The method of selection of free bases of porphyrins from their mixtures with hydrocarbons and hetero-organic components

 

(57) Abstract:

Usage: as catalysts of oxidation-reduction processes, such as elektrovozstroitel oxygen. The inventive product: free base porphyrins, which are separated from their mixtures with hydrocarbons and hetero-organic components extraction from hexane-benzene solution at a volume ratio of hexane and benzene (2 - 4) : 1 polyfluorinated alcohol, such as 5-hydro-2,3,4,5-octadecenyl-1. The degree of extraction of porphyrins 88,6%. table 1.

The invention relates to the refining, namely the production and purification of the free bases of petroleum porphyrins complexes with cobalt and iron, as well as the products of their thermal modification can find application as catalysts of oxidation-reduction processes, such as oxygen reduction [1]-[4]

Oil and products of its processing, a mixture of hydrocarbons and hetero-organic components contain only the metal complexes of porphyrins, in particular vandrove and Nickel. Therefore, the stage of allocation of free bases of porphyrins is preceded by a stage of acid demais oil mixture is chromatography or extraction methods.

There is a method of allocation of free bases of porphyrins from their mixtures with hydrocarbons and hetero-organic components, in particular of the products of acid demetilirovania oils or oil fractions, extraction of 50% aqueous solution of acetic acid from benzene or toluene solution [5] the Disadvantage of this method is the low degree of extraction of porphyrins.

The closest in technical essence to the proposed method is a method of allocation of free bases of porphyrins from their mixtures with hydrocarbons and hetero-organic components, in particular of the products of acid demetilirovania oils or oil fractions, extraction of 97% formic acid from benzene or toluene solution [6] the Disadvantage of this method is the low degree of extraction of porphyrins.

The aim of the invention is to increase the degree of extraction of porphyrins from the extracted object.

This is achieved by extraction of the free base of the porphyrins is from hexane-benzene solution acidic products of demetilirovania oils or oil fractions with a volume ratio of hexane and benzene from 2:1 to 4:1, and in quality is 1. The product acid demetilirovania petroleum fractions. 20 g dimethylformamide (DMF) extract the oil are thoroughly mixed at constant temperature (20-25aboutWith the heat) with an equal weight amount of 98% sulfuric acid for 2 h, the Reaction mixture is poured onto 100 g of ice, the acid is neutralized with 40 g of a 40% aqueous solution of sodium hydroxide, the products demetilirovania extracted in chloroform, treated sequentially with 8% aqueous solution of sodium acetate, water, the chloroform layer is dried over anhydrous sodium sulfate, the solvent is removed in vacuum. Received 19,000 g of a viscous dark brown mass. The content of free bases of porphyrins in the resulting product is determined by the spectrophotometric method according to the intensity of the absorption band in the region of 400 nm, of 0.41 wt.

P R I m m e R 2 (prototype). 1,0785 g of the product of demetilirovania DMF-extract diluted with 30 cm3benzene and extracted with vigorous stirring 30 cm397% formic acid. The time of extraction 0.5 hours the Acid layer is separated, the acid is distilled off, the extract was transferred to chloroform, treated sequentially with 8% aqueous solution of sodium acetate, water, the chloroform layer is dried over beanie free bases of porphyrins in the extract, specific spectrophotometric method according to the intensity of the absorption band in the region of 400 nm, 0,867 wt. The degree of extraction of porphyrins 19,0%

P R I m e R 3. 1,0000 g of the product of demetilirovania DMF-extract dissolved in 30 cm3the hexane-benzene mixture (volume ratio of hexane and benzene 4:1). Obtained solution is extracted with vigorous stirring 30 cm35-hydro-2,3,4,5-octadecenyl-1. The time of extraction 0.5 hours Alcohol layer was separated, the solvent is distilled off, the extract was transferred to chloroform, treated sequentially with 8% aqueous solution of sodium acetate, water, the chloroform layer is dried over anhydrous sodium sulfate, the solvent is removed in vacuum. Is received 0,1447 g (14,47%) of a viscous brown mass. The content of free bases of porphyrins in the extract was determined by the spectrophotometric method according to the intensity of the absorption band in the region of 400 nm, of 2.51 wt. The degree of extraction of porphyrins 88,6% of the Data for different volume ratios of hexane and benzene in the original solution in the range of 2:1-4:1 presented in the table.

P R I m e R 4. 1,0000 g of the product of demetilirovania DMF-extract dissolved in 30 cm3the hexane-benzene mixture (volume ratio of hexane and benzylfentanyl-1. The time of extraction at each step of 0.5 h, the Extracts are separated and treated as in example 3. Analogously to example 3 determine the content of free bases of porphyrins in each extract and the degree of extraction at each step in relation to the original object. The results, as well as data on the total extract is given in the table.

As can be seen from the table, when using the proposed method, the degree of extraction of the free base of porphyrins increases in comparison with the known method of 4.38-4,66 times. This is achieved by using as the extractant 5-hydro-2,3,4,5-octadecenyl-1. Using more than two stages of extraction is impractical as it does not lead to a significant increase in the degree of extraction of porphyrins. At the same time it increases the consumption of reagents and the total duration of the allocation process.

Reducing the volume ratio of hexane and benzene is less than 2:1 is undesirable because in this case there is no phase separation of the extractant and the extracted solution. The increase in volume ratio of hexane and benzene than 4: 1 is undesirable because it leads to the formation of heterogeneous phase resin-aspalathin GROUNDS of PORPHYRINS FROM THEIR MIXTURES WITH HYDROCARBONS AND hetero-organic COMPONENTS by dilution of the mixture with hydrocarbons, extraction with organic solvents having acid properties, characterized in that the dilution carried out with a mixture of hexane and benzene in their volumetric ratio (2 4) 1, and extraction was carried out polyfluorinated alcohol, such as 5-hydro-2,3,4,5-octadecenyl-1.

 

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