The method of obtaining esters of fatty acids

 

(57) Abstract:

The invention relates to a method for producing esters of fatty acids lower monohydroxy n-alcohols by transesterification of glycerides of fatty acids in the presence of basic catalysts. After carried out the transesterification of the ester phase is washed with glycerine, crude glycerine or glycerin phase of the previous stage interesterification, completely separated from the last glycerin phase and process of bleaching clay, silicic acid, or other physico-chemical like substances. The method allows of unrefined natural oils without the rinsing process with water and without the use of aqueous acid to neutralize the catalyst in the ester phase to get a quality product. 2 C.p. f-crystals.

The present invention relates to a method for producing esters of fatty acids lower monohydroxy n-alcohols with 1-4 c atoms by interesterification glycerine fatty acids with the corresponding alcohols in the presence of basic catalysts under very special conditions.

To use the thus obtained esters of fatty acids as raw materials, about the quality, which cause the need for suitable technologies for obtaining and purifying.

The receipt of such esters of fatty acids has been known for a long time and on an industrial scale is catalyzed by bases interesterification glycerine fatty acids with lower monohydroxy alcohols under different reaction conditions [with the description of the invention to unaccepted application for patent in Germany NN 3 020 612, 3 421 217, 3 932 514, 3 727 981 , European patent 0 391 485, WIPO 92/00 268]. To achieve high degrees of conversion it is necessary to carry out the reaction in two or more stages, depending on the circumstances, to use the optimal ratio of components of the reaction to each other and continuously removed from the reaction equilibrium by-product of the reaction is glycerol. Further, it is known that as initial products for the reaction of preterition you can apply refined and unrefined oils and fats of natural origin, as well as the native waste oils, which differ in their content of free fatty acids and therefore require different amounts of catalyst. A significant part of the known methods is the purification of esters of fatty acids to score the AI required for full interesterification excess alcohol should be considered as one.

Significant disadvantages of the known methods consists in the purification by distillation in a high energy cost, and expensive technical equipment, and applying water to remove residual glycerol, Soaps, catalyst, excess alcohol and other water soluble products in education and primary processing loaded above products wastewater process respectively diluted with water glycerin phase. When using purified natural oils and fats in the process of interesterification loaded with organic substances leaching water and process are formed in the refining.

Therefore, the objective of the invention is to develop a method, which avoids the mentioned disadvantages and which enables the production of esters of fatty acids corresponding to the established norm of quality of triglycerides without the use of wash water and water process.

Unexpectedly been found that the disadvantages of the known methods can be avoided when glycerides of fatty acids enter into cooperation with the lower monohydroxy n-alcohol with 1-4 C-atoms in a molar ratio of 1:3 -1:6, in particular 1:3.5 to 1:5, in the presence of a catalyst is a number from 0.01 to 0.05 mol, in particular between 0.02 and 0.035 mol, per 100 g used glycerides of fatty acids, including the amount of alkali metal hydroxide, which is equivalent contained in the glycerides of fatty acids acidic components, at temperatures from room temperature up to 70oC, in particular at 40 - 60oC, at least for the two-stage method interesterification, carried out after interesterification phase of ester of fatty acid to remove any remaining impurities and to provide a better separation of the phases are washed with glycerine, crude glycerine from the processing of glycerol or glycerin phase from the previous phase interesterification, and then treated with bleaching clay, silicic acid or other physico-chemically similar substances in quantities of 1 to 5%, especially 1.5 to 3%, based on the used glycerides of fatty acids. The number used for washing of glycerol depends on the amount remaining in the ester phase contaminants, particularly dissolved glycerol, residual catalyst, Soaps, excessive alcohol and other substances, which reduce the weight of eye-catching heavier glycerin phase, and from the purity and density of the used washing was glycemically density [specific gravity] of 1.03 g/cm3[20oC] in the case of detachable glycerin phase. The washing process can be performed under stirring using a conventional for this purpose, technological systems implemented after interesterification and before or after separation of the last glycerin phase in multi-phase ways of working, with, however, there is no need to separate the last glycerin phase before the addition of the leaching glycerin.

In contrast to the known methods, in which the problematic separation of one last glycerin phase or together with the washing water due to the large time for phase separation or the formation of emulsions, the invention method comes good effect flushing and cleaning of the ester phase, however, does not face any problems during the separation of the phases, and the ester phase already after a short time has can be separated, allowing significantly improves the output in time and volume. In addition, not formed any Laden with impurities of waste water or diluted with water, glycerin phase. Unexpectedly due to leaching by glycerol does not slow down the establishment of the reaction equilibrium reaction praeteritio is more severe glycerin phase, if necessary, you can even speed up or improve through the use of coalescence separator or separator.

Another disadvantage of known methods is the use of aqueous organic or inorganic acids, acid salts or ion to neutralize the alkalinity of the ester phase. However, of the remaining salts of fatty acids are liberated acid, which leads to increased acid number of the target product, because free fatty acids are best dissolved in the ester phase than in the aqueous glycerol phase.

