United States
Environmental Protection
Agency
Research
and
Development
Industrial Environmental Research
Laboratory
Cincinnati, Ohio 45268
EPA-600/7-78-065
April 1978
SAMPLING AND ANALYSIS
RESEARCH PROGRAM
AT THE PARAHO SHALE OIL
DEMONSTRATION
Interagency
Energy-Environment
Research and Development
Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protectthe public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-065
April 1978
SAMPLING AND ANALYSIS RESEARCH PROGRAM
AT THE PARAHO SHALE OIL DEMONSTRATION PLANT
by
J. E. Cotter, C. H. Prien, J. J. Schmidt-Collerus,
D. J. Powell, R. Sung, C. Habenicht, and R. E. Pressey
TRW Environmental Engineering Division
Redondo Beach, California 90278
and
Denver Research Institute
Denver, Colorado 80210
Contract 68-02-1881
Project Officer
Thomas J. Powers III
Energy Systems Environmental Control Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
This study was conducted
in cooperation with
Laramie Energy Research Center, ERDA and
Development Engineering, Inc. Rifle, Colorado
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio, and
approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the U.S. Environmental
Protection Agency, nor does mention of trade names or commercial products
constitute endorsement or recommendations for use.
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FOREWORD
When energy and material resources are" extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on
our health often require that new and increasingly more efficient pollu-
tion control methods be used. The Industrial Environmental Research
Laboratory-Cincinnati (lERL-Ci) assists in developing and demonstrating
new and improved methodologies that will meet these needs both efficiently
and economically.
New synthetic fuel processes under development need to be characterized
prior to commercialization, so that pollution control needs can be identified
and control methods can be integrated with process designs. The sampling
and analysis research program, conducted at the Paraho shale oil demonstra-
tion plant, represents a first step in process characterization. The work
reported in this document will serve as a basis for the determination of
improved sampling and analysis procedures in future shale oil plant test
programs, as well as the selection of testing priorities. Further informa-
tion on the environmental aspects of shale oil processing can be obtained
from the lERL-Cincinnati Fuels Technology Branch.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
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ABSTRACT
A sampling and analysis research program was conducted at the Paraho
oil shale retorting demonstration site at Anvil Points, Colorado. The
work was carried out by TRW and the Denver Research Institute. The overall
objective of the test program was to obtain preliminary quantitative and
qualitative measurements of air, water, and solid compositions, and to gain
experience that would lead to improved sampling procedures and the determi-
nation of priorities for sampling and analysis of shale oil recovery opera-
tions.
The existing Anvil Points operations include two vertical retorts:
a larger semi-works unit in which a portion of the off-gas was recycled
and heated externally to supply heat to the retort and a smaller pilot
plant in which air was introduced with recycle gas to support combustion
of carbon on retorted shale as a source of process heat. The test plan
included both retorts, as their process streams (with the exception of oil
product) are essentially different. Selection of sample locations was
based on need for information on process streams relative to emissions
and effluents expected in a full-scale plant.
Samples taken included the recycle gases .(HUS, SCL* NO . NhU, and
trace organics), recycle condensate, product oil/water, processes shale
discharged from the retorts, and dust in the vicinity of crushing, screen-
ing, and conveying equipment. A variety of laboratory analysis methods
were used, including wet chemical analysis, spark source mass spectrometry,
high pressure liquid chromatography, thin layer chromatography, gel permea-
tion chromatography, and gas chromatography/mass spectrometry methods (GC/MS),
Condensate water inorganic analyses were done for calcium, magnesium,
sodium and potassium salts, ammonia, gross parameters, and trace elements.
Condensate and product water samples were also analyzed for organic neutrals
(particularly aromatics), organic acids, and organic bases. Elemental deter-
minations of both retorted shale and raw shale particulates were made.
This report was submitted in partial fulfillment of Contract 68-02-1881
by TRW Environmental Engineering Division under the sponsorship of the U.S.
Environmental Protection Agency. This interim report covers the period of
June 1, 1975 through December 1, 1976.
