Liquid Fuels Technology

ISSN: 0737-7266 (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/lpet18

AN INVESTIGATION OF WAXES ISOLATED FROM

HEAVY OILS PRODUCED FROM NORTHWEST
ASPHALT RIDGE TAR SANDS

J. F. Branthaver , K. P. Thomas , S. M. Dorrence , R. A. Heppner & Michael J.

Ryan

To cite this article: J. F. Branthaver , K. P. Thomas , S. M. Dorrence , R. A. Heppner & Michael

J. Ryan (1983) AN INVESTIGATION OF WAXES ISOLATED FROM HEAVY OILS PRODUCED
FROM NORTHWEST ASPHALT RIDGE TAR SANDS, Liquid Fuels Technology, 1:2, 127-146,
DOI: 10.1080/07377268308915312

To link to this article: https://doi.org/10.1080/07377268308915312

Published online: 06 Feb 2007.

Submit your article to this journal

Article views: 16

View related articles

Citing articles: 1 View citing articles

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=lpet20
LIQUID FUELS TECHNOLOGY, 1 ( 2 ) , 127-146 (1983)

AN INVESTIGATION OF WAXES ISOLATED FROM HEAVY OILS

PRODUCED FROM NORTHWEST ASPHALT RIDGE T A R SANDS

J. F . B r a n t h a v e r ,
K . P. Thomas, 5. M. Dorrence,
R. A . Heppner, a n d Michael J. Ryan*

U n i v e r s i t y o f Wyoming Research Corporation**

P.O. B o x 3395, U n i v e r s i t y Station, Laramie, WY 82071

ABSTRACT

D u r i n g t h e late 1970'5, t h e Laramie E n e r g y Technology

C e n t e r operated two i n - s i t u combustion p r o j e c t s i n t h e N o r t h w e s t
A s p h a l t Ridge t a r sand deposit o f Utah. Some o f t h e heavy o i l s
p r o d u c e d were observed t o have h i g h p o u r points, w h i c h r e s u l t e d
i n h a n d l i n g problems i n cold weather. These h e a v y o i l s contain
waxes, w h i c h were f o u n d t o b e n-alkane homologues r a n g i n g p a s t
c a r b o n number 60. These alkanes seem t o have been d e r i v e d
f r o m what a r e p r o b a b l y Ozokerite veins, which a r e f o u n d in t h e
t a r sand deposit. Samples from these v e i n s a n d waxes d e r i v e d
from p r o d u c e d heavy o i l s were s t u d i e d u s i n g NMR, I R , a n d
chemical ionization mass spectrometry.

INTRODUCTION

D u r i n g t h e late autumn of 1975, t h e Laramie E n e r g y T e c h -

n o l o g y Center operated an in s i t u combustion project i n the

N o r t h w e s t Asphalt Ridge t a r sand deposit o f U t a h ( L a n d e t al.,

* Associated Western U n i v e r s i t i e s P a r t i c i p a n t
" Formerly Laramie E n e r g y Technology C e n t e r

127
1977). T h i s p r o j e c t was terminated 23 days a f t e r ignition. One

o f the reasons f o r termination o f t h e experiment was t h e coinci-

d e n t onset of severely cold weather and t h e p r o d u c t i o n o f materi-

als h a v i n g h i g h p o u r points.

A second i n s i t u combustion p r o j e c t was b e g u n i n t h e late

summer of 1977 i n a p a t t e r n adjacent to t h e locale o f t h e f i r s t

project (Johnson et al., 1980). T h i s project was operated f o r 183

days after ignition. Materials h a v i n g high pour p o i n t s were

produced again, b u t t h e equipment had been designed to handle

such p r o d u c t s .

