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Charles G. Scouten
Amoco Oil Company
Research and Development Department
Naperville, Illinois
OIL SHALE
Charles G. Scouten
Amoco Oil Company
Research and Development Department
P.O. Box 400, Naperville, Illinois 60566
Prepared for publication in the Handbook of Fuel Science and Technology
J. G. Speight, Editor
Table of Contents
Page
I. ORIGIN AND OCCURRENCE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
A. INTROOUCTION.................................................. 1
B. DEFINITIONS AND TERMINOLOGy................................... 4
C. ORIGIN........................................................ 5
1. Sedimentation and Mineralogy............................. 11
2. Production of Organic Matter............................. 27
3. Kerogen Types and Maturat i on. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4. Preservation of Organic Matter........................... 38
5. Marine Oil Shales........................................ 41
6. Lacustrine Oil Shales.................................... 46
D. OCCURRENCE.................................................... 47
II. CHARACTERIZATION, TESTING AND CLASSIFICATION OF OIL SHALES........ 51
A. FISCHER ASSAY: DETERMINATION OF OIL yIELD.................... 51
1. Modified Fischer Assay: The Standard Method............. 53
2. Shortcomings of the Fischer Assay.................... .... 55
B. ALTERNATIVE METHODS FOR EVALUATING OIL yIELD.................. 57
C. ELEMENTAL COMPOSITION AND OIL yIELD........................... 57
D. BITUMEN CONTENT AND COMPOSITION............................... 64
III. PHYSICAL/CHEMICAL PROPERTIES..................................... 71
A. ATOMIC H/C AND N/C RATIOS..................................... 71
B. ALIPHATIC AROMATIC AND CARBON CONTENTS........................ 74
C. NMR DATA...................................................... 74
D. NEWER NMR TECHNIQUES FOR KEROGEN CHARACTERIZATION............. 79
E. ESR RESULTS................................................... 81
F. DENSITY METHODS............................................... 82
G. THERMAL METHODS OF ANALySES................................... 88
H. HEAT CAPACITY AND HEAT OF RETORTING........................... 99
I. MECHANICAL PROPERTIES......................................... 102
J. POROSITY AND PERMEABILITy..................................... 106
IV. THE CHEMICAL STRUCTURE OF OIL SHALE KEROGENS...................... 108
A. KEROGEN ISOLATION............................................. 108
1. Sample Selection and Preparation......................... 109
2. Chemical Methods......................................... 109
3. Physical Methods......................................... 111
B. STRUCTURAL INFERENCES FROM BITUMEN AND SHALE OIL ANALySES..... 115
C. STRUCTURAL ANALYSES OF KEROGENS............................... 118
1. Oxygen Functional Groups................................. 118
2. Oxidation................................................ 120
a. Al kal ine Permanganate............................... 121
b. Chromic Acid Oxidation.............................. 131
3. Depolymerization under Mild Conditions:
Heat-Soak/Extraction.................................... 131
4. Micropyrolysis/GC-MS..................................... 135
5. ACid-Catalyzed Hydrogenolysis............................ 138
D. STRUCTURAL MODELS FOR KEROGEN................................. 138
1. Burlingame Model of Green River Oil Shale Kerogen........ 139
2. Djuritic-Vitorovit Model of a Green River
Oil Shale Network....................................... 141
- i -
3. Green River Kerogen Model Proposed by
Schmidt-Collerus and Prien.............................. 143
4. The Yen-Young-Shih Multi-Polymer Structure............... 145
5. Characterization of Organic Material in
Rundle Ramsay Crossing Oil Shale........................ 149
6. Generalized Models for Types I, II and III Kerogen....... 161
V. RECOVERY.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
A. OVERVIEW...................................................... 173
B. MINING TECHNOLOGy........ ......... ............................ 176
I. Underground Mining....................................... 176
2. Surface Mining........................................... 179
C. SIZE REDUCTION................................................ 180
VI. RETORTING......................................................... 183
A. ABOVE-GROUND RETORTING PROCESSES.............................. 185
I. N-T-U Process... ... ... ... ..... ..... ... .......... ..... .... 185
2. Gas Combustion Process................................... 190
3. Lurgi-Ruhrgas Process.... .......... ............ ...... .... 195
4. TOSca II Process......................................... 204
5. Shell Pellet Heat Exchange Retorting (SPHER) Process..... 211
6. Shell Shale Retorting Process (SSRP)..................... 213
7. Exxon Shale Retort (ESR) Process......................... 219
8. Chevron STB Retorting Process............................ 220
9. Petrosix Process......................................... 225
10. Moving Grate Processes................................... 229
(a) Allis-Chalmers Roller Grate Process................. 229
(b) Dravo Circular Traveling Grate Process.............. 232
(c) Superior Oil/Davy-McKee Circular Grate Retort....... 236
11. Paraho Process........................................... 238
12. Unocal Oil Shale Processes: Retort A, retort B, SGR..... 248
13. Kiviter and Galoter Processes (U.S.S.R.)................. 263
14. HYTORT Process (IGT)..................................... 273
B. IN SITU RETORTING...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
1. Laramie True In Situ Retorting Studies................... 285
2. Geokinetics Horizontal In Situ Process................... 289
3. Occidental Vertical Modified In Situ (VMIS) Process...... 294
4. Rio Blanco Modified In Situ Process...................... 300
5. Equity Oil/ARCO BX Project............................... 308
VII. SHALE OIL UPGRADING AND REFINING................................. 312
A. COMPOSiTION................................................... 312
B. UPGRADING STRATEGIES.......................................... 316
C. DEWATERING AND SOLIDS REMOVAL................................. 318
D. ARSENIC AND IRON REMOVAL...................................... 320
E. UPGRADING BY NON-CATALYTIC THERMAL PROCESSES.................. 323
F. CATALYTIC PROCESSING METHODS.................................. 325
1. Sohio ............... :.................................... 326
2. Gulf Shale Oil Upgrading Process......................... 334
3. Catalytic Cracking (Ashland, Chevron).................... 336
4. Amoco Hydrotreating-Hydrocracking........................ 338
VII I. CONCLUSIONS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
REFERENCES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
i i
I. ORIGIN AND OCCURRENCE
A. INTRODUCTION
Oil shales comprise a truly enormous. and largely untapped fossil fuel
resource. As readily accessible petroleum sources dwindle, utilization of the
oil shale resource to meet world needs for energy and chemical feedstocks will
become both necessary and economically attractive. World-wide oil shale
deposits are estimated to contain 30 trillion barrels of shale oil, but only a
small fraction of this amount is easily recoverable using current technology.
Thus, the utilization of oil shale to replace petroleum will mean finding
economically efficient and environmentally acceptable methods for recovering
the energy-rich organic material locked inside the oil shale's rock matrix and
for upgrading the recovered shale oil. This is a formidable challenge. Oil
shales are complex and intimate mixtures of organic and inorganic materials and
vary widely in their compositions and properties. Some, such as the "oil
shale" of the Green River formation are not even true shales. Today. some
three centuries of research and development lie behind, as we address the
scientific, technological and environmental aspects of the oil shale challenge.
OIL SHALE Page 2
Oil shale technology has a long history. Oil shales were sources of oil
as early as 800 AD and the British oil shale deposits were worked in Phonecian
times.' The use of oil shale was recorded in Austria in 1350. The first shale
oil patent, British Crown Patent No. 330, was issued in 1694 to Martin Eele,
Thomas Hancock and William Portlock, who "after much paines and expences hath
certainely found out a way to extract and make great quantityes of pitch, tarr
and oy7e out of a sort of rock".2 Oil shale utilization on an industrial
scale did not, however, follow immediately. Not until 1838 was the first
industrial oil shale plant put into service at Autun, France.
3
Scotland (1850), Australia (1865) and Brazil (1881) followed.
Soon, plants in
In addition to
being a source of refined shale oil products, it was soon discovered that
torbanite, an especially organic-rich type of oil shale, was useful for
increasing the luminosity of illuminating gas flames.
4
This provided an
important market for the early Scottish oil shale industry and later, as the
Scottish torbanite deposits were depleted, for the early Australian, shale
industry. By the 1870
1
s, Australian torbanite was being exported not only to
Great Britain, but also to the United States, Italy, France and Holland.
s
The
invention of the Welsbach gas mantle and the advent of low-cost, high-quality
kerosene from American petroleum spelled the end of this period. As the need
for liquid transportation fuels increased, the Australian oil shale operations
consolidated. Elsewhere, oil shale plants followed in New Zealand(1900),
Switzerland (1915), Sweden (1921), Estonia (now USSR, 1921), Spain (1922),
China (1929) and South Africa (1935).6 The high point of this stage of oil
shale development was reached during, or just after, World War II. However,
OIL SHALE Page 3
the oil shale industry in Estonia and neighboring Leningrad Province still
flourishes, most of the mined shale being burned directly in electric power
generating plants with the remaining 10% or so retorted to provide chemical
feedstock and smaller quantities of refined products.
7
The Japanese began in
1926 the commercial production of shale oil from the large Chinese oil shale
deposits at Fushun in Manchuria. Improved retorts were installed at this
complex in 1941 to provide important supplies of liquid fuels for the Japanese
forces during World War II. At Maoming, near Canton in southern China, a
second oil shale project was developed. Shale oil production in the PRe peaked
about 1975 and has since declined as emphasis has shifted to newly-discovered
petroleum supplies.
1
,7
The near-term future of oil shale is uncertain. Very clearly, this future
will be influenced by international crude oil prices and supplies. Indeed, as
pOinted out by Hutton, et aT., the rise of interest in oil shale during the
late 1970's was due largely to the high prices and tight supply of crude oil.8
With the decline of crude prices and growth of a crude oil surplus, interest in
oil shale and other synfuels waned. How long this will continue is difficult
to predict. At present, commercial oil shale development is hard to foresee,
unless impetus is provided by political or security concerns. However, the
current lull in development activity offers a golden opportunity for scientific
research to attack the many chemical, physical and material problems that were
uncovered or brought into sharper focus during the late period of activity.
Prudence suggests that we sieze this opportunity.
OIL SHALE Page 4
B. DEFINITIONS AND TERMINOLOGV
There is no "easy!! scientific definition of oil shale; the definition is
strictly an economic one: According to Gavin, "Oil shale is a compact,
laminated rock of sedimentary origin, yielding over 33% of ash and containing
organic matter that yields oil when distilled, but not appreciably when
extracted with the ordinary solvents for petroleum."9 Materials containing
<33% ash should be considered coals, however this distinction will be of little
importance in the following discussion. Thus, we will use oil shale to denote
an organic-rich rock that contains little or no free oil.
Shale oi7 is defined as the oil produced from an oil shale on heating.
Three other terms will used extensively, hence their definitions are
important: Bitumen is defined as the organic material which can be extracted
by ordinary organic solvents, such as benzene. toluene, tetrahydrofuran (THF)
and chloroform (CHC1
3
) or mixtures (generally azeotropes) of such solvents,
such as benzene-methanol (60:40). Kerogen, which comprises the major part of
the organic material, is not soluble in such solvents.
1o
Of course, these are
operational definitions and the relative proportions of bitumen and kerogen
depend on the choice of solvent and extraction conditions. Nevertheless, these
are useful definitions provided their limitations are kept in mind. The third
term. kerogen concentrate, refers to the organic concentrate that is produced
by beneficiation or chemical demineralization of an oil shale. Strictly
speaking. this term should refer only to that part of the organic concentrate
that is insoluble in organic solvents. However, in common usage, kerogen
concentrate refers to the total organic material {kerogen + bitumen} obtained
by removing minerals. The common usage will be followed in this discussion,
except where specifically indicated.
OIL SHALE
Page 5
C. ORIGIN
Oil shales were formed by the inclusion of materials containing organic
carbon into sediments that eventually become sedimentary rocks. To understand
their origin and formation, we begin by considering the distribution and
cycling of carbon in the environment.
Carbon cycles through the biosphere by photosynthesis and oxidation.
C02
Atmosphere
Photosynthesis
Degradation
(oxidation)
Combustion
Organic Carbon
Fossi! fuels
Figure 1. Carbon cycle in the biosphere.
Plants use CO, from the atmosphere to build their cells. Animals eat the
plants and return CO
2
to the atmosphere as a product of metabolism. The decay
of dead organisms returns additional CO
2
to the environment. The action of
acids on carbonate rocks liberates CO
2
into the atmosphere, while rain and the
precipitation of insoluble carbonates remove CO
2
Only a minute fraction of
the carbon that cycles through this marvelously complex cycle is preserved in
the sediments that yield fossil fuels.
Hunt has estimated the amount of carbon present in sedimentary rocks as
hydrocarbons (including N-, $- and O-containing hydrocarbon derivatives that
contain reduced carbon forms) and as oxidized carbon forms (Table 1).11
OIL SHALE Page 6
Table 1. Global carbon inventory_ Carbon, 10
18
grams in sedimentary rocks.a
All Sediments
Clays and Shales
Carbonates
Sands
Coal beds thicker than 15 feet
Non-reservoir Rocks
Aspha It
Petroleum
Reservoir Rocks
Aspha It
Petroleum
Organic Carbon
(reduced forms)
Insoluble Organic
Matter
8,900
1,800
1,300
15
Soluble Organic
Matter
275
265
0.5
1.1
-13,000
Carbonate Carbon
(oxidized form)
9,300
51,100
3,900
-64,000
(a) Data from Ref. 11. One barrel of oil contains about 10
5
grams of carbon.
While these data are only approximate, they do indicate that about one-
sixth of the global carbon is present in reduced forms. Unfortunately. much of
this reduced carbon is widely dispersed an not easily recovered. This is
especially true for the very large amount of reduced carbon held in clays and
shales, where the organic matter is almost always a minor -- often a trace --
constituent. Consequently, only a small fraction of the carbon in clays and
shales is likely to be useful as a fuel resource.
OIL SHALE
Table 2. Shale-Oil Resources of the World's Land Areas
8
,109 bblb
Recoverable
Known
Range in grade, Resources Known Resources
oil yield in gal/ton' 10-100 5-10 10-25 25-100
Africa 10 ne ne ne
Asia 20 2 3,700 ne
Australia and New Zealand 24 ne 84 200
Europe 30 100 200 ne
North America 80 900 2,500 4,000
South America 50 ne 3,200 4,000
Total 214 1,000 9,600 8,000
(a) Data from Duncan and Swanson, Reference 3j Cane, Reference 5.
(b) To convert bbl to m', divide by 6.29.
Page 7
Total Resources
c
5-10 10-25 25-100
4,000 80,000 450,000
5,500 110,000 590,000
1,000 20,000 100,000
1,400 26,000 140,000
3,000 50,000 260,000
2,000 40,000 210,000
17,000 325,000 1,750,000
(c) Includes oil shale in known resources and anticipated extensions of known resources.
(d) To convert gal/ton to L/t, divide by 0.2397.
OIL SHALE Page 8
As shown in Table 2, the current oil shale technology is well suited for
processing the richest (organic-rich) oil shale deposits; those that yield over
10 barrels of shale oil per ton of rock. Using the data in Tables 1 and 2, we
can calculate that present oil shale technology can efficiently recover only
0.06% of the potential oil in relatively rich shales (>10 gal/ton) -- and only
about one-billionth of the total carbon in clays and shales! The challenge is
clear; even a marginal improvement in technology could greatly increase this
minute fraction of recoverable shale oil.
Compared to known -- or even anticipated -- petroleum resources, the oil
shale resource is enormous. This is not surprising, since shales are source
rocks for many of the world's crude oils. Moreover, geochemical studies indi-
cate that only a small fraction of the carbon in a source rock is typically
released as liquids into migration channels that lead to a petroleum reservoir.
Indeed, many crude oils can be regarded as shale oils produced by natural
heating and upgraded into petroleum during migration from the shale source rock
to the reservoir. Thus, a more useful comparison is between the proven and
anticipated reserves of crude oil, coal and natural gas with the shale oil that
could be recovered using current or improved technology (Table 3).3,12,14
OIL SHALE Page 9
Table 3. World reserves of shale oil, coal, bitumen and asphalt and petroleum.
Shale Oil
Resource in place 4,300
Recoverable 30
Billions of Tons
Natural
Coal Bitumen Natural Gas Petroleum
11,000 3,000
663 75
200
80
544
130
(a) Data from References 3,5,12,14 and 77.
Thus, both the coal and oil shale resources dwarf the petroleum resource;
the problem is economical recovery. This is difficult to achieve because of
the widely varying properties of oil shales. The characteristics of some of
the world's best-studied oil shales are summarized in Table 4.14
OIL SHALE Page 10
Table 4. Properties of SOO\e IllflOrtant oil shales from around the world. (Data of Thorne, H. M.; et at. USBM Circ 8126, Reference 14.)
Modified Fischer assay
01 L, L/t
C
Oil, lOt X
Water, lOt X
Spent shale, lOt X
Gas and loss, wt X
Austral ia
(Glen
Davls)a
414
30.0
0.7
64.1
4.3
Conversion of organic
material to oil
d
, lOt % 66
Rock characteristics
Sp. gr. (at 16-C)
Heating value, MJ/Kg
f
Ash, lOt X
Organic carbon, lOt %
Assay oil
$p. gr. (at 16C)
carbon, lOt %
Hydrogen, lOt %
Nitrogen, wt %
Sulfur, lOt %
Ash analysis, lOt X
SiOz
At""
",0
,.0
HgO
other oxides
1.60
18.8
51.6
39.8
0.89
85.4
12.0
0.5
0.4
81.5
10.1
3.0
0.8
0.8
3.8
Grall I
(Treme!!be-
reubate)a
156
11.5
6.2
78.4
3.9
59
1.70
8.2
71.4
16.5
0."
84.3
12.0
1.1
0.2
55.8
26.7
8.5
2.8
3.7
2.5
,,,, ....
(Nova
Scotia)b
257
18.8
0.8
12.7
2.7
12.6
62.4
26.3
0.88
61.1
30.1
5.0
1.1
1.6
1.1
129
9.7
3.2
84.0
3.1
44
2.03
8.9
70.8
18.8
0.90
84.9
11.4
0.8
0.3
55.1
27.6
9.3
1.7
1.9
4.4
New Scotland South
Man- ZeaLand Israel
, ...
Garek)b
Leba- churia (Ore-
non
b
(FushLt1)b pukO
b
78 307
6.4 24.8
2.2 11.0
88.4 56.5
3.0 7.7
48
60.0
10.6
0.97
79.6
9.8
1.4
6.2
ca 26
ca 45
18.8
0.96
83.2
10.3
0.6
1.5
38
3.0
4.9
90.3
1.8
33
2.29
3.4
82.7
7.9
0.92
85.7
10.7
62.3
26.7
6.1
0.1
1.8
3.0
331
24.8
8.3
57.6
9.3
45
1.46
21.3
32.7
45.7
0.90
83.4
11.8
0.6
0.6
44.2
28.1
20.5
4.6
1.4
1.2
111
8.2
2.2
86.6
3.0
56'
2.22
5.9
12.8
12.3
0.88
55.7
25.1
9.9
2.6
3.1
3.6
Africa
(Erm'
etO)a
228
17.6
3.0
75.6
3.8
34
1.58
19.1
42.5
43.8
0.93
84.8
11. 1
0.6
61.3
30.5
2.9
1.6
1.7
2.1
Spain
<Puertol-
leno)a
234
17.6
1.8
78.4
2.2
57'
1.80
12.5
62.8
26.0
0.9<J
0.9
0.3
56.6
27.6
9.1
2.6
2.2
1.9
Swedei'!
O:varn- Thailand
torp)a (Maesod)b
70
5.7
2.0
87.2
5.1
26
2.09
9.0
72.1
18.8
0.98
85.0
9.0
0.7
1.7
62.4
17.6
10.7
1.2
1.7
6.4
357
26.1
3.8
66.3
3.8
71
1.61
15.4
56.4
30.8
0.88
84.4
12.4
1.1
0.4
60.8
19.9
4.8
3.3
3.8
7.4
Unl ted
States
(Colo-
rado)a
122
9.3
1.0
87.5
1.6
70
2.23
5.1
66.9
11.3
0.91
84.6
11.6
1.8
0.5
43.6
11.1
4.6
22.7
10.0
8.0
(a) Average sample. (b) Selected sample. (c) To convert LIt to gal/short ton, multipLy by 0.2397. Cd) Based on the recovery of carbon in oiL from organic
carbon In the shale. (e) Carbon content of oil ca. 84 lOt %. (f) To convert MJ/kg to STU/lb, multiply by 430.4.
OIL SHALE Page II
1. Sedimentation and Mineralogy
Oil shales are fine-grained sedimentary rocks in which are dispersed a
minor fraction of organic matter as tiny particles. Formation of an oil shale
requires simultaneous sources of both fine-grained minerals and organics, under
conditions where the organics can be preserved. In addition to these clastic,
detrital components, biogenic and authigenic minerals are also present tn most
shales. Detrital minerals typically include quartz, feldspar and clays (often
including illite, montmorillonite and kaolinite), and sometimes volcanic ash.
Biogenic minerals include amorphous silica and calcium carbonate, usually in
very minor amounts. Authigenic minerals typically include pyrite and other
metal sulfides, carbonates (calcite, dolomite, siderite), chert and phosphates.
Authigenic silica from clay diagenesis is also an important mineral in many
shales, serving to cement together the larger detrital particles. The saline
minerals, trona, nacholite, dawsonite and halite, are often important in oil
shales (e.g.Green River shales) formed in stratified lacustrine environments.
Not surprisingly, halite (NaCl) is usually present in marine oil shales.
The mineralogy of some representative oil shales from around the world is
summarized in Tables 5 and 6.
OIL SHALE Page 12
Table 5. Mineralogy of some oil shales (After H;rus, Reference 16.)
ShaLe Mh MineraL Amorphous Feld Clay
GyP''''
Pyrite Calcite Magnesite
a
Siderite
(Xl matter sHica ard
'W
minerals (CaSO, " (FeSZ) (MgC0:3) (FeC0
3
)
(%) quartz 0:> (Xl (Xl 2 HzO (%) (%l <Xl
(%) (Xl
Kukersite,
Estonia 36.3 47.87 9.0 6.75 13.9 1.1 4.25 56.1
Kohst,
H.W.F.P.
India 68.7 8 ... 3 12.40 2.47 40.68 0.49 trace 22.68 8.34 3.76
Broxburn,
Main 67.4 76.15 16.55 11.30 45.85 0.43 1.76 2.91 2.63 11.24
Kirrmericige,
Dorset 37.8 40.89 38.97 5.74 20.68 8.56 4.64 3.51
Ermelo,
Transvaal 44.9 47.85 50.13 5.14 29.45 0.24 2.03 1.73 0.24
Tasmanite,
Tasmania 79.2 82.05 56.3 6.0 23.75 1.45 1.64
Antlerst,
Burma 43.9 46.78 34.33 5.63 27.45 5.49 0.19 trace
Boghead,
Autm 65.0 79.2 32.4 n.d. 17.4 1.1 0.7 37.3
1 75.0 83.45 24.6 n.d. 22.9 trace 2.35 5.8 4.15 2.15
II 66.3 86.77 19.3 n.d. 22.9 0.3 1.35 26.7 12.1 5.1
Middle Dumet 77.6 84.76 26.5 n.d. 54.65 0.3 0.55 4.25 3.65
Newnes, N.S.W. 20.1 20.79 74.0 n.d. 17.9 0.3 0.4 3.3
Cypris shale,
Brazi I 65.9 69.50 66.33 n.d. 17.13 0.78 1.24 5.25 0.62
Massive shale,
Brazil 72.8 48.5 n.d. 37.2 37.2 0.4 1.4 2.6 1.1
n.d. '" not determined.
(.,
Apparently lIimus did not consider presence of dolomite (Editorial conment).
OIL SHALE Page 13
Table 6. Mineralogy of Selected Australian and Overseas Oil Shale Samples. (After Hutton, Reference 17.)
Satrple Specific Quartz Clay Calcite Siderite Dolomite Pyrite Apatite Others
, of
Clays
Feld$par Gravity Min$l'sls
" "
II Ch
Condor (Carb.) 1.66 A A T 85 15 T
Jolt. Coolon A A T 85 15
Nagoorin (Carb.) 1.60 A A T T 75
"
Horwell 1.12 Not determined, less than 1% mineral matter
Alpha 1.10 A A T T 70 20 10
Glen Davis 1.16 A A T F fOO
Joadja 1. 17 A A T a5 15
Byfield 1.92 A A T T T B 30 20 50
Condor (Brown) 2.41 A A T T T B 70 20 10
Duaringa (Top) 1.52 A A T T 95 5
Duaringa (Base) 1.60 A A T T 30 55 15
,-'"
1.66 C A T T ao 20
Hereor!n (Brown) 1.94 A A T T ao 5 15
Nagoorin South 1.65 A A T T 25 75 T
RU'ldle (Me Member) 1.41 A A T T 20 70 10
RlI'Idle (Re Menber) 1.62 A A T T T 25 65 10
Stuart (lie Menber) 1. 76 A A T T 15 55 30
Stuart (Ke Member) 1.52 A A C T 5 90 5
,,"""
1.48 c A T 60 40
Green River 2.01 C T A T T A,
Canooweal 2.50 A A A A T
"
25 50
Jut ia Creek 2.02 A A A T 20 20 50 fO
Irati * 2.15 A A T T 35 65 5
Kentucky (C HeRber) 2.24 A A T T 5 5 ao fO
Kentucky ($ Shale) '* 2.12 A A T T 5 5 ao fO
Paris Basin '* 2.26 A A C T T 25 10 55 10
Hersey River 2.04 A A T T 5 75 20
Coorong! te 1.01 onl y surface sand
Carb."Carbonaceous MC-Munciuran Creek RC-Ramsay Crossing IIC-Hutpy Creek KC-Kerosene Creek Ka-Kaol inite Mo-MOI"Itrrori lIonite ll-lttite
en-Chlorite A-abundant C-cOfm'W)n T-trace S-8uddlngtonite (trace) F-Feldspar (traca) Ac-Analcime (coomon)
T-trace (much less than 5%.) *-Percentage of total clay minerals No entry indicates not detected
OIL SHALE Page 14
Minerals in the Green River Oil Shales: Mineral assemblages vary from shale to
shale, from top to bottom within a given oil shale deposit; even from sample to
sample within a given stratum. This complicates mineralogy studies. As a
result, comprehensive mineralogy studies of oil shales are few; most studies
have focused on the occurrence or genesis of one particular mineral or mineral
type, while other studies have concentrated on- minerals of economic interest.
This makes it difficult to get a broad view of the mineral assemblages in even
major deposits. The Green River formation has been extensively studied and a
summary of its mineralogy. based largely on the work of Bradley18,19 and
reviews by MiltonZO and Smith
Z1
, serves to illustrate the range of minerals
that can be present in a single oil shale deposit:
Table 7. Major minerals in Green River oil shale.
a
Ubiquitous
Quartz SiD, III i te KA 1, (A 1 Si, lO, 0 (OHl,
Dolomite CaMg(CO,), Calcite CaCO,
Pyrite, Marcasite FeS, Nachol ite NaHCO,
Soda Feldspar NaA1Si,O, Short ite Na,Ca, (CO,),
Potash Feldspar KA1Si,O, Trona Na, Co, NaHCO, 2H
z
O
Dawsonite NaAl (OH),CO,
(al After Milton, Reference 20.
OIL SHALE Page 15
Table 8. Authigenic SiLicates in Green River Formation (Modified after MiLton, Ref. 20).
Hami of mineral
Clay minerals
Kaolinite
Stevens i ta
Loughlinite
Sepiolite
TaL c
Zeolites
Analcite
Natrotite
Hermotome"wellsite
ClinoptiLolite"
Mordenite
Boros; lleates
Searles! te
Garrels; te
leuc9sphenite
Reedmergnerite
Other 51 lleates
Quartz
Orthoclase
Albite
Acmite
Riebeckite
labunts9vite
Vinogradovlte
Elpidl te
Hatron-catapleiite
Biotite
Hydrobiotite
f-Qf'muLa
H4AlZSix09
(ALO.06feO.04M9Z.81liO.04)
(Si3.9S
A1
0.OZ)010(OH)Z
N8
0.04
H16Ns2M93Si60Z4
H4M9ZSi3010
M93(OH)25;4010
NaAlS1Z06 H20
N8ZAlZSi3010.6 H20
(Ba,Ca,KZ)AlZSi6010' 6 H20
NaBSiZ0
6
6 H20
(8a,Ca,M9)BZ Si 06(OH)3
CaBaNa3BTi3Si90Z9
NaBSi30S
Si02
KaLSi30a
NaAlSi30a
NaFeSIZ06
Ha(FeMg)3 Fe Z(OH,F)(Si4o11>Z
(K,Ba,Ha,Ca,Mn,Ti,Hb)
(Si,AlZ(O,OH)7 HZO
Ha5TI4AlSi60Z4 3 HZO
H6HaZZrSI6018
H
4
(HaZCa)ZrSi3011
K(Fe,MS)3AlSI3010(OH)
(K,H20)(Mg,Fe,Mn)3AtSi3010(OH,HZO)Z
Abundance
Loca It Y abundant
Locally abundant
Locally abundant
Rare
Rare
Widespread
Rare
Rare
Rare
Locally abundant
Rare
Rare
Rare
Ubiquitous
Widespread
Widespread
Rare
Rare
Rare
Very rare
Very rare
Very rare
Very rare
Very rare
OIL SHALE Page 16
The Green River oil shales were formed in the waters of ancient lakes that
covered much of what is now northwestern Colorado, southwestern Wyoming and
northeastern Utah (Figure 2). There were two, and possibly three. of these
lakes; lake Gosuite in Wyoming. Lake Uinta in Colorado and an unnamed lake in
Utah. These lakes existed for a very long time, some 4-6 million years through
the Early and Middle Eocene. As climatic conditions varied the lakes expanded,
sometimes (at least partially) merging, and contracted. Nevertheless, contin-
ued subsidence caused by downward warping of the lake beds enabled the deposi-
tion of sediments that are more than 2000 feet thick in some areas (Figure 3).
Green River oil shales have a very fine texture. In a composite sample
from the U.S. Bureau of Mines site at Rifle, CO, Tisot and Murphy23 found that
>99 wt% of the mineral particles were smaller than 44u, 75 wt% were in the
range of 2 ~ 2 0 p and 15 wt% was smaller than 2p. Surface area of these particles
was low and mainly external surface. Some mineral micropore structure was
found; pore sizes ranged from 10 to 100 A. Essentially all of the organic
matter was in particles lodged between the mineral grains; it was estimated
that less than 4% of the organic matter was contained within mineral particle
pores.
The lithology of the Green River formation is complicated, in part at
least because fluvial material was deposited by creeks and rivers at the edges
of the lakes; edges that moved as the lake levels rose and fell. McDonald has
extensively reviewed this lithology.23 There are, however, some striking
uniformities. The composition of the organic matter in the oil shale is re-
markably uniform, especially within the Piceance Creek Basin on which the
following discussion will concentrate. The most prominent variation going from
top to bottom of the deposit is a decrease in carboxylic acid groups (increased
decarboxylation) in the more deeply buried shales. lateral uniformity is also
OIL SHALE Page 17
Figure 2. The Green River Formation. (Reproduced with permission from
Reference 22. Copyright 1980, Colorado School of Mines.)
10 (I 1(12010 1: ...
- ~ - ' 10 (I 10 20 IOMi
"' .. rt !
P/77.1.7il GltEEN RIVER
~ FOII.MATION
s
CLEAR
CREEK
'"
- .. .::-,
"
"
" \'
, ,
\'
,\
"
"
"
\'
"
"
, "
"
"'''/,?> '
Y. '
LEGEND PARACHUTE
OIL SHALE WITH ;j: CREEK '\
NAHCOLITE MEMBER '"
17'7'7::1 Oil SHALE WITH '" ,/ /'
"'"" DAWSONITE Co ", ,_... .-
"'f. ,/
!:"':":! HALITE AND .... _ ...