IV
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CONTENTS
Disclaimer ii
Foreword iii
Abstract iv
Figures „ vi
Tables „ vii
Abbreviations and Symbols viii
Acknowledgment ix
1. Introduction . 1
Program Objectives and Utility 1
2. Conclusions and Recommendations. ...... 10
3. Sampling and Analysis Procedures ...... 12
Test Plan and Execution 12
Laboratory Analysis Methods 18
4. Summary of Analysis Results 22
Gaseous Samples 22
Liquid Samples ..... 25
Solid Samples. 29
5. Discussion of Procedures and Results 41
Sampling Procedures 41
Recommendations for Future Sampling and
Analys-is 43
Appendices ....... ....
A Absorption Train Sampling and Analysis
Methods 46
B Laboratory Analysis Methodology and Data 50
C Summary of Collected Samples ............. 64
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FIGURES
Number Page
1 Paraho Plant at Anvil Points, Colorado 2
2 The Paraho retort 5
3 Paraho direct mode flow diagram (pilot plant operation). 6
4 Paraho indirect mode flow diagram (semiworks operation). 7
5 Sampling recycle gases at the semiworks unit 13
6 Sample point locations on plan view 15
7 Impinger sampling train mounted in position 17
8 Mobile chemical laboratory on site 19
9 Analysis of PAH compounds, using thin layer chromato-
graphy techniques 38
10 Two dimensional mixed T.L.C 39
11 Determination of PAH compounds with spectrophoto-
fluorometry 40
VI
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TABLES
Number Page
1 Recycle Gas Analysis from Selective Absorption ..... 23
2 Trace Organics Identified by GC/MS in the Recycle Gas
Stream (Direct and Indirect Mode) Summary of All
Samples 24
3 Inorganic Analysis of Condensates 26
4 Condensate Water and Process Water (SSMS Analysis) ... 28
5 Size Ranges of Solids 29
6 Mass Fraction of Raw Shale Particulates 30
7 Numerical Fraction of Raw Shale Particulates 30
8 Particle Size vs. Mean Elemental Composition of Raw Shale
Air Particulates as determined by X-Ray Fluorescence . 31
9 Elemental Analysis of Retorted Shale, Particulates and
Organic Extracts 32
10 Trace Element Analysis of Retorted Shales 34
11 Benzene and Water Extractables of Retorted Shale, and
Raw Shale Particulates 35
12 Comparison of PAH to Polar Compounds in Solid Samples. . 33
13 RR Values for PAH Fraction of Benzene Solubles from
Direct Mode Retorted Shale 36
14 Evaluation of Benzo(a)pyrene Content in Samples of Benzene
Extracts from Direct Mode Retorted 38
15 Classes of Organic Compounds eluting in Each Liquid
Chromatography Fraction 46
vn
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List of Abbreviations and Symbols
Abbreviations
BaP — Benzo (a) pyrene
BOD — Biochemical oxygen demand
COD — Chemical oxygen demand
DEI -- Development Engineering, Inc.
EDTA -- Ethylenediamine-Tetracetic-Acid
GC-MS -- Gas Chromatography and mass spectrometry
GPC -- Gel permeation chromatography
HPLC — High Pressure liquid chromatography
LC -- Liquid chromatography
K -- Equilibrium coefficient
meq -- Mi Hi equivalents
ml — Milliliter
mm — millimeter
MSA -- Mine Safety Appliances, Inc.
PAH — Polynuclear aromatic hydrocarbons
RB -- Relative TLC spot location
SPF — Spectrophotofluorometry
SSMS -- Spark source mass spectrometry
TIC — Total inorganic carbon
TLC -- Thin layer chromatography
TOC — Total organic carbon
USBM — U.S. Bureau of Mines
>ig -- Micrograms
jum — Micron
vm
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ACKNOWLEDGMENTS
The interest and wholehearted support of the Paraho management in the
planning and conduct of the test program is gratefully acknowledged. In
addition, the involvement and assistance of personnel from the Laramie
Energy Research Center (ERDA) has been most helpful in planning the test
program, reviewing the data, and coordinating the assembly of data for the
final report.
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SECTION 1
INTRODUCTION
PROGRAM OBJECTIVES AND UTILITY
Relationship of the Program to Other Work
TRW and the Denver Research Institute are currently performing under
contract to the EPA, an environmental assessment of typical shale oil
recovery processing. The assessment is particularly oriented towards
the evaluation of effluents produced by typical recovery processes, and
the appropriate emission control technology and solid waste management
techniques.
