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Metallopetroporphyrins as Process Indicators: Separation of Petroporphyrins in Green River Oil Shale Pyrolysis Products A. K. Lee A. M. Murray J. G. Reynolds

This paper was prepared for submittal to Fuel Science and Technology International

November 1994

Thisisa preprint ofapaperintended forpublicafionina journalorproceedings. Since changes may b~ madebefore publication, this preprint is madeavailable with the understandingthat it will not be cited or reproduced without the permission of the author.

DISCLAIMER This documentwas prepared as an account of work sponsored by an agency of the United States Government.Neither the United States Government nor the University of California nor any of their employees,makesany warranty, express or implied, or assumesany legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use wouldnot infringe privately owned rights. Referenceherein to any specific commercial product, process, or service by trade name,trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or the University of California, and shall not be used for advertising or product endorsementpurposes.

METALLOPETROPORPHYRINS AS PROCESS INDICATORS: SEPARATION OF PETROPORPHYRINS IN GREEN RIVER OIL SHALE PYROLYSIS PRODUCTS

Albert K. Lee, Ann M. Murray, and John G. Reynolds*

University of California Lawrence Livermore National Laboratory Livermore, California 94551

ABSTRACT Product oils from the LLNLHot-Recycled-Solids (HRS) retorting process were separated to isolate and concentrate the metallopetroporphyrins. A modified column chromatography procedure developed previously for heavy crude oils and tar sand bitumens was used. The fractions were then examined by UV-vis spectroscopy to determine categories of porphyrins and other related metal-containing species. No porphyrins were found in the hexane fraction (least polar fraction); Ni porphyrins were found in the methylene chloride fraction (moderate polar fraction); and a free-base porphyrin-like species was found in the methanol fraction (the most polar fraction) of some of the oils. The CH2C12fractions were further examined to quantify the amount of porphyrins detected. In the whole oil samples examined, ~ 40 wt % of the Ni was found as Ni petroporphyrins. The vacuum

residua of two product oils had - 20 wt % of the Ni bound as Ni porphyrins indicating that the vacuum distillation process destroys porphyrins. INTRODUCTION Petroporphyrins have been studied in geochemistry for years, both for structural characterization and application as geochemical maturation parameters [Yen (1975), Filby and Branthaver (1987)]. The temperature but long reaction times found in source rocks and formations are thought to be sufficient conditions to generate metallopetroporphyrins from precursors in the kerogen. These porphyrins encompass a wide variety of structures and isomers. Although not universally agreed upon, maturation appears to generate DPEP porphyrins and etio porphyrins at different rates and expulsion times, convert DPEPporphyrins to etio porphyrins through cleavage of the isocyclic ring, and decompose DPEP porphyrins faster than etio porphyrins [Barwise and Park (1983), Louda and Baker (1981), MacKenzie et (1980), Barwise (1987), Corwin (1960), Didyk et al. (1975), Barwise Roberts (1984), Sundararaman et al. (1988)]. These structural differences, interconversions, and decompositions are though to be controlled by specific diagenesis conditions, and this control allows the petroporphyrins to be related to maturation conditions on the geological time frame, i.e. to be biomarkers.

Studies have been performed on the behavior of petroporphyrins under processing conditions [Rankel and Rollman (1983), Rankel (1981), Reynolds and Biggs (1986), Reynolds et al. (1987)] but none utilized petroporphyrins as process severity indicators. Pyrolysis of oil shale will liberate petroporphyrins from the kerogen structure [Morandi and Jensen (1966), Sundararaman et al. (1988), Van Berkel and Filby (1987)]. In oil shale retorting, the high temperature and short reaction times should produce petroporphyrins having a variety of structures and substitutions. Paralleling the use of petroporphyrins as maturation parameters, perhaps these pyrolysis-generated petroporphyrins can be used to reflect the chemistry and severity of retorting

process conditions, through distribution DPEP/etio ratio, types of homologous series,

of homologous series, and other properties.