I t was suspected t h a t waxes believed to b e i n t h e t a r sand

deposit were mobilized d u r i n g t h e project a n d c o n t r i b u t e d t o t h e

h i g h p o u r p o i n t s o f t h e p r o d u c t s (Dorrence e t al., 1978). The

c u r r e n t investigation r e p o r t s t h e discovery and s t r u c t u r a l d e t e r -

mination o f wax-like materials in a heavy oil produced d u r i n g t h e

second project

EXPERIMENTAL

O r i q i n of Samples

A p o r t i o n of a core from well 1-1-3, footage 313-315 (95-

96 m), 1975 project site, was p u l v e r i z e d and extracted in a

Soxhlet e x t r a c t o r w i t h a m i x t u r e o f benzene and ethanol. The

e x t r a c t s were d r i e d and dewaxed as described below. T h e waxes

were collected by filtration and were labeled TSC-75-66. An

elemental analysis i s g i v e n in Table 1, sample number 1.

A p o r t i o n of a core f r o m well 2-1-5, footage 160-170 (49-

52 m), 1977-8 project site, was observed t o consist of sandstone

WAXES ISOLATED FROM HEAVY OILS

TABLE I

Elemental Analyses o f Waxes

Sample Element, wt. percent

no. Source o f sample C H N S Total H/C

3 TSF-77-15 and -16

Asphaltene
fraction
soluble i n
xylenes 84.27 13.70 0.18 0.08 98.23 1.94

4 Petrolene
waxes 78.60 8.82 1.42 4.42 93.26 1.34

5 Waxes from
polar aromatic
fraction o f
petrolenes 80.16 8.58 1.53 4.83 95.11 1.28

impregnated w i t h a wax-like material. The wax was collected b y

melting and filtration. This wax was labeled TSC-76-59; an

elemental analysis i s given i n Table 1, sample number 2.

T h e locations o f t h e above two coreholes have been published,

(Land e t al., 1977; Johnson e t al., 1980).

Materials TSCF-77-15 and -16 were collected a t t h e head of

production well 2-P-1 d u r i n g t h e second project. T h e location of

t h i s well has been published (Johnson e t al., 1980).

F u r t h e r Processing o f Materials TSCF-77-15 and -16. F i f t y grams

each o f samples TSCF-77-15 and -16 were combined and dissolved

i n toluene and dried -azeotropically in a B a r r e t t apparatus. After

t h e toluene was removed b y evaporation, 72 g o f material was

left. T h i s was swirled in 1.43 1 n-heptane, and t h i s new m i x t u r e

130 BRANTHAVER ET AL.

was allowed t o s t a n d o v e r n i g h t . A s p h a l t e n e s (6.6 g) w e r e sepa-

r a t e d from p e t r o l e n e s b y f i l t r a t i o n , a n d t h e n - h e p t a n e was r e -

moved f r o m t h e p e t r o l e n e s b y e v a p o r a t i o n .

T h e asphaltenes w e r e t a k e n u p in c o l d toluene, a n d it was

o b s e r v e d t h a t a l l t h e asphaltenes did n o t completely d i s s o l v e in

t h i s solvent. T h e m a t e r i a l i n s o l u b l e in c o l d t o l u e n e was e x t r a c t e d

w i t h b o i l i n g t o l u e n e until l i t t l e d i s c o l o r a t i o n , o f t o l u e n e was o b -

served. Each b a t c h o f t o l u e n e was f i l t e r e d t h r o u g h a C - p o r o s i t y ,

sintered glass funnel. T h e r e s i d u a l m a t e r i a l was c o n t a c t e d w i t h a

boiling xylene mixture. T h i s a p p e a r e d t o d i s s o l v e o r m e l t almost

all remaining organic materials. T h e f i l t r a t e s w e r e a g a i n heated

to boiling and filtered through an M-porosity, sintered glass

funnel. Some sand a n d i r o n o x i d e w e r e c o l l e c t e d by t h e f i l t e r .

T h e f i l t r a t e was e v a p o r a t e d in a fume hood t o remove x y l e n e .

T h e r e m a i n i n g b r o w n w a x was a n a l y z e d f o r elemental composition,

g i v e n in T a b l e 1, sample n u m b e r 3, a n d was i n v e s t i g a t e d b y a

number o f spectroscopic techniques.