The invention method, the residual alkalinity of the ester phase is removed by treatment with bleaching clay, silicic acid or other physico-chemically similar substances. For this purpose ester phase is treated with such substances, in the amount of 1-5%, especially 1.5 to 3% per used glycerides of fatty acids, when the process temperature. This process is not identical to known processing bleaching clay in the refining of vegetable oils. Processing can be performed alone or in combination with removal of volatile components from the ester phase. Branch Laden with impurities of bleaching clay from the ester phase is carried out by filtering off or centrifuger who has the advantage what with it are also deleted other remaining in the ester phase hydrophilic contamination /impurities/, as, for example, glycerin, glycerides or oil-soluble contained in plant matter. When using crude glycerides of fatty acids or native waste oil as raw material for the process of interesterification this stage of the method is a great advantage and leads to good quality parameters of the target product, and in particular in the case of native waste oils with special stains can be used for cleaning special sorbents.

The invention is illustrated by the following examples.

Example 1. 4.5 g of potassium Hydroxide dissolved 47.5 g of methanol and 55 ml of this solution, with stirring and at room temperature, is added to 300 g of the crude rapeseed oil [acid number = 1,2]. Then heated to 60oC and stirred for 30 minutes at this temperature. An hour later separated heavy glycerin phase [46 ml, density = 1.85 g/cm3/20oC/]. To the ester phase, add the remaining quantity /7 ml methanolic solution of potassium hydroxide. The mixture is stirred for 30 minutes at 40oC, then mixed with 10 ml of untreated glits is completely separated [20 ml, density = 1,127 g/cm3(20oC)]. After treatment with 6 g of bleaching clay at the process temperature and the simultaneous removal of volatile components obtained after the extraction of the loaded pollution bleaching clay 270 g of light yellow sub-standard complex methyl ester of rapeseed oil [glycerides of < 0.1% of free glycerol < 0,001%, acid number 0 = 0,23, pH = 5, pH-value is measured in the aqueous phase obtained by extraction by shaking complicated methyl ester, rapeseed oil with an equal volume of distilled water].

Example 2. The reaction is carried out analogously to example 1 when using 6 g of the silicic acid for processing when the process temperature and the simultaneous removal of volatile components. Get 265 g corresponding to the established norm complicated methyl ester of rapeseed [glycerides of < 0.1% of free glycerol < 0,01% , acid number= 0,15, pH = 5,8].

Example 3. The reaction is carried out analogously to example 1 with the use of 20 ml of glycerin phase from the first stage of esterification [density = 1,075 g/cm3at 20oC] as the washing medium. Receive 30 ml of the second glycerol ester of rapeseed [glycerides of < 0.1% of free glycerol < 0,001% acid number = 0,25 pH = 5,4.]

Example 4. The reaction is carried out analogously to example 3 when using mitterolang waste oil [acid number = 1,8] as the original product and 5.2 g of potassium hydroxide. The first glycerin phase: 49 ml, density = 1,057 g/cm3at 20oC. a Second glycerol phase: 30,5 ml, density = 1,030 g/cm3at 20oC. methyl ester waste oil: 262 g glycerides of < 0.2% of free glycerol < 0,01%, acid number = 0,4, pH = 5,8.

Example 5. to 0.72 g of Sodium are dissolved in 22 g of ethanol [96%] and 85% of this solution, with stirring and at room temperature, is added to 100 g of refined rapeseed oil. Then heated to 45°C. and stirred for 30 minutes at this temperature. The mixture is left to stand over night and the heavy phase is separated by centrifugation [ for better separation of the phases can already the reaction mixture of the first stage of the transesterification process glycerol]. To the ester phase, add the remaining quantity of a solution of sodium alcoholate. The mixture is stirred for 30 minutes at 40oC, then mixed with 5 ml of glycerin, mix the next 20 minutes and completely OTDELA is one methyl ester of rapeseed oil [glycerides of < 0.1% of free glycerol < 0,001 %, acid number = 0,18. pH=5,9.]

Example 6. The reaction is carried out analogously to example 5 with the application of 25 g of n-propanol and the reaction time is 4 hours at 70oC. Obtain 62 g of complex n-propyl ester of rapeseed oil [glycerides of < 0.1% of free glycerol < 0,001%, acid number = 0,18. pH = 5,9.

Example 7. The reaction is carried out analogously to example 5, using 31 g of n-butanol and the reaction time is 4 hours at 70oC. Obtain 82 g of a complex n-butyl ester of rapeseed oil [glycerides of < 0.15% of free glycerol < 0,001%, acid number = 0,21, pH= 6,1.]

1. The method of obtaining esters of fatty acids lower monohydroxy n-alcohols with C1- C4atoms by interesterification of glycerides of fatty acids with lower alcohols in the presence of a basic catalyst, followed by washing the obtained ester phase, characterized in that the transesterification is conducted by the two-stage method with a molar ratio of acid and alcohol from 1 : 3 to 1 : 6, at a temperature of 70oC and washing is carried out, either glycerol or crude glycerol, or glycerin phase of the previous stage glycerin phase and process of bleaching clay or silicic acid or other bleaching agents with similar physico-chemical characteristics, taken in quantities of 1 to 5 wt.% the calculation used the glycerides of the fatty acid.

2. The method according to p. 1, characterized in that the additive leaching of glycerol is carried out before the separation of the glycerin phase.

3. The method according to p. 1, wherein the process is carried out at a temperature of 40 - 60oC, molar ratio of acid: alcohol of 1 : 3.5 to 1 : 5 and bleaching agents are used in amounts of 1.5 to 3 wt.% the calculation used the glycerides of the fatty acid.

 

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