T. MUNIYAPPAN University of Illinois, Urbana, Illinois
PoRmwRms are nitrogen-containing pigments of biological origin and are intimately related to the ironcontaining hemoglobin in the blood of animals and the magnesium-containing chlorophyll in the leaves of plants. Porphyrins can be considered to have been derived from the parent substance called porphin which has the heterocyclic strncture of four pyrrole nuclei united by four methine (-CH=) groups (Figure 1). Imido porphins containing -N= groups instead of -CH= groups have been synthesized. Porphyrins encountered in the plant and animal kingdoms are derivable from porphin by the substitution of various groups like methyl, ethyl, vinyl, carboxylic, for the hydrogen atoms of pyrrole nuclei. They are probably flat molecules in which a slight oscillation of the metal will cause a rhythmic shift of all double bonds, making it a dynamic molecule. Usually metal atoms like Fe, Mg, Cn, Ni, V, are held between the four nitrogen atoms of the four pyrrole nuclei of the porphyrin molecule. The porphyrin structure is stable. The occurrence of porphyrins in coal, bitumen, shale oils, petroleum, etc., is quoted as evidence in support of their organic origin. Porpbyrins combine with many proteins and form complexes with metals. These porphyrin metal complexes play very vital roles in the living cell as respiratory pigments (hemoglobin), oxidation catalysts, photosynthetic agents (chlorophyll), etc. They are very widely distributed in nature (1,9,3). Porphyrins are crystallizable and deeply colored substances; their color depends on the nature of the solvent, concentration, and the pH value of the solution. In general, porphyrin solutions are brownish-red in alkalies, red in neutral solvents, and purplish-red in acids. These color changes are closely linked with alterations occurring in the structures. They are freely soluble in many organic solvents like pyridine and petroleum. Porphyrins exhibit a great tendency to form colloidal dispersions in electrolyte-free media; they have well marked absorption spectra in the visible region; they have intense red fluorescence in ultraviolet light, and act as photosensitisers. Adsorption chromatography is ideally suitable for the separation and identification of porphyrins. DISCOVERY AND ROLE O f PORPHYRINS IN PETROLEUM
In 1934, Triebs reported the discovery of the presence of porphyrins in petroleum (A, 6). Later Skinner, and Moore and his co-workers (6, 7) identified vanadiumand nickel-porphyrin complexes in petroleum. Of the many substances possessing interfacial activity and film-forming tendency so far isolated from petro-
leum, like naphthenic acids, mercaptans, thiophene, and quinoline derivatives, the metal-porphyrin complexes are among the major contributors to the interfacial activity and film-forming tendency exhibited. The discovery of the porphyrins in petroleum is a significant milestone in the study of the origin of petroleum. Skinner isolated a vanadium-porpbyrin complex from Santa Maria Valley crude oil and found it to be interfacially active and film forming at a benzene water interface. Moore, et al., (6, 7, 8) have obtained nickel-porphyrin complexes and a smaller amount of the vanadium complex from a California crude oil and have correlated the film-forming tendency of the crude oil with the presence of metal-porphyrin complexes. These remnants of chlorophyll and hematin in petroleum are proving to have great practical interest in several aspects of the petroleum industry. Because of their surface-active and film-forming properties, they affect the wettability of petroleum reservoir snrfaces and thus influence the flow of liquids in these reservoirs. They may indicate the source beds of petroleum and petroleum migration from the studies of trace elements and porphyrins. Because many of these metal-porphyrin complexes are extremely stable, they introduce complications in the analysis of core samples and in the formation of stock tank emulsions in the field. Further, the porphyrin complexes came the poisoning of the catalysts employed for cracking petroleum-and are carried over into certain relined petroleum
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JOURNAL OF CHEMICAL EDUCATION
of relatively polar and nonpolar porphyrins by the pentane extraction (7). Further, the pentaneinsoluble portion of the waterspray extract hss been successively extracted with hexane, isooctane, cyclohexane, and benzene, and their spectra have been studied. The spectra of the alcoholic extracts of pentane-soluble and pentane-insoluble portions indicated the presence of metal-porphyrin complexes.
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PURIFICATION OF PORPHYRINS
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Recently Groennings has devised a method whereby porphyrin aggregates in petroleum can be determined. He extracted them into hydrogen bromide in glacial acetic acid and then transferred them to chloroform before transmittance was measured a t the two characteristic wavelengths of 5000 and 5300 A. (9). Kennedy has devised a special apparatus for the fractional separation of eluates in the chromatographic separation and identification of porphyrins (10). Also, quite recently Kennard and Rimington have obtained methyl esters of carefully purified porphyrins by chromatographic techniques. They have classified and identified porphyrins by X-ray diffraction studies (11).