The petrolenes recovered in t h e a b o v e experiment were

t r e a t e d in t w o d i f f e r e n t ways. In o n e t r e a t m e n t , t h e petrolenes

w e r e d e w a x e d c o n v e n t i o n a l l y by d i s s o l v i n g t h e m in 3.75 ml t o l u e n e

p e r g r a m of p e t r o l e n e s a n d t h e n a d d i n g 11.25 ml o f 2 - b u t a n o n e

p e r g r a m o f petrolenes. T h i s m i x t u r e was s t i r r e d a t O•‹C f o r 2

hours, and waxes that were precipitated were recovered by

filtration. An elemental a n a l y s i s of these waxes i s g i v e n in

T a b l e 1, sample n u m b e r 4. In a second t r e a t m e n t , 1.5-g samples

o f p e t r o l e n e s w e r e c h r o m a t o g r a p h e d o n a 20.5-mm i.d. column

WAXES ISOLATED FROM HEAVY OILS 131

f i l l e d t o a h e i g h t o f 102 cm w i t h W. R . Grace g r a d e 62 silica gel

swelled in n - h e p t a n e . T h e column was e l u t e d w i t h 1 l i t e r o f

n-heptane, followed b y 1 l i t e r of benzene a n d f i n a l l y w i t h 1 l i t e r

of a 9:l m i x t u r e o f benzene a n d methanol ( v o l / v o l ) . These

eluants yield saturate, aromatic, a n d p o l a r aromatic f r a c t i o n s ,

respectively (Barbour et al., 1976). All fractions from nine

chromatographic r u n s were collected and weighed. The nine

s a t u r a t e f r a c t i o n s were combined, as w e r e t h e n i n e aromatic f r a c -

t i o n s a n d t h e n i n e p o l a r aromatic f r a c t i o n s . Each of these com-

b i n e d f r a c t i o n s was dewaxed as d e s c r i b e d above. O n l y t h e com-

bined polar aromatic fractions yielded significant amounts o f

precipitate. Elemental analyses o f p r e c i p i t a t e d waxes from t h e

combined p o l a r aromatic f r a c t i o n s a r e g i v e n in T a b l e 1, sample

number 5 .

Materials

S o l v e n t s w e r e J . T . B a k e r analyzed r e a g e n t s ( J . T . Baker,

Inc., Phillipsburg, N.J.) which were redistilled p r i o r t o use

e x c e p t f o r t h e x y l e n e m i x t u r e , w h i c h was u s e d as r e c e i v e d .

Elemental Analyses

Elemental analyses w e r e p e r f o r m e d u s i n g s t a n d a r d combustion

techniques.

Spectroscopic Methods

The solid state I3C nuclear magnetic resonance (NMR)

s p e c t r u m was recorded on a JEOL FXGOQ spectrometer. The

c r o s s - p o l a r i z e d magic-angle s p i n n i n g mode was u s e d w i t h a sample

of d r i e d s o l i d w a x . A d e t a i l e d d e s c r i p t i o n of t h i s t e c h n i q u e i s

g i v e n by Netzel a n d M i k n i s (1982), a n d references t h e r e i n .

132 BRANTHAVER ET AL.

T h e infrared spectrum was obtained w i t h a Nicolet model

MX-1 F T I R spectrometer. T h e wax sample was m i x e d w i t h K B r ,

a n d t h e solid m i x t u r e was p r e s s e d i n t o a disc.

Mass. spectra were obtained u s i n g a VG-ZAB-1F h i g h r e s o l u -

t i o n mass spectrometer. A Finnigan-lncos model 2300 d a t a system

was used f o r a c q u i r i n g a n d analyzing t h e spectra. Sample ma-

terials were i n t r o d u c e d i n t o t h e mass spectrometer v i a t h e d i r e c t

i n s e r t i o n p r o b e w h i c h was s l o w l y heated from ambient temperature

t o 500•‹C. Mass s p e c t r a o f t h e materials d e r i v e d f r o m t h e N o r t h -

west A s p h a l t R i d g e deposit w e r e e v o l v e d o v e r a r a n g e o f 300-

400•‹C. Mass spectra o f p h y t a n e a n d triacontane were evolved a t

100•‹C and 200•‹C, r e s p e c t i v e l y . T h e i o n source temperature was

maintained a t a constant 240•‹C. A mass r a n g e of 100 t o 1300

AMU (8KV accelerating voltage) was scanned; perfluorokerosene

a n d tris-(perfluoro-heptyl)-s-triazine were u s e d t o c a l i b r a t e t h e

mass scale.