NAHCOLITE 1
LEACHING Y
WYO,
,,10 ---:
- p'
,.,. &<l$ln
IteOllce
"IV II: Creek
, S '"
I cC::>
location of (rau uel;on
o
S(lie in milu
, ,
j , I , I
6
,
UINTA
fORMATION
N
SURFACE
Figure 3. South-north cross-section of Colorado's Piceance Creek Basin.
(Reproduced with permission from Reference 22. Copyright 1980,
Colorado School of Mines.)
0
-r
CO
'"
roo
r
7000
;;
z
0
5000
'000
OIL SHALE Page 19
remarkable. Many fine details in core samples can be tracked across distances
of 100 mile.s and major features can be tracked over twice this distance. This
uniformity of organic matter is the more remarkable given the great diversity
of the accompanying minerals and suggests that it may be possible to draw some
general conclusions about the conditions of deposition. To explain the lithol-
ogy and the chemistry that formed the organic-rich oil shales, Bradl ey25 pro-
posed that the ancient lakes were stratified through much of their existence.
Though Bradley later moved away from his proposal, it was developed and greatly
extended by, Smith and his co-workers (Figure 4}.2
1
,22
---- ---- ---- ----- _____ c"_C"_"""" -__
Monimolimnion
Figure 4. Stratified lake,
OIL SHALE Page 20
Mineral Deposition in a Stratified lake: The lake history can be divided into
three main periods. During an initial period of 1-2 million years, clay-rich
oil shales (Garden Gulch and Douglas Creek Members in the Piceance Creek Basin,
Tipton Shale in the Gr.een River Basin) were deposited. Following Smith's
argument, Lake Uinta probably began as a normal, shallow lake and deposited
typical lacustrine sediments for a considerable period as it grew, both in
depth and extent. Thermal density differences abetted by low circulation in
the isolated lake probably initiated stratification and hydrolysis of
aluminosilicates began to build up chemical stratification. Using albite as an
example, G'arrels and Mackenzie give the following example:
26
(1 )
2 NaAISi,O. + 2 CO, + II H,O --) AI,Si,O, (OH), + 2 Na' + 2 HCO,' + 4 H,SiO,
Albite Kaol inite
In this reaction, CO
2
(from decomposition of organic matter) is consumed
as albite is transformed into the clay, kaolinite, while sodium and bicarbonate
ions are produced. Thus, as the lower, clay-rich sediments were deposited the
concentrations of dissolved sodium carbonates increased in the lower stratum of
water just above. This would increase the density of the lower layer of the
stratified lake. At the same time, CO
2
production depleted the oxygen content
OIL SHALE Page 21
of the lower layer providing a reducing environment conducive to preservation
of new organic sediment falling from the oxygenated and productive upper layer.
As HzS was produced by sulfate-reducing bacteria, the precipitation of pyrite
and marcasite would be limited only by the availability of iron in solution.
Eventually, precipitation of the sodium carbonates, such as nacholite (NaHC0
3
),
commenced. The resulting transition from normal lacustrine sediments to oil
shale was not abrupt, and there is no evidence for evaporite deposition at this
point. low circulation in the lake is indicated by even deposition of organic
matter in tiny layers (varves). Under these conditions large clastic matter
would be deposited near the lake shore and only airborne particles and the
finer particles would be deposited in the deeper, stratified zone further from
shore. Note that the anoxic lower layer (monimolimnion) in Figure 4 does not
extend to the shoreline. The upper layer (mixolimnion) was oxygenated, hence
capable of depositing normal lacustrine sediments, including the larger clastic
particles" in the shallow water along the water's edge. Of course, as the lake
expanded and contracted with variations in rainfall and runoff the shore moved
and with it the region where lacustrine sediment was deposited.
The s:econd stage in the evolution of the Green River formation, was a
relatively arid period. As the water level dropped, the large lakes separated
into several smaller lakes in what we now know as the Piceance Creek (Colorado),
Uinta (Utah), Green River and Washakie Basins (Wyoming). These isolated lakes
had individual characteristics that are reflected in a series of saline miner-
als, largely nacho1ite (NaHCO,), halite (NaC1), dawsonite [NaA1(OH),CO,] and
some nordstrandite [Al(OH),] in the Piceance Creek Basin. Mostly trona
OIL SHALE Page 22
[Na,CO, NaHCO, 2 H,O] and shortite [Na,Ca,(CO,),] were deposited during
this period in the Green River and Washakie Creek basins of Wyoming.
In the Piceance basin, the lake was relatively deep and remained strati-
fied. As evaporation proceeded, the concentrations of sodium and aluminum ions
in the lower layer increased to the point that precipitation of the nacholite,
which is 3-4 times less soluble than N a 2 C ~ , commenced. When both CO
2
and
aluminum ions were available dawsonite was precipitated, with occasional
nordstrandite [Al(OH)3] precipitation occurring under conditions of CO
2
deple-
tion.
In contrast, the Wyoming lakes were shallow and did not remain stratified
as evaporation proceeded to dryness, or nearly so. This exposed the lower
layer of t.he lake to the atmosphere leading to increased oxidation of organic
matter. A.s a result sediments formed during this period contain little organic
material. Also, exposure of the concentrated aqueous Na
z
C03 solution of the
lower layer to atmospheric COz led to trona precipitation, accompanied by
calcite and shortite limited by the availability of calcium. Intermittent rain
falling in this playa lake may have contributed to trona evaporite formation by
dissolving previously-deposited Na
z
C01, thereby exposing it to atmospheric COz.
Under these conditions, trona deposition would no longer be limited by the rate
of COz production from organic decomposition. Deposition of today's thick
trona beds was the result.
The presence and types of authigenic minerals is an important indication
of the conditions present during sedimentation and subsequent burial. For
example, the presence of authigenic sulfides and high levels of organic materi-
al together in an oil shale suggests deposition and burial in an anoxic, re-
OIL SHALE Page 23
ducing environment of low Eh (Eh is the oxidation potential of the solution,
referred to the standard hydrogen half-cell).15 Since the typical surface
waters (rain water. flowing streams, ocean surface) are strongly oxidizing,
this probably means an environment of low circulation, such as a lower level in
a stratified lake or sea, where oxidation of the organic matter is minimal.
The fine grain size of the detrital clays generally found in in oil shales is
also consistent with this kind of stagnant depositional environment.
Oxidation-Reduction and Hydrogen Ion Potentials: In general, the deposition of
non-clastic, non-evaporite minerals can be understood in terms of oxidation-
reduction (redox, Eh) and hydrogen ion (pH) potentials, subject of course to
the availability of aqueous ionic species. Figure 5 shows a classification of
sediment types based on Eh and pH and the region occupied by natural
environments is shown in Figures 6 and 7. Note that the region of Figure 5 and
the region of Figure 7 where the points are most dense, correspond to only the
center of Figure 6. Most oil shales of interest were formed within a very
restricted region of Eh - pH space, namely the region where pH > 6 and Eh is
below the "sulfate-sulfide fence." This was alluded to in the discussion of
Green River oil shales above and will be referred to often in subsequent
discussions; Figures 5-7 are key to our understanding of oil shale formation.
OIL SHALE Page 24
Figure 5. The relation of Eh and pH to the (non-evaporite) minerals in
sedimentary rocks. (After Pettijohn
27
and Krumbein and Garrels
28
)
eH
-0.3
pH 7.0
I
HEMATITE
LIMONITE
MN OXIDES
SIUCA
CHAMOSITE'
0
ORGANIC MATTER
0
o.
'"
SILICA
"
ORGANIC
PEAT MATTER
w
SIDERITE u
<
w
GLAUCONITE
-
J
RHODOCHROSITE
CHAMOSITE
>
PHOSPHORITE
,
--===::
w
<
sU{PJ.flltr;
"
'"
"
-
w
u
<
w
-
- SUt
PItIOf:
ORGANIC
PEAT MATTER
PyRITE
PHOSPHORITE
PYRITE
SILICA
'* ," ",." "*'. "
01 Ih .. """ "';'0''',
w
<
0
>
w
,
J
8.0
I
,
CALCITE
FENCE ftl1 0
CALCITE
ORGANIC
MATTER
'0
'c
o
CALCITE
ORGANIC
MATTER
""f.lct:
CALCITE
ORGANIC
MATTER
OIL SHALE
Page 25
Figure 6. Eh and pH characteristics of some natural environments. (After
Garrels and Christ, Reference 29. Reprinted with the permission of
Harper & Row) Inc.}
EH
+0.8
-+0.6
:+0.2 -
0.0 .
-0.2
-0.4 -
-0.6
-0.8
1.0
OIL SHALE Page 26
Figure 7. Measured Eh and pH of some natural environments. (Baas Beeking,
et aI.3o Reprinted with the permission of Pergamon Press.)
! 000
800
600
400
Eh 200
Zero
-200
-400
" ,
,
, .'
,
.,
Iy,
';,
"
pH
OIL SHALE Page 27
2. Production of Organic Matter
Earlier. the terms kerogen (insoluble organics) and bitumen (soluble in
organic solvents) were defined. These are the biogenous materials that are the
major reason for our interest in oil shales. Many oil shales also contain
readily discernable skeletal fragments, fossilized fish bones, insect parts,
diatoms and even bacterial cell walls. These fossils are interesting and are
important indicators of conditions through geological time, but generally have
little effect on the technological properties of oil shales. Oil shales depos-
ited in near shore areas generally contain significant amounts of woody terres-
trial material that have an important adverse effect on oil generating
potential.
As shown in Figure 1, only a minute fraction of the carbon cycling through
the biospn,ere becomes incorporated into sediments, and of that only a small
part is preserved to become fossil fuels. It is important to understand how
conditions, affect this process because it helps to identify potential oil shale
basins, to locate oil shale deposits within these basins, to predict the g e o m e ~
try of oil shale seams and to pinpoint the most valuable areas that have thick
deposits of high-yielding oil shale. Without trying to be too precise, three
oil shale types can be identified by depositional environment: marine shales
that were deposited in salt water are widespread, lacustrine shales that were
deposited in fresh water are extensive as discussed above, while the less
common, coal-associated shales were formed in areas subjected to uplift which
altered the environment from aqueous to swampy. In each case, characteristics
of the oil shale organics were determined by two factors: production and
preservation.
OIL SHALE Page 28
Production of Organic Matter in Aqueous Environments: Photosynthesis by
phytoplankton, especially algae (Cyanophycaej, diatoms,
dinoflagellates, and in warmer waters by phytobacteria, is ultimately
responsible for producing nearly all of the organic matter in the ocea05.
31
,32
The relative importance of different life forms to primary productivity in the
aquasphere through geologic time is summarized in Figure 8.
33
A precise quantitative relationship between the fossil record and organic
productivity is not available; many productive species have no hard body parts
that are easily preserved, hence their productivity may not be reflected in the
surviving fossils. Nevertheless, as pointed out by Moore, the fossil record
indicates significant differences between production in marine and lacustrine
environments.
34
These are summarized in Figures 9 and 10, where the forms that
are predomjnantly organic in composition are shown in black, while other forms
(e.g. silicious diatoms) are unshaded.
Photosynthetic productivity is mainly controlled by light, temperature and
nutrient availability. Light seems not to be the controlling factor, except in
deep water, polar regions or turbid coastal regions.
31
The availability of
CO
2
, which is essential for photosynthesis, is not limiting in the "eutrophic
zone" -- the top 200 meters, or so, where productivity is highest. Rather,
nutrient availability -- often nitrogen (as ammonium or nitrate) in marine, or
phosphate in lacustrine, environments -- seems to be the most common limit on
productivity.35 The availability of vitamins, especially of vitamin 8
12
, and
other trace organics is important, and seems to be a limiting factor in some
OIL SHALE Page 29
Figure 8. Importance of phytoplankton types to primary production through
geologic time. (after Tappan and loeblich;33 reprinted with the
permission of the Geological Society of America.)
estimated
total amount
(a general lrend)
Distribution with respect to type of organisms
Tertiary
- e
2 .,! ... "0
'! ic-----+ '" _"0 _E _"i:
.: <'II ';::: 0 II
CretaeoUli
Jurassic
o .D ... -
uw.,!O>
1-----+ . --0 - ~ - ~ -"'--11-41--11-11--1
Triassit:
a
Permian
Cambrian
Precambrian
100
ISO
150
'"
'00
\\0
600
E
OIL SHALE
Figure 9. Main groups of
reprinted with
upper'
;upper
,lower
Triaute
Devonian
Silurian
Ordovician
Precambrian
" a
w
microfossils in
the permission
<n
w<n
aw
:r"
<n
:r
OW
(J
J:"
a
(J"
"
"
z
'"
<n
z
::>
(J
>-
"
J:O
Page 30
marine environments. (Moore;34
of Springer-Verlag.)
<n
"
z
<n <n
"
a
"'
0
:r
w
w
"
<n
0
'"
0
z
0
<n
"
N
;;
a
0
0
0
0
"
(J
0
"
z
"
(J
0
(J
0
Ow
0
"
0
w
(J"
"
'"
(J ...
15
z 0
-" '"
0
"
:r
0
"
<n 0 (J
(J
0
(J
'"
0
(J
<n
OIL SHALE
Page 31
Figure 10. Main groups of microfossils in lacustrine environments. (Moore;34
reprinted with the permission of Springer-Verlag.)
a:
Z
if)
if)
Z
w
w
w
W
l-
I-
<.!> a: ...J
Z
U Z <.!>
0
...J
::;:
:::>
...J
Q. 0 ...J W
co ....
if)
Q. Q. a:
Tertiary
;Iower
lCretaceous
Mesozoic urassic
riassic
IP,'rlmian
upper QUS
'Ionian
lower
mbrian
Precambrian
OIL SHALE Page 32
areas, Productivity in lakes follows the same general pattern as in oceans,
but deposition in the confines of a lake is much more subject to local climatic
variations and periodic changes in clastic input (e.g. volcanic ash) than is
marine deposition.
3. Kerogen Types and Maturation
While most of the organic matter in oil shales was produced in an aqueous
environment. some terrestrial material is often present. Moreover, conditions
of burial affect the nature of the organic matter. The concepts of kerogen
type and kerogen maturation provide a useful framework for understanding and
classifying these effects.
Kerogen types, I, II and III, are determined by the kind of debris that is
deposited in the sediment. As initially deposited in a "recent sediment", each
type of sediment has a (reasonably) characteristic range of composition. As
the sediment becomes buried deeper and/or hotter and for a longer time, the
organic material in the sediment undergoes "maturation" to give oil, gas or a
mixture of the two. The following discussion is based largely upon information
about kerogen type and maturation that has been developed in the context of
petroleum exploration.
11
,13,38
Type I kerogen is rich in lipid-derived aliphatic chains and has relatively
low polyaromatic and heteroatom contents. The initial atomic H/e ratio is high
(1.5, or more) and the atomic o/e ratio is generally low (0.1, or less). Such
kerogens are generally of lacustrine origin and have very high oil generating
potentials. Organic sources for the Type I kerogens include the lipid-rich
OIL SHALE Page 33
products of ualgal blooms" and the finely divided and extensively reworked
lipid-rich biomass in oil shales that, like those of Green River, were
deposited in stable stratified lakes. The rubbery material, Coorongite, that
results from periodic Botryococcus blooms in the Coorong district of Australia
and the sediments of Big Soda Lake (Nevada), a stratified, saline lake provide
contemporary examples of Type I kerogens.
38
,39 Oil shales that contain Type I
kerogen include the Autun and Campine boghead shales, and torbanite (Scotland),
as well as the Green River oil shales. Tasmanite is a marine sediment that
contains Type I kerogen.
Type II kerogens include most of the marine oil shales, of which many are
important petroleum source rocks. Atomic HIC ratios are generally lower than
for Type I kerogens, while generally higher o/e ratios reflect more ketones,
carboxylic acids and esters. Organic sulfUr levels are also generally higher,
generally reflecting more thiophenes and in some cases sulfides, as well. The
oil generating potentials of Type II kerogens are generally lower than those of
the Type I kerogens; that is less of the organic material is liberated as oil
upon heating a Type II kerogen (at the same level of maturation, see below).
The organic matter in these kerogens is usually derived from a mixture of zoo-
plankton, phytoplankton and bacterial remains have been deposited in a reducing
environment. The Devonian shales of the U.S. and Canada (Chattanooga, Sunbury,
New Albany, Duvernay), the Jurassic shales of Europe (e.g. Toarcian, Paris
basin), and the Paleozoic shales from North Africa contain Type II kerogen.
Type III kerogen is found in coals and coaly shales. Easily identified
fossilized plants and plant fragments are common, making it clear that this
type of kerogen is derived from woody. terrestrial material. These materials
OIL SHALE Page 34
have relatively low atomic H/C ratios (usually < I), relatively high atomic O/C
ratios (0.2 -0.3 or even higher). Aromatic ~ n d heteroaromatic contents are
high and ether units (especially of the diaryl type) are important, as expected
for a lignin-derived material. Oil generating potentials are low, while gas
generating potentials are high. No oil shales contain predominantly Type III
kerogen, but many oil shales contain some clastic material of terrestrial
origin. Because this material is easily identified under the microscope. it is
often disproportionately emphasized in petrographic studies. Moreover, because
of its high aromaticity a small contribution of clastic Type III material can
greatly complicate attempts to elucidate the chemical structure and reactivity
of Type I or Type II kerogens. Thus, in oil shale studies it is important to
identify and understand the contribution of Type III kerogen.
After the relatively rapid alterations that take place shortly after the
initial deposition of organic matter in a sediment, the surviving (preserved)
organic matter undergoes additional changes. This is the process of kerogen
maturation, which is responsible for the generation of crude oil and natural
gas. Oil shales contain relatively immature kerogen; that is the kerogen has
not been extensively "cooked", except where exposed to an unusual geothermal
gradient, such as an intrusion of volcanic magma (geologic sill or dike). Over
geologic time, however, further alteration does occur. Thus to understand the
chemical structure and reactivity of oil shale organics, it is necessary to
know not only the origin but also the maturity of the kerogen.
The van Krevelen Diagram provides a simple way of graphically representing
the relationships between kerogen type, kerogen composition and maturation
(-Figure II).
OIL SHALE Page 35
Figure II. The van Krevelen Diagram traces the evolution paths of Types I. II
and III kerogen as a function of increasing burial (increased time-
temperature exposure). Note that maturation eventually leads to a
hydrogen- and oxygen-depleted, carbon-rich residue without regard
for kerogen type. (After Tissot and Welte, Reference 13, p 152.
Reprinted with the permission of Springer-Verlag).
,
T
9
l'
,
E
9
"
'0
0'
__
o 000 0.10 0,15 020 0.25 0.:';0
T""
I
][
][I
Atomic mHo OIC
Mo,n potl> at oomic e<Xll. {elh" ()Y,ond .1 01,1976)
....... _- Boondar;"s of lile htld a! ktroqtn
....- [voMion paIn. of tile p,jndfl(ll lyPU of ke'<><JM
Age Ind / or f6rm.tion Buin,country
Green Ri.e< sholes (PoIt<lCtr>e _ E<K,,"")
Ui!\lo. Uloh, USA
AIQOI M'09_ j BoI1yoc<x:cl/$, e1c ..J.VQrious <:>it >IIoles
lOwe, Toore;on st>ote. f'<I<i$.F<"<If'IC",W.Germony
$iIo.ttion .tmI<!. Soh<;l<o,AIQ"'" ond libyQ
Vorio...$ oil "",,"S
Ooual<l,eom."""",
UIwo. """te. Albedo, Conod"
1"Dwe. Morwwillt' $IlQIes (Me Iver ,19671
Alb .. Io,Conod<>
0
0
OIL SHALE Page 36
As shown above, maturation involves the loss of hydrogen and oxygen from
the kerogen. Oil shales are generally immature and only the earlier stages of
maturation, termed diagenesis, need be considered. During diagenesis, hydrogen
is lost primarily as methane and other light hydrocarbon gases, water and
hydrogen gas, while oxygen is lost primarily as water and carbon oxides. These
losses are, however, significant in determining the processing characteristics
of the oil shale kerogen in retorting for liquid fuel production.
As maturation proceeds into the "oil generation window", the atomic Hie
ratio decreases due to hydrogen loss as hydrogen-rich liquids that are expelled
from the rock (Figure 12); see Brooks40.41 for discussions of recent progress
in understanding kerogen maturation.
Maturation increases with increased exposure of the organic matter to
time, temperature and pressure. The catalytic effects of minerals in the oil
shale accelerate this process. Thus, maturation involves exposure of organic
matter to a time-temperature-pressure-catalysis history. Similar effects are
seen in "simulated maturation" experiments in the laboratory and in oil shale
retorting to produce shale oils.
OIL SHALE
% WEIGHT OF INITIAL ORGANIC MATTER
I SEDIMENTARY ORGANIC MATTER)
.....
. ': .. :.'
: : .. " ...
SIMPLE MOLECULES (CO!"H!,O,CH4,H!'J
CARBONACEOUS RESIDUE
~
Page 37
A
c
Figure 12. Evolution of hydrocarbons, water and carbon oxides from kerogen
during maturation. (After Durand, Reference 36. Reprinted with
the permission of Editions Technip.)
Legend:
I. CO
2
+ H
2
0
2. Oil
3. Wet Gas
4. Methane (dry gas)
5. Resins + Asphaltenes
6. Kerogen
7. Base-solubles (humic and fulvic acids)
8. Acid-solubles (hydrolyzable material, e.g. lipids)
OIL SHALE Page 38
4. Preservation of Organic Hatter
A fundamental problem in basin geochemistry is to understand how organic
stratigraphy data from rock analyses relate to the occurrence and variability
of oil shale beds. Efforts to understand how the preservation of sedimentary
organic matter forms kerogen types I, II and III led to the concept of organic
facies (Figure 13).42
* The geologic term facies refers to a stratigraphic rock unit, differentiated
from adjacent or associated units by appearance or characteristics that usually
reflect its ori9in.43
The relationship between kerogen type and the origin of the sedimentary
organics was discussed above, as was relationship between organic preservation
and the redox potential of the benthic (bottom) environment. Two additional
facets are needed to round out the background for the organic facies concept:
First. kerogen type strongly correlates with depositional redox potential;
that is, Type I and II kerogens are usually found in situations where the
depositional environment was strongly reducing. Under these conditions, organic
preservation was high and reworking was done primarily by anaerobic bacteria
which attack hydrocarbons, especially aliphatic chains (e.g. lipid-derived waxy
material), much less aggressively than their aerobic counterparts. Further,
anaerobic bacteria feeding on non-lipidic plankton remains are efficient
producers of lipids. Thus. anaerobic bacterial action can actually increase
the content of lipid material that converts easily into shale oil upon heating.
OIL SHALE Page 39
Figure 13. Organic facies mapping depends upon a clear understanding of the
relationships between early diagenetic factors (i.e. the benthic,
or "bottom
tl
environment) and kerogen type. (After Oemaison, et
a 7 . ~ Reference 42. Reprinted with the permission of John Wiley
Sons, Inc.)
BACTERIAL
AEROBIC
OXIDATION
ORGANIC
FACIES
OXIC
lAEROBIC)
LOW .... ,---
IV III
GAS-PRONE
TO
NON SOURCE
SUB-OXIC
(DYSAEROBIC)
III
MODERATELY
OIL-PRONE
TO
GAS-PRONE
ANOXIC
(ANAEROBIC)
WATER
I
STRONGLY (cmltlt
OIL- PRONE twAtIUISnCS
OIL SHALE Page 40
In contrast, organic degradation in the oxidizing surface waters of a shallow
swamp tends to give coaly material containing highly aromatic Type III Kerogen.
In part, at least, this is because aromatics and hydroaromatics are much less
attractive substrates for bacterial growth than the aliphatic chains of lipids
(i.e. aromatics are less biodegradable). Thus, not only is the initial aromatic
content of terrestrial material generally higher than that of the algal and
bacterial material, but the aromatics are selectively preserved.
Second, Type II kerogens are often associated with situations where the
environment was moderately oxic, but the depositional rate was high. Under
these conditions, the role of high depositional rate was to minimize the time
the organic sediment was exposed to benthic reworking. Of course this means
that organic productivity also had to be high if the organic content of the
resulting oil shale is high enough to be useful. Otherwise, we would have a
little organic diluted in a lot of sedimentary rock!
This leads to to a description of the four organic facies types:
Organic facies I (strongly oil-prone) are typical of the strongly anoxic
environments of stratified lacustrine and marine systems. Organic contents are
often high. The strata are laminated, the absence of bioturbation (mixing)
indicating the absence of benthic worms in the depositional environment.
Organic facies II (oil-prone) is typical of anoxic environments or of the
moderately oxic environment with high depositional rate. Carbon contents are
generally lower than in facies type I, often in the range of 1 - 10% TOe. The
sediments may be partially laminated, showing evidence of benthic worm burrows
and possib1y evidence of bioturbation by other benthic organisms.
OIL SHALE Page 41
Organic facies III (gas-prone) is typical of the mildly oxic conditions in
coal swamps or shallow marine environments. Any planktonic or algal material
deposited in such an environment will usually be degraded quickly by benthic
bacteria and/or worms. Preserved material of aquatic origin is usually thor-
oughly bioturbated.
Organic facies IV (non-source) is typical of aquatic environments where
organic matter spends a long time in the oxic zone where aerobic bacteria are
active. Such environments occur even at great ocean depths with circulation,
as well as in shallow, circulating seas with high energy input. low organic
contents in the rocks reflect efficient degradation, even where the initial
organic productivity was high. Extensive bioturbation usually precludes the
observation of laminations (varves).
5. Marine Oil Shales
Marine oil shales are usually associated with deposition in one of two
settings (Figure 14).
The anoxic silled basin shown in Figure 14a can occur in the shallow water
of a continental shelf. High phytoplankton growth rates near the surface will
give a high deposition rate. The sill shields the trough from the circulation
of oxygen-laden water. Under these conditions, the decomposition of organic
sedimentary matter will rapidly deplete oxygen within the confines of the
baSin, thereby providing the strongly anoxic (reducing, low Eh) environment
that is needed for efficient preservation.
The anoxic zone in an upwelling area (Figure 14b) arises from circulation
of an open*ocean current over a cold, oxygen-depleted bottom layer. Mixing of
OIL SHALE
Figure 14a. Anoxic silled basin.
ANOXIC SILLED BASIN
I I
14b. Upwelling region.
t
SILL
(CRATON)
ANOXIC ZONE CAUSED BY UPWELLING
( UPWELLING CURRENT-too-
ANOXIC ZONE
Page 42
OIL SHALE Page 43
nutrient-rich current. such as the Gulf Stream, into the CO
2
- and light-rich
eutrophic zone gives an environment capable of sustaining very high organic
production. Such environments occur today along the west coasts of Africa and
the Americas, where good fishing is found along with the potential for or9anic-
rich sediments.44
Information about the nature of organic matter in marine environments has
resulted from studies of recent deposits and the contemporary oceans.
45
-
47
Only
a small part of primary production in the oceans reaches the bottom. Of an
estimated annual production of 9 x 10
19
tons of dry matter, Trask has estimated
that about 2% reaches the floor in shallows and only about 0.02% in the open
sea.
4S
The major part of marine primary production is consumed by predators;
most of the rest by microbes. The principal marine microbial scavengers are
bacteria that live free in the water or are attached to organic particles. In
ocean water, organics occur in solution, in colloidal suspension and as partic-
ulate matter comprising bodies and body fragments of living and dead organisms.
Except in -regions of a seaweed or plankton "bloom", the dissolved organics
usually predominate. As a result, marine bacteria are most abundant only in
the very upper part of the water column and in the organic detritus at the very
bottom. Even in the oceans, the adsorption of organics onto inorganic detri-
tus, such as the silica parts of diatoms, plays an important part in sedimenta-
tion.
After the organic sediment reaches the bottom, reworking begins. Bottom-
dwelling (benthic) organisms feed on both the sediment and dissolved organics
and, in turn, are fed on by predators (e.g. crustaceans). In this sphere, the
benthic bacteria are largely responsible for the decomposition of organics and
the synthesis of new organics through enzymatic transformations. Moore has
estimated that 60-70% of the sedimentary organic carbon is typically liberated
OIL SHALE Page 44
as CO
2
during this reworking, while most of the rest is converted into new
compounds. The result is a very complex mixture.
Cane; has discussed the contributions of various organic compound classes
to oil shales.
48
The compound classes included carbohydrates, 119nin5, humates
and humic acids, lipid-derived waxes and the saturated and polyene acids in
a 1 9a 1 1 i p.ids whi ch can serve as precursors of these waxes, and bi 0109; ca 1
pigments and their derivatives (e.g. carotenoids. porphyrins). Only the latter
three were judged to have sufficient inertness to be major contributors to oil
shale kerogens.
Degens and co-workers have studied the role of proteins, carbohydrates and
humates in marine Protein-derived materials included both
original and altered proteins and their decomposition products (amines. amino
acids, amino complexes). Carbohydrates are rapidly hydrolyzed and generally
not important in oil shales. Humates can be important, even in marine shales,
when deposited near shore, though obviously humic material has been found in
marine sediments that were deposited far from land. It is possible that some
humic material may be derived from proteins and/or carbohydrates, perhaps when
these materials are adsorbed on inorganic particulates (e.g. clays, volcanic
ash) in a moderately oxidizing environment.
lipids are produced by phytoplankton and also synthesized from carbohydrates
by microbi.a1 activity.47 With respect to oil shales, the polyene fatty acids
are especially interesting. It is well-known that adverse conditions can lead
to very high lipid production by algae. At low temperature and with limited
oxygen. for example. Chlorella may produce lipids to >75% of their body weight.
Much of these lipids is unsaturated. Abelson and co-workers found that polyene
acids in lipid fats from Chlorella disappeared upon heating, while saturated
acids remained unaltered.
53
Evidently, the polyene acids polymerized. Cane
OIL SHALE Page 45
has extensively studied the role of unsaturated lipid acids in the products
left by Botryococcus braunii blooms in the Coorong of southern Australia.
4s
Polymerization of the unsaturated lipid residue gives "coorongite", a tough,
resilient, insoluble material that, in many respects, resembles kerogen. 150-
and anteiso-fatty acids have been found in some oil shales, but these are
probably secondary products. leo and Parker have found that bacteria are active
in transforming n-alkanoic acids into the branched iso- and anteiso-acids.
54
,55
Other bacterially-induced transformations include the hydrogenation of oleic
and linoleic acids, decarboxylating and polymerizing alkano;c acids and lipid
hydrolysis.
56
.
58
Carotenoid pigments have been found in many oil shales, and in petroleums
and coals, as well. A recent article by Repeta and Gagosian discusses the
carotenoids and carotenoid transformation products in the waters and sediments
of the Peruvian upwelling and provides leading references to much earlier work
on carotenoids in marine sediments.
59
Studies of the carotenoids isolated from
DSDP (Deep Sea Drilling Project) cores from the Quaternary sediments in the
Cariaco Trench shows that the chemistry of these materials is largely reductive
and traceable over 50,000 - 350,000 years.
60
,61 This work gives useful insight
into the diagenetic transformations of carotenoids which lead to the observance
of partial1y- and perhydrogenated carotenoids in marine oil shales.
62
The black marine shales formed in shallow seas have been extensively
studied, as they occur in many places. These shales were deposited on broad,
nearly flat sea bottoms, hence usually occur in thin deposits (10-50 m thick),
but may extend over thousands of square miles. The Irati shale (Permian) in
Brazil extends over more than 1000 miles from North to South!.' The Jurassic
marine shales of western Europe (Toarcian, Paris Basin,13 also source rock for
Paris Basin crudes; Kimmeridge, England,64-66 also an important source rock
OIL SHALE Page 46
for North Sea crude 011
67
), Silurian shales of North Africa and the Cambrian
shales of northern Siberia and northern Europe are other examples of this kind
of marine oil shale.
6. Lacustrine Oil Shales
The lacustrine oil shales of the Green River Formation, which were dis-
cussed above, are among the most extensively studied of sediments. However,
their strongly basic depositional environment is certainly unusual, if not
unique. Therefore, it is useful to discuss the characteristics of the organic
material in other lacustrine shales.