The TRW contract involves the study of eight oil shale retorting pro-
cesses that are candidates for commercialization in the near term. To
assess oil shale development impacts, the study is designed to establish
characteristics which are common to most of the eight processes, rather
than to perform an assessment of each individual process. In addition to
the preliminary sampling and analysis effort just completed, much longer
term testing programs are anticipated at Paraho during 1977 and 1978.
Aims of the Test Program
The Paraho demonstration site is the largest operating surface retort
operation going on within the United States (Figure 1), The opportunity
to sample and analyze process streams at the site provided an extremely
valuable input to the TRW contract. The Paraho Demonstration program, in
its current phase, was terminated early in April, 1976, forcing quick exe-
cution of the testing program.
The test program was targeted to establish sampling and analysis
techniques for obtaining operating data on air and water compositions
relative to the crushing, handling, and retorting operations, as well as
compositions and quantities related to the retorted shale output of the
plant.
The sampling and analysis program at the Paraho site included only
those measurements of effluents directly applicable to normal operations
of the Paraho process. No ambient air or surface and ground water measur-
ments were made. Because Paraho is an old site (35 years approximately)
particular care was exercised to ensure that measurements did not include
residual emissions associated with past operations.
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Figure 1. Paraho plant at Anvil Points, Colorado
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The actual mining operation was not functional at the time of the test pro-
gram, precluding emissions testing within the mine and at the mine mouth.
Estimates of emissions from mining operations will have to be obtained
during future test efforts.
Sponsorship of the Program
The test program was accomplished under contractual arrangements with
the EPA, with the concurrent support of the Paraho operating management
and personnel from the Laramie Energy Research Center (ERDA). The repre-
sentatives from these various organizations formed a management team which
was responsible for:
• Determination that testing and analysis methods were accepted
standard procedures wherever possible
• Verification of Quality Assurance procedures and completeness
t Review of subsequent data analysis, presentation, and interpre-
tation.,
Limitations and Uses of the Test Results
The data obtained from the crushing and retorting operations must be
considered unique to the Paraho Oil Shale Demonstration. Because much of
the equipment and many of the operating procedures used at Anvil Points
are not employed in a commercial venture, data pertaining to particulate
and dust quantities in the site vicinity cannot be compared to those from
full scale Paraho-type operation. A detailed discussion of the Anvil Points
equipment and operating procedures is developed more fully in this section.
DESCRIPTION OF THE PARAHO PROCESS AND SITE
The present Paraho oil shale demonstration project utilizes some of
the facilities originally developed by the U.S. Bureau of Mines (USBM) at
Anvil Points, including an underground room and pillar mine, crushing
plant, retort structure, various storage tanks, shale disposal area, and
associated laboratories, maintenance shops, and water supplies.
Underground Mining, Crushing,
The mine at Anvil Points is a room and pillar operation encompassing
the Mahogany Ledge of the Green River Formation, at an altitude of approxi-
mately 2440 meters (8000 ft). Mined shale is trucked some 8.8 kilometers
(5.5 miles) by road down to the processing area.
At the plant site the mined shale is processed through the primary
and secondary circuits of the USBM crushing and screening plant, to pro-
duce a feed of approximately minus 7.6 cm (3 in) plus 6 mm (% in) size,
which is sent to storage bins. The 10-15% fines from the screening plant
are stock-piled.
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Retorting Plant
Two Paraho-type retorts (Figure 2) have been erected in a steel structure,
adjacent to the old USBM gas combustion unit. These include a 1.4 meters
(4.5 ft) O.D. (2.5 ft I.D.) by 18 meters (60 ft) high pilot plant unit; and
a semi-works retort which is 3.2 meters (10.5 ft) O.D. (8.5 ft I.D.) by 23
meters (75 ft) high. The old USBM gas combustion unit has been converted to
a thermal oxidizer for retort off-gas incineration.