We have been developing the use of petroporphyrins as process indicators in oil shale processing. Because of the relatively low concentrations of Ni and V in the product shale oils, we needed to develop further purification methods. This report summarizes the results from separation and isolation of metallopetroporphyrins by column chromatography and UV-vis spectroscopy. EXPERIMENTAL Because petroporphyrins are light sensitive when isolated, the

porphyrin fractions were wrapped in aluminum foil, and hood lights were kept off during the separations and handling of the separated materials. Solvents and Chemicals. Hexanes, CH2C12, and methanol (MeOH) were purchased as chromatography grade from Burdick and Jackson Brand, and used as received. Ethyl acetate was purchased from Baker. Alumina, Bockman Grade II & III, was purchased from Allied Signal Corp. Macroporous silica was Marix brand (Amicon Corp., Danvers MA)and was 250~ porosity with 35 to 70 micron particle size. Ni etioporphyrin (etio) was purchased from Midcentury (IL). We had no standard for Ni deoxophylloerythroetio (DPEP). Samples. Shale oil was generated by the LLNLHRS process from selected retort runs and used directly without pretreatment [Cena and Thorsness (1992)]. Separations. The general separation scheme used for the oils was Chemicals porphyrin

an adaptation of a column separation method used previously for the separation of vanadyl petroporphyrins from heavy crude oils and tar sand bitumens [Reynolds et al. (1989)]. The separation was designed remove hydrocarbons into a non-polar fraction by elution with hex-

anes/diethyl ether (Et20), concentrate the normal Ni and V petroporphyrins into a polar fraction by elution with methylene chloride (CH2C12), and isolate acidic or polar petroporphyrins into a very polar fraction by elution with MeOH.Modification to this procedure had to be made to accommodate different properties of shale oils. Shale oils are generally known to have much lower concentrations of Ni and V (10 ppm is average) and to have potentially different metals in the porphyrin ring (for example, Fe). Shale oils are also thermally produced and generally are more polar and less stable than heavy crude oils and tar sand bitumens. The high N content of shale oil (N 2 wt %, N i wt basic N) also affects the chromatography. Initial separations showed that over one-half of the Ni porphyrins were separated into the non-polar fraction when using hexanes/Et)_O as the elution solvent. Switching to 100% hexanes as the first elution solvent solved this problem. Approximately 100 g of alumina were packed in an approximately 1-in diameter chromatography column using hexanes as the packing solvent. Approximately 0.5 g of shale oil was mixed with equal amounts or more of sand or alumina to give a loosely paste-like material. This coated mixture was placed on top of the packed column. Approximately 1 to 1.5 in of quartz sand were placed on top of this layer to inhibit mixing. The column was then eluted with the following solvents: 100% hexanes, 100% CH2C12, and 100% MeOH. The amounts of solvents used varied for each separation, but were usually around 500 to 1000 ml for each fraction. The solvents were removed by blowing N2. The residual material was recovered for closure. Some samples took several days of drying in vacuo to reach a constant weight, especially the hydrocarbon fractions. For the silica separations, the dried, isolated fraction front the alumina column separation above (usually the CH2C12fraction) was dissolved in approximately 0.5 to 1 ml of CH2C12. This solution was loaded onto a column of macroporous silica prepared from ~ 20 g of silica slurried in a minimum amount of hexanes. The normal metal-

lopetroporphyrins were eluted with about 150 ml of CH2C12,the acidic metallopetroporphyrins were eluted with approximately 200 ml of ethyl acetate, and the residual material was collected with - 100 ml of MeOH. .Detection. The fractions were examined for porphyrin content by UV-vis and second derivative UV-vis spectroscopy utilizing an HP 8452A diode array system. The spectra were collected as zero order using maximumintegration time. Second derivative spectra were calculated after averaging. The entire fraction was dissolved in either CH2C12 or 50% CH2C12/50% MeOH (for methanol fraction). The amount of solvent was determined by diluting the sample so the spectral region above than 380 nm was on scale. This ranged from 25 to 100 ml in most cases. From previous work [Reynolds et al. (1989)], the and 13 bands of Nietio porphyrins are known to be at 514 and 550 nm, respectively, while for vanadyl etio porphyrins are know to be at 534 and 574 nm, respectively. The Soret bands are at 390 nm for Nietio porphyrin and 408 nm for VOetio porphyrin. In the results presented here, etio and DPEPporphyrins are lumped together. Quantitation. The petroporphyrin concentrations were calculated using Beers law, A" = e"CZ [Freeman and OHaver (1990)], where A" the 2nd derivative absorbance, e" is the 2nd derivative extinction coefficient, C in molar concentration of the absorbing species, and Z is cell path length, e" was obtained from calibration curves derived from measurement on dilute concentrations. solutions of pure Nietio porphyrin at different

RESULTS Pyrolysis Process. The HRSretorting process converts kerogen in

selected oil shales (in particular, Green River oil shale) to liquid fuels while burning residual carbon to produce energy to drive the process [Cena and Thorsness (1992)]. Figure 1 shows a schematic of the process. The raw shale enters the process and is mixed with hot combusted