Electron impact ionization was performed with a nominal

e l e c t r o n e n e r g y o f 70eV a n d a n o p e r a t i n g resolution o f 15000. An

operating resolution o f 5000 was u s e d t o o b t a i n t h e chemical

ionization mass spectra. Research g r a d e isobutane ( ~ c i e 6 t i f i cGas

Products) was u s e d a t a n indicated i o n s o u r c e vacuum chamber

pressure of 6.7mPa ( 5 ~ 1 0 - T~o r r ) in t h e chemical ionization

exoeriments.

RESULTS AND DISCUSSION

Examination o f cores f r o m each p r o j e c t site revealed t h a t

t h e r e were c e r t a i n l i g h t - c o l o r e d zones scattered t h r o u g h t h e t a r

WAXES ISOLATED FROM HEAVY OILS 133

sand deposit. These light-colored zones were not b a r r e n of

o r g a n i c m a t e r i a l b u t c o n t a i n e d t a n , w a x - l i k e materials. A sample

o f t h i s w a x - l i k e - m a t e r i a l was manually r e t r i e v e d f r o m a section of

c o r e f r o m t h e s i t e o f t h e second p r o j e c t . T h i s material, d e s i g -

n a t e d TSC-76-59, was o b s e r v e d t o m e l t o v e r t h e r a n g e 9 1 - 9 3 T .

Wax-like materials also w e r e o b t a i n e d b y d e w a x i n g t h e benzene-

e t h a n o l e x t r a c t s o f a s e c t i o n o f c o r e f r o m t h e s i t e of t h e f i r s t

project. T h e s e materials, d e s i g n a t e d TSC-75-66, were o b s e r v e d

t o m e l t o v e r t h e r a n g e 93-96'C. M e l t i n g p o i n t v a l u e s s u c h as

these fall within the ranges reported for some Ozokerites

(Marschner and Winters, 1976), which are known to consist

l a r g e l y of homologous s e r i e s o f l o n g c h a i n n - a l k a n e s .

Elemental compositions o f t h e a b o v e w a x - l i k e m a t e r i a l s a r e

g i v e n in T a b l e 1, sample n u m b e r s 1 a n d 2 . B o t h a r e composed

almost e n t i r e l y o f H a n d C in a r a t i o o f 1 . 9 : l . T a b l e 1 also

c o n t a i n s elemental analyses of t h r e e o t h e r samples, all d e r i v e d

f r o m a h e a v y o i l p r o d u c e d during t h e second p r o j e c t . One of

these, sample n u m b e r 3, was d e r i v e d f r o m t h e a s p h a l t e n e f r a c t i o n

of t h e h e a v y o i l a n d resembles samples 1 a n d 2 in elemental

composition. Sample n u m b e r 3 melts o v e r t h e r a n g e 93-96OC,

save f o r a small amount of r e f r a c t o r y material. Samples 4 a n d 5

a r e d e r i v e d f r o m t h e p e t r o l e n e f r a c t i o n o f t h e above h e a v y o i l b y

solvent dewaxing. T h e s e t w o so-called waxes d o n o t resemble t h e

other t h r e e samples in elemental composition. Samples 4 a n d 5

h a v e high c o n c e n t r a t i o n s of heteroatoms a n d H t o C r a t i o s of

a b o u t 1.3.
134 BRANTHAVER ET AL.