A particularly thorough study was made of the lacustrine sequences from
the Permian oil shales of Autun (France) and the Devonian bituminous flagstones
of Ciathness (Scotland).68 Several series of biomarkers were prominent in
extracts from these shales: hopanes, steranes and carotenoids. Algal remains
were abundant in both shales. Blue-green algae, similar to those that contrib-
uted largely to the Green River oil shale kerogen, were found in the Devonian
shale, for which a stratified lake environment similar to Green River has been
proposed.
6
'
9
In contrast, Botryococcus remains were found in the Permian Autun
shale and are presumed to be the major source of organic matter, except for one
sample. No Botryococcus remains were found in this sample and the oil produced
by its retorting was nearly devoid of the straight-chain alkanes and l-alkenes
which are prominent in oils from Botryococcus-derived shales. Evidently,
some, as yet unidentified, algae contributed to the organic matter in this
stratum. Biodegradation cannot be ruled out, but seems unlikely due to the
lack of prominent ;so- and anteisoalkanes. Straight-chain alkanes and I-
alkenes were also evident in gas chromatograms of the retorted oils from the
Devonian shale. However, in this case a pronounced hump, which usually indi-
OIL SHALE Page 47
cates polycyclic derivatives, was also prominent. Both extracts and oil from
the Devonian shale were found to be rich in steranes and tricyclic compounds.
Oi- and triterpenoids have been suggested as precursors for the di-and
tricyclic compounds found in many oil shales.
7o
-
72
Rock-Eval pyrolysis results
indicate that these shales have high hydrogen indices; the kerogens are all
Type I or Type II, with one of the Devonian samples being clearly Type I.
Other major lacustrine oil shale deposits include the Triassic shales of
the Stanleyvil1e Basin in Zaire and the Albert shales of New Brunswick, Canada
(Mississipian).
D. OCCURRENCE
Oil shale deposits are located throughout the world.
3
73
,74 but it is the
features of the major deposits (Table 9) that are of particular interest in the
present context. Such depOSits are of interest because of their potential to
produce large amounts of oil and (hopefully) having minimal recovery problems.
OIL SHALE Page 48
Table 9. Age and geologic setting of major oil shale deposits.
Average Estimated
Type of Grade, Resource,
Materi a1 Geological Age Geologic Settjng gal/ton lQ6 barrel s
Green River Oil Shale Tertiary Eocene Stratified lake 25 4,300,000 (22)
Phosphoria (Montana) Oil Shale Permi an Mari ne PI at form (76)
Eastern U.S. (Sunbury, New Albany,
Chattanooga, etc. Oil Shale Devonian Sha 11 ow Sea 10 2,600,000 (75)
Alaska Tasmanite Jurassic Marine 10 Large (3 )
Oil Shale Mississippian Mar; ne PI atform 10 ?
Austria
Australia
Rundle, Stuart Oil Shale Tertiary 65,000 (8)
Toolebuc Oi 1 Shale Cretaceous Sloping Marine Platform 18 365,000 (8 )
Condor Oil Shale Tertiary 107,000 (8)
Dauringa Oil Shale Tertiary 20 63,000
New South Wales Torbanite Permian Marine 33 40 (8,48)
Tasmania Tasmanite Permian lacustrine 42 55 (8,48)
OIL SHALE Page 49
Table 9. Age and geologic setting of major oil shale deposits.
Average Estimated
Type of Grade
t
Reserves,
Materi aJ Geological Age Geologic Setting gal/ton lQ6 barrel s
Brazil
Irat i Oil Shale Permi an Marine Platform 21 800,000 (3)
Tremembe-Taubate Oil Shale Tertiary lacustrine 15-18 2,000 (3,74)
Marahu Marahuito Tertiary Boghead, Coaly 42 Small (3,74)
Canada (Albert) Oil Shale Mississippian lacustrine 13-30 150,000 (3)
China (PRC), Fushun Oil Shal e 01 igocene Boghead 15 1,000 (7)
France
Autun Oil Shale Permian Boghead, Coaly 10-18 160 (3)
Severac-le-Chateau Oil Shale Jurassic Marine 10 250 (3)
Germany Oil Shale Jurassic Marine 12 2,000 (3)
Great Brita in
Kimmeridge Oil Shale Jurassic Marine 10-45 1,000 (3 )
Scotland (Lothians) Oil Shale Carboni ferous Lacustrine, Estuary 16-40 400 (3)
Italy (Sicily) Oil Shale Triassic Matine 25 7,000 (3 )
OIL SHALE Page 50
Table 9. Age and geologic setting of major ojl shale deposits.
Average Estimated
Type of Grade
t
Reserves,
Material Geological Age Geologic Settjng gal/ton lQ6 barrels
Israel, Jordan, Syria Oil Shale Cretaceous Marine 10-25 120,000 (3 )
Morocco
New Zealand
Orepuki Oil Shale Tertiary 45 8 (3)
Nevis, Otago Central Oil Shale Tertiary Boghead 11-15 300 (3)
Portugal Oil Shale Carboniferous Boghead 30 80 (3 )
Spain Oil Shale Tertiary lacustrine 25 280 (3)
Sweden Oil Shale Cambrian-Ordovician Marine 10-25 3,000 (3)
Union of South Africa
Ermelo Torbanite Permian-Carboniferous Boghead, Marine 25 130 (3 )
USSR (Estonia) Kukersite Ordovician Marine Platform 50 6,500 (3 )
Yugoslavia
Aleksinac Oil Shale Tertiary Lacustrine 45 210 (3)
Zaire (Congo) Oil Shale Triassic Lacustrine 25 100,000 (3)
OIL SHALE Page 51
II. CHARACTERIZATION, TESTING AND CLASSIFICATION OF OIL SHALES
Early Scottish workers estimated the quality of cannel coal by the curl of
its shaving when cut with a knife. Similarly, workers at Fushun, Manchuria
found that rich shale curled when chipped with a glass shard, while lean shale
crumbled. There is still a need for methods to evaluate oil shale quality, and
such qualitative methods are still used, especially in the field. However,
these methods have now been supplemented with a variety of Quantitative methods
employing the latest in laboratory instrumentation to determine chemical and
physical properties. In this section, the more important methods currently
used for testing and classifying oil shales will be discussed;
the properties of twelve representative oil shales will be compared and the
methods used to determine these properties will be discussed to illustrate the
general approach.
A. FISCHER ASSAY: DETERMINATION OF OIL YIELD
In the discussion above, the term, "oil yield", was used repeatedly, but
without defining how the values are measured. Related terms include "grade"
(usually in gal/ton), which is synonymous with oil yield, while "rich" and
"lean" refer to shales with higher and lower oil yields, respectively. The
Fischer Assay -- more specifically the "Modified Fischer Assay" (ASTM 03904-80)
is the standard method for measuring oil yield. Because of its importance,
it is appropriate to introduce the Fischer Assay as the first topic in this
section which deals with measuring the properties of oil shales.
The aluminum retort was originally designed by Fischer and Schrader for
assaying coals by pyrolysis.
7
! It proved to be superior to existing methods
for analysis of oil shales.
79
In early practice, a sample of -20 g was heated
OIL SHALE Page 52
rapidly to a maximum temperature of 520-550C, using a gas burner, and the
experiment was concluded 15 minutes after the final drop of distillate was
collected. Stanfield and Frost produced a version holding 100 9 of sample and
containing aluminum discs to minimize local overheating (Figure 15).80
'"
"(> --
, <l,a '"'
w
" ,
:;
'n __ I' ,.,
,
"-
; I __
0'.' 1(/
00 0'
D3904
,
o
,
" ,
..
. .
. ,
,
"" ; ,"
',,' ""1
"n IT/a ,., 0 ....
L-
,
"
,
.i
,::on ..,
.... !" ..
Figure 15. Modified retort for Fischer Assay. Capacity is 100 g.
OIL SHALE Page 53
1. Modified Fischer Assay: The Standard Method for Oil Shale Assay
Using the new retort, modifications to the procedure have been made to
improve both accuracy and reproducibility. These include the use of retorts
with standardized heat capacity, standardized heating programs, carefully
controlled condenser and cooling bath temperatures, and continuation of the
assay at a maximum temperature of 500C (Figure 16) until no more oil is pro-
duced. In its present form, the Modified Fischer Assay (ASTM 03904-80) is a
widely used and generally accepted standard method for evaluating oil shales
(Figure 17).81.82
500
400
200
100
o
10 20 30 40 50 60
ELAPSED RETORTING TIME, MINUTES
figure 16. Heating profile during Fischer Assay.
OIL SHALE Page 54
Figure 17. Standardized Fischer Assay apparatus (ASTM 03904.80).
V'== - VfNI 10 (X,jAU51
OV[N
100 ",I CNIRlfllGE 1lJ6<
COOUNG BATH
OIL SHALE Page 55
The shale to be assayed is crushed to provide a on-pound sample of -8 mesh
material. An aliquot is removed for drying to determine total moisture. The
retort is charged with 100 9 of the crushed oil shale in layers. the layers
being separated by the perforated aluminum discs. The retort is then heated to
SOOC over 40 minutes, then held at that temperature for 20 minutes, or until
no more oil is collected (10-20 min. longer for shales richer than 20 gal/ton).
The heavier liquid products and some water are condensed in the centrifuge tube
which is maintained at 100C. Lighter products and the balance of the water
are liquefied in the condenser which is maintained at OC by a circulating
coolant.
When the heating period is complete) the retort and centrifuge tube are
cooled to room temperature and weighed. The tube is centrifuged to separate
oil and water. The water is determined volumetrically and subtracted from the
liquid product weight to obtain the oil yield. The specific gravity of the oil
is determined and used to convert the weight of oil produced to the oil yield
in gal/ton.
2. Shortcomings of the Fischer Assay
Despite acceptance as a standard method, the Fischer Assay has technical
shortcomings. Gases are not determined directly, but by difference as 'gas and
loss'. Some liquid hydrocarbons are also lost as mist. Thus) the yields of
these important parts of the product slate can only be inferred. To provide a
OIL SHALE
Page 56
more c o m ~ l e t e assay, the Toseo Material Balance Assay was introduced in 1974 by
GoodfellOw and Atwood (Figure 18).83
MERCURY SWITCH
MANOMETER --\\.
RETORT
THERMO-
COUPLE
ICE WATER
CONDENSER
SOLENOID VALVE __ ! _____ .J
ICE WATER
GAS 80MB
CENTRifUGE TUBE
Figure 18. TOSCO Material Balance Assay apparatus. (Reference 83. Reprinted
with the permission of the Colorado School of Mines.)
OIL SHALE Page 57
An extensive survey comparing the results of Modified Fischer Assay and
several closely related alternatives for Green River oil shales was recently
reported ,by workers at lawrence Livermore National laboratory.B4 Good inter-
laboratory precision was found, but these workers strongly recommend the use of
one of the material-balance methods for maximum accuracy. These workers also
conclude that lean shales may give product distributions that are significantly
different from richer samples from the same area.
B. ALTERNATIVE METHODS FOR EVALUATING OIL YIELD
Oil yields depend not only upon retorting temperature, but upon heating
rate. Higher oil yields are generally obtained by rapid heating to an optimum
temperature. The Fischer Assay is not useful for evaluating oil yield under
such conditions. This has led to the development of alternative thermal assay
methods (of which the Rock Eval method
SS
is notable), which have recently been
reviewed by Williams.
86
The more important of these, and some non-pyrolytic
alternatives to the Fischer Assay, will be discussed below in the context of
the various instrumental analysis methods.
C. ELEMENTAL COMPOSITION AND OIL YIELD
Most oil shale stUdies have been limited in scope. One of the handful of
studies that both encompassed a wide variety of shales and a wide variety of
techniques was that reported by Robinson and Dinneen at the 7th World Petroleum
Congress.
87
This study provides a starting point for the discussion of how oil
shale properties are determined and the relationships among these properties.
OIL SHALE Page 58
Geological perspective on the twelve oil shales to be discussed Geologically
youngest of the shale samples is the Tertiary Pliocene Sao Paulo shale of
Brazil (1-13 million years old), while the oldest is the Canadian shale of the
Carbonife,rous Period (280-350 million years). Figure 19 shows that the twelve
shale samples represent a wide range of geologic ages and geographic
locations.
GEOLOGICAL PERSPECTtV[ ON Oil SHALES TO BE DISCUSSED
''"' iU1if
1i
,
TEIIT [ARY
Jl!ik""
CRHACOUS
u
0
I """""
"
TRIASSIC
1-""
I '"''''''
,,;;';ii'
CARBONIfEROUS
1-'" , S. AFRICA. SPAIN
"
. UM"
SilURIAN
CO""
Ii
f-'"
CAI1IlIIIAN
I
I'RECAKlR1AH
Figure 19. The twelve oil shales to be discussed represent a wide range of
geologic ages and come from locations around the world. The
table ranks these shales in terms of geologic age. (After Robinson
And Dinneen, Reference 87.)
The twelve samples are also representative of a wide range of depositional
environments, kerogen types and organic facies (Table 10).
OIL SHALE Page 59
Table 10. Geological perspective on the twelve oil shales: Location, depositional environment, geologic
period, kerogen type and organic facies type. (After Robinson and Dinneen. Reference 87.)
Kerogen Organic
Name Location Geologic Period Environment Type Facies Type
Brazil Sao Paulo Tertiary (Pliocene) Lacustrine I I
Oregon, USA Shale City Tertiary (Oligocene) Marine I I
Colorado, USA Piceance Creek Tertiary (Eocene) lacustrine I I
New Zealand Orepuki Tertiary Assoc. Lignite II I I I
Alaska, Tasmanite Kil igwa River Jurassic Marine I I I
Argentina San Juan Triassic-Permian Marine I I I I
France SL Hilaire Permian Assoc. Coal II III
Australia Cool away Mt. Permian-Carboniferous Assoc. Coal (Probably II, probably III)
Spain Puerto 11 ano Permian-Carboniferous Assoc. Coal (Probably I I , probably III)
South Africa Ermelo Permian-Carboniferous Assoc. Coal I I III
Scotland Dunnet Lower Carboniferous Lagoon-Marine I I II
Canada New Glasgow Carboniferous Assoc. Coal II III
OIL SHALE Page 60
'1"1._ 1""_1_. __ -' _ ___ ......' "-
sample are lacustrine shales that are representative of organic facies Type I
and contain Type I kerogen. The Alaskan, Argentine, Oregon and Scottish shales
are of marine origin, representing organic facies Type II with Type II kerogen.
The remaining samples represent the coal-associated organic facies type III.
However, as we shall see, not all contain primarily Type III kerogen.
At this point, the casual reader may be wondering about the introduction
of two apparently redundant concepts, that of kerogen types I, II and III and
organic facies types I, II and Ill. It is tempting to try to simplify matters
by eliminating one. The South African sample provides a compelling illustration
of the need for both concepts.
Microscopic examination revealed that the organic material of the Alaskan,
Australial1 and South African shales contains mostly algal remains. "yellow
bodies" which are generally accepted as being the remains of algal colonies.
Thus, these shales contain Type II kerogen and are classified as torbanites.
The Alaskan and Australian shales are apparently the result of algal blooms in
the shallow waters of a marine platform or shelf. The Alaskan and Australian
shales show little evidence of woody plant remains (terrestrial input). Thus,
these fit cleanly into organic facies type II, as well as having Type II
kerogen. However, the South African shale deposit is coal-associated and has
appreciable terrestrial input. Presumably. this shale was formed from the
remains of the algal blooms in a stagnant lagoon or stream near a coal-forming
swamp. Thus, the South African sample is an example of a shale that has mostly
Type II kerogen, yet fits into organic facies type III.
OIL SHAL Page 61
Organic ~ a r b o n Content and Oil Yield Table 11 summarizes the elemental
compositions and oil yields of the twelve oil shales and data for their
corresponding kerogen concentrates. The organic carbon (TOC) contents vary
from 7.9% for the Canadian shale to 81.4% for the Australian sample. (Strictly
speaking, the Australian sample does not contain 33% mineral matter, hence
should not be termed an oil shale. We will ignore this distinction, for the
purpose of the present ill ustrat i on. ) The oil shales conta i n hydrogen. not
only in organics, but also as water and in the minerals (e.g. as 5i1aoo1s).
Hence, the hydrogen contents of the oil shales are not reported. The kerogen
concentrates were freed of their hydrogen- containing minerals by HC1-HF
treatment and carefully dried. Consequently. the hydrogen contents of the
kerogen concentrates reflect only the organic hydrogen present in the starting
oil shales. (See Appendix A for a description of the calculations used to
extract the reported values from the results of elemental analysis.) Not
surprisingly, the assay oil yields generally increase with the organic carbon
content of the shale. However, the situation is not that simple! Note, for
example that the Colorado and Brazilian shales have nearly identical TOC
contents, but the oil yield from assay of the former shale is much higher
(27.7 gal/ton vs. 17.8 gal/ton). Evidently. factors other than TOC are also
important in determining the quality of an oil shale.
OIL SHALE Page 62
Table 11. Elemental compositions and oil yields of the twelve oil shales. (Data from Robinson
and Dinneen
t
Reference 87.)
Geological Age
Raw oil shale
Organic C, wt% TOC
Total N, wt%
Total S, wt%
Ash, wt%
Mi nera 1 CO
2
, wt%
Assay oil, gal/ton
Kerogen concentrate
Organic C, wt%
Organic H, wt%
Ash, wt%
5
Alaska
53.86
0.30
1.30
34.1
0.1
139.0
83.28
11 .48
1.5
6
Argentina
8.88
0.26
0.48
82.6
4.5
14.2
51.66
6.60
34.9
8
Australia
81.44
0.83
0.49
4.4
0.1
200.0
83.58
10.69
1.7
I
Brazil
12.79
0.41
0.84
75.0
0.6
17.8
64.88
8.52
12.5
12
Canada
7.92
0.54
0.70
84.0
2.4
9.4
54.78
5.57
33.4
4
Colorado
12.43
0.41
0.63
65.7
18.9
27.7
66.38
8.76
12.9
OIL SHALE Page 63
Table 11. (Continued) Elemental compositions and oil yields of the twelve oil
(Data from Robinson and Dinneen, Reference 87.)
Geological Age
Raw oil shale
Organic C, wt% TOC
Total N, wt%
Total S, wt%
Ash, wt%
Mi nera 1 CO
2
, wt%
Assay oil, gal/ton
Kerogen concentrate
Organic C, wt%
Organic H, wt%
Ash, wt%
7
France
22.25
0.54
2.32
66.3
8.4
25.0
70.47
6.45
17.7
2
New
Zealand
45.69
0.78
4.79
32.7
0.1
66.2
63.89
7.48
9.9
3
Oregon
25.83
0.51
2.20
48.3
0.2
48.0
47.32
6.00
36.2
11
Scotland
12.33
0.46
0.73
77.8
3.2
22.2
67.61
7.62
18.6
shales.
9
South
Africa
52.24
0.84
0.74
33.6
0.9
99.8
81.14
9.12
1.3
10
Spain
26.01
0.55
1.68
62.8
2.3
46.9
61.08
7.04
26.0
OIL SHALE Page 64
o. BITUMEN CONTENI AND COMPOSITION
Bitumen contents of the shales were by exhaustive extraction
with benzene.
99
It is interesting to note that there is no simple correlation
between the organic carbon contents and the amounts of extractable bitumen
(Table 12). The Australian shale with the highest organic carbon content gave
one of the lowest bitumen yields, while the Colorado shale with a relatively
low organic carbon content gave one of the highest. likewise, no simple
correlation exists between age and bitumen content. The relatively young
Tertiary shales of ColoradO, Oregon and New Zealand gave higher bitumen yields
per per weight of carbon (9 - 15.5%) than did the older shales (3.4 - 6.2%).
However, the South African shale which is also of Tertiary origin, gave the
lowest bitumen yield, both in absolute terms and on a per weight of carbon
basis (0.3% and 0.7%, respectively). There does appear to be a relationship
between carbonate mineral content and bitumen yield for this limited set of
samples, but such a relationship would not be apparent were the data for a much
larger sample set examined. There are, however, some interesting relationships
between bitumen composition and geologic age and these will be discussed in an
upcoming section.
OIL SHALE Page 65
Table 12. Bitumen contents, extraction ratios, organic carbon contents and
contents of carbonate minerals for the oil shales.
8
Extraction
Mineral
Bitumen. Ratio,b TOC, carbonates,
wt% wt% wt%
Oregon 4.0 15.5 25.83 0.2
New Zealand 4.3 9.3 45.69 0.1
Colorado 2.7 9.0 12.43 18.9
France 1.4 6.2 22.25 8.4
Scotland 0.7 5.4 12.33 3.2
Canada 0.4 5.3 7.92 2.4
Argentina 0.4 5.1 8.88 4.5
Spain 0.9 3.4 26.01 2.3
Brazil 0.4 3.3 12.79 0.6
Alaska 0.5 0.9 53.86 0.1
Australia 0.5 0.7 81.44 0.1
South Africa 0.3 0.7 52.24 0.9
(a) Data from Robinson and Dinneen, Reference 87.
(b) Extraction ratio = 100 x % bitumen / % organic C.
The benzene extracts were fractionated into asphaltenes (pentane-insolubles)
and pentane-solubles at OC. The pentane-solubles were further fractionated by
chromatography to obtain n-alkanes, branched- and crelo-alkanes, aromatics,
polars and resins (Table 13).
OIL SHALE Page 66
Table 13. Distribution of components in the bitumen extracted from the oil sha1,
Branched
+ cyclic Tota 1
n-Alkanes, alkanes, Aromatics, Polars, Resins, i n ~ , hydrocarbons,
wt% wt% wt% wt% wt% wt%
Canada 14.9 31.7 0.5 0.6 40.7 47.1
Scotland 11.4 32.6 2.1 0.1 44.0 46.1
Alaska 4.7 34.5 5.3 0.5 35.7 44.5
Spain 6.9 35.1 2.2 0.1 54.2 44.2
Australia 10.6 28.4 0.9 0.1 40.9 39.9
South Africa 16.5 20.0 0.9 0.1 49.4 37.4
Argentina 0.4 29.8 3.6 0.3 61.5 33.8
France 0.2 23.9 3.5 0.1 56.8 27.6
Colorado 1.1 13.7 0.9 0.1 66.2 15.7
Brazil 1.1 9.6 1.3 0.1 37.4 12.0
Oregon 0.2 7.0 0.2 0.2 43.2 7.4
New Zealand 1.1 1.4 0.2 0.1 9.5 2.7
<a) Data from Robinson and Dinneen, Reference 87.
OIL S H ~ L E Page 67
It is interesting to note that the bitumen from the Canadian shale (one of
the oldest) contains 47% hydrocarbons and 53% non-hydrocarbons, while the New
Zealand shale (one of the youngest) contains only 3% hydrocarbons the other 97%
being non-hydrocarbons. Evidently, oil shale bitumen, like petroleum, loses
heteroatoms as it matures. What is not clear is whether heteroatom loss to
produce hydrocarbons, or reaction of heteroatom species to produce insolubles,
is responsible for this phenomenon. The observation that the older bitumens
contain less of the heteroatom-rich pentane-insolubles suggests that the latter
may be more important.
The n-alkane fractions were analyzed by GC and the results were used to
calculate the arbon Rreference indices (CPI)* for the C'4 - C'9 and C
25
- C
29
ranges (Table 14).89
* Several ways of expressing the odd preference have been proposed. The
original definition by Bray and Evans used the C
24
- C
34
interval:
89
CPI = 0.5
C
25
+ C
27
+ ... + C
33
(25 + C
27
+ ,., + (33
----------------------- + ---------------------
Analogous expressions, that average the preferences in overlapping even-
carbon ranges, were used to calculate (PI's in the ranges discussed above.
OIL SHALE Page 68
Table 14. Bitumen CPI values for the C
14
- C
'9
and C
25
- (29 n-alkanes.
s7
CPI Values
C
'4
-
C'9 C"
- C
29
New Zealand 1.04 4.76
Brazil 0.50 4.00
Colorado 1.18 3.17
Australia 0.60 2.03
South Africa 1.00 1.44
Oregon 0.72 1.33
Alaska 1.03 1.28
Scotland 1.04 1.21
Spain 1.03 1.18
Canada 1.04 1.16
France 0.41 0.99
Argentina 1.08 0.96
In the higher MW range, alkanes with an odd preference often indicate
terrestrial input; higher plants produce even-numbered carboxylic acid groups
which give odd alkanes upon decarboxylation. No such preference is observed in
material of marine origin.
91
Because of the abundance of cuticular waxes in
higher plants, the terrestrial contribution usually determines CPI in a mixture
of marine and terrestrial material. Generally, (PI in the higher MW range
decreases with age, as cracking produces lower MW species. Concomitantly, any
initial preference in the lower range is generally overcome by dilution. This
pattern is generally evident in Table 14.
OIL SHALE Page 69
Carboxylic (fatty) acids were isolated from the shales by washing with
mineral acid to remove carbonates, then heating with aqueous KOH for 18 hours
under reflux to saponify esters. The acids were methylated and adducted with
urea to separate the esters of straight-chain acids from those of cyclic and
branched-chain acids. The straight-chain esters were then analyzed by Ge. A
close relationship was observed between the n-alkanes and the carboxylic acids
having one more carbon atom.
Five acyclic isoprenoid compounds expected in the oil shale bitumens were
2,6,10,14-tetramethylhexadecane (C,o, phytane); 2,6,10,14- tetramethylpentadecane
(C'9' pristane); 2,6,IO-trimethylpentadecane (C,.); 2,6,IO-trimethyltridecane
(C'6); and 2,6,IO-trimethyldodecane (C,,). The iso- and eyelo-alkane fraction
chromatograms were obtained using identical injection amounts and conditions
(Figure 20).
The Brazilian and New Zealand bitumens contained only small amounts of the
expected isoprenoids, while the Oregon bitumen contained the most. Phytane:
pristane ratios varied widely. In general the younger bitumens contained more
phytane than pristane. The compounds eluting in the range of 250" - 32S"C
include the steranes and hopanes. Gammacerane, a pentacyclic triterpane with
five six-membered rings (not a hopane), was isolated from this sample of
Colorado bitumen.
92
OIL SHALE
Page 70
Figure 20. Isoprenoid compounds in the oil shale bitumens. Chromatograms are
arranged in descending order of phytane:pristane ratios. (From
Robinson and Dinneen, Reference 87. Reprinted with the permission
of Elsevier Publishing Company.)
II.",
)
II
I
M.
. .
"-
HEW It'l'..o
./
l " 1i
hA I
iSt:<
.A IA il
.I ,M.
sP".
Go " "'1
J,
,
'"
,Ny,
eUltl
Jv..
I
"
m
'"
..
OIL SHALE Page 71
III. PHYSICAL/CHEMICAL PROPERTIES
The correlations of the oil yield and heating value of oil shales with
their chemical and physical properties are based upon many different kinds of
measurements. These range from simple, qualitative tests that can be performed
in the field to highly sophisticated quantitative measurements using the latest
in laboratory instruments. This section describes some of the more useful
correlations and the measurement methods on which they are based.
A. ATOMIC H/C AND N/C RATIOS
The relationships of the organic hydrogen and nitrogen contents, and assay
oil yields, to organic carbon contents is shown in Table 15. StOichiometry
suggests that oil shales with higher organic Hie ratios can yield more oil per
weight of carbon than those that are hydrogen-poor. Figure 21 shows that this
is generally the case. However, H/e is not the only important factor. The
South African shale with an H/C ratio of 1.35 has an oil yield/TOC of 0.72,
while the Brazilian shale with an H/C ratio of 1.57 gives an oil yield/TOC of
only 0.52. In general, the shales whose kerogen is converted efficiently to
oil, contain relatively low levels of nitrogen. However, the Brazilian and
Colorado shales have very similar nitrogen contents, yet give very different
oil yields.
OIL SHALE Page 72
Table IS. Ratios of hydrogen, assay oil yield and nitrogen to organic carbon.
(Data of Robinson and Dinneen, Reference 87.)
Kerogen Hie Nle x 10'
Concentrate (atomic) Oil Shale Oil/TOe Oil Shale (atomic)
Alaska 1.65 Alaska 0.95 Alaska 0.48
Colorado 1.58 Austral ia 0.92 Austral ia 0.87
Brazil 1.57 Colorado 0.85 South Africa 1.38
Australia 1.53 South Africa 0.72 New Zealand 1.46
Argentina 1.53 Oregon 0.70 Oregon 1.69
Oregon 1.52 Spain 0.68 Spain 1.81
New Zealand 1.41 Scotland 0.67 France 2.09
Spain 1.38 Argentina 0.61 Argentina 2.51
South Africa 1.35 New Zealand 0.54 Brazil 2.74
Scotland 1.35 Brazil 0.52 Colorado 2.82
Canada 1.22 Canada 0.44 Scotland 3.19
France 1.10 France 0.43 Canada 5.85
OIL SHALE Page 73
Figure 21. Conversion of oil shale organics as a function of atomic Hie ratio.
(Data from Robinson and Dinneen, Reference 87.)
100
~
.
z
80
0
VJ
.1
a::
w
>
z
60
0
0
1
0
z
<:
0
40
a::
0
20
1.00 1.20 lAO 1.60 1.80
ATOMIC Hlc RATIO
OIL SHALE Page 74
B. ALIPHATIC AROMATIC AND CARBON CONTENTS
A high atomic Hie ratio, as in the Alaskan and Colorado shales indicates
little unsaturation or aromatic. coal-like structure. Conversely, a low atomic
Hie ratio generally indicates high content of material with coal-like aromatic
structure. Infrared spectra of the kerogen concentrates qualitatively confirm
this conclusion, as shown in Figure 22.87
C. NHR DATA
The advent of high-resolution, solid-state NMR techniques has provided the
geochemist a powerful tool for probing the structures of the organic material
in solid oil shale kerogens and coals. Miknis and co-workers
93
Maciel and
Dennis,94 Resing and co-workers
95
and Hagaman and co-workers
96
have used
13C NMR with ross-Qolarization and magic-gngle 1pinning, the so-called CPMAS
technique, to determine the fractions of aliphatic and aromatic carbon in a
variety of oil shales and the corresponding kerogen concentrates. Typical oil
shale spectra are shown in Figure 23.
About this same time, the sensitivity of quantitative CPMAS NMR results to
the cross-polarization contact time was pOinted out by Vucelic, Juranic and
Vitorovic.
97
The importance of this contribution can hardly be overemphasized.
Thus, to obtain the highest accuracy it is necessary to optimize contact time
for each sample. However, experience has shown that accuracy sufficient for
most purposes, especially for comparisons of closely-related samples, can be
obtained using a contact time of 1-2 milliseconds.
Paramagnetic and ferromagnetic species can also affect the quantitative
accuracy of NMR spectra obtained using the CPMAS technique. The problem of
quantitative reliability in solid-state "c NMR spectra of oil shales was first
OIL SHALE Page 75
Figure 22. Infrared spectra (in KBr) of the kerogen concentrates. Intensity
of the band at 1600 em-' increases with aromatic content. (After
Robinson and Dinneen, Reference 87. Reprinted with the permission
of Elsevier Publishing Company.)
100
80
80
40
20
80
60
40
20
"
0
80
e
~
80
.;
40
0 80
0
60
i
40
20
0
0
e
ArganU,.,.
Australia
Brazl!
~
60
40
ro
0
Canada
80
60
40
ro
0
Colorado
40
Frequency, em'
Significant mineral bands appear below 1200 cm-t. For organic struc-
tural comparisons use absorptions In regions of: 1600 em,l (aromatic),
1700 em" (carbonyl), and 3450 cm,1 (hydroxyl)
-Low aromatic: Alaska, Colorado, Australia.
-Significant aromatic structure: New Zealand, Oregon, Brazil-
tertiary shales.
-Carbonyl strongest in Colorado, Brazil, Argentina and France.