Delayed-Fall

::;:..t c
Spent ~FlueGas ~ ~.,~.#~,~~ (~mbustor

~
Raw

--~- AIr/N 2

Feed Packed-Bed Pyrolyzer

Pneumatic Lift Pipe

Figure 1. Schematic of the Hot-Recycled-Solids Oil Shale Retorting Process at Lawrence Livermore National Laboratory. shale. The heat transferred from the spent shale provides energy to pyrolyze the fresh shale, producing product oil and gases which, because of the counter current gas flow, exit at the top of the fluid-bed mixer. The spent shale goes through a gas block at the bottom of the pyrolyzer, and enters the combustion system at the bottom of the lift pipe. The combustion is controlled by composition of the injection gas. Combustion continues through the delayed-fall combustor and the fluid-bed combustor. The combusted shale then goes through another gas block and is either sent to the spent-shale hopper, or is recycled back

with incoming raw shale. The pyrolyzer typically operates between 475 to 550C, where the purge gas is usually N2 at slightly above ambient pressure, with a gas residence time of approximately 10 sec. The combustors typically operate between 600 and 800C, where the carrier gas varies between pure air and mixtures of air and N2. Table I Metals Analyses (ppm) of Selected Shale Oils (Water and Ash Free) by ICP-AES Oil C D E F G J L Q C 1000F + D 1000F + Ni 16.4 13.1 10.8 9.3 9.0 9.4 5.7 13.3 85.8 63.4 V 1.8 2.1 1.6 2.1 1.8 1.0 <0.7 !.9 10.7 8.2 Fe 340 500 112 288 288 125 61.5 282 1769 2097 Ca 4.4 1t5 62 38 18.0 1.8 12.2 1.0 0.2 59.6 Mg 5.8 45 89 3.1 4.2 7.9 8.3 1.5 <0.2 53.8 A1 5.6 17.5 2.2 <1.0 1.4 <1.0 11.9 0.5 <0.2 7.3

Metals Analyses. Several oils were selected for the separation studies. Selected metal analyses are shown in Table 1. These runs were selected because of smooth operation of the retort as well as additional characterization of the oils [Coburn et al. (1994)]. All analyses were done on water and ash free samples. Ni levels vary as low a N 5 ppm + residua for oil L (a condensate) to over 16 ppm for oil C. Both 1000F show significantly higher concentrations indicating most of the Ni is concentrated into the non-distillable portion. V levels are virtually invariant for the product oils. The residue both show the concentration effects of vacuum distillation. The higher Ni than V content is consistent with lacustrine depositional environments like Green River oil shale [Tissot and Welte (1984)]. The Fe levels are quite high consistent with tramp Fe due to corrosion and contamination [Speight (1991), Coburn et al. (1994)]. Ca and Mglevels vary considerably due to mineral fines. In no cases was there evidence of Fe,

Mg, or Ca porphyrins in any fractions

by UV-vis spectroscopy.

Alumina Separation qf Samples. To concentrate the petroporphyrins in the shale oils, two types of chromatographic separations were utilized: alumina, and alumina followed by macroporous silica of the porphyrin fraction from the alumina column. Table 2 Weight Distributions Number of Samples C 3 D 11 3 E F 3 G 3 3 J L 3 Q 3 1 + C 1000F 1 + D 1000F a. one methanol fraction Sample for Separated Fractions, %of Starting Sample CH2C12 Fraction 28.3+5.4 3O.4_+3.7 27.3+15.2 31.3+12.0 31.8_+6.1 27.4+11.4 32.7+3.1 25.6+3.5 21.4-+10.9 38.1_+13.4 31.3+3.5 26.8+7.7 33.9+4.3 27.0+5.9 31.8+4.8 27.2+7.1 35.6 3.9 3.1 35.6 not included. Hexane Fraction Methanol Fraction a 8.8+0.5 12.9+4.0 6.5+1.2 11.4-+2.1 9.8_+1.3 8.0+2.0 8.1-+1.2 11.4_+1.7 22.1 22.1 Closure a 66.8_+14.8 71.3+14.0 65.8+17.5 69.8-+3.6 68.2_+0.2 67.0+5.4 68.5+4.4 70.4+9.3 63.7 64.0

Table 2 shows the weight distribution of the fractions from the alumina column separation of the shale oils. For the product oil separations, even though the variations in the amount of material separated into the hexanes fraction for each oil varies considerably, the average values for each oil are very similar (32.2%_+3.1%). The behavior is also true for the CH2C12fraction (26.9%+2.2), and the closures (68.5%+1.9%). These similarities agree with the observation that these oils are fairly similar in bulk properties [Coburnet al. (1994)]. The variation of the weight distributions of the fractions for a specific oil mainly reflects variations in separation conditions, principally differences in solvent volumes, column integrity, and