T h e wax-like material isolated f r o m t h e heavy oil p r o d u c e d

d u r i n g t h e second p r o j e c t (sample number 3 of Table 1) was

investigated u s i n g a number o f spectrometric techniques.

T h e solid state 13c NMR spectrum i s shown i n F i g u r e 1.

O n l y two peaks are observed--at 15.72 and 34.11 ppm. These

peaks correspond t o m e t h y l a n d methylene groups, respectively.

It is n o t possible t o differentiate between methine peaks and

methylene peaks in t h i s spectrum because of t h e o v e r l a p p i n g

r a n g e o f the two chemical s h i f t s and t h e magnitude of t h e m e t h y l -

ene peak. However, i n a n y non-cylcic saturated aliphatic h y d r o -

carbon, wherever t h e r e i s even one methine function, t h e r e must

be three methyl groups. From t h e small size o f t h e m e t h y l peak,

it follow^ t h a t t h e number o f methine functions i s negligible.

A n i n f r a r e d spectrum ( I R ) of sample 3 o f Table 1 i s shown

i n F i g u r e 2. T h i s spectrum confirms t h e h i g h carbon number

alkane s t r u c t u r e . The peaks a t 720 a n d 730 cm-' are v e r y

prominent, i n d i c a t i v e o f long chains. T h e spectrum i s similar t o

t h a t of an n-alkane o f carbon number 36 (Pouchert, 1975).

A n electron impact mass spectrum o f sample 3, Table 1 is

shown in F i g u r e 3. T h e u n i f o r m 1 4 AMU mass difference between

t h e p r i n c i p a l ions I n t h i s spectrum a n d t h e monotonic decrease i n

peak i n t e n s i t y w i t h increasing mass i s characteristic o f t h e elec-

t r o n impact mass spectra o f n-alkanes. U n d e r electron impact,

t h e h i g h e r molecular w e i g h t n-alkanes e x h i b i t p a r e n t ( P ) peaks o f

low Intensity. This is because peaks r e s u l t i n g f r o m carbon-

carbon b o n d cleavage a r e much more prominent, a n d in a long-

chain alkane t h i s cleavage may o c c u r anywhere i n t h e chain. It

WAXES ISOLATED PROM HEAVY OILS

Fig. 1 . I3C NMR Spectrum of Wax Sample 3

Fig. 2. IR Spectrum of Wax Sample 3.

136 BRANTHAYER ET AL.

i s t h e r e f o r e d i f f i c u l t t o d e t e r m i n e molecular w e i g h t s o f l o n g - c h a i n

n-alkanes from electron impact mass spectra. The spectrum

s h o w n in F i g u r e 3 may b e i n t e r p r e t e d t o c o r r e s p o n d t o t h a t o f a

h i g h c a r b o n n u m b e r n-alkane, o r t o a m i x t u r e of n-alkanes, some

o f w h i c h h a v e c a r b o n n u m b e r s e x t e n d i n g p a s t 60.

T h e above elemental, melting point, and spectrometric data

show t h a t wax sample 3, T a b l e 1, d e r i v e d f r o m a h e a v y o i l p r o -

duced during the second project, is probably a mixture of

n-alkanes. It was t h u s d e s i r a b l e t o d e t e r m i n e how closely t h i s

wax resembles t h e w a x - l i k e materials o b t a i n e d f r o m c o r e samples

f r o m t h e p r o j e c t sites.

Samples 1-3, T a b l e 1, were s t u d i e d u s i n g chemical ionization

mass s p e c t r o m e t r y . In t h i s technique, a sample i s i n t r o d u c e d

i n t o t h e s o u r c e of a mass spectrometer along w i t h a m u c h l a r g e r

amount o f a n o t h e r compound, in t h i s case, isobutane. Electron

impact occurs mostly with the isobutane, and the resulting

c h a r g e d p a r t i c l e s r e a c t w i t h o t h e r isobutane molecules t o p r o d u c e

i s o b u t y l c a r b o n i u m ions. T h i s h i g h l y r e a c t i v e species t h e n r e a c t s

