EPA-625/9-77-QO2
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environmento sampling of the paroho oi sho e
retort process ot onv points
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technology transfer
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U.S. ENVIRONMENTAL PROTECTION AGENCY
Environmental Research Information Center
Cincinnati, Ohio
October 197?
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ON THE COVER. Paraho demonstration site in Colorado, with Anvil Points oil £fc
shale deposits in background. Laboratories and offices are located on the
entrance road. The mine opening is higher and to the left on the hogback If
formation. W
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ACKNOWLEDGMENTS II
m
This executive briefing was prepared for the Environmental Research Infor-
mation Center (ERIC) of the U.S. Environmental Protection Agency by the firm M
TRW, under the direction of L. G. Neal and J. E. Cotter. Major EPA contributors
and reviewers were T. J. Powers of the EPA Industrial Environmental Research *J|
Laboratory, Cincinnati, Ohio, and G. R. Nelson and T. E. Mosure of ERIC, «
Cincinnati, Ohio.
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NOTICE. The mention of trade names of commercial products in this publics- igf
tion is for illustration purposes and does not constitute endorsement or recom- %»
rnendation for use by the U.S. Environmental Protection Agency. Jr
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MEMBERS,
PRAHO OIL SHALE
DEMONSTRATION, INC.
PETROLEUM COMPANIES
Sohio Petroleum Company
Gulf Oil Co,
Shell Development
Standard Oil Company (Indiana)
Carter Oil Co. (Exxon)
Mobii Research and Development Corp.
Webb-Grey-Chambers-McLoraine (group)
Sun Oil Co.
Texaco, inc.
Phillips Petroleum Co.
Atlantic Richfield Co.
Marathon Oil Co.
Chevron Research Co. (Standard Oil of California)
Southern California Edison
The Cleveland-Cliffs Iron Co.
Arthur G. McKee and Co
Kerr-McGee Corp,
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THE PROJECT
Paraho is a Portuguese word meaning "for the good of mankind," The shale
oil retort1 process was so named approximately 17 years ago while some mem-
bers of the present consortium (Paraho Oil Shale Demonstration, Inc.) were
working on Brazilian oil shale, The name may prove especially appropriate
in view of the world's rapidly diminishing crude oil reserves if U.S. shale re-
sources are exploited by means of the Paraho Process with minimal environ-
mental disturbance.
The Paraho Oil Shale Demonstration Project is a privately financed research
and development (R&D) effort dedicated to:
• Demonstrating the Paraho Process and retort for extracting oil and gas from
shale
» Acquiring process and operating data
» Facilitating preliminary feasibility studies for process commercialization
The 30-rnonth project, now completed, was performed at the Anvil Points Ex-
periment Station of the Energy Research and Development Administration
(ERDA) near Rifle, Colorado, at an estimated cost of $7.5 million to the 17
members of the consortium.
The Paraho Process is one of several under serious consideration for commer-
cial shale oil extraction.
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Paraho semiworks retort (right) and production separation equipment at Anvil Points
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Ciiff face exposing typical oil
shale layers, Richer layers are
darker.
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U.S. OIL SHALE RESOURCES
fht United States holds Ihe world s largest deposits of oil shale These de-
posits primarily located in the contiguous sections of Colorado, Utah, and
Wvummg, contain an e&lmiafpj 2 200 billion Darre Is ot oil More than 25 cir.l-
Icris of crude oil are recoverable pet ton ot 'Jial« hut there are no commercial
plants tor extracting liquid hydrocarbon^ from this vast untapped resource—
laiyuly because the tequisite economic stimuli ire lacking
Growing awaioness of the dwindling domestic rin-i foieign crude oil te&ervos
and reooyiiition of in< reasoci future energy ripm.snds havf spurred consider-
able interest in the development and rortimercidli/alionof a shale oil mcluolry
The Paiaho Process is a notable example ol trie R&P projects that have been
undertaken in significant rurnber
Rocogni«.n]y the importance otthe development of this va*".l energy resource,
the Environmental Protection Agency is vitdlly concerned with the environ-
mentai de'jtadation tfiat could occur if such development were to materialize
without adcqudh pollution abatement pKHx^ures The EPA has sponsored
environrnenttil sampling ot (he Par.jho Process to t.cqui«o fh^ comprehensive
en irarterL'ation of the process slreams npne^sary for successful application
ot pollution abatement technology- and epuipmtrtt
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THE PARAHO PROCESS
Full-scale operation of the Paraho Process consists of mining, crushing, re-
torting and recovery of oil, and disposal of retorted shale. Shale will generally
be mined by conventional room and pillar methods. Crushing is necessary
before retorting. Shale is crushed in two stages—primary crushing at the mine
and secondary crushing at the retort site.
THE
Central to the process is the Paraho vertical kiln shown in cutaway isometric
in figure 1, It consists of a vertical vessel fed from the top with raw shale, which
moves down by gravity through four retorting zones. Energy produced by re-
torting fuels the process. The kiln is mechanically simple, encompassing few
moving parts, and construction and operating costs are low. The Paraho re-
tort can be operated in two modes distinguished by the method of shale
heating.