-Most hydroxy! groups: Brazil, Oregon, Colorado, New Zealand-
younger tertiary shales.
OIL SHALE Page 76
Figure 23. Solid-state "C NMR spectra of oil shales obtained under CPMAS
conditions. (Miknis, et al., Reference 93. Reprinted with the
permission of Pergamon Press.) Note that the samples used in
this work are not identical to the twelve shales discussed in
the previous section, though several are very similar.
a} Australia, Coolaway Mt.
200 gallton
PermlanCarbonlferous
Paludal
h) Alaska, Chandalar
136 gallion
Devonian
Marine
c) South Afrha, Ermels
68.8 gallton
Permlan-Carbonlferous
Paludal
d) Color,do, Green River
Formation
59.2 gallion
Tertiary-Eocene
Locustrlne
e) Bmz:ll, Irati Deposit
31.3 gallton
TartlaryPllocene
Locu.tlne
1---530 ppm--t
Higher Shielding
7
,1.'
(Reprinted with the permission of Pergamon Journals, Ltd.)
-...
o
OIL SHALE Page 141
Key features of this model include very large regions of undefined
structure containing trapped organics of unknown nature and bearing sidechains
linked to the main structure by non-hydrolyzable C-C and hydrolyzable ester
linkages. An ester linkage is shown connecting two such large regions. Also,
the model includes a carbocyclic ring. presumably derived from a Diels-Alder
reaction involving the allyl CC of phytol (3,7,11,15-tetramethyl-2-hexa-decen-
I-al), and the gem-dialkyl site on this ring is identified as a possible
location for oxidative cleavage to give an isoprenoid C
16
carboxylic acid. To
understand this model, it is important to recall that the oxidation products
(acids, ketones) upon which most of this structure is based, represented only
0.7 wt% of the total organic carbon.
2. Djuritit-Vitorovit Model of a Green River Oil Shale Network
Vitorovit and co-workers used stepwise alkaline permanganate oxidation
to obtain carboxylic acids in high yield (70% of total organic carbon) from
Green River oil shale kerogen.
193
The more recent studies that were discussed
in a previous section extended and confirmed this work. Based on their
oxidation results a crosslinked macromolecular network structure was proposed
(Figure 39).
MONOCARBOXYLIC
ACID
00
_ISOPRENOID
CHAIN
UNBRANCHED
-+-- ALIPHATIC CHAIN
ISO ACID 0
). 110
o
FATTY ACID
/
REGIONS SUSCEPTIBLE
TO KMnO, OXIDATION OR
ALKALINE HYDROLYSIS
t
SIMILAR
I I I I
-0 ISOPRENOID MONO.
CARBOXYLIC ACID
POLYMETHYLENE
BRIDGE
\
Figure 39. Djuricic and Vitorovic model Green River oil shale kerogen
as a crosslinked, three-dimensional macromolecular network composed
mainly of unbranched alkyl and alkylene chains. (Reprinted with
the permission of Pergamon Press. Ltd.)
...
N
OIL SHALE Page 143
The most striking feature of this model is the predominance of straight-
chain groups in the backbone of the network. The network bears both branched-
and unbranched sidechains. The branching points (indicated in the model by
open circles) must be of a type susceptible to oxidative attack, alkaline
hydrolysis, or both in order to yield the observed mixture of mono-, di-, tri-
and tetracarboxylic acids. This model accommodates many important experimental
observations, including reversible swelling and gel-like "rubbery" behavior in
the swollen state, but does not satisfactorily account for the aromatic carbons
observed by 13C-NMR or the appreciable Nand S contents found by elemental
analysis.
3. Green River Kerogen Model Proposed by Schmidt-Collerus and Prien
The kerogen model proposed by Schmidt-Collerus and Prien was assembled
from the subunits identified by their micropyrolysis-MS studies (see discussion
above).236 Key features of this model include formulation as a three-dimen-
sional macromolecular network and a very uniform hydrocarbon portion comprised
mostly of small alicyclic, and hydroaromatic subunits with few heterocyclic
rings (Figure 40). Long-chain alkylene and isoprenoid units and ethers serve
as interconnecting bridges in this structure. Entrapped species (bitumen)
include long-chain alkanes and both n-alkyl and branched carboxylic acids.
This model provides a useful view of the types and role of hydrocarbon units,
but de-emphasizes heteroatom functional groups and rings. This is not
surprising. The concentration of Nand $ in residues from thermal treatments
of Green River oil shale kerogen is well-known. Hence, groups containing these
elements would not be seen with high efficiency by the micropyrolysis technique
used by these workers.
su
su
N!!!j NHetero Matrix Subunit
-II! Entrapped Acidic Subunit
-11 Entrapped Neutral Subunit
SU Other Matrix Subunits
-
--
n
--
--
--
--
--
--
--
--
K
/'K
o
n
-0 MATRIX SUBUNIT NUCLEUS
K = OTHER KEROGEN SUBUNITS
Alkane Bridge (normal + branched)
-0- Ether Bridge
-'---,4" Methyl Terminal Alkanes
(normal + branched)
~ - - . " " Entrapped Aliphatic Acids
(normal + brllnched)
~ - - - , - Entrapped Alkanes
(normal + branched)
Figure 40. Small ring systems are highlighted in the Green River kerogen model
proposed by Schmidt-Collerus and Prien.'3. (Reprinted with the
permission of the American Chemical Society.)
o
-
r
V>
j;
r
m
-0
.,
'"
'"
-...
...
OIL SHALE Page 145
4. The Yen-YoungShih Multi-Polymer Structure
The structure of Green River oil shale kerogen has been probed by Yen and
his co-workers using a wide variety of techniques, including stepwise alkaline
permanganate and dichromate/acetic acid oxidations, electrochemical oxidation
and reduction (in non-aqueous ethylenediamine/liCl) and X-ray diffraction
techniques.238-243 Based on the results of these studies, Yen concluded that
aromaticity was low ("approaches zero) but isolated carbon-carbon double bonds
were possible, that the structure was largely comprised of 3-4 ring naphthenes,
that oxygen is present mostly as esters and as ethers, that the kerogen
structure comprises a three-dimensional network and that ethers serve as
crosslinks in this network (based on results obtained by Fester and Robinson)
with additional linkages provided by disulfides, nitrogen heterocyclic groups,
unsaturated isoprenoid chains, hydrogen bonding and charge-transfer
interactions (Figure 41).
Using these components as building blocks, Yen constructed a "multipolymer"
network (Figure 42).245 Further discussion of this model was provided by Yen
in References 242 and 246.
The Yen-Young-Shih model is characterized by a very irregular hydrocarbon
structure consistent with their X-ray results that indicated that the kerogen
is amorphous -- lacking any long-range order. This is in sharp contrast to the
very uniform structure envisioned in the model proposed by Schmidt-Col1erus and
Prien (Figure 40).
OIL SHALE Page 146
Figure 41. Components of Green River Oil Shale Kerogen. (After Yen,
Reference 244).
COMPONENTS BRIDGES
cS
0 -S-S- Disulfide
O
-0-
Ether
CD Isoprenoids
,0
E -C-O-
Ester
~
\
Isoprenoids Steroids
-1'="
H
N-H
0
0
CV Terpenolds
H Heterocyclic
0
I
A -C-N-
Amide
H
C + CH,-CH-(CH,).-CH +
"=15,17,19 R
Carotenolds
R = (CH,),-CH, Alkadiene
+CH,-CHR+
R = (CH,).CH,
n = 22,24,26,28 Alkene
OIL SHALE Page 147
Figure 42. The multipolymer model of Green River oil shale
kerogen. (Reprinted with the permission of Ann Arbor Science
Publishers, Incorporated.)
Circles:
Squares:
!IJ
E
C
S
I
C
!IJ
A
0
[BJ
Essential Components of Kerogen
Molecules trapped in Kerogen network
T
I. isoprenoids. S. steroids. T. terpenoids. C. carotenoids.
Bridges:
D. disulfide. O. ether. E. ester. H. heterocyclic. A. alkadiene.
OIL SHALE Page 148
Yen points out that the extractable bitumen molecules could reside, more
or less freely depending on their size, in c ~ v i t i e s (molecular free volume)
within this network.
To account for the observed variations in the products obtained from the
individual steps of stepwise permanganate oxidation, Yen suggested an unusual
"core plus shell II arrangement for the i ndi vidual kerogen part i C 1 es. The core
in this arrangement is a rather loosely crosslinked region containing most of
the alkyl and alkylene chains and the bulk of the kerogen as naphthenic ring
structures. The shell, on the other hand, is more tightly crosslinked and
contains most of the heteroatom functional groups and heterocyclic rings. This
has interesting geochemical implications. Recall that the outside of a
particle of Yen's kerogen concentrate is precisely the part of the kerogen that
was in contact with the mineral matrix in the starting shale. And that the
heteroatom groups tend to interact more strongly with minerals than do the
hydrocarbon chains. Perhaps, soon after deposition and before the kerogen
became rigidly crosslinked, the kerogen components organized themselves into a
micelle-like arrangement with the polar heteroatom groups on the outside and
the non-polar hydrocarbon groups within. Crosslinking could then "lock in"
this arrangement. Organic-mineral interactions in the resulting composite
would then be ideally situated to hinder physical separation of minerals from
kerogen. This picture is consistent with the results of Siskin, et al. on
chemically-assisted oil shale enrichment.
17o
,171 Clearly, confirmation of this
idea by more direct means (perhaps depth profiling by auger or ESCA) would be
desirable to provide a basis for the development of more efficient oil shale
beneficiation and/or grinding technologies.
,
OIL SHALE Page 149
5. Characterization of Organic Material in Rundle Ramsay Crossing Oil Shale
The organic material in oil shale from the Ramsay Crossing seam of the
Rundle Deposit of Queensland, Australia (RXOS) was characterized and modeled by
Scouten and co-workers, using an integrated, multi-technique approach.
163
Acid
demineralization yielded the kerogen concentrate (RXOS-KC) and the chemistry
that accompanied this demineralization was studied. Selective derivatizations
under mild conditions with isotopically labelled reagents followed by solid
state 13C_ and 29Si-NMR analysis enabled a comprehensive study to chemically
characterize the organic functionalities in the kerogen concentrate. Combining
this data with in depth MS and NMR analyses on shale oils produced under mild
conditions from RXOS and variable-temperature X-ray diffraction studies on the
kerogen concentrate led to the development of a detailed structural model of
the organic material. This work is summarized to illustrate both the features
of the Ramsay Crossing kerogen and the power of the closely integrated
characterization-modeling-reactivity approach.
The Ramsay Crossing oil shale used in this work contained 18.69 wt.%
organic material finely dispersed in a mineral matrix. Solid state 13C NMR
employing CP/MAS indicated an aromaticity of 23% which includes contributions
from olefin and carbonyl carbon types. Exhaustive Soxhlet extraction with THF
removed 8.5 wt.% of the organics as bitumen. The as-received moisture content
was >20%. After drying at 5 0 ~ C in a nitrogen purged vacuum oven, RXOS has
little surface area (16.6 m'/g) or porosity 0.05 cc/g), hence it is very
impermeable to organic solvents and reagents. As a result, organic reactions
which do not dissolve the minerals proceed slowly and often do not go to
completion. To circumvent this mass transport limitation, RXOS was demineral-
OIL SHALE Page ISO
ized, using aqueous HC1/HF at 2 0 ~ C 2 4 7 to produce the corresponding swellable
kerogen concentrate (RXOS-KC) prior to chemical reactions for derivatization of
organic functionalities. The 13C NMR aromaticity and the bitumen content of
the kerogen concentrate were unchanged from the raw shale values. However,
elemental analysis indicated that the bitumen had a significantly higher
hydrogen content, was lower in nitrogen and sulfur than RXO$-KC and had an
aromaticity of <1%. Analyses by Ge, MS and GC-MS indicated that aliphatic
carboxylic acids, esters and amides with long paraffinic chains comprised the
major portions of the bitumen. The elemental composition of the ground (-80
mesh) RXOS, and its kerogen concentrate give empirical formulas for the
organics of C'OOH16,Nz.3S0.70X and C'OOH16,N1.8SS0.709.Z, respectively,
indicating that 0.45 N's/lOOC's were lost during the preparation of the kerogen
concentrate.
Hydrolyzable Nitrogen. Nitrogen bases liberated during the acid washings
would be retained in the acid solutions as the corresponding ammonium salts.
To recover and identify these free bases all of the acid washings were basified
with 50% aqueous KOH under a nitrogen sweep. Any volatile free base evolved
during basification was swept through HCl solutions where it was trapped as the
corresponding hydrochloride. Complete evolution of bases was ensured by
heating the basic mixture until a small of water had distilled into the flask
containing the HCl solution. Solvent extraction of the basic solutions and
evaporation of the HCl solutions to dryness under reduced pressure afforded
0.S2 g of dissolved salts (%C, 0.39; %N, 7.63; %N, 2S.79; %K, 0.21; %C1,
6S.43). Theoretical for NH,C1 (%N, 7.54; %N, 26.18; %C1, 66.28). The very low
carbon content ruled out the presence of major amounts of organic amine
OIL SHALE Page lSI
hydrochlorides. Over 75% of the total ammonia was liberated during the Hel
treatments indicating the presence of primary ami des which are hydrolyzed by
the aqueous acids. The rest of the ammonia liberated during the HF treatment
is due to ammonium ions associated with silicate minerals.248-251
Non-hydrolyzable Nitrogen: Unhindered Basic Nitrogen. Quaternization of
unhindered basic nitrogen compounds (e.g. pyridines) with iodomethane at 50C
in THF gives the corresponding quaternary ammonium methiodides. Under these
conditions hindered nitrogen bases (e.g., 2,6-disubstituted pyridines) do not
react, or react slowly. Non-basic nitrogen compounds (e.g., pyrroles) do not
react. Thus, methylation with iodomethane {90% 13C enriched was used to
quantify unhindered nitrogen bases. The reaction was followed for 28 days by
"C NMR. Most of the methyl groups were added to oxygen (as esters) appearing
at 51 ppm and to carbon sites at -15 ppm. Nitrogen methyls were added slowly,
but after 14 days 0.1 N-methyls/IOO C's had been added at -40 ppm and this
value did not increase with additional reaction time.
Total Basic Nitrogen - Unhindered Basic Nitrogen"" Hindered Basic Nitrogen.
A sample of O.IN KOH washed (to remove any amine hydrochlorides) RXOS-KC was
treated with anhydrous HCI in methylene chloride at -78C for times of 5, 10
and 15 min. The number of chlorine atoms added at each reaction time was
obtained by elemental analysis. At the low temperature used, olefin
hydrochlorination to give the corresponding alkyl chloride should be much
slower than protonation (neutralization) of the basic nitrogen groups.
Consequently, the data were extrapolated to zero time to correct for the small
interference of the olefin reaction. This gave 1.0 basic N
/
s/100 C's as an
estimate of the total basic nitrogens in RXOS-KC. As discussed above, 0.1
OIL SHALE Page 152
unhindered N-bases/IOO C's were identified. The remainder, 0.9 N/s/IOO C's are
ascribed to sterically hindered basic nitrogen functionality.
Non-hYdrolyzable Nitrogen: pyrroles (and Alcohols). Although pyrroles
and indoles are not methylated under PT-O methylation conditions (below), even
highly hindered pyrroles can be quantitatively methylated under more severe
conditions of Qhase transfer atalyzed - nitrogen methylation (PTC-N
methylation) using methyl tosylate as the methylating reagent, 50% NaOH as the
base and tetrabutylammonium bromide (TBAB) as the phase transfer catalyst.'s,
PTC-N methylation of RXOS-KC with methyl tosylate (90% "C-enriched in the
methyl group) was carried out for 48h under reflux. Analysis by "c NMR (and
confirmed by combustion-MS) indicated the addition of 3.1 methyls/IOO C's;
2.2 O-methyls/IOO C's, 0.3 N-methyls/IOO C's and 0.6 C-methyls/IOO C's. The
2.2 O-methyls/IOO C's correspond to the 1.6 esters observed during PT-D methyl-
ation at 51 ppm. The additional intensity corresponding to 0.6 O-methyls/IOO C's
c.a. 56.5 ppm are assigned to derivatives of aliphatic alcohols generally
observed in the range of 55-59 ppm. The assignment of the carbon resonance at
57 ppm to derivatives of aliphatic alcohols is also supported by the results of
'9Si NMR studies of the silylated derivatives. The 0.3 methyls/IOO C's
correspond to derivatives of carbazole-like compounds (0.2 N-methyls/IOO C's),
plus methyl derivatives of pyrroles and indoles (0.1 N-methyls/IOO C's) which
were formed under more severe PTC-N methylation conditions.
Carboxylic Acids and Phenols. The quaternization reaction described
above was carried out in the absence of strong base. Under the influence of a
moderately strong hydroxide base, such as TBAH, acidic O-functionalities,
carboxylic acids and phenols, can be quantitatively methylated to give the
OIL SHALE Page 153
corresponding methyl esters and methyl ethers. This reaction when carried out
in 1:1 THF:CH,OH at 20'C is very selective for O-methylation. PT-O methylation
of RXOS-KC showed by "c NMR to add 2.1 methyls/IOO C's. These methyls were
distributed as 1.6 esters/IOO C's at 51 ppm, 0.3 C-methyls/IOO C's and
0.2 N-methyls/IOO C's.
Ketones. Sodium borohydride is a very mild reducing agent which selectively
reduces ketones in the presence of esters, carboxylic acids and carboxylate
salts. The resulting alcohols can then be converted into the corresponding
trimethylsilyl (TMS) derivatives by silylation. A sample of RXOS-KC was
treated with 0.5N sodium borohydride in diglyme (2-methoxyethyl ether) for 72h
at 20C. It was then silylated with MSTFA (N-methyltrimethylsilyltrifluoro-
acetamide) in THF for I week at 50C. Analysis of the resulting silyl
derivative by "c NMR indicated the presence of 3.9 TMS groups/IOO C's,
corresponding to 2.5 TMS/IOO C's derived from acids, alcohols and pyrrolic
N-compounds initially present in RXOS, plus an additional 1.4 TMS/IOO C's
assigned to alcohols derived from the corresponding ketones. These carbonyl
carbons, as well as those from acids, amides and carboxylates overlap with the
aromatic carbons in the 13C NMR and must be subtracted from the aromaticity.
Esters. Lithium aluminum hydride is a powerful reducing agent which
rapidly and quantitatively reduces carboxylic acids, esters and ketones to the
corresponding alcohols. Consequently, reduction with LiAIH, in THF for 16h at
20'C, followed by silylation with MSTFA and analysis of the silyl derivative
was chosen to quantify ester fUnctionalities in RXOS-KC. The "C NMR result
indicated the presence of 2.2 TMS/IOO C's arising from the LiAIH, reduction of
OIL SHALE Page 154
esters in RXOS-KC. Since LiA1H4 reduction produces two alcohols per ester
group, it follows that RXOS-KC contains 1.1 esters/IOO C's.
07efins. Olefins rapidly react in the dark with bromine in carbon
tetrachloride at O ~ C to produce the corresponding dibromides. Interference
from phenol bromination was ruled out because only traces of phenols were
detected during Pt-O methylation. Also, bromination of ketones should be slow
in a nonpolar solvent and in the dark. 8romination afforded a derivative
containing 3.14 Br/IOO C's. It follows that the RXOS-KC contains 1.57 C=C/IOO
C's. Also, 3 olefinic C's/IOO CiS must be subtracted from the total
aromaticity value seen by 13C NMR.
The Distribution of FunctionaliUes in RXOS. Combining the hydrolyzable
nitrogen results with the characterizations on the RXOS-KC enables a
comprehensive description of the distributions of hydrocarbon, and 0- and N-
heteroatom functionalities in the solid RXOS (Figure 43). It should be noted
that values for the non-derivatizable functionalities, ethers and
N-alkylpyrroles, were obtained by difference.
Non-Derivatizable FunctionaHties - Analysis of Liquids. The selective
derivatization chemistries described above led to quantification of 76% of the
oxygen (6.95 of the 9.2 O's/IOO C's) and 78% of the nitrogen (1.85 N's of 2.3
N's/IOO C's) present in RXOS. The balance of the oxygen and nitrogen, and
essentially all of the sulfur (0.7 S's/IOO C's) are present in functional groups
which are not easily derivatized. Identification of the bulk of these function-
alities was based upon analyses of liquids produced by thermal treatment of
RXOS at 425"C for I h, followed by THF Soxhlet extraction of the residue, which
afforded 86% recovery of the total organic matter as liquids and gas.
234
,235
OIL SHALE Page 155
Figure 43. Distribution of organic functionalities in Rundle Ramsay Crossing
oil shale.
100 C's
- ,
,
MODEll
-
77
-
C
paraffinic
C=O 4
-------,
3.66:
------..,
C::::::C 3 3.14 :
-
_____ -1
16 1
-
C
aromatic
9.2 0's1100 C's-_______ _
lMODEU
2.3
ETHERS
0.6
ALCOHOLS
1.4
METHYL
KETONES
2.2
ESTERS
2.3
CARBOXYLIC
ACIDS
,
AMIDES OA5
--
2.24:
-
-
0.63:
-
1 .4 1:
-
2
-
2
--
-
0
--
----{
Ar-OH <0,0 1: 0.05:
2.3 N's/100 C's ________ _
o 5
R-PYRROlES
PYRROLES 0.3
HINDERED
1 .0
BASIC N
BASIC N 0.1,
AMIOES 0.45
------'
-
-
-
-
-----,
0.31:
----'"I
-
-
-
-
OIL SHALE
Page 156
High resolution MS and NMR analyses of the liquid products, and of fractions
separated from these products using HPLe techniques, indicated appreciable
amounts of furans, thiophenes, and pyrroles bearing a substitution group on
nitrogen. These results also provided the distribution functions of aromatic
condensation, alkyl chain length, and provided information about the average
pattern of aromatic substitution.
Paraffins (average C
23
) and olefins (average (20) were essentially all
linear, and each comprised about 8% of the HPLe saturates. X-ray analysis of
the RXO$-KC indicated the importance of paraffin-paraffin interactions (gamma
band), and the unimportance of aromatic stacking (no 002 band), in the
secondary organic structure. Also the observation of a sharp band
corresponding to a d-spacing of 4.2A, characteristic of waxy paraffins having
long, linear chains and the disappearance of this band upon heating to 90C,
reinforces the importance of the paraffin interactions. Alpha- and beta-
olefins in approximately equal amounts comprised the bulk of the olefins, with
smaller contributions from gamma- and trisubstituted-olefins. Additional
olefins were found as olefinic side chains on aromatics (20% of the liquids),
and almost all of these olefins were conjugated with the aromatic nucleus.
Condensation of the aromatics in the RXOS liquids averaged 4-6 rings. The
average aromatic nucleus bears one methyl group, remnant of the benzylic
cleavage of ethylene bridges, and one very long side chain about 30 carbons
long. Side chains in RXOS are very linear.
Among the oxygen-containing compounds found in the liquids, there were no
carboxylic acids, alkyl ethers or alcohols. Thermal treatment results in
decarboxylation of acids to form alkanes, cleavage and dehydration of ethers to
OIL SHALE Page 157
form alkanes and olefins and dehydration of alcohols to olefins. Small amounts
of esters were present. Long chain methyl ketones (average 20 C's) were
prevalent. Most of the observed furans were 2- and 3- ring benzologs. Three
ring furans existed as naphthalenofurans.
All of the sulfur in the liquids were present as derivatives of thiophene
benzologs. The 3-r;n9 thiophenes (mostly dibenzothiophenes) comprised about
half of the total, with contributions from 1-, 2-, and 4-rin9 derivatives.
Among the nitrogen derivatives found in the liquids were benzologs of
pyridine and pyrroles, nitriles and N,D-compounds. Indole derivatives
comprised 25% of these N-derivatives - the largest single fraction - followed
by pyridines, quinolines and carbazoles. Aliphatic nitriles and smaller
amounts of aromatic nitriles (1- and 2-ring) were found. The aliphatic
nitriles were essentially linear (average C
40
). These aliphatic nitriles were
probably produced during thermal treatment of RXOS (e.g., by dehydration of
primary amides), as no nitrile absorption was detected in FTIR spectra of RXOS.
Smaller amounts of di-nitrogen compound, and compounds containing both N- and
0- heteroatoms (e.g., 2-pyridone) were also found.
OIL SHALE Page 158
Representative Structural Model of Organic Material in Solid Rundle Ramsay
Crossing Oil Shale. The model with a formula weight of 30,000 daltons (and an
empirical formula of C1ooH160Nz.2SS0.6S09.2Z) was required to accommodate the
large range of heteroatom functionalities and long side chains present in RXOS
(Figure 44). It was not possible to accurately represent the range of compound
types in the bitumen because of its small amount (8.5%) and the need to
maintain a finite model size. Because carboxylic acids comprise the major part
of the bitumen, all the bitumen in the model was represented as carboxylic
acids. The values shown in the dashed boxes in Figure 41 illustrate the good
agreement of the model with the experimental values for the distributions of
hydrocarbon, oxygen and nitrogen functionalities.
I.
P'O
o
,
o
,\ /,
o
0>0
o
-.
;.0
6S1 a6.d
o
o
"
.... 0
!
\\ /, '"
o
,
'.0
o
..,
-.
""
c
...
'"
...
...
V>
...
...
C
n
...
C
...
.,
"
0
c.
'"
0
....
...
'"
'"
...
'"
'"
...
.,
...
-.
<
'"
0
...
""
.,
n
"
.,
...
'"
...
.,
0
0
.
0
'"
c
c.
'"
'"
.,
"
.,
'<
'"'
...
0
""
0
= .,
'"
31VHS 110
OIL SHALE Page 160
A comparison with models for Green River oil shale (GROS) kerogen serves
to illustrate some of the key features of the RXOS kerogen.
Aliphatic material is the most obvious feature of the RXOS model and RXOS
is more aliphatic than typical samples of GROS. Aliphatics in RXOS are longer
and more linear than those in GROS and are present both as alkylene bridges and
as alkyl side chains. Isoprenoid chains are distinctly less abundant. Some of
the polymethylene chains in RXOS are very long and proximately situated to give
appreciable regions that have the ordering characteristic of paraffin wax
crystals. Thus, secondary structure due to paraffin-paraffin interactions is
important in the RXOS kerogen. No such waxy paraffin interactions are apparent
in the GROS X-ray diffraction results.
246
Hydroaromatic rings also make an
important contribution to the RXOS aliphatics.
The average ring system in RXOS is only slightly larger than that in GROS,
but the size distribution in RXOS is appreciably broader; a significant number
of the larger 4-5 ring systems are present.
Bitumen content of RXOS is lower than that of GROS. The typical biomarker
compounds are present, but are much less abundant than in GROS. Most of the
bitumen is a mixture of carboxylic acids.
The nitrogen content of RXOS is lower than that of GROS (2.3 N's/IOO C's
vs. about 3 N's/IOO C's). Some of the nitrogen in RXOS is present as primary
amides and additional nitrogen is present as aliphatic amines. However, the
major part of the nitrogen in RXOS is present in very stable aromatic nitrogen
heterocycles, derivatives of pyridine and pyrrole.
The organic oxygen content in RXOS is much higher than that in GROS
(9 O's/IOO C's vs. 3 O's/IOO C's) and present in a variety of fUnctional group
OIL SHALE Page 161
types. Carboxylic acids are important and some of the carboxylic acids that
were observed in the kerogen concentrate are initially present in the rock as
amides. Some free carboxylic acids are evidently present in RXOS, as they are
observed in the extractable bitumen. How the balance of the carboxylic acids
are bound in the starting shale is not yet known.
This discussion serves to illustrate the power of the closely integrated
characetrization-modeling-reactivity approach to provide a model of molecular
structure in sufficient detail to be useful as a tool for guiding oil shale
research and interpreting experimental results.
6. Generalized Models for Types I ~ II and III Kerogen
Workers at the Institut Francais du Petrole (IFP) have taken a distinctly
different approach to kerogen modeling. The studies discussed above were
directed toward modeling the structure of kerogen in a particular oil shale.
In contrast, the IFP workers have constructed generalized models representative
of the three types of kerogen and the of the asphaltenes from the corresponding
oils, as a function of maturity.254,255 Emphasis in this work was placed on
elucidating the chemistry of maturation for the three kerogen types -- in the
context of the IFP approach to the organic aspects of petroleum geochemistry.
The latest IFP models, those proposed by Behar and Vandenbroucke, repre-
sent the kerogen at the beginning of diagenesis sensu stricto (excluding the
early stages of diagenesis which is probably dominated by microbial action), at
the beginning of catagenesis (start of the oil generation window) and at the
end of catageneSiS where late gas begins to be generated. Type I kerogen was
modeled only at he beginning of diagenesis and the end of catagenesis, while
OIL SHALE Page 162
models of Types II and III kerogen were constructed at each stage of maturation
(Figures 45-47). The corresponding asphaltenes were modeled only at the end of
diagenesis/beginning of catagenesis, where they become most abundant (Figure
48). For the asphaltenes, a molecular weight of 8000 amu was chosen.
These models are based on the results of elemental, infrared and 13C-NMR
analyses, pyrolysis (Rock Eval, artificial maturation) and electron microcopy
(fringe analysis) results. The functional group contents that were used in
assembling these models are summarized in Table 25.
The IFP models provide an interesting view of the structural relationships
between the three types of kerogen. However, many oil shales contain Type I
kerogen at a maturation state corresponding roughly to that IFP designates
Stage b. Thus, it is unfortUnate that the IFP workers chose to omit this model
from their publication.
Even though the IFP models are generalized and not intended to precisely
represent the structure of any particular kerogen, some comments about the Type
I models seem in order. First, the emphasis on large 4+ ring aromatics seems
overdone. There is general agreement that most ring systems are small in Type
I kerogen and few of the larger systems are fully aromatized until late in the
maturation sequence. Second, in all the IFP models aromatics are shown in
parallel sheets. There is a common misconception that this is a low-energy
arrangement. It is not. Even pure aromatics, especially those of 1-4 rings
likely to be important in oil shales, do not crystallize in such parallel
sheets, but rather in a "herringbone" arrangement that maximizes edge-to-face
interactions. The highly substituted aromatic units in kerogens are even less
OIL SHALE Page 163
Table 25. Heteroatom functional group contents of the IFP models. Each kerogen type was modeled with an initial
collection of 1400-1500 carbons, some of which were lost as the kerogen matures. Thus, the numbers
shown dQ not represent the functional group contents based on a constant number of carbon atoms. The
contents are given at each modeled stage of maturation: Stage a corresponds to the beginning of dia
genesis, Stage b to the beginning of catagenesis and Stage c to the end of catagenesis. Asphaltenes
were modeled only at Stage b, the beginning of catagenesis, where they become most abundant.
(Data from Behar and Vandenbroucke, Reference 255.)
Heteroatom Functional Group Content of the Models
Aliphatic Aromatic Ketone+ Aliphatic Thio Thiol +
Kerogen Alcohol Phenol Acid Acid ~ Amide Quinone Ether Furan Pyridine Qhgng Disulfide Amine
Type I-a
-b
Type II-a
-b
-c
Type III-a
-b
-c
9
43
I
26
I
20
5
102
54
2
15
3
4
Asphaltene (at start of catagenesis)
Type I
Type I I
Type II I
2
14
3
I
7
1
48
6
2
14
45
27
16
14
4
5
5
31
6
9
I
48
10
44
2
52
33
9
80
46
19
13
15
14
I
2
2
12
6
7
17
37
5
2
5
I
4
16
8
14
18
9
I
6
6
I
2
22
11
2
5
6
6
1
2
2
I
2
2
26
2
1
OIL SHALE Page 164
Figure 45. Generalized IFP model of Type I kerogen.
(a) At the beginning of diagenesis (start of oil generation window)
OIL SHALE Page 165
Figure 45. Generalized IFP model of Type I kerogen.
(b) At the end of catagenesis (start of late gas generation)
(b)
OIL SHALE Page 166
Figure 46. Generalized IFP model of Type II kerogen.