w i t h t h e alkanes in t h e sample. Hydride ion abstraction i s the

dominant reaction o f i s o b u t y l c a r b o n i u m i o n w i t h alkanes. Some

o f t h e alkane c a r b o n i u m i o n s t h u s formed a r e e n e r g e t i c e n o u g h t o

fragment f u r t h e r b y cleaving carbon-carbon bonds. Thus, al-

kanes, w h i c h e x h i b i t v e r y small p a r e n t (P) peaks u n d e r d i r e c t

electron impact ionization, show fairly strong (P-1) p e a k s in

chemical ionization mass s p e c t r o m e t r y . T h e peaks c o r r e s p o n d i n g

t o c h a i n cleavage d o n o t dominate t h e mass s p e c t r u m ( F i e l d e t

al., 1966).
WAXES ISOLATED FROM HEAVY OILS

Fig. 3. Electron Impact Mass Spectrum o f Wax Sample 3

Chemical ionization mass spectra, u s i n g isobutane, o f two

model compounds, triacontane (n-C30H62) a n d phytane, a C-20

isoprenoid, are shown i n F i g u r e s 4 a n d 5 , respectively. The

mass spectrum o f t h e normal alkane e x h i b i t s a s t r o n g (P-1) peak

a t nominal mass 421. Peaks corresponding t o chain cleavage a r e

o b s e r v e d below mass number 400. Because of i t s b r a n c h e d s t r u c -

ture, t h e p h y t a n e spectrum e x h i b i t s a small (P-1) peak a t nominal

mass 281.

Figure 6 shows a p o r t i o n o f t h e chemical ionization mass

spectrum o f wax sample 3, Table 1. I n t h i s spectrum a series o f

 BRANTHAVER ET AL.

Fig. 4 . Chemical Ionization Mass Spectrum of Triacontane

WAXES ISOLATED FROM HEAVY OILS

Fig. 5. Chemical Ionization Mass Spectrum of Phytane.

 BRANTHAVER ET AL.

Fig. 6. Chemical Ionization Mass Spectrum o f Wax Sample 3 ,

WAXES ISOLATED FROM XEAW OILS 141

relatively intense ions occurs i n the range of nominal masses 534

to 856, corresponding t o a carbon number range of 38 t o 61.

These ions are the P-1 species associated w i t h t h e series o f

n-alkanes in the sample. Fragment ion intensities in t h i s mass

range may b e expected t o b e small (see F i g u r e 4). A t masses

below this range, the b u i l d u p of fragment ion peaks makes u n -

ambiguous determination o f P-1 peaks d i f f i c u l t . Mass values of

the h i g h e r (P-1) peaks i n Figure 6 and subsequent figures, are

even numbers r e s u l t i n g from r o u n d i n g o f f exact mass values; f o r

example, t h e exact mass value corresponding t o nominal mass 800

is 799.8999 AMU.

One characteristic o f Figure 6 warrants mention. T h e peaks

at nominal mass numbers 744 and 534 are h i g h e r than s u r r o u n d i n g

peaks. These peaks correspond t o (P-1) ions derived from

alkanes w i t h carbon numbers 53 and 38, respectively. Maxima

such as these were observed in gas chromatographic studies o f

Ozokerites (Marschner and Winters, 1976). These maxima are n o t

observed in t h e electron impact spectrum (Figure 3 ) , dominated

b y peaks corresponding to chain fragmentation.

Figures 7 and 8 show chemical ionization mass spectra, u s i n g

isobutane, o f core wax samples 1 a n d 2, Table 1 respectively.

These mass spectra are also dominated b y (P-1) peaks corres-

ponding t o ions r e s u l t i n g from h y d r i d e ion abstraction of alkane

homologues. These two mass spectra resemble that o f Figure 6,

p a r t i c u l a r l y in t h e h i g h e r mass range. I n Figure 7, t h e peak

corresponding to a n alkane o f carbon number 55 (MW=772) is

 BRANTHAVER ET AL.