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products where their presence is undesirable or ABSORPTION SPECTRA i produce harmful effects tively harmful. ~ h e thus The absorption spectra of porphyrin aggregates in the processing and utilization of petroleum (6, 7, 8). found in petroleum are characterized by four major EXTRACTION OF PORPHYRINS FROM CRUDE maxima in the visible region. . The etio-porphyrin and PETROLEUM phyllo-porphyrin spectra are of interest in studying The scheme of extraotiou of the s u r f a c ~ c t i v eand porphyrins from petroleum. It must be clearly underfilm-forming substances containing porphyrins, por- stood that even though the porphyrins prepared from phyrin-metal complexes, oxidized porphyrin rings, and chlorophyll have spectra of the phyllc-type and those their metal complexes and protein-metal complexes, prepared from hemoglobin commonly have spectra of etc., is indicated in the diagram. Water-spray extrac- the etic-type, there are a few exceptions to this gention is used a t first to concentrate the porphyrin-con- eralization-the root nodules may contain hemoglobin taining substances from crude petroleum oils. Pen- and thus give rise to spec& of the etio-type. Calculatane extraction of the aqueous extract has been found tion based on this concept showed that there is about to he very effective in the separation of surface-active two and a half times more plant porphyrin (phyllo-type) substances and those containing nitrogen, nickel, vana- than animal porphyrin (etio-type) . in the porphyrin dium, and porphyrins. There is considerable dif- aggregate from crude oil (8). Thus we get not only ference between the interfacial activities of the por- an idea about the organic origin of petroleum but also phyrin aggregates from pentane-soluble and pentane- we can visualize the proportionate plant or animal insoluble extracts and this indicates a good separation origin of a sample of petroleum. Crude oil
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MAY, 1955 THE INFRARED SPECTRA OF PORPHYRIN
The infrared spectra of porphyrin aggregates from the whole crude oil, pentane-soluble, and pentaneinsoluble extracts show an absorption peak a t 5.8 microns. This is tentatively thought to he due t o the carbonyl radical (Figure 3). The spectra of other extracts do not show this 5.8-micron absorption peak hut show other peaks a t 3.5, 6.9, 7.3, etc. Probably this indicates that porphyrins having a carboxyl group like phyllo-porphyrin (Figure 3) are extracted from the crude oil by the water-spray process rather selectively. This has been verified by experiments.
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ACIDITY AND INTERFACIAL ACTIVITY OF PORPHYRINS
The acidity of the porphyrin aggregates from the whole crude oil indicated a considerable content of interfacially active porphyrins. Since much of the interfacial activity of the porphyrins is due to their porphyrin having carboxylic-acid side no chains carboxyl(Figures group would 2 andnot 3),beetioexpected to be very active interfacially. But in a complexed form or in case the porphyrin molecules are verticallv orientated a t the interface. attractions between metailic constituents may stabilize the film (8). . .
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surface- and film-forming activity of t h e petroleum largely result from the presence of these complexes. The study throws light on the probable origin of Microchemical analysis of crude-petroleum samples has The study of porphyrins in reveals the presence of Zn, Cu, Ni, Ti, Mg, V, Fe, etc. stimulated the interests of petroleum engineers, chemThev are ~robablv resent as oil-soluble com~ounds. ists., and those concerned with bioloev. -" , surface active possibly as porphyrin-metal chelates or complexes with substances, film-forming agents, etc. This is one more nitrogen-containing compounds. The film-forming esample to show how the discovery and solution of fractions of petroleum appear to consist of proteins, problems in a, particular field prove to be of great theowaxes, and resins stabilized by orientated porphyrin retical and practical value to workers in diverse fields. rings, and the surface-active fractions may contain free porphyrins, porphyrin-metal complexes, oxidized por- ACKNOWLEDGMENT phyrin rings and their metal complexes, and proteinThe author is grateful and thankful to Professors . metal complexes (6). John C. Bailar and Therald Moellei, University of The pentane-insoluble portion of the waterspray Illinois, Urbana, for helpful suggestions and advice in extract of crude petroleum was successively extracted the preparation of this manuscript. with various organic solvents as indicated in Figure 3. The fihal extract gave a major absorption peak at 550 LITERATURE CITED mp and a weak absorption band a t 510 mp, and these 11) KIRK.R. E.. AND D. F. OTHMER."Encvclo~ediaof Chemical indicate the presence of nickel-porphyrin complex (8). Moore, et al., actually synthesized a nickel-porphyrin complex from the porphyrin aggregates isolated from Longmans, Green and Co., 1 ~etroleumand nickel acetate. The absorption maxi129. mum of this synthetic product and thai from the natural extract are identical, ~h~~ the (3) GRANT,"Hack's Chemicd Dictionary," 3rd ed., Blakiston Co., Philadelphia, 1950, p. 674. presence of nickel-porphyrin chelate in petroleum has (4) T ~A., A ~~ ~ . ~.. 42 (1934). , . ~ . ~ been established (7). (5j ibid., 5'17, '172 (i935). AND M. 0. DENEUS, Ind. Enq. The final extract also gave a weaker peak a t 570 mp (6) DODD,C. G., J. W. MOORE, Chem., 44, 2585 (1952). and a weak absorption hand a t 530 mr; these are caused 45, 1759 (1953), ,) the presence of vanadium-porphyrin complexes (8). ((8j H. N., J. W. MooRE, AND A. T. M m ~ s ibid., , SPECTROSCOPIC EVIDENCE FOR PORPHYRINMETAL COMPLEXES
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CONCLUSION
Thus, crude petroleum has been found to contain nickel- and vanadium-porphyrin complexes, and the
46, 2000 (1954). (9) GROENNINOS, SIQWD,Anal. Chem., 25, 938 (1953). (10) KENNEDY, SCAND, J. Clin. Invest., 5, 201 (1953). (11) KENNARD RMNQToN, Bimhm. J. (London), 55, 105 (1953j.