Provision has been made for operating the retorts in either the direct
mode or indirect mode. In the direct mode (Figure 3) the carbon on the re-
torted shale is burned in the combustion zone to provide the principal fuel
for the process. Low calorie retort gases are recycled to both the combus-
tion zone and the gas preheating zone.
In the indirect mode (Figure 4) heat for retorting is supplied by recy-
cling off-gases through an external furnace, thus eliminating combustion in
the retort and producing a high heating value, 8000 kcal/std cu meter (900
BTu/SCF) off-gas.
In either mode of operation, raw shale is fed into the top of a Paraho
retort and passed downward by gravity successively through a mist formation
and preheating zone, a retorting zone, either a combustion zone (direct mode)
or heating zone (indirect mode), and finally, a residue cooling and gas pre-
heating zone. It is discharged through a hydraulically-operated grate, which
controls the throughput rate and maintains even flow across the retort. This
grate, the feed mechanism, and the multi-levels of heat input, are among the
unique contributions of Paraho technology toward improving the retorting
principle in vertical kiln type retorts.
The retorted shale is discharged from the retort at about 150°C (300°F),
essentially unchanged from its feed size-distribution, and sent to the shale
disposal area originally developed by the Bureau of Mines.
The shale vapors produced tn the retorting zone are cooled to a stable
mist by the incoming raw shale (which is thereby preheated), and leave the
retort. This mist is sent to a condenser, and finally a wet electrostatic
precipitator, for oil separation. The resulting shale oil is transported to
storage. A detailed description of the Paraho process is given in another
report.*
Plant Conditions During Field Test Program
There has been considerable mining and pilot plant activity at this loca-
tion over the past 35 years, initially by the Bureau of Mines and later by a
petroleum company consortium. Much of the auxiliary equipment used by Paraho
^Technological Overview Reports for Eight Shale Oil Recovery Processes,
USEPA/IERL, Cincinnati, Ohio (December 1976).
-------
FEED SHALE
FEED HOPPER
ROTATING SOLIDS
DISTRIBUTOR
BOTTOM —
DISTRIBUTION
RETORTED SHALE
*from Jones, John B., "The
Paraho Oil Shale Retort,
81st Nat. Mtg., AIChE,
Kansas City, Mo., April 11-14,
1976.
OFF-GAS COLLECTORS
DISTRIBUTORS
HYDRAULICALLY OPERATED
GRATE CONTROLS
RETORTED SHALE
DISCHARGE
Figure 2. The Paraho retort.
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RAW
SHALE
i
OIL MIST
SEPARATORS
D-
MIST
FORMATION
AND
PREHEATING
RETORTING
ZONE
COMBUSTION
ZONE
RESIDUE
COOLING AND
GAS
\ PREHEATING
/
OIL
PRODUCT
GAS
i
GRATE SPEED
3LLER
ELECTROSTATIC
PRECIPITATOR
T
OIL
GAS RECYCLE
BLOWER
AIR BLOWER
RETORTED SHALE
Figure 3. Paraho direct mode flow diagram
(pilot plant operation)
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RAW
SHALE
OIL MIST
SEPARATORS
r i
MT CT
FORMATION
AND
PERMEATING
RETORTING
ZONE
HEATING
RESIDUE
COOLING AND
. GAS .
\ PREHEATING /
\ /
,|
\
FU
!
J
EL
STACK
j|
T
I
r —
4
OIL?
foi
~J
\
\
Tl
V
LJ
,GAS HEATER
(f)
\Ls
I
^3^
v "7
5BJT
-
(t} n'l
KtLYLLt GAS
BLOWER
DRODUCT
GAS
ELECTROSTATIC
PRECIPITATOR
COOLER
RETORTED
SHALE
Figure 4. Paraho indirect mode flow diagram
(semiworks operation)
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has been inherited from these previous operations, including crushing and screen'
ing equipment, and the gas and air compressors. All of this equipment is consi-
derably older than would normally be tolerated in a commercial operation, and is
certainly not in "as new" condition. In addition, the coverage of material han-
dling movement is not dust tight, and therefore is another source of particulate
emissions that would not be expected in a commercial operation. The storage tan!
are simple open-vented tanks, and the transfer lines have a certain amount of
liquid and vapor leakage at the valve fittings.