(a) At the beginning of diagenesis
OIL SHALE Page 167
Figure 46. Generalized IFP model of Type II kerogen.
(b) At the beginning of catagenesis (start of oil generation)
(c) At the end of catagenesis (start of late gas generation)
OIL SHALE Page 168
Figure 47. Generalized IFP model of Type III kerogen.
(a) At the beginning of diagenesis
OIL SHALE Page 169
Figure 47. Generalized IFP model of Type III kerogen.
(b) At the beginning of catagenesis (start of oil generation)
(c) At the end of catagenesis (start of late gas generation)
OIL SHALE Page 170
Figure 48. IFP models of generalized asphaltenes.
(a) Type I
(b) Type II
OIL SHALE Page 171
Figure 48. IFP models of generalized asphaltenes.
(cJ Type III
OIL SHALE Page 172
likely to arrange in parallel sheets. The implications of this kind of ordering
to coal structure (Type III kerogen) are important, as recently pointed out by
Larsen and his co-workers. 2 5 6 The imp 1 i cat ions for oil shale kerogen structure
,
should be similar, and no less important. Certainly, the X-ray diffraction
patterns of amorphous materials, such as kerogens, are properly interpreted in
terms of the Debye scattering formalism, rather than the diffraction formalism
of Bragg. This argument should also apply to electron diffraction. Perhaps a
re-interpretation using the correct formalism would yield a structure with more
physical meaning. Finally, the trends in functional group distributions do not
seem unreasonable, but it must be remembered that the details of the IFP models
reflect an average over many samples and were not intended to represent any
particular kerogen.
OIL SHALE PAGE 173
V. RECOVERY
A. OVERVIEW
Oil shale utilization will involve several different kinds of technologies.
In any case, the major areas will include mining, size reduction, retorting or
other means of recovering shale oil from the rock, disposal of the spent shale
and upgrading the shale oil into marketable products. A good overview of oil
shale technology through 1980 is provided by Oil Shale Processing Technology,
edited by V. D. Allred.'" The Synthetic Fuels Data Handbook by Baughman is
another extremely useful source of information on many aspects of oil shale
technology.154 It includes extensive discussions, as well as the voluminous
tables one would expect from its title. Chemical aspects of oil shale
retorting and shale oil upgrading are discussed in references 258-260. Other
good sources of information include the proceedings of the symposia held each
year at the Colorado School of Mines,261 papers of the symposia sponsored by
the Institute of Gas Technology262 and the Proceedings of the Australian Oil
Shale Workshops.263 Prien reviewed progress through the mid-1970's.6 The many
papers of workers at the U.S. Department of Energy (nee ERDA, nee U.S. Bureau
of Mines) and the U.S. Geological Survey are also good sources of information
about specific aspects of oil shale technology, as well as oil shale science in
general. The sources listed above do contain some information about foreign
oil shales, but are primarily concerned with technology applicable to the Green
River Formation in the U.S. Much information, unfortunately now dated, about
other shales is contained in the proceedings of a U.N. conference at Tallinn in
1968. Technology used in the Chinese (PRC) oil shale industry has been
reviewed.','4,'.' A bibliography listing over 5000 oil shale publications
OIL SHALE PAGE 174
(science and technology) up to 1977, and a supplement also containing well over
5000 references to 1981, are available from the U.S. Department of
Energy.266,267
Estimates of required selling prices for synfuels have. through the years,
been very badly off the mark. However, estimating the potential for lowering
shale oil costs by improving the economics of one or another of the various
technologies can be useful in assigning priorities for research and development
efforts. Cost breakdowns have been estimated for shale oil production from
Green River oil shale and Estonian kukersite (Tables 26_27).268,269
OIL SHALE PAGE 175
Table 26. Estimated cost breakdowns for shale oil production from Green River
oil shale. (Data from Reference 268.)
Capital Expense. % Operating Expense. % Scalability
Mining 8 35 Marginal
Shale preparation 10 15 Margi na 1
Preheat-Retorting 7 5 Very good
Combustion 15 12 Very good
Power/heat systems 20 12 Medium
Product upgrading 25 16 Very good
Infrastructure 15 5 Good
Table 27. Estimated cost breakdown for production of shale oil and chemical
by-products from Estonian kukersite. (Data from Reference 269.)
Production Costs, % of 1959 total
1959 1977
Shale feed (Incl. mining. prep. ) 64.5 58.6
Util ities: Electric 5.1 3.9
Heat 12.0 2.2
Water 0.6 0.9
Labor 6.3 2.3
Fixed costs 11.4 6.5
By-product credit -19.6 -24.4
Net production cost 80.4 74.4
OIL SHALE
PAGE 176
It is interesting to note how similar these estimates are, even though
their cost bases are obviously different, they differ by years in time (1980
V$. 1987) and were made for shales half a world apart. Yet. in each case the
costs of getting the shale out of the ground and ready to process represent
fully one-half the total cost. It is also interesting to note that substantial
reductions in the cost of the Estonian shale oil were achieved, even though
this industry is about 50 years old. hence should be relatively mature.
B. MINING TECHNOLOGY
Very thick seams of well-consolidated oil shale are characteristic of the
Green River Formation. Around the basin rims (especially of the Piceance
Basin), outcrops are numerous, while considerable overburden covers the rich
seams near the basin center. As a result, both underground mining and surface
(open-pit) techniques may have economic advantages in different locations. In
some locations. in situ methods may have advantages, but even in these cases
some mining will probably be required to provide a void into which rubble can
be blasted. Several general reviews have been made of the mining technology
applicable to oil shale.27o-275
1. Underground Mining
Underground mining was used at the Anvil Points Oil Shale Research Facility
(APF) that was operated from 1944 to 1956 by the U.S. Bureau of Mines,276 then
by others until when it was decommissioned.
283
Underground mining
was also used successfully by Union Oil, Mobil Oil and Colony Development, and
OIL SHALE PAGE 177
was planned for Exxon's Colony Shale Oil Project {now terminated).284,285 In
these cases, the mine was of a room-and-pillar design (Figure 49).
'"
-
Figure 49. One level of a roomand-pillar oil shale mine. (After East and
Gardner, Reference 276.)
The mine at APF was begun as a three-level mine, but in later operations
only two levels were mined.
Z76
Nevertheless, the mining at APF provided a
wealth of information about the safe design, operation and maintenance of an
underground oil shale mine in the unique environment of the Green River
Formation. Variations on this basic design can be tailored to mine the rich
OIL SHALE PAGE 178
strata, while selectively leaving the lean one5.
286
Such designs, however,
leave much of the shale in place, hence are not suited for zones that are both
thick and uniformly rich.
Bulk underground mining methods, such as sublevel stoping with full
subsidence or block caving methods, can provide more complete recovery of rich
oil shale from thick lones.
273
,287 However, spent shale cannot easily be
disposed of in the mined void. A stoping method with spent shale backfill may
be a compromise that is both reasonably efficient and environmentally
acceptable. longwal1 mining, a method widely used in underground coal mining,
is another alternative. longwall methods have been used for oil shale mining
in the USSR288 and its use in the U.S. has been contemplated.
289
Given the high
cost of mining, it is clear that, even incremental, improvements in oil shale
mining technology could have a major impact on the economics of a proposed oil
shale project. However. it must be realized that mine design is very much site
specific and an improvement applicable at one site may be inappropriate for
another. Moreover, safety considerations dictate a conservative policy with
respect to the amount of rock that must be left in place. Perhaps improvements
in subsurface imaging can be made to enable more precise three-dimensional
modeling of subsurface features using computer techniques. This will require a
much better fundamental understanding of wave propagation in inhomogeneous
media. However the benefits should be both .lowered cost of mine design and
more efficient deSigns that significantly increase the amount of rich oil shale
that can be removed without compromiSing mine safety.
OIL SHALE PAGE 179
From 1981 to 1984, an extensive oil shale fragmentation research program
was conducted at Anvil Points by a consortium comprised of Cities Service,
Getty Oil, Mobil Research & Development, Phillips Petroleum, Sohio Shale and
SunaCD Development. Science Applications, Inc. (SAl) managed the program and
provided technical direction. Los Alamos National Laboratory. and in later
stages Sandia National Laboratory, participated with SAl and the consortium and
shared the experimental work. This program included a wide range of tests,
ranging from single level/single borehole tests to obtain basic fragmentation
data, to multiple level/multiple borehole tests to explore fragmentation as a
function of explosive type, charge placement and detonation sequencing.28o-282
Some of the heavily-instrumented tests carried out late in the program provided
results that were used to verify and refine computer programs that simulate
with remarkable preCision, the behavior of the Green River oil shale under
explosive stress.
282
These results should prove invaluable in designing new,
more efficient mines and in formulating efficient operating procedures for
these mines of the future.
2. Surface Mining
At Fushun, in Manchuria (PRe), there is a very large open-pit mine where
450 feet of low-grade oil shale (15 gal/ton) overlies one of the world's
thickest coal deposits. Oil shale processing has accompanied coal production
since the Japanese initiated large-scale operations at Fushun in 1929.
7
,264,265
Surface (open-pit) mining is also practiced on a large scale in the USSR, espe-
cially in Estonia.290-292 Surface mining was planned for the (now deferred)
Rundle Project (Queensland, Australia) by a consortium comprised of Esso
OIL SHALE PAGE 180
Exploration and Production Australia, Central Pacific Minerals and Southern
Pacific Petroleum.
285
,293 Surface {strip} mining has also been envisioned for
the Toolebuc shale, Australia's largest oil shale resource, especially along
the St. Elmo Structure where the shale is 7-14 m thick below a nearly barren
oxidized zone about 18 m thick.s
Surface mining of Green River oil shale has never been practiced on a
large scale, though about 15% of the total reserve is potentially recoverable
by surface mining methods. A detailed engineering economics study was carried
out to explore the potential of open-pit mining of Green River oil shale.294.295
The potential environmental impact of such a large-scale surface mining
operation in the Piceance Basin was examined in a recent U.S. EPA study.296
Surface mining of Eastern U.S. (Indiana, Kentucky) shales was evaluated as one
part of an effort to develop plans for Devonian oil shale utilization.
297
,298
Surface mining is used extensively in ore recovery and for mining coals,
especially low-rank coals. It is anticipated that technology developed for
these applications will be adaptable to oil shale mining.
c. SIZE REDUCTION
In situ retorting will not require size reduction past that obtained by
blasting to rubblize the shale, however size reduction by crushing and grinding
will be required for above-ground processing. Moreover, size reduction is
expensive and becomes rapidly more so as the target particle size decreases
below about one-half inch. Nevertheless, closely controlled size reduction is
a necessary preliminary to the use of heavy medium cycloning and other of the
OIL SHALE PAGE 181
newer, more efficient methods for oil shale beneficiation. In addition, most
current above-ground retorts have severe particle size restrictions, especially
with respect to fines.
A detailed study of size reduction of Green River oil shale was made by
Salotti and Oatta.
299
Three types of crushers (gyratory, impact, roll) were
studied, using 200-ton samples collected from the R-6 (20.7 gal/ton) and R5
(24.9 gal/ton) zones of the Rio Blanco Mine (Tract C-a). The authors caution
that extrapolation of the results to leaner shales (-15 gal/ton) should be done
with caution and that extrapolation to appreciably richer shales should be made
only with trepidation. Major findings of this study are summarized below:
1. Power consumption for a similarly-sized feed and product is roughly the
same for all three types of crushers.
2. Variations in feed grade (20-25 gal/ton) have little or no effect on the
performance of the three crusher types for product having a top size of
3/8-inch or larger.
But,
3. When a crusher is producing 3lB-inch or finer top size product, the richer
oil shale tends to have a significantly finer size distribution.
4. Crusher throughput was about 70% of rated capacity.
5. Relative ability to process larger pieces (6-inch x 0) was in the order:
gyratory> impact> roll.
6. Relative percentage of recirculating load present as -3/4-inch material is
in the order: roll> impact> gyratory.
7. Relative production of oversize material is in the order: roll> impact>
gyratory.
OIL SHALE PAGE 182
8. Grinding of these relatively rich shales was roughly equivalent to grinding
a moderately hard limestone, and wear during oil shale grinding is antici-
pated to be similar to that suffered during grinding such a limestone.
A similar study of size reduction was made as part of a study of the
beneficiation of an Eastern U.S. Devonian oil shale.
30o
OIL SHALE PAGE 183
V I RETORTING
Retorting is the process of heating oil shale in order to recover the
organic material as shale oil + gas (less commonly, just as gas). To get
reasonable rates of product recovery. temperatures of 4000-600C (750
0
-1100*F)
are generally used. Therefore. to avoid unwanted combustion a retort in its
simplest form is a vessel in which the shale can be heated without exposure to
air and from which the product gases and vapors can escape to a collector.
Retorts used in early shale oil processes were just that. Modern retorts are
usually tailored to meet the needs of an integrated oil shale process, hence
are somewhat more complicated. Therefore, this section outlines not only the
major features of the different retorts, but also of the corresponding integ-
rated processes that have been developed/improved during the past two decades.
Sha 1 e oil recovery can be carried out above-ground or underground (in-situ).
In-situ processing is attractive because the requirements for mining, hauling,
crushing and grinding the oil shale rock are eliminated or greatly reduced.
Thus, in situ retorting offers the potential for corresponding savings in both
capital and operating expenses. Above-ground retorting, on the other hand,
generally affords better control of retorting conditions that can minimize heat
loss due to carbonate decomposition and lead to a better yield of higher-
quality products. Novel processes, using supercritical solvent extraction or
bioleaching to recover shale oil, are still in the early experimental stages,
but appear to have the potential for use either above- or underground. Most
work to date has been on above-ground retorting.
Above-ground retorting processes fall into three broad classes depending
on whether the process heat is generated internally (direct heated retort),
OIL SHALE PAGE 184
externally (indirect heated retort), or have the potential for both. Currently,
only the Kiviter retort used in the USSR for retorting of Estonian kukersite
simultaneously derives major fractions of its process heat from both internal
and external sources. Grouped by their method of heat generation, retorting
technologies include the following:
Above-ground Retorting Process
Direct Heated
N-T-U
Gas Combustion
Indirect Heated
Lurgi-Ruhrgas
TOSCO-II
Underground Retorting Process
OXY Modified In-Situ Retort Process
(Occidental Oil Shale, Inc.)
Horizontal Modified In-Situ (LETC)
Retorting Process
LLNL RISE (Rubble In-Situ Extraction)
Laramie True In-Situ Retorting Process
Multi-Mineral In-Situ (MIS) Process
Petrosix (Brazil) Geo-kinetics In-Situ Project
Exxon Shale Retort (ESR) Process Equity Oil BX In-situ
Shell Shale Retorting Process
HYTORT (IGT Hydrogen Atmosphere)
Superior Circular Grate
Allis-Chalmers Roller Grate
Galoter (USSR)
Combination
Kiviter (USSR)
Union Oil
Paraho
OIL SHALE PAGE 185
A. ABOVE-GROUND RETORTING PROCESSES
Although interest in directly heated retorting has waned, it is useful to
begin the discussion of retorting by examining two directly heated retorts of
relatively simple design.
I. N-T-U Process
Invented in 1923 by Dundas and Howes, The N-T-U retort takes its name from
the N-T-U Company (the letters stand for Nevada-Texas-Utah) which took the lead
in its early development.
301
,302 The N-T-U batch retort is relatively simple
and inexpensive to construct and proved to be durable in operation (Figure 50).
During the 1920's, the N-T-U Company constructed a 40-ton retort near
Santa Maria, California and the US Bureau of Mines (USBM) constructed a small
N-T-U retort at its Anvil Points facility. This first phase ended about 1930,
but interest was revived by the fuel demands of WWII. In Australia, N-T-U
retorts were used by Lithgow Oil Pty. Ltd. at their facility at Mangaroo.'"
Three 35-ton retorts were constructed, but seldom operated simultaneously due
to lack of feed shale. Nevertheless, nearly 2 million gallons of liquids were
produced during 1944-45. Interest was also revived in the U.S. Upon passage
of The Synthetic Liquid Fuels Act of AprilS, 1944, the USBM constructed two
identical 40-ton N-T-U retorts at Anvil Points to provide design data and
quantities of shale oil sufficient for refining studies. By the time these
retorts were dismantled in 1951, each retort had operated nearly 7000 hours to
process about 18,000 tons of oil shale and produce 6,000 barrels of shale oil.
Inspection showed that the retorts were still in good condition. This early
work was reviewed in 1951 by Cattell, Guthrie and Boyd."4
OIL SHALE PAGE 186
Figure 50. Schematic of the N-T-U Retort. Heat from the downward-moving flame
front drives the retorted oil before it. Gas produced by retorting
can be recycled to provide additional heat. (after Cattell,
Guthrie and Scramm, Reference 304.)
HINGED
BOTTOM
OIL
SHALE
_COMeUSTIO.
. AIR
". '
. SPENT, -:.
". SHALE.:',
, ....... .;. '';. J, .
:COM'euSTION:
ZONE .:. \"
. .: ..', .....
.
. .
. . , .
", ; ,- ...
. " .. ': :.' ' ..
. ' .... . " ' ..:.
: RAW ';
. -
. . . '. " ","
/ .
. /
/
.. /
I .
j
PYROLYSIS PROOUCTS
ANO
PRODUCTS OF COM8USTtON
OIL SHALE PAGE 187
In the 1960's, a 10-ton N-T-U retort was constructed at USBM's Laramie
Energy Technology Center (LETC, later the Laramie Energy Research Center (LERC)
of the Energy Research and Development Administration (ERDA) and now the
Western Research Institute). This retort, and the ISO-ton version added in
1968, have been used extensively to study many of the parameters important to
in-situ retorting. The 150-ton retort, located just north of laramie, Wyoming.
has an internal diameter of just over 6 feet and height of 45 feet (Figure 51).
To simulate an in-situ retort, the 150-ton unit is generally charged with
ungraded shale selected to simulate the wide range of sizes obtained by blasting
to produce a rubblized shale bed in an underground retort. Individual shale
blocks weighing up to 10,000 lb. have been retorted successfully. Results from
studies of the retorting of random-sized shale charges have been summarized by
Harack
t
et al.,305.306 Docktor.
307
and Ruark.308 Oil recovery from shale in
the range of 1/2 to 3-1/2 inches ranged from 80% of Fischer Assay for 30 gal/ton
grade to 87.5% of Fischer Assay for 50 gal/ton grade. Even very large pieces
of shale could be retorted. Harack, et a1. described the results of one run
where 20% of the feed was larger than 20 inches, 10% was smaller than 1 inch
and one very large piece of shale weighed 7500 pounds (Table 28).30'
The N-T-U retorts served well as research tools, but as batch units they
were not well suited for commercial use. This led to a search for a more
efficient and continuous retorting process.
OIL SHALE PAGE 188
Figure 51. The ISO-ton N-T-U retort at the Western Research Institute, Laramie,
Wyoming.
Sit, ,I".
tot.h ...
.uh.ne.
Elliftkal
.........
(After Cattell, Guthrie and Schramm, Reference 304.)
\ '""''''''' ktn ..
... uelline4 with c ..
tl>giw
.. !eliot
_.,
W
on
-{ .. " ...... ,. jIIIdiIIg- .......... - -. ... ,
/""" ......... --.. .
Ind uUs 10 olluin cWinotoIn .. I :.
SIolH", oIeck fo< l'isdo.-.. ol "''''t _'''i,l
OIL SHALE PAGE 189
Table 28. Results summary for a run in the ISO-ton N-T-U retort at the Western
Research Institute. This run included a single block of shale that
weighed 7500 pounds. (Data of Haraek, et al. Reference 305.)
Length of run days 12.25
Operating conditions:
Shale charge tons 178.67
Retort pressure psig 3.0
Air rate (dry sefrn 135
Do sef /ton shale 13,300
Avg. air temp. into retort
OF
28
Recycle gas rate (dry) sefm 67
Do sef/ton shale 6,600
Avg. recycle gas temp. into retort
of
43
Oxygen content of retorting gas pet 14.5
Space velocity ft' gas/fV bed/min 1. 94
Stack gas rate (dry) sefm 177
Do sef/ton shale 17,400
Gas produced in retort (dry) sefm 42
00 sef/ton shale 4,100
Max retort differential press in. H
2
O 0.6
Avg. ambient temp.
OF
26
Avg. retorting advance rate in/hr 1. 75
Max bed temp
OF
1,600
Bed compaction pet of initial height 5.6
Oil shale properties:
Fischer Assay gal/ton 25.4
Water content gal/ton 2.9
Bulk density lb/ft' 80.0
Gross heating value BTU/1 b 2,267
Recovery:
Oil gal 2,830
Spent shale tons 125.86
Oil recovery Vol pet of Fischer assay 62.2
Oil properties:
Gravity API 25.2
Pour point
OF
70
Viscosity SUS at 100F 79
Hydrogen wt pet 11. 76
Nitrogen wt pet 1.77
Sulfur wt pet 0.76
Carbon wt pet 84.58
Ash wt pet 0.01
Gross heating value BTU/1 b 18,660
Spent shale properties:
Fischer assay gal/ton 0
Gross heating value BTU/1b 117
OIL SHALE PAGE 190
2. Gas Combustion Process
Design objectives for the Gas Combustion Process grew out of the USBM work
described above. These included gravity flow to minimize mechanical complexity,
heating of the raw shale by hot gas, and generation of this hot gas by burning
the residual carbon on retorted shale within the retort vessel.
Work began in 1949 on the first version, known as the dual-flow retort. A
second and much improved version, the countercurrent retort soon followed. By
flowing combustion gases up and shale down, oil recoveries above 90% of Fischer
Assay were obtained from 25-20 gal/ton shale at throughputs of 200 lb./hr/ft'.
However, having the combustion zone at the bottom of the retort led to the
spent shale being discharged at high temperature, thereby wasting valuable heat.
Also, handling the hot shale was a problem. The Gas Combustion Process was
developed to alleviate these problems (Figure 52).309
The Gas Combustion Retort, itself, is a marvel of simplicity. No internal
baffles divide the zones and the flow of shale from the retort is controlled by
a movable grate at the bottom. Shale fed into the top of the retort through a
rotating lock is heated by the hot product vapors. This serves to cool the oil
vapors past the dew point into a mist that is swept out into the collector by
the upflowing gases. The preheated shale then moves down into the retorting
zone where, upon further heating, kerogen decomposition yields the oil and gas
products and a carbonaceous residue that adheres to the spent shale. Next the
shale moves into the hottest part of the system where air is introduced for
combustion of the residue and of the hydrocarbons in the recycle gas. In the
lowest part of the retort, heat from the combusted shale is transferred to the
recycled gas as it flows upward. Finally, the cooled, combusted shale is dis-
charged from the bottom of the retort:
Figure 52. In the Gas Combustion Retort, the spent shale is cooled by recycled product gas before being
discharged. Subsequent combustion of the hydrocarbons in the recycled gas provides additional
process heat. (After Matlick, et al., Reference 309.)
SHALE
OIL SHALE
I-
CRUSHING
AND
MINE
SCREEN
GAS
SIZING
-f FINEt DISCARD
" SEAL
PRODUCT
DUST AND rid 6
GAS
\.::1- OIL MIST
TYPICAL TEMPERATURE PROFILE
RECYCLE L SHALE
I,
GAS PREHEATING
BLOWER SHALE OIL ZONE
1-------
- --
SHALE
- --
CO BUST!
AIR
,
f-_
ZONE
-- ----
AIR BLOWER
DILUTION GAS
SPENT SHALE
V
COOLING ZONE
...
17
-
/
500 1000 1500
COOL RECYCLE GAS TEMPERATURE OF SHALE of
GAS
SEAL
SPENTtSHALE
SOLIDS
OIL SHALE PAGE 192
Table 29. General data SUlJII8ry. USSM evaluation ru'lS on the 150 tpd Gas Coobustion Retort.
Test nurber
lli1:1l
26(1-2) 26(3-5 ) 27(1-3)
lli1.::il
28(5-6)
length of test hours 120 48 72 72 96 48
Rates and quantities:
Shale sile inches 3/S-3 12 12 42 12 12
Bed height ft and in 9,11 9,11 9,11 9,11 7,2 7,2
Raw shale rate lb/(hr) (sq tt) 299 222 299 350 299 300
Air rate std cu tt/ton shale 3,940 4,230 3,910 3,840 4,010 4,290
Oitutlon gas rate std cu ftlton shale 2,&0 3,800 2,950 3,140 3,100 4,040
Recycle gas rate std cu tt/ton shale 13,340 12,400 12,650 12,660 12,500 10,260
TenperatUf'"es:
Product outlet 'F 162 142 141 143 141 126
Retorted shale out 'F 376 348 356 345 378 447
Raw shale in 'F 40 34 32 30 28 25
Recycle gas 'F 241 247 250 246 224 213
01 lution gas 'F 83 90 92 92 79 86
Air 'F 128 129 131 144 110 98
Yields:
Oil vol pet/Fischer assay 82.8 92.3 86.2 86.7 85,1 86.1
G .. std cu ft/ton shale 6,040 6,440 6,000 6,020 6,400 6,090
Retorted shale wt pet of raw shale 81.8 82.9 82.3 82.1 83.3 83.0
llq.,!id water lbltOf'l shale 0.2 5.0 0.9 1.1 4,9 11.2
Miscellaneous:
Retort preS$Uf'e df-op in "?lIft bed 0.90 0.37 0.73 1.02 0.58 0.45
Carbonate deeonposition wt pet 24.9 24.1 26.9 25.6 23.3 23.6
OIL SHALE PAGE 193
Table 30. Material Balances, USBM Evaluation Runs on the 150-Ton Gas COI'ltlustion Retort.
Test nunber
ill1.:.2l
26(1-2) 26(3-5) 27(1-3) 28(1-4 ) 28(5-6)
Materials in:
Raw shale .b 2,000 2,000 2,000 2,000 2,000 2,000
Recycle gas
'b
986 933 952 946 927 m
Oi lution gas
'b
211 286 222 235 230 304
Ai, .b
-1!IL
324
-l22.. --l2L
-lQL
---ll2..
Total materials in .b 3,499 3,543 3,473 3,475 3,564 3,406
Materials out:
Retorted shale
'b
1,636 1,658 1,646 1,642 1,666 1,660
Product 01 1
'b
185 185 178 183 189 184
Offgas
'b
1,644 1,705 1,625 1,631 1,609 1,536
Water in oil .b
---lliL
__ 5_ __ 1_
__ 1 _
__ 5_
11
Total materials out
'b
3,405 3,553 3,450 3,457 3,469 3, 391
Recowry percent 99.0 100.3 99.3 99.5 97.3 99.6
OIL SHALE PAGE 194
Three gas combustion retorts were constructed by USBM at Anvil Points:
6-ton/day and 2S-ton/day pilot units and a ISO-ton/day unit designed to furnish
engineering design data for a commercial unit. Results obtained during this
period were summarized by Matzick and Oannenberg.
310
Several problems of the Gas Combustion Retort were not solved by the USBM.
Oil yields were in the range of 85-90% of Fischer Assay, some 5-10% lower than
desired. The control of oil mist and the design of air-gas distributors were
persistent problems. Finally, the inability to efficiently process shale fines
(smaller than 1/4-inch) was felt a definite drawback.
The first stage in development of the Gas Combustion Process ended in 1955
when work was halted by USBM. Stage II began in 1961 with the passage of
Public Law 87-796 empowering the Secretary of the Interior to lease the
facility, in order to encourage fUrther development of oil shale technology.
After evaluating several proposals, the Interior Department leased the Anvil
Points facility to the Colorado School of Mines Research Foundation (CSMRF).
Under the terms of the lease, CSMRF became lessor, provided administrative and
logistic support, and made the facility available to a consortium that
eventually jncluded Mobil Oil (project manager), Humble Oil & Refining, Pan
American Petroleum Corp., Sinclair Research. Inc., Continental Oil Co. and
Phillips Petroleum Co. Under this agreement, the facility was reactivated in
1964 and was operated for about one year in 1966-67. During this time. nearly
300 runs were made, mostly in the 25- and ISO-ton/day units. Stage II efforts
have been summarized by Ruark, et a1.277.278 and by Lawson, et a1.311
Improvements made in Stage II solved many problems and throughput was just
about doubled to 500 lbs/hr/ft'. However, oil yields remained a disappointing
OIL SHALE PAGE 195
85-90% of Fischer Assay despite efforts to achieve improvement. Nevertheless,
progress was made and many of the results were incorporated into the Paraho
project. No work was carried out on the Gas Combustion Process after 1967, but
the Paraho Process in its directly heated mode is nearly identical, so Paraho
results can be used as a guide to the potential of the Gas Combustion Process.
3. lurgi-Ruhrgas Process
The lurgi-Ruhrgas oil shale process (LR process) grew out of an earlier
Lurgi process for making high-BTU gas from coal fines. Initially, a solid heat
carrier (e.g. sand) was mixed with the coal fines, but later the hot coal char
product was recycled to supply the needed heat. The process was tested on a
variety of coals, and was used commercially in Germany, England, Yugoslavia,
Argentina and Japan. Application to oil shale was a logical extension.
In the lR shale retort, hot solids recycled from a combustor and the raw
shale are fed (ratio 6-8:1) to a screw type mixer (Figure 53).312 Retortin9
takes place in the mixer and in the surge bin (accumulator) that follows. Gas-
solid separation takes place in the surge bin and the following cyclone. Most
of the solids are diverted to the lift pipe combustor where burning of the
residual carbon raises the temperature to about 1200F. The hot solids are
separated from the gases and returned to the retort, which is maintained at a
an optimum retorting temperature in the neighborhood of IOOOF.
OIL SHALE PAGE 196
Figure 53. Simplified flow diagram of the Lurgi-Ruhrgas oil shale retorting
process shows that the screw mixer section where retorting takes
place is actually a very small part of the system. (After Rammler.
Reference 312.)
lurgi - Ruhrgas Oil Shale Retort
Gas/Solids ----,l ____ rJ::
l
---1
Separation
Bin
Lift Pipe
Cyclone
Oil Shale
Screw Mixer
Air
Surge
Bin
Waste
Heat 1-___ _
Recovery
Flue Gas
Spen Shale
Gaseous &
011 & Gas
Recovery Liquid
Products
Cyclone
OIL SHALE PAGE 197
The use of the mixer provides rapid heat transfer and allows very short
residence times for the product vapors in the hot zone to minimize unwanted
cracking. The forced mixing also reduces the tendency for rich shales to
result, the critical materials problems are confined to a small, manageable
section of the overall facility. Also. it is important that no part of the LR
retorting system operates at high pressure; maximum pressures are a few inches
of water.
The product collector section is designed in stages to provide two, and
preferably three or more, product fractions. This is not to give fractions
defined by boiling range, but rather to avoid oil/water emulsions and for
improved dust control. The first section is an underflow scrubber, where the
product stream is concurrently cooled and scrubbed by injection of the aqueous
product and heavy oil. Fine dust not collected in the cyclone is concentrated
in the heavy oil and the subsequent fractions are essentially dust-free.
For commercial use, provision would be made to recover process heat from
spent shale and heat exchangers would be used to recover additional heat.'"
Also, two or three cyclones may be staged for more complete dust removal from
the product vapors; and scrubbing would be used in all stages to give efficient
cooling and condensation of the product vapors. Electrostatic precipitators
would probably be added to reduce particulate emissions in the flue gas from
the lift-pipe combustor.
OIL SHALE PAGE 198
One of the important features of the LR process is its ability to process
shale fines; the entire oil shale resource can be utilized in a single type of
reactor (Table 31). Good material balances were obtained in pilot plant
operations and oil yields were high from a variety of oil shales; yields were
commonly above 95% of Fischer Assay (Table 32). In favorable cases oil yields
went as high as 110% of Fischer Assay The product oil is 85% - 90% volatile,
though nitrogen and sulfur levels are high, and pour pOints are desirably low
(Table 33). Dust in the heavy oil is troublesome, but lurgi has a patented
process for oil dedusting. Alternatively, the dust-laden heavy oil can be
recycled to the mixer. Thus, The lR retort solved two of the most persistent
problems of the gas combustion retort, namely low oil yields and inability to
process shale fines (i.e. the entire oil shale resource).