Hexane Fraction
0.0003 --

>0

(/}

-0.0001

5o~

._.4,.40

VVavelength

e66 CH2CI2 Fraction

0.0004

--

-0.0004

5o~

Wavelength

0.0O02

--

Methanol Fraction

>0

500

5~0

Wavelength

6~0

&~o

Figure 2. Second Derivative UV-vis Spectra Alumina Column Separation of Shale Oil D.

of Fractions

from the

volatile loss [Reynolds and Lee (1993)]. The distributions for the + residua indicate a loss of primarily hydrocarbons in the distilla1000F tion. This is consistent with the highly paraffinic nature of oils produced from lacustrine deposits. Porphyrin Distributions. Figure 2 shows the second derivative UV-vis spectra of the three fractions collected from one of the alumina column separations of shale oil D. The hexanes fraction exhibits no absorbances in the range typical for petroporphyrins. The methylene chloride fraction clearly exhibits strong absorbance due to Nietio and/or NiDPEP porphyrin at 550 nm. The 2nd derivative minimum af 574 nm is probably just an artifact of the larger 2nd derivative minimumat 550 nm, although it could be due very low concentrations of vanadyl etio and/or DPEP porphyrins. The methanol fraction exhibits absorbance minima at - 495 nm (not shown) N 530 nm, - 570 rim, and N 620 nm. These minima are observed in the methanol fractions of oils E, F, L, and Q also, but were always found in extremely low concentrations. These are tentatively assigned as demetallated porphyrin [Quirke (1987)]. In some other cases, only the absorbance at 490 nm was observed at low concentrations. Table 3 Porphyrin Concentrations Determined by 2nd Derivative UV-vis Spectroscopy. Sample C D E F G J L Q + C 1000F + D 1000F Number of Determinations 2 3 3 3 2 3 3 2 1 1 % Ni as Ni Porphyrin 44.0+ 4.2 37.7+1.8 41.1+4.0 37.8+6.8 42.0+0.9 46.2+1.4 45.5+5.3 41.8+4.3 18.5 22.0 ppm Ni as Ni Porphyrin 7.2 4.9 4.4 3.5 3.8 4.3 2.6 5.6 15.9 13.9

Table 3 shows the quantitation of porphyrin cont.ent for each shale oil. In all product oil cases, the porphyrins were separated into the CH2C12fraction. Note also in all cases, about 50% of the Ni is accounted for as Ni porphyrin, and the concentration of Ni as porphyrin is always less than 10 ppm. Both residua show lower percentages of the Ni as Ni porphyrin, compared to the corresponding product oil. This is consistent with the behavior of petroporphyrins in heavy crude oils where porphyrin degradation was observed upon simple heating [Rankel (1981)]. Silica Separation of Samples. The utilization of the 2nd derivative UV-vis method over comes aromatic and heteroaromatic interferences associated with using the Soret band [Sugihara and Bean (1962)] when determining petroporphyrin concentrations [Freeman and OHaver (1990)]. However, further concentration of the petroporphyrins is desirable for good quantitation of porphyrins. As a result, fractions from the alumina separation were further separated on macroporous silica. Nietio and NiDPEP were found only in the CH2C12fraction and

these fractions from alumina separations of oils C and D were further separated on macroporous silica. Sample sizes were reasonably small that mass distributions were not attempted. The Ni porphyrins eluted in the CH2C12fraction. No porphyrins were found in other fractions, indicating no metallated acidic porphyrins [Johnson and Freeman (1990)]. The CH2C12fraction from the alumina separation of shale oil C

which previously required a minimum volume of 100 ml of CH2C12 dilution for quantitation, required only a 50 ml dilution after silica column separation. The second derivative UV-vis minimum increased a factor of 1.8, consistent with the concentration. A CH2C12 fraction from the alumina separation of shale oil D gave a similar result. Because of complications with artifacts in the mass spectral examination of these fractions, the macroporous silica separations were