During the period of the field testing program, the plant operating con-
ditions were intermittently changed as a result of the process R&D work being
conducted.
Mining and Feed Preparation
The Paraho mining operation had be£n shut down prior to the inception of
the testing program, and all the necessary raw shale for completing the cur-
rent development effort had been stockpiled at the primary crusher location.
The primary and secondary crushing and screening operations are enlcosed in
existing^buildings. Fugitive dust in' the interior air is collected in bag-
ho'use filters. The filtered fines are removed and stockpiled.
The minus 7.6 mm (3 in) plus 6 mm (% in) product from the crushing and
screening plant is lifted and transferred by an inclined belt to the top of
the two retorts. Shale crushed to this particular size does not visually
appear to cause much dusting. The inclined and lateral transfer belts are
not tightly enclosed.
It should be noted that the old USBM crushing and screening plant pre-
sently used by Paraho is not typical equipment, but has been used to reduce
R&D costs. In a commercial venture, all of this equipment, as well as the
material handling belts and elevators, will be well enclosed and sealed, with
dust removal systems attached.
Semi-Works Plant
The most representative piece of equipment at the Anvil Points site is
probably the Paraho semi-works retort itself, which has been specifically
designed to use the same configuration of solid and gas handling systems as
a full-scale plant. This retort is capable of being operated in either a
direct or indirect heating mode, at mass feed rates of up to 3423 kg/hr-sq
meter (700 Ibs/hr/sq ft). During the period of the test program it was oper-
ated in the indirect mode only.
In indirect-mode operation the retort off-gas, after removal of oil, is
compressed and reheated in a process heater before being introduced into the
vertical kiln. The present process heater is fired with conventional fuel
oil. The semi-works plant make-gas is sent to a thermal oxidizer for combus-
tion. The resulting flue gas is discharged to the atmosphere. No attempt
is made to recover by-product sulfur or ammonia.
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Spent retorted shale is removed from the bottom of the kiln and trans-
ferred by a belt conveyor to the retorted shale disposal area.
Pilot Plant
The pilot plant retort at the Paraho site has been used primarily as a
source of essentially inert gas for blanketing the semi-works retort during
startup and shutdown conditions. Since the pilot plant is operated in the
direct mode, it offered the opportunity during the test program of conducting
sampling and emissions testing in that particular mode.
Like the semi-works retort the pilot plant has a nominal throughput
capacity of 3423 kg/hr/sq meter. In the direct mode a portion of the residual
carbon on the retorted shale is burned to generate the heat for retorting.
The off-gas, after separation of oil, is also sent to the thermal oxidizer.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
The sampling and analysis research program described in this report
constitutes a preliminary effort that has laid the groundwork for more
extensive programs that are still in the planning stage. In spite of the
preliminary nature of the work, it was successful in accomplishing the
first multi-media sampling and analysis undertaking in a shale oil recovery
facility.
The test program was in keeping with current multi-media level field
testing philosophy within the Industrial Environmental Research Laboratory
(IERL) of EPA, according to a recent procedures manual.
A Level 1 test, as described in the manual, is designed as an initial
effort to obtain preliminary environmental assessment information, identify
problem areas and set priorities for additional testing. A subsequent
Level 2 procedure would be oriented towards identification and quantifica-
tion of specific compounds, using the knowledge gained from Level 1.
Finally, in the longer term, a Level 3 program would involve continuous
monitoring of indicator compounds.
The sampling and analysis program conducted at the Paraho site was
primarily a Level 1 type of effort, with the test findings intended for
input to a Level 2 test plan whenever further process research is conducted
at the demonstration plant. The principal conclusions of the reported
work relate to comparative effectiveness of sampling and analysis methods;
costs and manpower involved in specific procedures; and especially an order-
of-magnitude determination of constituents that can be used for later selec-
tion of testing accuracy and sensitivity requirements.
One of the major objectives of the testing program was the develop-
ment of a prototype sampling procedure. Consequently a number of different
sampling procedures were used and repetitive samples taken. Not all of the
sampling techniques proved applicable and some modification in methodology
is recommended in future test work. Collection and analysis of the recycle
gases for trace organics proved to be the most complex problem.