Gas products from the lR process are not diluted with combustion gas, so
BTU content is high and the gas should be suitable for reforming to produce the
hydrogen needed in product upgrading.
The aqueous product is only slightly basic and should not require special
materials of construction. It does contain phenols and ammonia that may be
recovered by steam stripping, however further treatment (e.g. biological oxida-
tion) may be required before the process water is environmentally acceptable
for mOistening the spent shale.
After removal of the kerogen by retorting and decomposition of some of the
carbonates during combustion, the spent shale is friable (Table 34). Shear
applied in the mixer retort does reduce particle size. On the one hand, these
characteristics make the combusted shale a very good SOx acceptor, while on the
other. the fine particle size means that special care must be exercised in
OIL SHALE PAGE 199
Table 31. Properties of Lurgi-Ruhrgas oil shale pilot plant feeds_ Abil i ty to
process fines means the entire oil shale resource can be processed.
(Data of Rammler, Reference 312).
TYPE OF SHALE
A C D E F
""' __ L ___
Residue
"
83.4 84.9 84.4 87.5 91.0 79.7
Gas and 1 ass " 3.8 3.9 4.4 2.3 2 .1 4 .1
Ultimate Analysis
Carbonate CO, wt % 18.7 16.4 13.7 9.1 19.6 14.6
Organic Carbon " 15.7 12.9 10.2 7.3 6.7 14.3
Hydrogen "
2.0 1.9 1.3 1.1 1.8
Nitrogen " 0.5 0.3 0.2 0.2 0.6
Total Sulphur
"
0.9 3.4 1.0 1.6 2.7
Gross Calorific Value kJ/kg 7400 6150 4770 3520 2830 5690
Grindability Index 30 76 49 90 69
(Hardgrove)
Size Analysis"
+5 mm wt % 2.8 0.0 0.0 0.0 0.1 0.1
4 -5 mm " 25.2 0.0 2.7 0.0 2.1 1.4
3 -4 mm
"
25.2 0.1 12.2 0.2 7.6 10.0
2 -3 mm " 17.1 16.7 17.5 14.0 13.8 58.2
1 -2 mm 18.3 26.8 23.2 25.8 19.5 29.1
0.8 -I mm 14.0 11.4 10.2 9.7 7.7 0.2
0.5 -0.8 mm 14.0 9.2 7.8 8.5 7.3 0.1
0.315 -0.5 mm 10.4 13.9 8.4 10.0 9.2 0.1
0.2 -0.315 mm 10.4 9.0 5.5 7.6 7.8 0.1
0.1 -0.2 mm 5.2 6.0 5.1 8.4 8.6 0.1
0.063 -0.1 mm 7.0 3.1 3.1 5.2 6.0 0.2
-0.063 mm 7.0 3.8 4.3 10.6 10.4 0.4
Median Grain Size mm 2.05 1.09 1.54 0.97 1.20 2.31
Bulk weight kg/l 1.15 1.25 1.09 1.23 1.18 1.00
Ash Analysis:
CaO wt % 24.0 11.5 31.3 25.9
Si0
2 "
38.4 46.6 29.5 39.1
AI,o. " 13.8 15.5 10.0 11.1
Fe,o. " 6.6 7.5 7.0 4.4
S0,
"
9.7 2.6 4.0 4.6
MgO
"
2.9 3.4 2.6 5.5
K,O " 2.1 2.0 1.6 1.4
Na,O
"
0.7 3.1 0.3 0.2
Others " 1.8 7.8 13.7 7.8
Crushing to 0-4 mm used in pilot plant work is not typical for larger units.
Oil SHALE PAGE 200
Table 32. Material balances were good in LR oil shale pilot plant operations.
Oil yields were high, generally over 95% of Fischer Assay. (Data of
Rammler. Reference 312.)
TYPE OF SHALE
_B _
_ C _ _ F_
Feed
Quantity kg 1000 1000 1000
Moisture wt % 0.4 3.5 5.9
Oil (Fischer Assay) wt % 9.4 5.6 8.0
Output
Circulated material discharged kg 266.7 464.3 510.5
Dust in flue gas kg 490.5 330.9 186.2
Oust in make gas kg 9.7 13.5 55.8
Heavy in oil (dust free) kg 62.9 28.8 50.6
Middle oil kg 26.5 18.8 23.5
Gas naphtha kg 10.7 5.4 5.5
Gas liquor kg 24.5 32.9 85.9
Make gas (dry, free of C,.) kg 29.4 27.1 32.8
CO
2
from carbonate decomposition in flue gas kg 42.7 42.9 II.I
Fixed C burned kg 36.4 35.4 38.1
Totals kg 1000.0 1000.0 1000.0
Yield of oil (% of Fischer assay) 106.5 94.6 99.5
OIL SHALE PAGE 201
Table 33. Inspections of dust-free total oils from the LR retort. Pour
points of the lR oils are low, but only 85% - 90% is volatile
and the nitrogen and sul fur 1 eve 1 s are high. (Data of Ramml er,
Reference 312.)
T ~ Q e of Shale
_ E_ _F _ _H_
Density (20'C) glcm' 0.985 0.971 0.882
Viscosity (20'C) JO-6""/s 21.5 11.5 6.3
(60'C) JO-
6
m
2
/s 5.1 3.7 2.3
Pour Point 'C -20 -23 +16
Flash Point 'C 103 n.d. +23
Conrad son C wt% 5.3 5.6 2.1
Bromine Number gl100 9 56 n.d. 56.5
H/C Atomic Ratio 1.37 1.49 1.57
Nitrogen wt% 0.89 1.47 0.84
Sulfur wt% 3.25 6.47 0.70
Gross Calorific Value kJ/kg 40,900 40,195 43,340
Initial Boiling Point 'C 130 78 69
5 vol% 'C 175 148 142
10 v01% 'C 200 167 170
20 v01% 'C 232 195 201
30 vol% 'C 260 227 228
40 v01% 'C 290 268 245
50 vol% 'C 318 308 276
60 vol% 'C 340 341 310
70 vol% 'C 370 377 347
80 vol% 'C 405 423 391
90 vol% 'C 450 (88.0%) 450 (85.4%) 440
Loss v01% wt% 1.0 0.9 0.4
*
Does not include gas naphtha.
OIL SHALE PAGE 202
above-ground disposal. This should not normally be a problem, since most of
the spent shale would be returned to the mine. Moreover, when moistened, the
spent shale acts like a cement and gives a hard, rock-like mass.
314
This will
reduce the tendency for dusting of the spent shale, hence should simplify
environmentally acceptable disposal.
In summary, the LR process uses relatively simple, inexpensive and
reliable hardware to achieve high oil shale throughput and high oil yields with
the ability to process the entire oil shale resource. Major environmental
concerns, save leachate, have been addressed.
286
On the other hand. the high
nitrogen and sulfur contents of the LR shale oil product will make upgrading
difficult and expensive.
Several suggestions were recently advanced by workers at Monash University
to improve overall efficiency of the lR process when handling oil shale from
the Rundle Deposit in Australia.
115
These suggestions included (a) using a
fluidized bed solid-solid heat exchanger for improved heat recovery from spent
shale. (b) staged drying of the raw shale with the added benefit of raising low
pressure steam, (c) the use of fluidized bed combustion to give better temper-
ature control than the lift-pipe combustor and thereby lower heat requirements
for carbonate decomposition, and (d) co-pyrolysis of coal with shale to obtain
higher liquid yields from a retort of given size.
OIL SHALE PAGE 203
Table 34. Inspections of spent shale from the LR retort show that particle
size is low and that the spent shale is much more friable that the
starting shale (i.e. gri ndabil ity is increased) . (Data of Rammler,
Reference 312.)
T ~ ~ e of Shale
_ E_
--L...
_H _
Organic C wt% 0.3 1.3 2.0
Carbonate CO, wt% 15.8 19.3 12.3
Hydrogen wt% 0 0.2 0.2
Total S wt% 0.3 1.5 2.5
Size Analysis
> 5 mm wt% 0 0 0
4 5 mm wt% 0 1.1 0
3 4 mm wt% 0 2.9 2.9
2 3 mm wt% 3.1 12.6 7.1
1 2 mm wt% 7.7 2.1 8.8
0.8 I mm wt% 3.3 5.2 2.0
0.5 0.8 mm wt% 3.0 5.7 4.7
0.315 0.5 mm wt% 6.9 8.3 8.0
0.2 0.315 mm wt% 7.9 8.2 6.5
0.1 0.2 mm wt% 5.4 11.8 14.6
0.063 0.1 mm wt% 4.4 10.7 11.1
0.045 0.063 mm wt% 3.8 7.9 28.0
< 0.045 mm wt% 54.5 23.5 6.3
Median Size mm 0.32 0.68 0.55
Grindability of the 150 124 n.d.
circulated material
(Hardgrove)
OIL SHALE PAGE 204
4. TOSCO II Process
Development of this process by Tosco Corporation (formerly The Oil Shale
Corporation) began in 1955 as an attempt to overcome the shortcomings of the
USBM gas combustion retorting process. Exploratory work proceeded through a
25 ton/day pilot plant built in 1957 at Golden, Colorado and a 1000 ton/day
semi-works plant constructed at Parachute Creek, Colorado in 1965 to detailed
engineering design work completed in 1968 for a 66,000 ton/day commercial
facility the Colony project. To implement the recommendations of the 1968
study, a second phase of developmental work was carried out in the 1000 ton/day
plant for acquisition of the data necessary for construction of the commercial
facility. The developmental phase results have been reviewed by Whitcombe and
Vawter.
316
Initially. the commercial facility was a joint venture of Tasca
(40%) and Arco (60%), with Arco as the operator, but in 1980 Exxon acquired
Areo's interest and assumed the role of operator. Construction of the facility
and the associated town of Battlement Mesa, began in 1980. However, faced with
increasing project cost estimates, ultimately reaching about $7 billion (nearly
twice the original estimate, due in large part to high interest rates) and
lower crude oil prices, the project was terminated early in 1982.
317
,318 At
that point, Exxon acquired Tosco's 40% interest in the Colony project.
In the Tosco process, hot ceramic balls are mixed with smaller oil shale
particles in a rotating drum retort. After retorting, the ceramic balls are
separated from the spent shale and reheated in a separate ball heater using gas
as the fuel (Figure 54).".
Raw shale
from eNsIler
shale
separator
Clean gas to
atmosphere
flue
Ball
elevator
Clean
R ~ .... -;;";,,;V
surge h<
lneluding
Hydroearbon
incinerator
flue
flue
To spent shale disposal
generator drum
'rum
Figure 54. The Tosco oil shale retorting unit decoup1es the heat generation
and kerogen pyrolysis steps, thereby simplifying process control.
(Reprinted with the permission of the Center for Professional
Advancement, New Brunswick, NJ.)
Cfean gas 10
atmosphere
OIL SHALE PAGE 206
The feed streams to the Tasca retort are I/2-inch ceramic balls heated to
about 1270'F (690'C) and the oil shale crushed to pass a 1/2-inch screen and
preheated by contact with hot flue gases from the ball heater. The streams are
rapidly mixed under an inert atmosphere. Heat transfer is rapid and at the
retort/s exit the shale and ceramic balls are essentially the same temperature
and the shale is fully retorted.
Retorting in the Tosco process is carried out in a rotating drum that is
mechanically a simpler device than the screw mixer of the lurgi process, but
like the Lurgi retort is only a small part of the total facility (Figure 55).
However, unlike the Lurgi process heat for the Tosco retort is provided by gas,
not combusted shale. The independence of gas flow and shale flow effectively
decouples retorting from heat generation and gives the Tasca retort unusual
latitude for processing shales of widely varying grades. Oil yields from the
Tasca retort generally exceed Fischer Assay. An oil yield nearly 108% of the
Fischer Assay was obtained from one 7-day test in the semi-works plant.
Product vapors from the retort are passed through a separator to remove
fines, then into a fractionator that yields heavy oil, distillate, naphtha and
product gas streams. Because combustion is separated from retorting in the
Tosco process, the product gas is a high-BTU stream that may be used as plant
fuel or reformed to give hydrogen for liquid product upgrading.
OIL SHALE PAGE 207
Figure 55. The Tasca retort is a rotating drum that comprises only a small
part of the total facility. (Reprinted with the permission of The
Center for Professional Advancement, New Brunswick, NJ.)
Rotary Pyrolysis Drum and Seals
Inlet seal Discharge seal
Inle ts
---
.:::
Accumulator
Retort
II Support w
Retort support
, ~
;e!i
'-
rollers
I
-,
JI
7
OIL SHALE PAGE 208
The ceramic balls and spent shale discharged from the retort are fed into
a cylindrical screen (trammel) inside the spent shale accumulator housing. The
ceramic balls, being larger than the holes in the screen, pass though the
accumulator and are recycled to the ball heater by a bucket elevator. The
spent shale falls into the accumulator at -900F and passes into a rotating
heat exchanger where its heat is used to raise steam in water-filled tubes.
The spent shale is further cooled in the moisturizer where is water content is
increased to 12-13% to reduce dusting before disposal.
One commercial-size Tasca retort would process about 11,000 tons of oil
shale/day to produce 4,500 barrels of crude shale oil (Table 35). Properties
of a typical oil produced from Mahogany zone Green River oil shale are similar
to those of a low-sulfur crude -- with three very important exceptions: olefin
and nitrogen contents are high, which make the oil very unstable with respect
to sludge and sediment formation (Table 36). like other oils from Green River
shales, the Tasca oil also has a high content of arsenic that is a powerful
poison for the catalysts needed for efficient upgrading.
OIL SHALE PAGE 209
Table 35. Projected products from a single 11,000 ton/day Tosco II Retort.
(Data of Whitcombe and Vawter, Reference 316.)
Shale Feed, 20 gal/ton
Pipelineable shale oil
Ammonia
Sulfur
Coke
II ,000 tons/day
4,SOO bbl/day
150 tons/day
177 tons/day
836 tons/day
Table 36. Inspection data for a typical Tosco II crude shale oil. (Data of
Baughman, Reference IS4,)
.""0 CHAMSER,'i===':;' 7
""
DRtER\L
HEAT j ........ \ t.!
EXCHANGER "REACTOR' (
LU __ ,--, /
SPENT ,
SHALE
600 C
t
Figure 75. Flowsheet shows that the Galoter Process shares many features with
the lurgi-Ruhrgas and Tosco II processes. (After Resource Sciences
Corporation, Reference 371. Reprinted with the permission of
Williame Brothers Engineering Company,)
OIL SHALE PAGE 270
From the rotary kiln, the retorted shale and product vapors pass into a
gas-solid separator, from which the vapors are sent to the product recovery
section and a part of the spent shale is discarded. The balance of the spent
shale is fed into an air-blown riser combustor where burning of residual carbon
raises the solid temperature to BDObe. The hot shale stream is used to provide
heat for retorting, while the hot gases are used to raise steam and then to dry
the wet incoming shale.
Oil yields 85-90% of Fischer Assay and an 82% overall thermal efficiency
are claimed for Galoter process operations with 40 gal/ton wet Baltic shale.
It should, however, be realized that the comparison with Kiviter is unfavorable
to Galoter for two reasons. First, shale for the Kiviter retort is processed
at the mine to remove sand and rock, while shale for the Galoter retort is not
cleaned. Second, the reported Galoter results were obtained with a shale that
contained appreciably more water (12.4 wt% VS. 9.0 wt%); removing this extra
water will lower overall thermal efficiency. Also, the gas product from the
indirectly heated Galoter retort is not diluted with combustion gases, hence
has a high heating value of 1170 BTU/scf and is suitable for pipelining.
The Galoter process was tested extensively in a 500 ton/day plant. As of
April 1975, this plant had operated for 68,000 hours, processed 1,400,000 tons
of shale and produced 186,300 metric tons of oil and 2.5 billion scf of gas.
Based on these results, a larger Galoter retort was designed to process shale
at the rate of 3,300 tons/day. A Galoter complex would include four of these
larger retorts, together with facilities for gas treatment and upgrading shale
oil to produce finished products. The first unit of this complex was scheduled
for completion in 1978. Eventually, Soviet workers envision shale processing
OIL SHALE PAGE 271
complexes that contain both Galoter and Kiviter retorts for more efficient
processing of the entire mined resource. In such complexes
t
the low-BTU gas
from the Kiviter retorts would serve primarily as plant fuel, while the high-BTU
Galoter gas would be pipelined (perhaps as a blend containing a small amount of
excess Kiviter gas).
The shale oils produced by Kiviter and Galoter retorts are reportedly of
essentially the same composition (Table 46),371
These results show that oils from the Baltic shales are much richer in
oxygenates, especially phenols, than a typical Green River shale oil which is
almost devoid of phenols. Also, the Hie ratio of the Baltic shale oil is much
lower than the 1.55-1.60 that is typical of retorted Green River shale oils.
In both respects, the Baltic shale oil is much more similar to shale oils from
retorting of Devonian shales from the Eastern U.S. Peterson and Spall have
reported a detailed comparison of Estonian and Green River shale products.
377
OIL SHALE PAGE 272
Table 46. Typical properties of crude shale oil produced from Baltic shale in
either Kiviter or Galoter retorts. (Data presented by Resource
Sciences Corporation, Reference 371.)
Density at 68"F, glcm'
Viscosity at 167F, Engler
Pour Point, of
Coking Value, wt%
Phenols, wt%
Calorific Value, Gross, BTUjlb
Distillation: Temperature. C
190 (IBP)
200
250
300
360
Elemental Composition (dry basis)
Carbon
Hydrogen
Sulfur
Oxygen + Nitrogen
Atomic HIC Ratio
I. 01
4.5
5
8
28
17,010
Vol%
1
6
21
45
83.3
10.0
0.7
6.0
1.43
OIL SHALE PAGE 273
14. HYTORT Process (IGT)
The Institute of Gas Technology (IGT) has been a leader in exploring the
use of a hydrogen atmosphere in retorting (hydrotorting). Initially. the
objective was gasification at high temperatures, however most of the products
obtained below the carbonate decomposition temperature were liquids.
378
Next,
IGT devised and patented a process for gasifying the shale liquids.
379
More
recent hydrogen retorting studies at IGT have focused on obtaining high liquid
yields and improved product quality, especially from Eastern shales.38o-391 In
addition to IGT, Texaco was active in this area during the 1960'5392-400 and
Phillips Petroleum studied process response for hydrotorting Indiana New Albany
shale in a recirculating loop reactor system.
401
Phillips also participated
with IGT. Bechtel and Hycrude Corp. in process design studies aimed at the
commercial use of the IGT technology with Eastern U.S. shales.386.387 Work at
Mobil Research & Development has resulted in the development of a Rapid Heat-Up
(RHU) Assay, especially designed to evaluate Eastern sha1es.
402
Most retorting studies have used Fischer Assay oil yield as a benchmark.
Some of the more efficient fluidized bed processes have achieved oil yields of
110%, or so, of Fischer Assay. However, Fischer Assay recovers only a small
part of the organic matter in many of the world's oil shales. Thus, potential
oil yield is several times Fischer Assay in these cases, notable among which
are the Devonian shales of the Eastern U.S. Hydrogen retorting affords greatly
enhanced oil yields in many such cases (Figure 76).
OIL SHALE PAGE 274
Figure 76. Hydrogen retorting dramatically increases oil yield over Fischer
Assay for many of the world's oil shales. (From Rex, et aI.,
Reference 388. Reprinted with the permission of the Colorado
School of Mines.)
SWEDEN - BILlINGEN
SWEDEN-NARKE
SICILY
..l.
MONTANA HEATH-FORMATION
CANADA-ONT ARlO
FEDERAL REPUBllC OF I
GERMANY AND LUXEMBOURG
JORDAN-El lAJJUN
BRAZIL-LOWER IRATI
MOROCCO
AUSTRAUA-CONDOR
CANADA-NEW BRUNSnCK
THAIlAND
AUSTRAUA-RUNDlE
WESTERN U.S. -COLORADO
BRAZIL -PARAlBA VALLEY
SOUTH AFruCAN TORBANITE
LOTHIANS-SCOTlAND Q
CONVENTIONAL,
THERMAL RETORTING 1:::::L_-L_-L_..L._..L._L-_L-_L----1
100 200 300 400 500
OIL YielD, % OF ASCHER ASSAY
OIL SHALE PAGE 275
The quality, in comparison to Fischer Assay oil, of the oils obtained by
hydrogen retorting depends markedly upon the type of shale (Table 47).403 The
oil produced from Green River oil shale by the HYTORT process is very similar
to the Fischer Assay oil; the main differences in elemental composition are a
somewhat lower oxygen content. Nitrogen content was slightly higher and this
seems to a general phenomenon in hydrogen retorting. In sharp contrast, the
oils from hydrogen retorting of the two Eastern shales were quite different
from their Fischer Assay counterparts. Moreover, the two Eastern shales were
quite different in their response to hydrogen (though oil yield increased in
both cases). In both cases, the HYTORT oils had appreciably lower atomic Hie
ratios than the Fischer Assay oil. However, the sulfur content was about the
same and the oxygen content only slightly lower for the New Albany HYTORT oil,
while both sulfur and oxygen contents were much lower for the Sunbury HYTORT
oil. The reason for this behavior is not known.
OIL SHALE PAGE 276
Table 47. Elemental analyses of shale oils and hydrotreated shale oils. (Data
of Netzel and Miknis, Reference 403.)
Colorado Shale Oil
Carbon
Hydrogen
Sulfur
Nitrogen
Oxygen
H/C Atomic Ratio
Kentuckv New Albany Shale Oil
Carbon
Hydrogen
Sulfur
Nitrogen
Oxygen
H/C Atomic Ratio
Kentucky Sunbury Shale Oil
Carbon
Hydrogen
Sulfur
Nitrogen
Oxygen
H/C Atomic Ratio
Elemental Analysis,
Fisher Assay
A B IGT HYTORT
85.08
11.44
0.73
1.80
I. 31
84.91
9.83
1.02
1.52
I. 72
84.36
9.96
1.33
1.33
2.12
84.30
11.42
0.63
I. 90
1.50
1.61 (Avg.)
1.40
I. 41
84.97
10.08
1.61
1.56
2.00
(Avg.)
84.59
9.98
1.59
1.48
2.36
(Avg.)
84.57
11.40
0.62
2.13
0.98
1.61
85.46
9.42
1.52
2.12
1.61
1.31
85.45
9.56
0.99
2.12
1.22
1.33
Wt%
IGTHYTORT
Hydrotreated
88.27
11. 70
0.05
0.40
0.12
1.58
87.30
12.60
0.06
0.17
0.28
1.72
OIL SHALE PAGE 277
Most hydrogen production involves the production of synthesis gas, which
is further processed to produce hydrogen. In coal liquefaction, synthesis gas
in the presence of liquid water has been shown superior to hydrogen alone for
improving reaction rates and oil yields. Hydrogen retorting was compared to
retorting in a mixture of synthesis gas and steam for three Eastern shales.
The oil yields and organic carbon conversions achieved with the synthesis gas
mixture were approximately those that would have been obtained by hydrogen
retorting at the hydrogen partial pressures used. However, the synthesis gas
mixture yielded oils with appreciably higher Hie ratios and API gravities, and
lower nitrogen contents (Table 48).404 Sulfur contents were, however, higher
for the oils produced with synthesis gas.
OIL SHALE PAGE 278
Table 48. Comparison of oil yields and properties of oils produced by hydroretorting and
syngas retorting of Eastern shales. (Data of Punwani, et al., Reference 404.)
HYQBOGEN HYDROGEN"
Maximum Temperature,C 649 654 568 569 502 487
'F 1201 1209 1055 1056 935 909
Total Pressure, atm 69.4 28.4 68.9 28.3 68.9 28.4
psig 1006 402 998 401 998 403
Hydrogen Partial Pressure,
atm 24.3 28.4 24.3 28.3 24.3 28.4
psig 350 402 350 401 350 403
Shale Oil Ultimate Analysis, wt%
Carbon 83.30 84.67 83.89 84.81 83.99 84.61
Hydrogen 9.86 9.62 10.16 9.63 10.02 9.97
Sulfur 1. 79 1.28 1.52 1.23 1.50 1.39
Nitrogen 1. 70 2.07 1.64 2.05 1.80 1.93
Ash 0.0 0.0 0.0 0.0 0.0 0.0
Oxygen (by difference) 3.35 2.36 279 2.28 2.69 2.10
Total 100.00 100.00 100.00 100.00 100.00 100.00
C/H Ratio 8.45 8.80 8.26 8.81 8.39 8.49
Specific Gravity
[15.6/16.6'C (60/60'F)) 0.947 0.978 0.945 0.986 0.960 0.967
API Gravity, 'API 17.9 13.2 18.2 12.0 15.9 14.8
Oil Yield
lITonne 89.2 100.5 90.06 103.4 92.1 97.6
Gal/Ton 21.4 24.1 21.6 24.8 22.1 23.4
Organic Carbon
Conversion, %*** 69.4 78.6 72.9 75.6 68.1 72.9
* Average of three tests ** Average of two tests
*** Elemental conversions based on solids and ash balance
OIL SHALE PAGE 279
Early work at IGT (1972-1979) focused on moving bed hydroretorting, the
HYTORT process. Tests were made with selected shales at rates up to 1 ton/hr.
Additional progress was made during 1980-1983 by the joint Hycrude-IGT-Bechtel-
Phillips Petroleum effort, especially in reducing hydrogen consumption.
38
6.
38
7
Based on these results, an engineering design study was made for a commercial
HYTORT facility (Figure 77).389 Possible environmental impact of such a HYTORT
facility vs. other alternatives for retorting Eastern shales has been examined
for a central Tennessee 5ite.
405
The HYTORT effort served to bring into focus the advantages of hydrogen
retorting for Eastern oil shales. However, the HYTORT moving bed technology is
mechanically complex and its large, high-pressure vessels are expensive to
construct. Moreover, fines are not readily processed in the moving bed system,
hence are usually discarded. Therefore, the emphasis of more recent work at
IGT has shifted to a pressurized fluidized bed hydroretorting (PFBH) concept.
The PFBH process will use a vertically-staged fluidized bed (Figure 78).40'
The PFBH is expected to afford higher throughput, hence lower reactor capital
costs, than the moving bed HYTORT process. Moreover, for Eastern shales the
use of smaller shale particles in the PFBH should boost oil yields, while
decreasing gas yields and having little effect on overall carbon conversion
(Figure 79). Thus, not only should the PFBH process more shale per capital
dollar than the moving bed, it should also give about one-third more shale oil
per unit weight of shale. As a result, the PFBH is expected to substantially
reduce the cost of producing shale oil from Eastern U.S. Devonian oil shales.
ISO
HIGH PRESSURE ..-
HYDRAUU(: LIFT
100
RAW SHAlE
'-
so SLURRY
MIXING
\
ON
DEWATERING
lA
SEPARATOR
,:,.:JfP
ff'." , (
r\
.' PA$WE ,I
. SOlIDS
' '
"""'"
,- ,
SH",",
OUENCH )
PREHEAT
TOWER )
ZONE
"-
Ii
FEED-
PRODUCT
SEAl. ZONE
OU""'"
1',';;:,':::'1
TOWER
='
."''''' ZON'
'" GAS-O';:-
S""'"
m
.. ,+- SEPARATOR
COOLING
ZONE
I
MASS FLOW DISCHARGE
,
CONVEYOR DISCHARGE \
. __.!
RAW OIL
"'T("'T J
Sf'ENT SHALE
LOCKHOf'PERS
WATER
SURGE
,
"'W
ROOUCT
GAS
RE(:Y(:LE
GAS
C<ON<
atr-
HIGH PRESSURE
TAN'
Y Y
SPENT SHALE
FEEDER
T+ Y
I--
G
FINES DISCHARGE
f IMoe
Figure 77. Retort area flowsheet for a commercial HYTORT facility, (Printed
with the permission of the Institute of Gas Technology,)
OIL SHALE PAGE 281
Figure 78. The PFBH Retort is a vertically-staged fluidized bed unit for
retorting hydrogen-deficient oil shales, such as the Eastern U.S.
Devonian shales, in a hydrogen atmosphere at high pressures.
(Printed with the permission of the Institute of Gas Technology.)
FEED SHALE
RAW SHALE
PREHEAT
SHALE
HYDRO-
RETORTING
SPENT
SHALE
COOLING
FLUIDIZING GAS-----'
PRODUCT
OIL AND GAS
'-----_ SPENT SHALE
OIL SHALE PAGE 282
Figure 79. Decreasing particle size substantially increases oil yield and
reduces gas yield, while having only a small effect on the overall
~
-
z
0
Vl
0::
w
>
z
0
u
z
0
CD
0::
<C
u
carbon conversion, in hydrotorting of an Eastern oil shale.
(Printed with the permission of the Institute of Gas Technology.)
90
80
70
60
50
40
30
20
10
o
0.0
TOTAL
LIQUID
0
0
(0)
INDIANA NEW ALBANY
H2
35 atm
HEAT -UP RATE: 20F/min
(0)
00
0
GAS
0.1 0.2 0.3 0.4 0.5 0.6
EQUIVALENT DIAMETER, inches
0
0.7
OIL SHALE PAGE 283
Other advantages of the PFBH vs. the moving bed HYTORT process stem from
the characteristics of the fluidized bed. The efficient gas-solid contacting
and good heat transfer characteristics of the fluidized bed should improve
thermal efficiency and the need to briquette beneficiated shale (required for
moving bed hydroretorting) will be eliminated.
Additional work is underway to develop a fluidized bed gasification system
that will utilize the carbon content of the fines to produce hydrogen.
407
,408
However
1
the shale processing facility will require process heat and steam, and
the carbon on spent shale is usually the energy source that meets these needs.
Therefore, even if technically successful, the impact of gasification as a
hydrogen source may not be dramatic. However, if chemistry can be found that
will enable the use of synthesis gas to increase the rate and/or lower the
overall pressure requirement for hydrotorting, the impact of gasification may
be very important.
Finally, it should be pointed out that the molecular chemistry responsible
for the striking yield enhancements often obtained by hydrogen retorting are
not yet well understood. Nor, for that matter, are the reasons why shales that
are remarkably similar in elemental and mineral composition sometimes respond
very differently to hydrogen pressure.
408
Perhaps, a better understanding of
the molecular structure of the kerogen, and of kerogen-mineral interactions, in
the Eastern shales might help to clear up some of these mysteries.
OIL SHALE PAGE 284
B. IN SITU RETORTING
In situ retorting involves heating the shale in-place to produce shale oil
and gas. Because the shale remains underground, the requirements for mining,
transporting, crushing and grinding the shale rock are eliminated or greatly
reduced. True in situ retorting also eliminates the costs of an above-ground
retort. Thus, in situ retorting offers the potential for corresponding savings
in both operating and capital costs. However, making an in situ retort work is
generally difficult because most oil shales have very low porosity and almost
no permeability. Without permeability, getting combustion air into the oil
shale formation, or oil and gas products out of the formation is not possible.
Permeability can be induced, for example, by blasting or by injecting high
pressure air or water. However, maintaining such induced permeability is
difficult because shale oil tends to fill the void space in the bed and because
oil shale swells (exfoliates) upon heating. Attempts to induce and maintain
permeability have led to the two main in situ retorting approaches: "true in
situ" methods that involve blasting and/or other fracturing techniques, but no
mining; and "modified in situ" methods that involve mining part of the shale
to generate free underground space followed by blasting to generate a permeable
zone of "rubblized" oil shale for retorting. B o ~ h true and modified in situ
methods use a moving flame front to generate heat for retorting, hence are
similar in basic principle to the above-ground N-T-U Retort described earlier.
In a few areas of the Green River Formation, leaching of water-soluble minerals
affords a porous zone of high permeability. One such case is the "leached
zone", located below the rich "mahogany zone" and extending across much of the
Piceance Creek Basin (see Figure 3). The BX In Situ Oil Shale Project was an
attempt to take advantage of this natural permeability.