F i g . 7. Chemical Ionization Mass Spectrum o f Wax Sample 1.

predominant. I n F i g u r e 8, t h e most prominent peak corresponds

t o a n alkane o f carbon number 53 (MW=744). A n o d d carbon

number preference i s noticeable i n t h e mass spectrum in F i g u r e 7,

a n d i s somewhat less noticeable i n t h e mass spectra in Figures 6

a n d 8. Overall, t h e mass spectra o f t h e t h r e e samples shown in

Figures 6-8 a r e so similar t h a t it may b e stated t h a t wax sample 3

was d e r i v e d f r o m materials s u c h as wax samples 1 a n d 2 w i t h

l i t t l e alteration.

Analysis of t h e above data indicates t h a t t h e wax sam-

ples 1 - 3 , T a b l e 1, a r e a homologous series of long chain n-al-

WAXES ISOLATED FROM HEAVY OILS

744
772
716
688

650 700 7 50 BOO 850 900

m/s

F i g . 8. Chemical Ionization Mass Spectrum o f Wax Sample 2.

kanes h a v i n g t h e c u r i o u s d i s t r i b u t i o n o f carbon numbers r e p o r t e d

f o r Ozokerites. As f a r as i s known, Ozokerites have n o t been

discovered i n t h e Northwest Asphalt ~ i d area,

~ e b u t there i s no

reason t o believe t h e y should n o t o c c u r t h e r e (Jock Campbell,

formerly of the Utah Geological a n d Mineral Survey, private

communication). Whether or n o t t h e waxy materials such as

samples 1 and 2, Table 1, a r e Ozokerites, it i s e v i d e n t t h a t

d u r i n g i n - s i t u combustion these materials a r e n o t c r a c k e d t o a

sufficient e x t e n t t o p r e v e n t t h e i r co-production w i t h produced

fluids. These waxy materials appear t o b e mobilized w i t h heavy

144 BRANTHAVER ET AL.

oils and bitumens, and thus adversely affect the pour points of

these products (Thomas et al., 1983). These waxes may be

removed b y deasphaltening, i n which .case they do not appear to

become incorporated into petrolenes. The materials derived from

conventional dewaxing of the petrolenes are quite different

(Table 1, samples 4 and 5).

I t has been proposed that some of the Uinta Basin t a r sand

deposits formed as a result o f bacterial invasion of pre-existing

lighter oil deposits and are not immature petroleum (Reed, 1976).

The t a r sand bitumens are evidently not inspissated deposits

because the pore saturation level is fairly h i g h (Johnson et al.,

1980). I f the tan wax inclusions found i n o u r Northwest Asphalt

Ridge cores are Ozokerites, then the wax inclusions probably

entered the t a r sand deposit via faults. T h i s is an explanation

offered to account for the occurrence of Ozokerite elsewhere in

the basin (Hunt, 1955). Such faulting should have occurred

after the formation of the tar sand deposit. If the tar sand

deposit resulted from, bacterial degradation of a petroleum, such

bacterial activity must have ceased before introduction of Ozoker-

ite, as bacteria preferentially attack n-alkanes. Had the t a r sand

deposit been occupied b y petroleum d u r i n g Ozokerite introduction,

intermingling should have occurred. Examination of cores shows

that intermingling has not occurred, yet the waxes can be mobil-

ized with the r e s t o f the bitumen found in t h e t a r sand deposit,

as our experimental results indicate. Once the waxes are mixed

w i t h f l u i d bitumen, the m i x t u r e appears to b e stable, requiring

addition of hydrocarbon solvents f o r separation to occur.

WAXES ISOLATED PROM HEAW OILS 145

CONCLUSION

Those interested i n p r o d u c i n g bitumen f r o m U i n t a Basin t a r

sands should b e aware t h a t a t least one of t h e deposits has h i g h

concentrations o f l o n g chain n-alkane waxes. The l o n g chain

waxes o c c u r in d i s c r e t e i n t e r v a l s w i t h i n t h e t a r sand deposit.

