2. The suggested mode and the method in General does not apply to the receipt and sulfonation of oxidativ some vegetable oils, including flax, sunflower, soybean or their mixtures with each other. However, the additive products of sulfonation of such oxidation can significantly improve the properties of emulsifiers and fatliquoring agents for skin and also to expand the field of use of such materials.

3. Sulfonation is carried out bis is lipitor sodium, which is unstable, it is stored for a long time the substances does not apply and prior to each sulfonation requires its receipt.

4. The process of sulfonation is long and strongly depends on the conditions of oxidation, including the nature and quantity of catalyst (transition metal salt).

The objective of the proposed solution is to perform a deep sulfonation not only obtained in different conditions, including in the absence of salt catalyst at all, and kept an arbitrarily long time oxidation sunflower and other vegetable oils, fish oils, mixtures thereof, and mixtures of oxidation, and the sulfonation conduct an aqueous solution of sodium sulfite at room temperature in a period commensurate with the known variants or shorter time.

This object is achieved in that oxidati vegetable oils, fats or mixtures thereof is treated with sodium sulfite in the reaction mixture, consisting of oxidate or mixture of oxidation, sodium sulfite, water and additives sodium soap, phenol, carboxylic acid and water-soluble salts of copper (II) as catalyst, in a bead mill, vertical type with glass beads as pereirago agent mass ratio with loading the reaction mixture is at least 1.5:1 when the tempo is the atur 15-25° With up to almost a full stop or quantitative spending just downloaded sodium sulfite, then stop stirring, the reaction mass is drained and used for a purpose.

The sulfonation take oxidate or their mixtures with conventional viscosity 33-75 s rheometer VZ-4 at 20°With flax, sunflower, soybean or cottonseed oils, mixtures of vegetable oils and pork or fish oil or fish oil individually, and the dosage of sodium sulfite is calculated on the basis of the loaded mass of oxidate or mixture of oxidation (current) and the average iodine number (IC)OKby the formula

and the sulfite is introduced into the bead mill was the first in the form of a previously prepared aqueous solution with the addition of the last of phenol in the amount of 2.5% by weight of oxidate or mixture of oxidation and water-soluble catalyst in water, after which the dose intended for the sulfonation oxidat. As a sodium soap, enter in the amount of 2.0% by weight taken on the sulfonation of oxidate use stearate or sodium oleate, or products virtually quantitative alkaline hydrolysis of fats and vegetable oils. Carboxylic acid represented benzoic, oxalic acid, malonic acid or lemon and put it in the amount of 4% by weight taken on self is the formation of oxidate after downloading the latest and soap. As for the water-soluble catalyst, then use a sulfate, acetate, and other water-soluble salts of copper (II) number (2-7,5)·10-4mol/(kg of total load)in which the mass to be processed sulfite sodium oxidat and water are in the ratio 1:4÷1:2,5.

Characteristics of the raw materials used

Flaxseed oil GOST 5791-81 and substandard without any restrictions on the source of the acid number and water content.

Sunflower oil inedible according to GOST 1129-81 and substandard without any restrictions on the initial acid number and water content.

Soybean oil substandard without any pre-cleaning and drying.

Cottonseed oil spec.

Technical fish oil 3thgrade according to GOST 1304-76 "Fats of fish and marine mammals technical and non-conforming without any restrictions on the initial acid number and water content.

Animal fat 3thgrade according to GOST 1045-73 "technical animal Fat".

Technical sodium sulfite according to GOST 5644-75 "sodium Sulfite anhydrous".

Stearate (oleate) sodium received direct interaction of stearic (oleic) acid and sodium hydroxide and transformation in practically anhydrous condition by removing moisture during thermal processing.

The hydrolysis of fats and rastitel the x oils were aqueous alkali at a temperature of 80-90° With intensive mechanical stirring until almost complete consumption calculated quantity of sodium hydroxide. The final reaction mixture to dehydration were not exposed. The water content was taken into account when determining the dosage of the product.