*
IERL-RTP Procedures Manual: Level 1 Environment Assessment, EPA-600/2-76-
160a, June 1976.
10
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The qualitative analytical results obtained are probably more signifi-
cant than the quantitative data. Various retorting emission constituents
have been postulated by others, without any experimental evidence. This
test program has helped identify the relative split of trace elements in
the retorting products. Arsenic, for example, is usually found in raw
shales. From the test results, it appears that trace amounts of arsenic
will be found in retorted shale and dusts, and the process water; no ar-
senic was detected in the recycle gas. Other gaseous-phase measurements
were unable to detect COS or C$2. Each of these respective measurements
was accomplished by solution absorption and wet chemical analysis.
Now that a considerable amount of information has been gathered on
the qualitative nature of various process streams in the Paraho demonstra-
tion plants, future work should focus on quantitative determination of
those constituents that may appear in a process residual. Longer-term
monitoring programs will be needed, in order to characterize the process
throughout its range of operation, rather than at one point in time. The
scope of subsequent testing programs should be expanded to include parti-
culate and gaseous measurements during mining and blasting; upwind-down-
wind particulate sampling beyond the plant boundaries; and raw shale sam-
pling coordinated with plant holdup rates and retorted shale sampling.
On-site gas chromatography is recommended to measure inorganic and
light-end hydrocarbons in recycle gas streams. Solid adsorbents may be
used to capture trace organics after aerosol removal. But studies are
needed to determine the selectivity and efficiency of these materials
under field conditions.
Finally, it is recommended that biological screening tests of aqueous
and solid samples should be conducted, in conformance with EPA published
procedures.
11
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SECTION 3
SAMPLING AND ANALYSIS PROCEDURES
TEST PLAN AND EXECUTION
Selection of Sampling Points
The test plan was discussed with Paraho management and ERDA representa-
tives. The meetings between TRW/DRI personnel and Paraho/ERDA personnel were
helpful in determining representative sampling of the process operations at
Anvil Points, with minimum interference from background sources and previous
retorting operations.
Pilot Plant and Semi-works Recycle Gases
Absorption train samples of the recycle gases (Figure 5) were taken
at a point between the electrostatic precipttator and the recycle gas blower
(Sample points A and E, Figures 3 and 4). This location was chosen because
of the moderate pressure and temperature of the recycle gas at this point.
These moderate conditions allowed the sample to be drawn through a heated
tygon tube, and minimized the leakage problems caused by high pressure and
temperature. At this sampling point, the gas is relatively free of oil
mist and (in the case of the pilot plant) dilution air.
Positive pressure was an aid to gas sample collection on adsorption tubes
Consequently, a valved tap on the discharge side of the recycle gas blower
was selected as a sample point: for the pilot plant, see Point B on Figure
3; and for the semi-works retort, refer to Point F on Figure 4.
Pilot Plant and Semi-works Recycle Gas Condensate
The condensate from the pilot plant recycle gas was collected through a
sample condenser (cooled to 0°C) at the discharge side of the recycle gas
blower. This point (B on Figure 3) was chosen because it had a positive pres-
sure which allowed the sample to be drawn without a pump, and because the
gas is relatively free of oil mist at this point.
The semi-works condensate was sampled from the bottom gas cooler at a
temperature of about 67°C. The point at which the condensate is withdrawn
from the system is shown on the semi-works retort schematic, Figure 4, as "G."
12
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Figure 5. Sampling recycle gases at the semi-works unit,
13
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Crushing Area Particulates
Particulate matter was collected with high volume and low volume samplers
positioned near the jaw crusher, primary screen, and the polishing screen.
These locations were chosen to give a representative sample of the particulate
emissions from this operation. The locations are shown on the plot plan
Figure 6, together with other sampling points as follows:
1. High-Vol Air Particulate Sampler Ground Level
2. High-Vol Air Particulate Sampler Upper Level
3. High-Vol Air Particulate Sampler Lower Level
4. Low-Vol Membrane Filter Particulate Sampler
5. Pilot Plant Recycle Gas Stream Tap (Blower Outlet)
6. Semi-Works Recycle Gas Stream Tap (Blower Outlet)
7. Semi-Works Recycle Gas Condensate Tank
8. Pilot Plant Retorted Shale Collection Point
9. Semi-Works Retorted Shale Collection Point
10. Semi-Works Retorted Shale Collection Point
11. Product Oil
Retorted Shale
Semi-works and pilot plant grab samples were collected as close to their
respective retorts as physically possible, from the conveyor belt (Points C
and H on Figures 3 and 4, respectively).