OIL SHALE PAGE 285
1. laramie True In Situ Retorting Studies
In the early 1960's, Laramie workers began to lay the foundation for
development of in situ retorting technology for Green River oil shale. Data
obtained from the above-ground 10- and 150-ton N-T-U Retorts at Laramie provided
basic information about the ignition of rubblized shale beds and the use of a
moving combustion front to provide heat for retorting.
304
*308 A series of nine
field experiments to explore true in situ retorting were carried out in the
Green River Basin near Rock Springs, WY (Figures 80_81).410w415
The major object of these experiments was to demonstrate that fracturing
of the oil shale formation could induce sufficient permeability to support
underground combustion. A variety of techniques - electrical, hydraulic and
explosive - were evaluated for inducing permeability (Table 49).
Table 49. Types of research carried out at Rock Springs Sites 1-9.
Fracturing Research In Situ Steam
Site Electrolinking Hydraulic Explosive Combustion Injection
I X X X
2 X X X
3 X
4 X X X X
5 X X
6 X X X
7 X X X
8 X X
9 X X X
OIL SHALE PAGE 286
Figure 80. The laramie in situ retorting experiments were carried out near
Rock Springs, WY in the Green River Basin, which lies north of the
Piceance Creek Basin where most oil shale activity has been focused.
(From Burwell, et a7., Reference 413.)
r
,OG
I JJV//
,
EVANSTOth
UTA H
5,.1_, ... lIn
10 1) 10 20 30
"'"'" 1
Jill!!Q.
GIIEEH R!VR fORMA.TION
N G
liNN IIIVER
RIFLE
OIL SHALE PAGE 287
Figure 81. layout of the Rock Springs exploratory in situ retorting sites.
(From Burwell, et al., Reference 413.)
Sile I ~
lOO O,-=:::;:'Ci"=::::i'OO
~ - : =j
Seole, fee!
OIL SHALE PAGE 288
The major objective of the laramie studies was met: sufficient permeabil-
ity was induced for combustion to be initiated, and for the combustion front to
be maintained and moved through the rubblized shale bed. Although post-burn
coring established that significant amounts of shale were retorted in the cases
where jn situ combustion was sustained, oil recoveries were poor. In part,
this was due to recurring problems with pumps that plugged with shale debris.
However, non-uniform combustion and inadequate product containment also contrib-
uted to low oil recovery in these exploratory studies.
In parallel with, and following, the test burns, Laramie workers carried
out an extensive program of environmental studies.416-419 These studies
identified the disposition of the produced retort water as a key environmental
concern. This water is produced during thermal retorting and is derived from
dehydration of shale minerals, as well as from combustion. The intrusion of
ground water may also contribute to the water recovered with the oil. Retort
water is odoriferous, yellow to brown in color and contains high levels of both
organic and inorganic dissolved constituents. It is usually quite basic, with
a pH in the range of 8-9.5. The amount of retort water is large; about equal
to the volume of oil produced, in favorable cases. However, testing revealed
that the retort water is not particularly toxic, and indicated that standard
purification techniques should be adequate for its environmentally acceptable
disposal.
OIL SHALE PAGE 289
2. Geokinetics Horizontal In Situ Process
The Geokinetics Horizontal In Situ Retorting Process (HISP) is a true in
situ process, designed to retort shallow shale seams with no mining.420-422
Because no mine construction is involved, a key feature of HISP is its very low
initial capital cost. In 1974, HISP development began as a joint effort of
Geokinetics Inc. and Aminoil USA. In 1976, ERDA (later DOE) joined the effort.
In 1978, Aminoll withdrew, leaving Geokinetics and DOE as the remaining
participants. In 1984, DOE withdrew and Geokinetics completed the project at
its own expense.
In the process. the soil and subsoil are first removed using earthmoving
equipment, then a pattern of holes is drilled through the overburden and shale
seam to be retorted (Figure 82). Explosive charges are then loaded and
detonated sequentially to create the jn sjtu retort. The blasting pattern is
precisely designed so that the initial blast lifts its rubble some 10-20 feet
at the While this rubble is still aloft, about 0.5 second
after the initial blast, the subsequent rows of charges fire at approximately
0.1 second intervals to laterally displace rich shale into the void. The
result is a disruption of the surface (spalling) only at one end of the retort.
Offgas well are then drilled at the disrupted end and air injection wells at
other. Oil production wells are associated with sumps to facilitate oil
collection (Figure 83). Observation, thermocouple and gas sample wells
complete the required drilling. The subsoil is then replaced and thoroughly
tamped to seal the retort before ignition.
Figure 82. Geokinetics blasting sequence. (a) Site preparation involves removing soil and subsoil, then
drilling blastholes. (b) First blast initiates vertical uplift. (c) Subsequent charges displace
rich shale laterally into created void space, without disrupting overburden. (d) Retort at the
end of the blasting sequence. (After lekas, Reference 420.)
"'''"'''''''''''''-
..,.., ...."' .. , .. _ .............. _n'., " .. '''' .... , .. ..
...... _ ........... _"""'.,_".".' .. "'d .
f, ..... , ... .,_ "', .,." ...... ' ..... _
o
-
r
Figure 83. The subsoil is replaced and thoroughly tamped to provide a good seal, before the Geokinetics
Horizontal In Situ Retort is placed in operation. (After Lekas, Reference 420.)
Off"'''-''
to cleanup
system
Gas-ol.lt pipe
Oil pump
10il '" stor ... I' I
Oil pump
(oil to sto' ... I\
i from blowers
Air inl.t
i i
~ ___________________________ 3ro' ____________________________ ~
Side view
10'
OIL SHALE PAGE 292
Geokinetics field studies were carried out at the Seep Ridge site dubbed
"Kamp Kerogen" located south of Vernal, UT. A total of twenty-eight retorts
were designed. Twenty were blasted and burned; six were blasted, but not
burned; and one retort was abandoned prior to blasting. The final five,
Retorts 24-28, were of commercial size.
Oil recoveries from Retorts 25 and 26 were 59% and 51% of Fischer Assay,
respectively, where superficial gas velocities were maintained at or above 0.8.
Due to substantially lower air injection rates, oil recoveries and production
rates from the other retorts were much lower.
Quality of the oil produced by HISP will vary from retort to retort, due
to variations in shale composition, and also varies with time during production
from a given retort. However, a composite analysis of oils from Retorts 27 and
28 shows that oil quality is quite good (Table 50). In particular, the metals,
asphaltenes and residuum contents are desirably low.
OIL SHALE PAGE 293
Table 50. Properties of crude shale oil from the Geokinetics Horizontal In
Situ Retorting Process.
1
(Data of Lekas, Reference 420.)
Gravity 25-26 'API
Viscosity: at 100 'F
at 140 'F
Flash Point (ASTM 093-23):
as & W (Maximum):
Ash:
Pour Point:
Aspha Henes:
Elemental Analysis:
Carbon:
Hydrogen:
Oxygen:
Nitrogen:
Sulfur:
Metals:
Iron:
Arsenic:
Vanadium:
Nickel:
Heat of Combustion (Gross):
Distillation (ASTM 01160):
12-16 cSt
6-8 cSt
180-200 'F
1.0 Wt%
0.015-0.030 Wt%
70-80 'F
0.5 - 1.5 Wt%
83.0 - 84.7 Wt%
11.8 - 11.9 Wt%
0.9 - 1.6 Wt%
1.5 1.6 Wt%
0.6 1.0 Wt%
87
8
I
6
740 ppm
II
3
58
19,000-19,500 BTU/1b
Vol %
IBP
10
30
50
70
90
FBP
'F
160 255
420 470
520 - 580
600 - 675
775 - 790
900 - 920
980 - 1150
(I) Data derived from analysis of raw shale oil samples produced from HISP
Retorts #27 and # 28 during Geokinetics' development program.
OIL SHALE PAGE 294
3. Occidental Vertical Modified In Sjtu (VHIS) Process
The true in situ retorting processes discussed above involved drilling,
but no underground mining. In contrast, the modified in situ methods discussed
below involve mining 15-40% of the shale to create void space within the
formation, then blasting to rubblize the remaining shale to fill the resulting
retort. The retort is ignited at the top and burned with a downflow of air
(Figure 84}.427
w
431
In 1972, Occidental began field development of VMIS retorting at its Logan
Wash oil shale mine north of DeBeque, Co. Early work at Logan Wash included
the construction and processing of three small retorts and one commercial-sized
retort. The small retorts were about 30 feet square by 72-113 feet in height.
Retorts IE and 2E used a vertical raise in the center of each retort, with a
single room at the bottom to provide void volume. Three horizontal rooms were
spaced vertically to distribute void volume in Retort 3E, which improved yield
relative to IE and 2E. Retort 4, with two vertical slots parallel to each
other across the retort width, was an attempt to scale up the vertical void
concept. The lower yields obtained from Retort 4 were ascribed to limitations
imposed by rock mechanics that led to non-uniform flows and bed stability
problems.
Retorts 5 and 6 were commercial-sized units that were developed under a
1976 cooperative agreement with US OOE.430-432 Retort 5 used a single vertical
slot mined across its width to provide void volume, while Retort 6 was a scale-
up of the Retort 3 design with three horizontal rooms (Figure 85). The latter
design again afforded a superior oil yield.428-429
OIL SHALE
PAGE 295
Figure 84. Occidental Oil's Vertical Modified In Situ (VMIS) Retort. (After
McCarthy and Cha, Reference 427. Reprinted with the permission of
the Colorado School of Mines.)
Pillar
Air & Recycle """._ ....
Or Steam
- -...
-- - "-
........ --
.:::-> " -
- - - - -
- -
"::"- -...........- ",,-
Combustion Zone
Front -'
Movement
Retorting Zone
. . '.
0"
t
Pillar
OIL SHALE PAGE 296
ILL PILLAR . ___ -'---:OS;;;;;;;;;:;;j UPPER SHALE LAYER
UPPER
INTERMEDIATE LEVEL
__
INTERM
"-"t_.
165'
PRODUCT LEVEL
100' x 100'
LOWER SHALE LAYER
BULKHEAD
Figure 85. Isometric view of the Oxy VMIS Retort 6 before blasting, (After
Ricketts, Reference 428. Reprinted with the permission of the
Colorado School of Mines,)
Retorts 7 and 8 were constructed under the second phase of the Occidental-
DOE cooperative agreement.
432
These were identical, commercial-sized retorts,
measuring 165 x 165 feet across x 241 feet tall. They were constructed side- by-
side, using the Retort 6 design, and burned at the same time in order to obtain
reproducibility data not available from single retort tests (Figure 86),433'43.
Retorts 7 and 8 afforded even higher oil yields than Retort 6 (Table 51).434
OIL SHALE PAGE 297
Figure 86. Isometric view of Oxy VMIS Retorts 7 and 8, with partial height
Retort 8X in the background. (From Ricketts, Reference 433.
Reprinted with the permission of the Colorado School of Mines.)
-- ,
"
R8
"
,
,
,
R8X
-,
"
-
R7
,
,
,
,
,
/
/
,
,
/
.
,
,
OIL SHALE PAGE 298
Table 51. Summary of the retort operating parameters and results for Oxy
Retorts 7 and 8. (After Stevens and Zahradnik, Reference 434.)
Superficial Gas Velocity, ft/min
Air/Steam Ratio, Average
Fischer Assay of Target Rubble, gal/ton
Oil-in-place in Target Rubble, bb 1
Produced Oil, bbl
Yield, % of Fischer Assay
Void Rock Mined, tons
Yield, bbl oil/ton of rock mined
Retort 7
0.54
80/20
17.3
143,200
92,326
64.5
111,604
0.83
Retort
0.54
80/20
16.9
140,100
106,200
75.8
114,042
0.93
8
17.1
283,300
198,526
70.1
225,646
0.88
It is interesting to note that dividing the amount of oil produced in
Retorts 7 and 8 by the amount of shale mined gives a value of 0.88 bbl/ton.
This value compares very favorably with the value of 0.41 bbl/ton that would
have been obtained if the mined shale had been retorted under conditions
affording 100% of Fischer Assay_ In a commercial operation, the mined shale
would probably be processed in such an above-ground retort. In this scenario,
for maximum overall efficiency the bulk of the shale would be retorted using
the cost-effective underground method, while surface retorting of the mined
shale would provide nearly complete resource utilization.
The distance between Retorts 7 and a was 160 feet. To assess the effect
of a shorter inter-retort distance, the partial height Retort ax was
constructed 50 feet behind Retort 8. Retort 8 had the 165 x 165 foot cross-
section of Retorts 7 and 8, but was only 63 feet tall. It was blasted first,
so that blasting of Retort a could provide information about the deformation,
OIL SHALE PAGE 299
stresses and fracturing that would occur at the shorter distances called for in
the commercial development plan. No specific problems associated with the
50-foot inter-retort distance have been mentioned, and Retort 8 performance
does not seem to have suffered. However, rock structure is highly site-
specific and it would be unwise to assume that such a short distance would be
acceptable in any other site.
4. Rio Blanco Modified In Situ Process
The Rio Blanco Oil Shale Company (RBOSC) was originally a 50/50 joint
venture of Gulf Oil Corporation and Standard Oil Company (Indiana), and is now
a division of Amoco Corporation. It was formed after winning a bid in January
1974 for Federal Oil Shale lease C_a.
437
Site preparation for modified in situ
(MIS) development on Tract C-a began in late 1977. Two retorts were designed,
constructed, then successfully rubblized and burned to demonstrate the RBOSC-
MIS technology. The MIS retorting phase was completed during the first part of
1982. Following successful completion of the RBOSC effort, an extensive study
of above-ground retorting based on Lurgi technology, was made at the Gulf Oil
Research Center at Harmarvil1e, PA. Because Tract C-a is suitable for open-pit
mining, current RBOSC interest has shifted to the above-ground technology. The
Tract C-a operation has now been suspended until RBOSC can obtain off-tract
land for disposal of overburden and spent shale. During suspension, RBOSC is
maintaining the leasehold and continuing environmental monitoring work. while
proceeding with internal oil shale research and development programs at the
Amoco Research Centers.
Figure 87 is an isometric view showing the mine and the two experimental
retorts; Retort 0 is to the right of the much larger Retort 1.43' At 400 feet
tall, Retort 1 is the tallest in situ retort ever built.
OIL SHALE PAGE 300
Figure 87. Rio Blanco Oil Shale Company's experimental Retort 0 is to the
right of the much larger Retort 1 in this isometric view, that
a 1 so shows the 1 ayout of the three-l eve 1 mi ne. (From Berry, et
aI., Reference 438. Reprinted with the permission of the Colorado
School of Mines.)
Sicst Holes
Shaft
Instrument Shaft
Exhoust Shaft
Off.Ga. Shaft
Production Shaft
. , le .... el
level
Separator
, level
Romp to Shoft Bottom
OIL SHALE PAGE 301
Key features of the RBOSC mine include the production shaft which was
constructed first using conventional shaft-sinking equipment, the exhaust shaft
which was then raise-bored to the surface to establish a conventional ventil-
ation system for the mine, and the service/escape shaft which was also raise-
bored to the surface. A separate circuit for supplying air and steam to the
retorts through the surface-drilled blastholes, and for piping offgases back to
the surface through the offgas shaft, was sealed off from the working areas of
the mine. a unique feature of the RBOSC design is the underground oil-water
separator that is a mined cavity, that minimizes the capital cost of large
above-ground tankage.
The main production level is the G-level, 850 feet below the surface. The
G-level provided access to the bottoms of the retorts before bulkheads were
installed to seal off the mine from the retorts.
Retort 1 extends through the Upper Aquifer of the Piceance Basin in which
the pressure is several hundred feet of water. Initially a ring of surface
wells was drilled to dewater the area around the production shaft; later the
sub E level was mined and drain holes were drilled into the aquifer. After
water production rates as high as 3600 gal/min., water rates stabilized near
1100 gal/min and only 10-30 gal/min was entering Retort I at its ignition.
Retort 0 was not instrumented. In contrast, Retort 1 was heavily instru-
mented with over 150 thermocouples and many pressure taps drilled into the
rubble to provide a clear picture of conditions inside the operating retort.
The RBOSC proprietary rubblizing procedure that affords high void-volume,
hence high permeability, is felt to be the single factor most responsible for
the success of the process. The first step in this procedure is to drill blast
OIL SHALE PAGE 302
holes from the surface to the full depth of the planned retort and undercut a
room that will serve as a product drain is then mined (Figure 88). In Step 2,
the lower part of each blast hole is loaded with explosive that is detonated to
blast a segment of roof down into the room at the bottom. Part of the rubble
is mucked, leaving the rubble at its angle of repose. The load, blast and muck
sequence is repeated until the desired void space is obtained. In Step 3, the
remaining roof rock is rubblized without mucking, until the entire retort is
constructed with only a small free space at the top to serve as a feed gas
distributor.
The RBOSC rubblizing procedure was found to give a relatively small average
particle size with a random size distribution that is conducive to high, even
and maintainable permeability. This was confirmed by extensive cold flow tests
with Freon tracer gases. These tests indicated an overall sweep efficiency of
85% for both retorts. Sweep efficiency in Retort 1 could be investigated in
more detail, because of its instrumentation. In this case, it was found that
sweep efficiency in the top two-thirds was 100%, while that in the lower third
was only 60%. leak rates were measured under stable pressure conditions and
void volumes were calculated from pressure changes with the effluent valves
closed. Cold flow pressure drop as a function of flow rate could be calculated
from the Ergun Equation, using the experimental void volume and a calculated
effective mean particle size.
Figure 88. Construction of RBOSC's high-void retort involves three steps. (From Berry, et al., Reference
438. Reprinted with the permission of the Colorado School of Mines.)
V Explol,ve C ~ O ' g e
Undue",! ROQm
Step 1: Undercut Working room
and raise-bore blastholes.
Step 2: Rubblize lower part of
retort and remove excess rock.
Step 3: Blast upper part to complete
preparation of the retort.
~
"'
w
'"
w
OIL SHALE PAGE 304
Ignition of the retorts was achieved within 28 hours, using gas-fired
burners lowered downhill. Durability of the burners, a problem in some
other in situ studies, was demonstrated by repeated shut-down/re-ignition
cycles. It was found that the higher pressure drop in ignited rubble tended to
direct flow to unignited rubble, and thereby to promote even spreading of the
f1 arne front.
Stock
Scrubber
Incinerator
Water, Oil
to Surface
Go,
Underground
Sepofolor
Flo re
I
Air
steom-L
.- Boder
R e 10 rt
Figure 89. Block flow diagram of Rio Blanco production at Tract C-a. (From
Berry, et al., Reference 438. Reprinted with the permission of
the Colorado School of Mines.)
OIL SHALE PAGE 305
Air and steam were fed to the ignited retort through the same boreholes
used for blasting (Figure 89). Products flowed to the underground separator?
from which oil and water were pumped separately to the surface. The philosophy
for operation was to maximize the flame front advance within the safe operating
limits of the available equipment. Consequently, the advance rate decreased
with time, due to the increasing pressure drop from the top of the bed to the
front. Even though some problems that limited advance (air leakage, sulfur
emission limits) were encountered, the front advance averaged about 3 ft/day
and were considerably higher during the early stages (Figure 90).
Oil production, which totaled 24,444 bbl for Retort I, includes liquid oil
from the separator room, the C
6
+ condensables from the exit gas, and any oil
mist found as an aerosol in the exit gas. The first liquid oil appeared about
15 days after ignition. and thereafter oil production tended to mirror the
flame front advance (Figure 90).
Oil recovery in the RBOSC tests was very good, 68% of Fischer Assay from
each retort (Table 52). The maximum yield value in Table 52 was calculated
using a computer model from Lawrence Livermore National Laboratory which takes
into account the shale grade, particle size, air/steam ratio and front advance
rate.
439
The maximum calculation assumes 100% sweep efficiency. However, it
will be recalled that efficiency was only about 85% for these retorts. Thus,
the experimental values are in reasonable accord with expected behavior.
Figure 90. Flame front advance and oil production in RBOSC Retort 1. (From Berry, et a7., Reference 438.
Reprinted with the permission of the Colorado School of Mines.)
400 - , . . . ~ 40
300
30
-
-
24,444
'-
c
---
0
........
-
- ,;,;
0
200
,;
20
0-
;'
....
"
-
C ,,-
0
",-
~
'"
u..
",-"
100
_/
10
.... -
",-
/
/
",-
0
0
J u I Aug
Sept 0, Nov De,
1981
.D
"' '-
~
."
~
,
~
>
0
u
~
'"
0
o
-r
'"
l>
'"
m
w
0
'"
OIL SHALE PAGE 307
Table 5Z. Oil Yields and operating parameters for Rio Blanco Modified In Situ
Retorts 0 and I. (Data of Berry, et al., Reference 438.)
Air/Steam Ratio
Front Advance Rate, Avg. ft/day
Actual Oil Yield, bbl
Fischer Assay of Available Rubble, gal/ton
Maximum Calculated Oil Yield, % FA
Actual Oil Yield, % FA
Retort 0
SO/50
2.7
1,876
17.3
70
68
Retort I
70/30
3.0
24,444
21.6
79
68
In summary, the Rio Blanco effort led to a simple design that approaches
laboratory results in oil recovery efficiency. The high void-volume retorts
are suitable for MIS retorting at high burn rates. The entire retort can be
developed from a single mine level (e.g. the G-level); no access to the upper
part of the retort is needed for ignition. Safe and very effective ignition
was achieved using downhole burners. In addition, it has been demonstrated
that successful retorting can be achieved in the dewatered Upper Aquifer. Even
though current Tract C-a interest has shifted, the success of the RBOSC-MIS
effort suggest that the technology may be applicable to other depOSits situated
even deeper beneath the surface than that at Tract C-a.
5. Equity Oil/ARCO BX Project
In the "leached zone" of the Piceance Basin, dissolution of water-soluble
minerals has led to a relatively rich oil shale of high natural permeability.
The Equity Oil BX Project took advantage of this peremeability for in situ
retorting, using injected superheated steam to heat the oil shale.
44o
,441 The
project was carried out on a 1000-acre fee property jointly owned by Equity Oil
OIL SHALE PAGE 308
and Atlantic Richfield (AReO) and located in Rio Blanco County, CO, about
midway between Tracts C-a (Rio Blanco) and Cob (Occidental). At the project
site, the leached zone averages 540 feet thick with shale assaying 24 gal/ton.
The project comprised a pattern of eight injection wells. five production
wells and three observation wells covering an area of 0.7 acres (Figure 91).442
Initial plans were to inject steam at 1000'F, 1500 psig and a total pattern
rate of 974,000 lb steam/day (2,784 bbl/day water). This was to be maintained
over a 2-year period to produce a total of 650,000 bbl of shale oil (100% of
Fischer Assay). Because of equipment limitations and mechanical problems,
these injection targets were not met. As a result, very little shale oil was
actually produced. The initial oil observation was made only after a year of
steam injection and 18 months of steam injection yielded 46 barrels of crude
shale oil.
Not only the quantity, but also the quality, of permeability seems to be
important. The permeability of the leached zone shale is not uniform; it is
appreciably lower in the vertical direction, than in the horizontal direction
(bedding plane). The effects of this anisotropic permeability are readily
apparent in Figure 92, which shows that efficient heating was confined to the
two steam injection zones. These results do not preclude using the Equity Oil
steam injection scheme, but does mean that more complicated and expensive
injection equipment would be needed for distribution of the steam into multiple
injection zones to provide uniform heating of the shale formation.
OIL SHALE PAGE 309
Figure 91. The Equity Oil/ARCO BX project included sixteen wells drilled in a
pattern covering 0.7 acres. (Dougan and Docktor, Reference 442.
Reprinted with the permission of the Colorado School of Mines.)
<:)-
N
50 fEET (15.2m)
I I
SCALE
1\2
'\!J
@
WELL PATTERN
lll: II'< SHU Oil SHAU HOl(CI
o INJECTION WEll
o PRODUCTION WEll
o TEMPERATURE OBSERVATION WEll
OIL SHALE PAGE 310
Figure 92. The temperature profile vs. depth for BX Observation Well No.2,
located near the center of the pattern, shows that efficient
heating was confined to the two steam injection zones. (Dougan
and Docktor, Reference 442. Reprinted with the permission of the
.
~
W
o
Colorado School of Mines.)
300,----------------------------------------.
500
700
900
1100
1300
TEMPERATURE OBSERVATION WELL NO 2
JUNE 29. 1980
INJECTION ZONE
INJECTION ZONE
1 5 0 0 ~ - - ~ - - - - ~ - - ~ - - - - ~ - - - - ~ - - ~ - - - - ~ - - ~
50 100 150 200 250 300
TEMPERATURE. OF
350 400 450
OIL SHALE PAGE 311
In summary, the BX Project attempt to take advantage of the leached zone's
natural permeability for in situ retorting by superheated steam injection did
not result in high oil recoveries. In large part, the BX results were traced
to equipment limitations. However, the results also showed clearly that the
anisotropy of leached zone permeability is a factor to be reckoned with in any
future work along these lines.
OIL SHALE PAGE 312
VII. SHALE OIL UPGRADING AND REFINING
Crude shale oil, sometimes termed retort oil, is the liquid oil condensed
from the effluent in oil shale retorting. Crude shale oil typically contains
appreciable amounts of water and solids, as well as having an irrepressible
tendency to form sediments. As a result, it must be upgraded to a synthetic
crude oil (syncrude) before being suitable for pipelining or substitution for
petroleum crude as a refinery feedstock. However, shale oils are sufficiently
different from petroleum crudes that processing shale oil presents some unusual
probl ems.
A. COMPOSITION
Shale oils, especially those from Green River oil shale, have particularly
high nitrogen contents -- typically 1.7 - 2.2 wt% vs. 0.2 - 0.3 wt% for a
typical petroleum. In many other shale oils (including those from Eastern U.S.
shales) nitrogen contents are lower than in the Green River shale oils, but
still higher than those typical of petroleums. Because retorted shale oils are
produced by a thermal cracking process, olefin and diolefin contents are high.
It is the presence of these olefins and diolefins, in conjunction with high
nitrogen contents, that gives crude shale oils their characteristic instability
towards sediment formation. The sulfur contents of shale oils vary widely, but
are generally lower than those of high-sulfur petroleum crudes and tar sand
bitumens.
Figure 93 shows the nitrogen and sulfur distributions, as a fUnction of
boiling pOint, in raw shale oils produced from the Utah part of the Green River
Formation.
356
Surprisingly, the sulfur content is relatively constant in all
the fractions, while nitrogen is concentrated in the higher boiling fractions.
OIL SHALE
3.0
z
w
'"
0
0:
....
2.0
z
...J
;::
0
1.0 ....
~
0
I-'
3
O + - - - - - - - - . - - - - - - - - r - - - - - ~
gj 1.0
u.
...J
::>
(J) 0.5
<f!.
o 30 60 90
I-'
3 0 +----,-----,-----,
o 30 60 90
VOLUME % DISTILLED
PAGE 313
Figure 93. Nitrogen and sulfur concentrations in raw Green River shale oil, as
a function of distillation range. The shaded band in each case
shows the range of data from oils produced by the Union-B and
Paraho-DH (directly-heated) retorts. (From Lovell, Reference 356.
Reprinted with the permission of the Colorado School of Mines.)
In addition to the olefins and diolefins mentioned above, The Green River
shale oils contain appreciable amounts of aromatics, polar aromatics and
pentane-insolubles (asphaltenes).356 The distribution of compound types as a
fUnction of distillation range is shown in Figure 94, where the concentration
of polar aromatics and pentane-insolubles in the hig,her-boil ing fractions
parallels the nitrogen concentration in these fractions.
OIL SHALE
100
~ 75 - t " : ~ , ,
=>
..J
o
>
W 50
>
I-
<l:
..J
i 25
=>
u
o
PAGE 314
AROMATICS'
30 60 90
MID-VOLUME %
Figure 94. Distribution of compound types in Crude Green River shale oil, as
a function of distillation range. (From Lovell, Reference 356.
Reprinted with the permission of the Colorado School of Mines.)
Oxygen contents are higher than those typically found in petroleum, but lower
than those of crude coal liquids. Crude shale oils also c.ontain appreciable
amounts of soluble arsenic, iron and nickel that cannot be removed by
filtration. The compositions of some representative crude shale oils are
shown in Table 53.
OIL SHALE PAGE 315
Table 53. Compositions of some crude shale oils.
Paraho-DHa Occidental MISb Oravoc CSRd
Colorado Colorado Kentucky JUlia Creek
Gravity, "API 20.4 22.9 12.0 10.1
Pour Point, of 85 65 15 -Il
Viscosity at IOO"F 213 SSU 15.9 cSt
122"F 44.9 SSU 21. 94 cSt
210"F 5.27 cSt
BS&W, Wt% 0.05 0.2
Conradson Carbon, Wt% 2.98 (r) 1.36 6.9
Elemgntal Analysis
Carbon, Wt% 83.68 84.85 83.19 83.0
Hydrogen, Wt% 11. 17 12.27 9.84 9.5
Nitrogen, Wt% 2.02 1. 51 1.14 1.3
Oxygen, Wt% 1.38 0.65 1.97 1.3
Sulfur, Wt% 0.70 0.64 3.86 4.9
Ash, Wt% 0.014 0.092
Metals
Arsenic, ppm 28 27.5 100 26
Iron, ppm 53 45 IlO 55
Nickel, ppm 2.4 6.7 3
Vanadium, ppm 0.17 0.42 153
Sodium, ppm 0.3 Il
Hydrocarbon Tyge
Saturates, Wt% 11.4
C"
=
51.6%
Aromatics, Wt% 54.7
H"
=
12.4%
Polars, Wt% 14.6
Hot ""
3.2%
Asphaltenes (c
7
), Wt% 0.89 0.34
Bromine Number 23.6 57
{ASTM D-Il60l, "F
IBP 90 376
5% 255 467 439
10% 324 570 477
30% 454 670 598
50% 572 712 714
70% 675 820 836
90% 834 953 981
95% 895
EP 972
% Recovered 97 87
(a) Reference 469.
(b) Reference 465.
(c) Reference 345.
(d) Reference 476.
OIL SHALE PAGE 316
B. UPGRADING
Upgradjng, or partial refining. to improve the properties of a crude shale
oil may be carried out with different objectives, depending on the intended use
for the product:
Stabilization to produce a pipelinable oil that can be transported to a
distant refinery
More complete upgrading to produce a premium refinery feedstock with low
nitrogen, low sulfur and essentially no residuum
Upgrading to produce chemical feedstock streams
Complete refining of the crude shale oil or selected fractions to produce
finished end products {e.g. gasoline, diesel, jet fuel}
It is difficult to generalize regarding shale oil processing. Not only do
the shale oil properties vary, refineries vary widely. For example. there are
about 300 fluid atalytic racking (FCC) units in free world refineries -- and
these use more than 260 different cracking catalysts! Therefore, several of
the reported large-scale studies have been selected to illustrate the major
features of shale oil upgrading and refining. These studies have generally
used one of three approaches:
Thermal Conversion (Visbreaking, Coking) followed by Hydrotreating
Hydrotreating followed by Fluid CatalytiC Cracking
Hydrotreating followed by Hydrocracking
Much of the recent information about oil shale upgrading and refining has
come from studies sponsored by the U.S. Department of Defense and Department of
Energy, and carried out under contract by petroleum refiners (Table 54).
OIL SHALE PAGE 317
Table 54. Shale oil upgrading and refining studies sponsored by the U.S.
Department of Defense (DOD) and Department of Energy (DOE).