Benzoic acid6H5COOH according to GOST 6413-77

Citric acid, 1-water noos(HE)(CH2COOH)2·N2O according to GOST 3652-79

Malonic acid of NOESN2COOH under MRTU 6-09-397-63

Oxalic acid, 2-water H2With2O4·2H2O according to GOST 22180-76

Phenol With6H5HE GOST 23519-93

The water-soluble salts of metals:

Copper (II) nitrate, 3-water Cu(NO3)2·3H2O according to GOST 4168-79

Copper Duhlata, 2-water CuCl2·2H2O according to GOST 4167-74

Copper (II) sulfate, 5-water CuSO4·5H2About GOST 4165-78

Copper (II) acetate, 1-water (CH3Soo)2Cu·N2About GOST 5852-79

Oxidati vegetable oils and fish oils were obtained by liquid-phase oxidation with air in the bubble column type in intensive bubble mode sparging at 105±5°With control of the viscosity and the accumulation of peroxide, unsaturated, carbonyl compounds, acids and changes in viscosity. The resulting oxidate kept from 1 day up to 1-1,5 years and over, closed the flask in the absence of prolonged exposure to light. If necessary, they were mixed in any combination.

The process of deep sulfonation of oxidative or mixtures of oxidation by the claimed method consists in the following. In a ball mill, vertical type, outcrop in the atmosphere and the drain pipe with a grate to separate the beads from the reaction mixture, load in the form of pre-prepared solution of the calculated amount of water, sodium sulfite and water-soluble additives, i.e. phenol and salts of copper (II). Then enter oxidat or a mixture of oxidation, sodium soap and carboxylic acid. Include mechanical mixing and lead the process at the natural folding temperature in the range of 15-25°C. Inspection is carried out by the method of sampling and determination in them residual content of unsaturated compounds and sodium sulfite. As soon as the latter will cease to change or be less than 3% of the original quantity, the process is stopped, and the reaction mixture is poured into the container for later use.

Example 1

In a ball mill, vertical type, outcrop in the atmosphere, the drain pipe protected from beaded mesh with cell size 1×1 mm and containing 360 g of glass beads with a diameter of 1.9 to 3 mm, load 181,14 g of an aqueous solution containing 31,51 g anhydrous sulfite NAT the Oia, 1.13 g of phenol and 0,0114 g of copper sulfate (CuSO4·5H2O). After that, type 45 g oxidate linseed oil with a viscosity of 65 seconds on the OT-4 (20° (C) and iodine number of 116.7 g I2/100 g, 0.9 g of sodium stearate and of 1.80 g of benzoic acid. Total download was 228,84,

Close the charging port cover bead mill, include mechanical stirring (1560 rpm) and the time taken for the beginning of the process. The temperature at this point was 17°C. every 20-25 minutes during the process, take samples of the reaction mixture, give them standing to delaminate from the aqueous phase re-select the sample and determine its content of sodium sulfite by iodometric method. The remaining part of the initially selected sample return in the ball mill through its free release into the atmosphere. On the 120ththe minute residual content of sulphite was 2.3% of the original value, and the temperature at this point up to 24°C. At 125 rpm process stop, turn off the stirring, the reaction mixture is poured into the container for storage to the target using pre-determining the degree of sulfonation on the decrease of the content of unsaturated compounds in the system due to the conversion into the sodium salt of the sulphonic acids. In this case it was equal to 33.9%.

Examples 2-7

Installation for processing oxidate with what lipitor sodium, the boot order components, the sequence of operations when carrying out the process, monitoring and discharge of the reaction mixture similar to that described in example 1. Different nature and characteristics of oxidate used soap and carboxylic acids, the nature and content of water-soluble catalyst. In particular, use oxidat sunflower oil with a nominal viscosity of 69 seconds on the OT-4 at 20°and iodine number 98 g I2/100 g characteristics of the process are summarized in table 1. Legend: St - sodium stearate, Ol - sodium oleate, PSG - product of the alkaline hydrolysis of pork fat, PLA (MRP) is a product of the alkaline hydrolysis of linseed oil (sunflower) oil, Philippine Gad - product of the alkaline hydrolysis of fish oil; acid: B - benzoic, O - oxalic acid, M - Malone, L - lemon; salt of copper And acetate Cu(C2H3About2)2·N2Oh, N - nitrate Cu(NO2)2·3H2O - sulfate CuSO4·5H2Oh, X is chloride CuCl2·2H2O.