T h e y a r e p r o b a b l y ozokerites, i n t r o d u c e d i n t o t h e t a r sands v i a

faults. If these waxes are n o t s u f f i c i e n t l y cracked d u r i n g p r o -

duction, t h e y w i l l mobilize w i t h p r o d u c e d bitumens a n d h e a v y oils

a n d adversely a f f e c t p o u r points.

ACKNOWLEDGEMENTS

T h e 13C NMR Spectrum was obtained b y D r . G a r y Maciel o f

the Colorado State U n i v e r s i t y , F o r t Collins, Colorado, under

c o n t r a c t DE-AS20-82LC10930.

Elemental analyses were performed by Multichem Labora-

tories, lnc., Lowell, Massachusetts.

REFERENCES

B a r b o u r , R. V., S. M. Dorrence, T . L. Vollmer, and J. D .

Harris. 1976. P y r o l y s i s o f U t a h T a r Sands-Products a n d K i n -
etics. P r e p r i n t s , Division of Fuel Chemistry, Amer. Chem. Soc.,
21(6), 278-283.

Dorrence, S. M., K. P. Thomas, J. F. Branthaver, a n d R. V.

Barbour. 1978. Analyses of Oil Produced D u r i n g i n - S i t u Re-
verse Combustion of a Utah T a r Sand. A d v . Chem. Ser.
P. C . Uden, S . Siggia, and H. B. Jensen, Eds., Amer. Chem.
=,
Soc., Washington, D.C., 150-158.

Field, F. H., M. S. B . Munson, a n d D. A . B e c k e r . 1966.

Chemical Ionization Mass Spectrometry, in I o n Molecule Reactions
i n t h e Gas Phase, A d v . Chem. Ser. 58, P. J. Ausloos, Ed.,
Amer. Chem. Soc., Washington, D . C . , 167-193.
146 BRANTHAVER ET AL.

H u n t , J. M., F. Steward, and P. A. Dickey. 1955. Origin of

Hydrocarbons of Uinta Basin, Utah. Amer. Assoc. Petroleum
Geologists B u l l . , 58, 1671-1698.

Johnson, L . A , , L. J. Fahy, L . J. Romanowski, R. V . B a r b o u r ,

and K . P. Thomas. 1980. A n Echoing In S i t u Combustion Oil
Recovery Project i n a Utah T a r Sand. J . Petrol. Technol., Feb.
1980, 295-305.

Land, C. S., C. Q. Cupps, L. C. Marchant, and F. M. Carlson.

1977. Field T e s t of Reverse-Combustion Oil Recovery f r o m a U t a h
T a r Sand. J . Can. Petrol. Technol., A p r i l - J u n e 1977, 34-38.

Marschner, R. F., and J . C . Winters. 1976. Differences i n

Ozokerites, in Shale Oil, T a r Sands, a n d Related Fuel Sources,
A d v . in Chem. Ser. 151, T . F. Yen, Ed., Amer. Chem. Soc.,
Washington, D . C . , 166-178.

Netzel, D. A , , and F. P. Miknis. 1982. NMR S t u d y of U.S.

Eastern and Western Shale Oils Produced b y P y r o l y s i s and H y d r o -
p y r o l y s i s . Fuel, %, 1101-1110.

Pouchert, C. J., ed. 1975. T h e A l d r i c h L i b r a r y of I n f r a r e d

Spectra, Second Edition, A l d r i c h Chemical Co., Milwaukee, p. 5.

Reed, W. E . 1976. Molecular Compositions o f Weathered Pet-

roleum a n d comparison w i t h i t s Possible Source. Geochimica et
Cosmochimica Acta, 5, 237-247.

Thomas, K . P., R. V . B a r b o u r , J. F . B r a n t h a v e r , a n d 5. M.
Dorrence. 1983. Composition of Oils Produced D u r i n g an Echo-
i n g , I n - S i t u Combustion o f a Utah T a r Sand. Fuel, %, 438-444.

RECEIVED: JULY 22, 1983

ACCEPTED: AUGUST 4, 1983.