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PARAHO
Direct heating is illustrated schematically in figure 1. Raw shale is introduced
into the top of the retort and, by a rotating spreader, into the preheating zone,
from which it passes successively through the retorting zone, the combustion
zone, and the cooling zone. Shale emerges at the bottom of the retort with most
of its energy value removed and in essentially the same size distribution. Off-
gases are recycled to the retort at three levels. These gases, together with air,
promote combustion of part of the carbonaceous residue on the spent shale
(retorted shale in the combustion zone) to provide heat for the process. Oil
vapors formed in the retorting zone pass up through the preheating zone,
condense to a stable aerosol mist, and pass out with the retort gases for re-
covery in mist separators. With countercurrent flow of shale and gases, thermal
efficiency is high.
PARAHO INDIRECT-HEATING
Indirect heating (fig. 2) is essentially identical to direct heating, except that
an external heater, which provides the heat necessary for retorting, is used to
heat the recycled gases. No combustion occurs in the retort. In a manner
similar to direct heating, part of the retorted gas is used to fuel the process.
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ENVIRONMENTAL SAMPLING
The environmental-sampling program at the Paraho demonstration site was
suonsored by EPA and performed under Ihe cogni?anceot the Laramie Energy
Research Center (ERDA), wilh support from the Paraho operating manage-
ment Ihe sampling and analysis contractors v,ere TRW. Inc, and Denver
Research Institute The program's major objective, was to determine, qualita-
tively and quantitatively, the character of the Paraho process streams and
associated gaseous and paiticulate emissions, product water, and solids dis-
charge Environmental sampling in both direct- and indirect-healing modes
was earned out while other process R&D tests wore in progress
Sampling methods., equipment, and stations vvete specific to the nature of
the specie monitored Sampling approaches included
» Proportional and grab sampling of the recycle process gas stisam tor anal-
ysts by instrumental and wet chemical methods
« Giab sampling of the product aude oil, lecvcie process gas condensate
water, and retorted shale for organic and trace element analysis
* Grab sampling of recycle process gas stream condensate water for gross
parameter analysis—for example, biochemical oxygen demand, chemical
oxygen demand, and total oigame carbon
* High-volume sampling of paniculate emissions from raw shale crushing
» Cascade irnpactor sampling fo? participate si/mci of airborne crushing
emissions
AND
Standard analytical methods weie used wherever possible5 Specific tech-
niques wore developed to handle some of Ihe various procesa samples
Figures 3, 4 and 5 chow plans (or processing and analysis of the Paraho
gaseous, liquid and solid sample? Analytical methods included
» inoKjanic and tract elements analysis
~-WHt chemistry
—atomic absorption spectrophotometry
-spark source mass spectrometry (SSMSs
» Organic analysis, separation with
--gas chromatography (GC)'mass speclrometry (MS">
—thin layei chrcmatoqraphy (TLC)
—hiqh pressure liquid chrarnalogtaphy (HPLC)
spectrophotofluoremelry (SPF)
^ Polynuclear aromatic hydrocarbons analysis—two-dimensional elutron with
TLC
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Figure 4
SEPARATION AND ANALYSIS SCHEME
TLC analytical scheme.
Aqueous
phase
Headspace
(nitrogen
stripping)
Tenax
absorption
Plaster
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AND AIR
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S4 if1 -i^ni ii r f 4lJF'1-irJ "^ '
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0 Carbon,
b Not on air ,
c TLC analytical scheme,
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Gaseous stream sampling at the Paraho retort.
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SIGNIFICANT FINDINGS
The analysis of recycle gases included measurements of H2S and NH3- In
either the direct or the indirect mode of a commercial operation, the need for
NH3 and H2S removal can be anticipated before a recycle purge stream is
used as fuel. Some other postulated species were not detected. The recycle
gas was found to contain no COS, CS2, HCN, or AsH3.
Condensate water inorganics appear to contain essentially ammonium car-
bonate and bicarbonates. Trace elements were not significant in the eon-
densates. Trace organics were found in the retorted shale, condensate, and
product water; the range of compounds included organic neutrals (particu-
larly aromatics), organic acids, and organic bases,
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Colorado's oil-shale-rich Piceance Basin, rising 4,000 feet from the Grand Valley,
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CONCLUSIONS
The Paraho program has provided a basis for determining testing priorities
and establishing the need for effective, standardized sampling and analysis
procedures. A considerable body of information has been gathered on the
qualitative nature of various process streams at the Paraho R&D plants. Future
work should focus on quantitative determinations of those constituents that
may appear in a process residual stream,
Longer term monitoring programs will be needed to characterize the process
throughout its range of operation, rather than at a given time. Much work is
needed to provide design criteria for pollution control equipment and pro-
cedures, but there is every indication that shale oi! recovery processes can
be operated in an environmentally acceptable manner.
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