45,0 B
Table 1
FeaturesExample No.
download and process234567
Mass BMR, g37,544,360,048,050,0
weight of sodium sulfite, g22,0526,0526,4635,2828,9229,40
the mass of water, g150,0to 150.6KZT 166.5150,0182,4175,0
weight of phenol, g0,941,111,131,501,201,25
the mass of soap, g0,750,890,901,200,961,00
the mass of the acid, g1,501,771,802,401,922,00
The amount of catalyst(salts of copper (II)), mol/(kg of total load)7-10-45·10-46·10-44·10-42·10-43-10-4
The mass ratio of OPM: water1:41:3,41:3,71:2,51:3,81:3,5
Nature soapArticlePSGPPMPLAPhilippine GadOl
The nature of the carboxylic acidShchMLLB
Salt of copper (II)AndXN
Temperature, °
in the beginning of the process151617171815
at the time of termination222325242523
The content of sodium sulfite in the time of the termination process, % of original value1,42,33,14,12,74,8
The process duration, min132141128130118123
The achieved degree of sulfonation of unsaturated compounds, %41,338,737,4to 33.839,342,4

Examples 8-16

The installation for carrying out the sulfonation of unsaturated components oxidation, the boot order of the basic reagents, water and additives, as well as holding and mo is the same process similar to that described in example 1. Different nature of the used oxidate or mixture of oxidation, average iodine numbers associated with these adjustments in dosage. The data are summarized in table 2. Designation: SG, R j - pork, fish oil; LM, PM, SM, HM - flax, sunflower, soybean and cottonseed oil, ahead Of oxidat, for example OPM - oxidat sunflower oil; O(PM+SG) - oxidate mixture of sunflower oil and lard, etc.

The positive effect of the proposed solution is as follows.

1. Sulphonation, and deep subjected not only oxidati fish oil, but oxidati vegetable oils, and mixtures of vegetable oils and fats, mixtures of different oxidation.

2. Deep sulfonation commanded not only freshly prepared oxidaton, but oxidative obtained before carrying out this process.

3. Sulfonation is conducted and sodium sulfite, i.e. connection, more affordable and more stable than bisulphite, which must be obtained immediately prior to use.

4. Sulfonation of oxidative conducted at ambient temperatures, i.e. no cost involved in creating and maintaining the temperature.

5. In General, the complex characteristics of the proposed process of sulfonation is simpler, less energiek the m and leads to production of products, having a wider field of use.

1. The way to obtain sulfated oxidative vegetable oils, fats and their mixtures, characterized in that an aqueous solution containing sodium sulfite, phenol in the amount of 2.5% by weight of oxidate and the catalyst is a water-soluble salt of copper (II) number (2,0-7,5)·10-4mol/kg total load, are mixed with oxidation or a mixture of oxidation with conditional viscosity 33-75 seconds by the viscometer VZ-4 at 20°when the mass ratio of oxalate and water is 1:4-1:2,5, with the addition of sodium soap and a carboxylic acid in the amount of 2.0% and 4.0% respectively by weight of oxidate, the dosage of sodium sulfite are calculated according to the formula

where- weight of sodium sulfite,

mOK- weight of oxidate or mixture of oxidation,

(IC)OKaverage iodine number of oxidate or mixture of oxidation,

and the mixing is carried out in a bead mill, vertical type with glass beads as pereirago agent in its mass ratio to the loading of the reaction mixture is at least 1.5:1.0 at a temperature of 15-25°With up to almost complete deep sulphonation, then stop stirring, the reaction mass is drained and used for a purpose.

2. JV the property according to claim 1, characterized in that the sulfonation take oxidati flax, sunflower, soybean or cottonseed oils, mixtures of vegetable oils and pork or fish oil or fish oil individually.

3. The method according to claim 1, characterized in that as the sodium Soaps are used stearate or sodium oleate or products virtually quantitative alkaline hydrolysis of fats and vegetable oils.

4. The method according to claim 1, characterized in that carboxylic acids using benzoic, oxalic acid, malonic acid or citric acid.

5. The method according to claim 1, characterized in that as the water-soluble catalyst is used a water-soluble salt of copper (II), such as sulfate or copper acetate (II).



 

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