Processing Program Crude Shale Oil Soyrce Upgrading Contractor
1975
Shale I (000) Paraho 1 Gary Western
443
1975 - 1976
Aviation Turbine Fuels Exxon Research
from Synthetic Crudes
& Engineering444w446
(DOD)
1978
Shale 11 (DOD) Paraho II
Sohio (Toledo)447,448
Advanced Catalytic
Processes (DOE) Paraho
Chevron449-454
1978 - 1981
Process Methods Paraho IIjOxy #6
Ashland45So457
Process Methods Paraho IljOxy #6
Suntech455.456,458
Process Methods Paraho I1jOxy #6
Amoco459461
1979 -1981
Catalyst Development Occidental Retort #6
Amoco462w464
1980
Shale III Geokinetics HRI - Suntech
OIL SHALE PAGE 318
C. DEWATERING AND SOLIDS REMOVAL
Crude shale oil usually contains emulsified water and suspended solids.
Therefore, the first step in upgrading is usually dewatering/desalting.
Sikonia and his co-workers at UOP found that a conventional two-stage
electric desalter reduced the water content of a crude Occidental MIS shale oil
to 0.05 wt%, but was not able to achieve the 10 ppm toluene-insoluble solids
level desired for hydrotreating.
46s
The 100-500 ppm solids left in the feed
necessitated special measures to prevent or alleviate fouling and pressure-drop
problems in fixed-bed reactors.
Sullivan and Stangeland described dewatering of a crude shale oil produced
by the Paraho semi-works retort (indirectly- heated mode).454 As-received. the
crude shale oil was an emulsion containing 6 wt% water and about 0.5 wt% fine
solids. Heating to 170F broke the emulsion; most of the water and suspended
solids settled out after standing at 170'F for 6 hours. Passage through a 15"
filter removed little additional material, however, a O . 4 5 ~ filter retained
252 ppm fine solids (Table 55).
OIL SHALE PAGE 319
Table 55. Properties of the dewatered Paraho-IHa crude shale oil that was
upgraded at Chevron's Salt Lake City refinery. (Data of Sullivan
and Stangeland, Reference 454.)
Gravity, API
Pour Point, of
Total Nitrogen. Wt%
Sulfur. Wt%
Arsenic, ppm
Iron, ppm
b
Carbon, Wt%
Hydrogen. Wt%
Atomic H/e Ratio
Oxygen, Wt%
Chloride, ppm
Ash, Wt% (ASTM 0-486)
Filter Residue Ash (0.45p filter):
Total solids. ppm
Ash, ppm
BS&W (sediment +water), Vol%
Bromine Number
Average Molecular Weight
Viscosity, cSt
122'F
210'F
Acid Neutralization Number, mg KOH/g
Base Neutralization Number, mg KOH/g
pH
Maleic Anhydride Number, mg/g
Heptane Asphaltenes
(includes any fines), Wt%
ASTM 0-1160 Distillation, 'F
IBP/5
10/30
50
70/90
EP
% Overhead (excludes trap)
% In Trap
% In Flask
(a) Produced in the indirectly-heated mode.
20.2
90
2.18
0.66
28
70
84.30
11.29
1.60
1.16
< 0.2
0.03
252
194
0.1
51
326
25.45
5.54
2.3
38
9.2
40.6
0.17
386/456
508/659
776
871/995
1022
94
1
5
(b) This iron was not removed by filtration through a 0.45p filter.
OIL SHALE PAGE 320
D. ARSENIC AND IRDN REMOVAL
If not removed, the arsenic and iron in shale oil would poison and foul
the supported catalysts used in hydrotreating. Because these materials are
soluble, they cannot be removed by filtration. Several methods have been used
specifically to remove arsenic and iron. Other methods involve hydrotreating;
these also lower sulfur. olefin and dialefin contents and thereby make the
upgraded product less prone to form gum.
Workers at Atlantic Richfield (ARCO) found that contacting the crude shale
oil with hydrogen at 800'F and 1400 psig (visbreaking conditions) resulted in
precipitation of arsenic and selenium, and also lowered the pour point of the
011.466 A crude shale oil containing 17.4 ppm arsenic and having a pour point
of 7S
e
F was processed to obtain an upgraded oil with 2 ppm arsenic and a pour
point of 30'F.
Dhondt has described Union Oil's treatment to remove solids and arsenic.
364
Two-stage water washing removes suspended solids, which are recycled. Arsenic
is removed by a proprietary, nickel-containing absorbent at 288
8
_343C in the
presence of hydrogen at moderate pressure.
467
,468 It is claimed that this
absorbent will lower arsenic content from 500 ppm to less than 1 ppm, and that
the absorbent can pick up arsenic to about 80% of its own weight.
For commercial-scale processing (73,000 bbl) of crude Paraho shale oil,
Sohio workers installed a guard bed containing layers of high-surface 1/16-inch
alumina extrudate loaded between layers of low-surface 1/4 and 1/2-inch alumina
balls (Figures 95 and 96),469 No active metal was deposited on the guard bed
packings and the bed was only operated at 420'F. As a result, little or no
arsenic was removed by the guard bed. However, iron was removed as iron pyrite
OIL SHALE PAGE 321
which remained in the guard bed. Also deposited in the guard bed was a black
pitch material, whose formation may have been caused by inadvertent recycle of
sulfuric acid to the shale feed tank during start-up of the acid treater used
as a final polishing step for the jet and diesel fuels. Build-up of pyrite and
pitch was sufficient to cause bed plugging after 24 days on-stream.
Figure 95. Sohio Hydrotreating unit used to process 73,000 barrels of crude
Paraho shale oil into military transportation fuels. (Robinson and
[vin, Reference 469. Reprinted with the permission of Butterworth
n
1
HED
DRUM
Publishers.)
HYOROTREATER
REACTOR
HYDROGEN
RECYCLE
MAKEUP
HYDROGEN
CONDENSATE
I
(
)T
I-
I-
V--
HIGH o!
PRESSURE
COAlESCER
:,:\:f I FOUL CONDENSATE
'1 .. 1 'Q
BED
Off
GAS
!
STRIPPER
COLUMN
-@ ..
CRUDE SHALE
SPITlER BOTTOMS LIQUID RECYCLE
=:J.
CRUDE SHALE Oil
OIL fIl TER
SPUTTER
COLUMN
REflUX
DRUM
l
)
n JET FUEL
r--' STRIPPER
r"-
Of.
STRIPPER
Y
GASOLINE
RANGE
STOCK
JET FUEl
Of.
HEAVY
fUEL
Oil
OIL SHALE PAGE 322
Figure 96. The guard bed used in Sohio's shale oil hydrotreating study was
packed with alumina extrudate and alumina balls. (Robinson and
Evin, Reference 469. Reprinted with the permission of Butterworth
Publishers.)
OUTLn
OUTLET SCRHN
o SAMPle LOCATIONS
,
,
o 000
,
MANHOLE
T Of EXTRUOATES
REPLACED AFTER
fIRST PlUGGAGE
,
'J, SAllS I
,
,
,
~ ~ - - - - - - 22't, Of ALUMINA EXTRUOAHS ------ .11
DIRECTION Of FLOW
<::;========
NOTE: GUARD BED WAS MOUNTED VERTICAllY OURING RUN
TRASH
BASKETS
INLH
OIL SHALE PAGE 323
E. UPGRADING BY NON-CATALYTIC THERMAL PROCESSES
Thermal conversions, coking and visbreaking, are conceptually simple, 000-
catalytic methods for lowering the high pour 'point and viscosity of raw shale
oils, in order to make the oil more suitable for hydrotreating that is needed
to remove nitrogen and sulfur. Coking also separates suspended solids.
Visbreaking is a mild thermal treatment that lowers viscosity and pour
point, to make the shale oil pipelinable. As noted above, it also precipitates
arsenic, but does little to reduce the contents of nitrogen, sulfur or olefios.
In visbreaking, the oil is heated to 420
0
-480C for a short time (seconds to
minutes) under hydrogen, during which some product is cracked to gas, along
with the desired cracking. Capital costs for visbreaking are low, but energy
consumption is high for the benefits obtained. As a result, visbreaking is not
a preferred method for upgrading.
Delayed coking followed by hydrotreating was used in the upgrading of
8,505 bb1 of crude Paraho shale oil at the Gary Western Refinery in 1975.
443
Hawk and co-workers used coking, followed by severe hydrotreating, to produce
experimental quantities of military jet and diesel fuels in the hydrogenation
pilot plant at USBM's Bruceton, PA faci1ity.47. Delayed coking was studied at
the bench- and pilot plant scales at Chevron
451
,453 and a bench-scale study was
carried out at Phillips Petroleum.
471
Delayed coking was also used to process
about 3400 bb1 of Occidental MIS crude shale oil at Chevron's Salt Lake City
refinery, but in this case the shale oil (13% - 19%) was co-processed with the
refinery's normal petroleum residuum.
453
OIL SHALE PAGE 324
In delayed coking, the oil is heated to 480'C and fed to one of two coke drums
that are typically 10 feet in diameter and 100 feet tall. Pressure in the
drums is sufficient to prevent vaporization, hence coking reactions take place
in the liquid phase. Liquid is continuously withdrawn and coking is allowed to
proceed until the coke drum is nearly full. Feed is then switched to the
second drum and the first is cooled and emptied. Because no catalyst is
involved, coking is very tolerant of metals and solids. However, in the Gary-
Western test about 20% of the shale oil feed was converted to low-value gas and
nearly 30% was converted to coke. Thus, the yield of highvalue transportation
fuels amounted to only one-half the shale oil fed to the coker. Moreover,
because of its high impurity content the shale-derived coke was not suitable
for making carbon electrodes and could only be used for fuel. In the USBM and
Phillips studies, considerably lower coke makes were achieved, but the coke
makes of 27% and 13%, respectively, still represented a substantial loss of
valuable oil. Consequently, delayed coking cannot be regarded as a preferred
method for shale oil upgrading. Nevertheless, the Gary-Western, USBM and
Phillips refining tests did demonstrate that shale oil can be processed into
transportation fuels, using conventional refining technology with suitable
adjustments of operating parameters.
Two more advanced coking technologies, Exxon's Fluid Coking and Flexicoking
processes warrant mention. Although no reports were found of their application
to shale oil upgrading, they have been successfully used to upgrade the heavy
bitumen from Canadian tar sands, as well as conventional petroleum residua.
472
OIL SHALE PAGE 325
Fluid coking is carried out with steam as a fluidizing gas that also
serves to strip liquid products from the coke. Coke particles are continuously
withdrawn from the cqker and fed to a burner, where they are fluidized in air
and partially burned and heated to about 620'C. The hot coke is returned to
the coker where it heats the incoming feed, leading to deposition of more coke.
Only about 5% of the coke is actually burned to raise heat, so the "fluid coke"
is withdrawn as a product. Compared to delayed coking, fluid coking offers the
advantages of being a continuous and more rapid process. the shorter pyrolysis
time leading to higher liquid yields than delayed coking.
Flexicoking combines fluid coking with gasification of the fluid coke.
The product gas can be used as fuel or reformed to produce hydrogen. Coking,
combustion and gasification are all high-temperature operations with high heat
demands. By integrating all three operations into a single close-coupled unit,
Flexicoking achieves very high thermal efficiency, while retaining the high
liquid yield capability of fluid coking.
F. CATALYTIC PROCESSING METHODS
Hydrotreating is more flexible and less destructive than coking as a way
to remove nitrogen, sulfur, oxygen, arsenic and metals. (Here we discuss the
hydrotreatment of crude shale oil, not the hydrotreatment of sync rude that
would be used to produce finished products for market.) One approach has been
to distill the .crude shale oil, then to hydrotreat the fractions. Shaw et al.
suggested that a more reasonable processing approach would be to hydrotreat the
whole (dewatered/desalted) shale oil and then to process at least the 900'F-
product in a conventional refinery.444 This approach was followed by Chevron
OIL SHALE PAGE 326
in their 1977 pilot plant study of Paraho shale oil upgrading,451,453 and Sohio
in refining 73,000 barrels of Paraho oil at Toledo (Figures 94, 95).447,448,469
1. Sohio
The problems caused in the Sohio test by pyrite fines accumulation in the
guard bed were discussed above. The Sohio hydrotreater also accumulated fines.
but did not experience a pressure drop problem during the 24-day test period.
However, catalysts activity declined significantly, as shown by the whole
product nitrogen plot (Figure 97). After completion of the shale oil test. the
top 10% of the catalyst bed was replaced with fresh Shell 324 Ni/Mo catalyst
and the reactor was placed back in service for petroleum hydrotreating. The
reactor was still in service with the same catalyst four years later! These
results demonstrate the need for an effective guard bed to remove arsenic.
Table 56. Summary of products from Sohio refining of crude Paraho shale oil.
(Data of Robinson and Evin, Reference 469.)
Gasoline (including butanes)
Jet Fuel: JP-5
JP-8
Diesel Fuel, Marine (DFM)
Residual Fuel Oil
Total
Barrels
8.473
9.546
490
18.939
37.220
74.939
Volume %
11.96
13.73
25.90
50.91
102.50
% Nitrogen
0.067
0.220
0.430
0.220
OIL SHALE PAGE 327
Figure 97. Increased nitrogen content of the product reflects deactivation of
the catalyst during the 24 days needed to process 73,000 barrels of
crude Paraho shale oil in Sohio's Toledo refinery. Data from the
WHOLE
PRODUCT
NITROGEN
WT.%
0.40
0.30
0.20
0.10
Sohio pilot plant study are included for comparison. (Data of
Robinson and Evin, Reference 469. Reprinted with the permission
of Butterworth Publishers.)
10
----@--- TOLEDO DATA
- -@ - - PilOT PLANT DATA
/'
/'
----
/' .
/'
---
-.--
40 50
CUMULATIVE FEED 11000 BBlS. SHALE OIll
60 70 80
OIL SHALE PAGE 328
Table 57. Properties of raw and upgraded Paraho shale oil. The Sohio oil was
from the refinery test,448 while the LETC oil was from Holmes' study
in a bench-scale unit.473
Paraho Sohio LETC
Crude Hydroprocessed Hvdroprocessed
Carbon, Wt% 84.0 86.5 86.1
Hydrogen, Wt% 11.4 13.1 13.3
Nitrogen. Wt% 2.19 0.43 0.42
Sul fur, Wt% 0.66 0.02 0.05
Oxygen, Wt% 2.0 0.12 0.27
HIC Atomic Ratio 1.63 1.82 1.85
Gravity, 'API 21.4' 33.8' 34.9
Pour Point, 'F
85' 85' 70
Average Molecular Weight 311 265 295
Aromatic Carbon, rar 21 10 9
Aromatic Hydrogen, Har 5.8 10.8 3.0
Simulated Distillation (GC)
Cut Point. 'C Weight % of Shale Oil
38 nil nil 0.3
93 0.2 0.2 0.8
149 0.7 2.8 3.8
204 3.7 7.5 8.2
260 8.9 12.9 15.0
316 11.9 14.0 15.3
371 14.8 18.3 16.4
427 16.3 15.7 15.0
482 17.7 12.4 14.2
538 13.1 5.4 8.3
Residuum 12.7 10.7 2.7
( a) Data from Sohio.
OIL SHALE PAGE 329
Extensive hydrodenitrogenation (HON) studies were carried out by Holmes at
the laramie Energy Technology Center (now Western Research Institute) in a
small continuous unit, but under conditions that closely approximated the Sohio
refinery conditions, except that Shell 514 support balls were used in the guard
bed in the place of SOhlO/S alumina extrudate and no residuum was recycled to
the hydrotreater.
185
,473,474 Adsorption chromatography on alumina and silica
gel separated the starting Paraho crude shale oil and the Sohio and LETC
upgraded oils into six fractions each, and the nitrogen content of each
fraction was determined (Table 58).
Fourteen nitrogen compound types were identified and quantified in the
fractions, using a combination of infrared, high-resolution mass spectroscopy
and differential potentiometric titration. Because both the Sohio and LETC
hydroprocessing removed about 80% of the total nitrogen, and nearly all the
remaining nitrogen was characterized the nitrogen compound distributions in the
two products can be compared and correlated with hydroprocessing conditions.
The extent of removal can be compared with the overall nitrogen removal of 80%
to evaluate the relative susceptibility of each compound type to HDN. Nitrogen
types that were more than 80% removed were relatively susceptible to HDN. while
those less than 80% removed were relatively resistant to HDN.
Little difference was found in the susceptibility of different nitrogen
base types to HDN; weak bases were only slightly more difficult to remove than
very weak or non-basic species (Figure 98). Within experimental error, removal
of nitrogen bases was the same for both hydroprocessing conditions.
OIL SHALE PAGE 330
Table 58. Weight distributions and nitrogen contents of the fractions obtained
by chromatography of the hydroprocessed shale oils. (Oata of
Holmes, References 473 and 474.)
Hydrocarbon
Pyridine I
Pyrrole
Pyrrole/Arylamine
Pyridine II
Amide/Pyridine III
Total Sample Recovery
Hydrocarbon
Pyridine I
pyrrole
Pyrrol e/Aryl amine
Pyridine II
Amide/Pyridine III
Recovery, % of Total N
Paraho Crude
Shale Oil
31.7
16.9
3.56
5.47
19.2
20.8
97.6
Sohio
Wt% of Sample
81.6
2.84
0.48
2.54
2.88
0.45
91'
Nitrogen, Wt% of Fraction
0.003
1.22
1.10
3.92
4.11
4.53
100
0.0006
4.51
0.34
4.65
5.79
5.99
102
LETC
77.6
7.71
2.43
1.03
2.91
1.09
93'
0.0035
1.68
3.62
4.21
3.89
3.29
98
(a) Low recovery in these cases is probably due to evaporation of the lighter
components from the hydrocarbon fraction during removal of chromatographic
solvent.
OIL SHALE PAGE 331
Figure 98. Removal of nitrogen bases was the same for both Sohio and lETC
hydroprocessing conditions. Weakly basic nitrogen was only
slightly more difficult to remove than very weak and non-basic
nitrogen. (Holmes, Reference 473. Reprinted with the permission
*'
<0
>
0
E
'" a:
c:
'"
0>
0
~
.1::
Z
of the Colorado School of Mines.)
100
80
60
40
20
o L..-_
Sohio
~ LETC
Weak
Base
I
I Uncertainty
Weak
Base
II
Very
Weak
Base
Nitrogen Base Types
Nonbasic
OIL SHALE PAGE 332
Significant differences were, however, observed in the distributions of
the individual compound types and ascribed to differences in HDN susceptibility
and hydroprocessing conditions (Figure 99). With the exceptions of very weak
bases of unknown structure (G) and N-alkylcarbazoles (H), the susceptibility of
nitrogen compounds to HDN was similar under both the Sohio and LETC conditions.
It is most difficult to remove hindered alkylpyridines/quinolines (A), basic
alkylpyrrolesjindoles (F), and non-basic alkylpyrrolesjindolesjcarbazolesjben-
zocarbazoles (I). The less hindered alkylpyridines/quinolines/acridines were
removed in amounts proportional to the overall nitrogen removal, while the weak
base II compounds of unknown structure (D) were only slightly more difficult to
remove. The easiest nitrogen species to remove were the non-hindered
alkylpyridinesjquinolinesjhydropyridines (C), alkylhydroxypyridines (E) and
alkylcarboxamides/diazaaromatics (J). The very weakly basic compounds of
unknown structure (G) were apparently removed more effectively under the tETe
conditions and the reason is not understood, but the amounts were small.
The buildup of N-alkylcarbazoles during Sohio processing was ascribed to
residuum recycle, since these heavy compounds become concentrated in the
residuum.
Figure 99. Removal of nitrogen compound types by hydroprocessing. Compound types are identified in the
text. (Holmes, Reference 473. Reprinted with the permission of the Colorado School of Mines.)
100
80
,"-20
--40
B
I Sohio
~ LETC
c o E F G
Nitrogen Compound Types
I Uncertainty
H
OIL SHALE PAGE 334
2. Gulf Shale Oil Upgrading Process
The shale oil upgrading process developed by Gulf Oil is often described
as two-stage hydrotreating. but would be more properly termed a three-stage
hydrotreating process (Figure IOO). Data have been reported on upgrading of
both Western (Paraho, Union-B) and Eastern (Oravo/Kentucky shale) shale
oi15.
345
,475
The pretreating section of the Gulf process is designed to remove arsenic.
iron, trace metals and residual solids, and to stabilize the oil before it
enters the main hydrotreater. The first pretreating reactor is designed to
remove most of the arsenic, iron and solids with minimal hydrogen uptake. It
operates at low hydrogen pressure with a low-cost disposable catalyst, and is
duplicated so that one reactor can be on-stream while the other is being
recharged with fresh catalyst. The second pretreating reactor stabilizes the
oil, removes a substantial part of the sulfur. The main hydrotreating reactor
contains a catalyst selected for high hydrodenitrogenation activity. and
produces an effluent that typically contains 7S0 ppm nitrogen. This effluent
is fed to the flash separator, from which the 6S0F- vapors enter a vapor
hydrotreater. Using about IS% of the total hydrogen, this final stage yields
,37soF- naphtha that typically contains < 4 ppm nitrogen, hence can be used as
reformer feed and 37S' - 6S0'F distillate that contains 10-IS0 ppm nitrogen.
The 6S0'F+ separator bottoms typically contain 1000-2000 ppm nitrogen and is a
good cracking feedstock.
Figure 100. Flow diagram of the Gulf Shale Oil Upgrading Process. (Jones, et al., Reference 345. Reprinted
with the permission of the Colorado School of Mines.)
r-------------
! PRETREATING I
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OIL SHALE PAGE 336
3. Catalytic Cracking (Ashland, Chevron)
Fluid catalytic cracking (FCC) of shale oils has been studied by Moore
and his co-workers at Ashland Petroleum.
4s7
Pilot plant FCC studies were made
by Chevron.
449
,451,453 Sikonia and co-workers at UOP have carried out small-
scale studies of hydrotreating as a pretreatment for FCC.465 Both bench-scale
and pilot plant FCC studies of shale oil were carried out at Gulf.
345
In the FCC process, relatively small (40 - SOp) catalyst particles are
fluidized by upflowing shale oil vapors in the reactor vessel, which is
maintained at 950' . 1000'F (Figure 101). As the cracked vapors exit the
reactor, they pass through cyclones, where the catalyst particles are separated
from the products and recycled. Along with the desired cracking reaction, some
coke is deposited on the catalyst surface. Therefore, catalyst is continuously
withdrawn from the cracking reactor and transported by an air stream into a
combustor where the coke is burned. When returned to the cracking reactor the
hot, regenerated catalyst supplies heat for vaporization of the feed.
Shale oils are rich in high-molecular weight, waxy paraffinic material.
Thermal cracking lowers molecular weight, but yields straight-chain products of
low octane number. Fluid catalytic cracking not only lowers molecular weight,
but also causes isomerization to produce branched products with higher octane
numbers. As a result, the so-called "cat cracked" shale naphtha is a more
desirable feedstock for hydrotreating to make gasoline blend stock, than is the
naphtha from thermal cracking or coking of shale oil.
OIL SHALE PAGE 337
FLUE_--,
GAS
,.......-- REACTOR PRODUC T
AIR
. " ,
I,::,: .... :.
.... ,. ' ..
.' " .'
,' ...
. '.'
mJIo--CYCLONES
REGENERATOR II
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REACTOR
.''-:.:. :
,," .....
.: .. : ",
'", '. ';"
",,' ....
.
t" STRIPPING
j """ GAS
STANDPIPES -1
TRANSFER
GRID
OIL
FEED
'\..--,,- LI NE S
(RISERS)
Figure 101. Fluid catalytic cracking unit.
Hydrotreating of the raw shale oil to remove basic nitrogen that would
poison the acidic cracking catalyst, and would also promote unwanted coking, is
required as an FCC pretreatment.
465
Workers at Gulf found that hydrotreated
syncrudes from Union-B (Colorado shale) and Dravo (Kentucky shale) retorts
performed well as FCC feeds in a MAT test, and the atmospheric tower bottoms
from a Paraho syncrude gave good results in an FCC pilot plant test.'4S
OIL SHALE PAGE 338
4. Amoco Hydrotreating-Hydrocracking
Under an Air Force contract, Tait. Miller and Hensley at Amoco investigated
all three of the upgrading routes outlined at the start of this section.
459
464
Of these, hydrotreating followed by hydrocracking offered the most flexibility
and was the only approach to efficiently maximize jet fuel production. This is
an important consideration, since Western U.S. shale oils characteristically
have high contents of straight-chain, waxy paraffins and low contents of the
aromatics that are undesirable in jet fuel. (Aromatics set the smoke point in
jet fuel.) Coal liquids, on the other hand, are characteristically highly
aromatic and well suited for processing into gasoline blend stocks. Thus, its
molecular structure makes shale oil a prime source for jet fuel.
As part of the Air Force contract, the Amoco workers developed catalysts
that are capable of direct upgrading of a whole shale oil into high yields of
JP-4 jet fuel boiling range material in a single-stage process. In contrast to
the multi-step processes discussed above, the Amoco catalyst has the ability to
sequentially saturate, denitrogenate, and crack, the whole shale oil in the
presence of contaminants such as ammonia, water and basic organic nitrogen
compounds, while maintaining high selectivity towards the jet fuel boiling-
range materials.
The catalyst development studies were carried out on an Occidental MIS
crude shale oil that contained 1.32 wt% nitrogen, 0,64 wt% sulfur, 1.33 wt%
oxygen. 26 ppm arsenic and about 60 ppm iron. Although it was recognized that
an effective guard bed would be required for commercial operation, none was
used in the development study. nor was the oil pretreated to remove arsenic or
iron.
Screening of existing catalysts revealed that a proprietary catalyst
containing cobalt, chromium and molybdenum could effectively remove nitrogen
OIL SHALE PAGE 339
and effect moderate conversion of the feed into the JP-4 boiling range. By
screening catalysts in which the metals loading was systematically varied, it
was found that optimal metal oxide loadings were 1.5% cobalt oxide. 10%
chromium oxide and 15% molybdenum oxide. The high loading of chromium oxide
actually lowered denitrogenation activity, but was necessary to impart high-
temperature stability.
A study of different supports revealed that 20% silica/alumina was better
than alumina, and that 50% ultrastable molecular sieve/alumina was more active
yet. Next, a series of eight supports containing 50% ultrastable sieve, but
having varying surface area (SA), pore volume (PV) and average pore diameter,
were prepared. These variations were achieved by modifying the alumina
component, since modification of the sieves, themselves, could destroy their
inherent cracking activity. Evaluation of catalysts prepared from these
supports revealed that optimum activity was obtained with a catalyst having a
narrow pore size distribution and APD of about 7 nm. Variations in product
yields and hydrogen consumption, as a function of support are summarized in
Figures 102 and 103.
Activity testing was plagued by several upsets, yet the optimized catalyst
proved very durable.
464
Based upon the temperature response factor calculated
from data obtained during the activity tests, an expected catalyst life of
about 4.5 months was estimated for a constant JP-4 yield of 75% and reactor
temperatures increasing from 775' to 800F (686 to 700K). Because of the
upsets encountered during testing. this was judged to be a minimum life
expectancy and a catalyst life of six months was considered probable.
OIL SHALE
PAGE 340
Figure 102. The effect of ultrastable molecular sieve concentration in the
support on the product distribution from single-stage hydrotreating-
hydrocracking of Occidental MIS crude shale oil. (Data of Tait,
Miller and Hensley, Reference 461.)
o o r - - - - - - - - - - - - - - - - - - - - - - - - - - - ~
+"'
c:
60
(I) JP4
(.)
...
(I)
Co
+"'
~
c:
40
0
.-
+"'
(.)
(t)
...
u..
Diesel
20
Gas oil
o ~ ~ - - __ ~ ~ - - - - - - ~ - - - - - - ~
20 30 40 50
Wt percent sieve in alumina
OIL SHALE PAGE 341
Figure 103. Correlation of JP-4 jet fuel yields with total hydrogen consumption
for catalysts containing 0%, 20%, 30% and 50% ultrastable molecular
sieve (left to right) in the support. (Data of Tait, Miller and
Hensley, Reference 461.)
8 0 r - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ~
70
60
...
C
Q)
50
u
...
Q)
c.
...
40
~
..r
,
c..
30
'"")
20
10
1300 1400 1500 1600 1700
Hydrogen consumption, SCFB
OIL SHALE PAGE 342
Separate distillations of the product were carried out to produce JP-4 and
JP-S jet fuels. The analytical data indicate that the samples would meet all
specifications, with perhaps one exception (Table 59). The pour point of -40
G
F
(233'K) for the JP-S fraction is somewhat higher than the JP-S specification of
-5S'F (223'K). A slight lowering of the boiling point range would lower the
pour point to give a product that meets all JP-B specifications.
The results demonstrated that the single-catalyst system was capable of
hydrocracking a whole shale oil containing large amounts of nitrogen. However,
analysis of kinetic data from the studies above led to the development of a
dual-catalyst system that affords the same high product quality, plus higher
throughput.
464
Using the dual-catalyst system with recycle of the 520'Ft
distillate (#2 fuel oil) afforded a 91 wt% (lOS vol%) yield of JP-4 boiling
range material as the only liquid product. With recycle operation, the gas
make increased slightly, based on fresh feed, from 6.1 wt% to 7.9 wt%. As a
result. the hydrogen consumption also increased on a fresh feed basis from
ISOO scf/bbl to 2060 scf/bbl. However, because of the higher yield obtained,
the hydrogen consumption dropped on a JP-4 basis from 2320 scf/bbl of JP-4 to
1920 scf/bbl for the recycle operations.
Thus, the Amoco work led to novel catalyst systems capable of directly
upgrading a whole shale oil into high yields of jet fuels in a single step.
First a single-catalyst hydrocracking system was developed. Then an even more
active dual-catalyst system was developed with a catalyst specifically designed
for high denitrogenation activity at high nitrogen content preceding the
hydrocracking catalyst. The development of these catalysts is significant,
since their use could eliminate the need for complex, multi-step, multi-catalyst
processing of whole shale oils.
OIL SHALE PAGE 343
Table 59. Properties of the Occidental MIS crude shale oil feed, the composite
product and jet fuel fractions from the hydrocracked shale oil.
(Data of Tait, Miller and Hensley, Reference 464.)
Co/Cr/Mo on Alumina, 1800 psi Hz, 0.55 LHSV, 790F, Hz Consumed = 1400 scf/bbl
Occidental MIS Composite
Crude Shale Oil Feed Product JP-4 JP-8
Gravity, API 12.8 39 49.4 (49-57) 43.4 (37-51)
Weight, % 100 76 61
Pour Point,
of
60 -5 -85 -40
Aromatics, Vol % 16.0 (25.0) 18.0 (25.0)
Olefins, Vol% 1.0 ( 5.0) 2.5 ( 5.0)
Nitrogen, ppm 13,200 1.1 0.7 1.1
Carbon, wt% 85.82 85.99 86.10
Hydrogen, wt% (AtomiC H/C = 1.67) 14.17 14.00 (13.6) 13.86 (13.6)
Sulfur, wt% 0.64
Oxygen, wt% 1.33
Distillation, 0-2887
IBP, OF
-47 22 250
10% 203 190 322 (367)
20% 268 238 (266) 353
30% 321 276 390
40% 372 312 413
50% 410 346 (365) 436
60% 446 377 461
70% 487 408 489
80% 547 440 520
90% 624 480 (482) 564
EP, OF
789 553 (608) 622 (626)
Values in parentheses
limits.
are maximum (minimum for hydrogen content) specification
OIL SHALE PAGE 344
CONCLUSIONS
The oil shale challenge is clear. Sooner or later, we will need to make
use of the world's abundant oil shle resource -- if not for fuel, then for
chemical feedstock -- to replace dwindling petroleum supplies. The timing will
probably be dictated more by political cosiderations than by purely technical
factors. As a result, our need to use oil shale may come upon us suddenly,
giving no time for the development of new technology. We must be ready.
Technology is now available that could be used to provide liquid fuels and
feedstock from oil shale, but is expensive. A rapid shift to such technology
could have dire and far-reaching consequences. Continued research and
development is needed to provide further improvements in oil shale science and
technology, so that when the need arises we can use oil shale economically and
in an environmentally acceptable manner.
OIL SHALE
PAGE 345
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