used only sparingly [Lee et al. (1994)]. DISCUSSION Development of Separation Procedure. Retort product oil D was examined in detail to adapt the chromatography method developed for separating heavy crude oils and tar sand bitumen to separating shale oils [Reynolds et al. (1989)]. Product oil D was chosen because it was, the time, the freshest available oil, and was also considered typical of product oil from the HRSprocess. Initial separations were attempted using 90% hexanes/10% Et20 to elute hydrocarbons in the non-polar fraction. UV-vis examination of these fractions, however, indicate Ni porphyrins were coeluting. This was not a complete surprise, because the Ni porphyrins are less polar than the V porphyrins for which the separation was developed. When we replaced the hexanes/Et20 mixture with 100% hexanes, the Ni porphyrins no longer eluted into the non-polar fraction. As expected, though, the total amount of material collected in this fraction was considerable less (N 65 wt % of sample for hexanes/Et20, N 27 wt of sample for hexanes). This incremental material was recovered when the 100% hexanes was followed by 90% hexanes/10% Et20. For example, one separation yielded a hexanes fraction of ~ 42 wt % of sample and a hexanes/Et20 fraction of 21 wt % of sample. The overall closure was also - 20% less when using 100%hexanes only as the first eluting solvent (closure for hexanes/Et20 separations, 89+7 wt % of sample). UV-vis examination of the CH2C12fractions indicated the Ni porphyrins eluted, as expected. Traces of V porphyrins were possibly observed consistent with the behavior for V porphyrins seen in heavy crude oil and tar sand bitumen separations. UV-vis examination of the MeH fractions revealed an unidentifiable material eluted thought to be porphyrin by the spectroscopic behavior. Further separation using macroporous silica of the methanol fraction from the alumina column separation of oil D revealed a weakly absorbing species with four

absorbances (~490, 530, 560, and 620 nm). Because of the low concentration, this species can only be tentatively identified as a demetallated petroporphyrin. Porphyrins as Process Severity Indicators. To test whether the petroporphyrin properties measured here and the metals properties in general reflect relative or absolute severity of the retorting process, correlations between several process parameters and Ni, V, Ni/V ratio, Ni porphyrin distribution and concentrations were attempted. Table 4 shows two types of process parameters were chosen -- those which exhibited process control (temperatures and recycle ratios), and those which were product properties which may reflect severity (hydrogen and methane formation). Table 4 Selected Process Conditions for HRSRetort Fluid Bed Mixer, Ternperature, OC

Pyrolyzer a, Temperature, Recycle Hydrogen a, Methane Ratio vol % Oil vol % C 5.4 478 2.9 9.0 500 C 4.8 3.1 9.3 500 505 D 0.3 1.0 509 3.8 500 E 10.5 8.6 498 3.2 550 F 9.7 2.1 13.0 500 G 500 4.2 7.5 500 2.3 499 J 0.1 0.5 499 1.9 499 L 13.4 8.8 497 na 495 Q E and L from once-through recycle gas operation, all others from recycle pyrolysis gas operation No correlation between Ni, V, and Ni/V ratio and pyrolyzer or fluid-bed mixer temperatures were observed. For recycle ratio, Ni and the Ni/V ratio increased with recycle ratio (increasing severity), while V again was invariant. Although there was possibly a trend, the scatter was sufficient to not rely on the relationship to indicate process severity. No correlations were found between the percentage or ppm

of Ni porphyrins and H2 or light gas formation. (In a narrow process severity range, H2 and light hydrocarbon concentrations in the gas formed during fossil fuel pyrolysis can exhibit changes due to changes in run conditions [Speight (1990), Venkatesan et al. (1982)].) The relative, and perhaps roughly, the absolute porphyrin contents of the product oils are similar because the thermal conditions in the pyrolyzing areas of the retort were roughly the same. This eliminates porphyrin content as a potential parameter by itself under these operating conditions. However, the use the porphyrin homologous series distributions as potential process indicators is still possible. The results of the mass spectral examination of these series for product oil D will be presented elsewhere [Lee et al. (1994)]. CONCLUSIONS Shale oils from the retorting of Green River oil shale at different condition were successfully fractionated by column chromatography to isolate the metallopetroporphyrins. Ni porphyrins were found only in the CH2C12 fraction. V porphyrins were possibly observed, but because of the weak absorbances, could not be unequivocally identified. Determined by UV-vis spectroscopy, ~ 40 % of the Ni was found to be bound as Ni petroporphyrins. This similarity in relative porphyrin concentration regardless of the severity of run conditions indicates porphyrin concentration alone is not a good process severity indicator. More detailed analyses (mass spectrometry) is necessary to determine the utilization of petroporphyrins as process indicators. ACKNOWLEDGMENTS We thank Theresa I. Duewer of LLNLfor the metals analyses of the oils, London Breed for experimental assistance, Robert J. Cena of LLNLfor partial support through the Oil Shale Program, and Associated Western Universities, Inc. summer program for partial support. Work performed under the auspices of the U.S. Department of Energy

by the Lawrence Livermore W-7405-ENG-48.

National

Laboratory

under Contract

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