Lists of all samples taken and removed from the Anvil Points site were
reported to Paraho management. These reports included type of sample, date
and time the samples were taken, and anticipated analysis technique. These
are included in Appendix Section C.
Sampling Procedures and Methods
Recycle Gas Stream, Adsorption Samples
Organic vapor samples were drawn through tubes (MSA* tubes, Tenax,**
Bendix charcoal flasher tubes) using a Bendix permissible air sampling pump
and calibrated rotometer assembly. Quadruplicate samples were taken for each
adsorbent type for 1 and 5 minute sampling durations. Samples were taken direct-
ly at the recycle gas sampling ports, and after the gases had been .passed through
an ice-cooled teflon condenser. Tubes were capped for storage.
Recycle Gas (cold) Condensates
The ice-cooled teflon condenser discharge was put into ice-jacketed
quart glass bottles for collection of water and light ends. The bottles had
been previously HMO^-washed and distilled water rinsed.
*Mine Safety Appliances, Inc.
**Applied Science Corp, Mfg.
14
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COVERED BELTS
SEMI-WORKS RETORT
OIL SEPARATOR
RECYCLE GAS
BLOWER
RECYCLE __
CONDENSATE W^~^ 7
TANK
FINAL STATIONARY BELT
BINS
AND
V€IGH HOUSE
RECYCLE GAS
5 — BLOV€R
BAG HOUSE
-PILOT PLANT RETORT
MOVABLE BELT ASSEMBLY
CRUSHING BUILDING
CI3
BAG HOUSE
RETORTED SHALE DUMP
Figure 6. Sample point locations on plan view.
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Samples were preserved with HNO^ to a pH of 2 for inorganic trace ana-
lysis or with benzene for trace organic analyses. Unpreserved samples were
collected for headspace analyses of volatile components.
Recycle Gas (hot) Condensates, Indirect Mode Semi-works Only
The bottom gas cooler tank was sampled from a port above the tank bottom.
The condensate was allowed to flow through a stainless steel cooling coil and
was collected in acid-washed one quart glass bottles, followed by sample pre-
servation. Inorganic trace analysis, trace organic analysis, and volatile
component analysis could then be done.
Bendix Gastec Analyzer Tubes
Bendix Gastec Analyzer tubes were used to sample the gas streams of both
the pilot pi ant and semi-works, as a semi-qualitative backup. Gases were
drawn through the tubes using a hand pump, yielding a direct colormetric
reading. Specific tubes for NH3, HCN, CO, F^S, and S02 were used.
Gas Bottle Samples
250 ml gas bottles were connected to the recycle gas port and allowed
to purge for approximately ten volume changes. The stopcocks were then seal-
ed. Triplicate samples were taken both from directly off the gas stream and
after the teflon condenser for both the semi-works and pilot plant.
Absorption Train Sampling
Standard EPA absorption train methods for criteria pollutants (S02, $03,
NOX) were used for the recycle gas streams (Figure 7). For other constitu-
ents, commonly accepted methods of sampling and analysis were used, as sum-
marized in Appendix A.
High Vol Particulate Samples
Samples were collected on preweighed glass filters. Flow rates were
taken at the start and end of each run. The filter with collected sample
was then sealed in a benzene-washed storage bag.
Low Vol Particulate Samples
These were collected on 0.2p and O.Sjj Millipore filters and 0.2jj Nucleo-
pore filters. Air was drawn through the filters at 1 liter/min with a samp-
ling pump. Sampling times were 1, 2, 5, and 10 minutes for each sampling
location.
Retorted Shale Samples
Grab samples were collected in benzene-washed buckets. Samples were
taken from the discharge belt from each retort. Immediately upon filling,
the cans were lidded, crimoed closed and sealed with tape.
16
-------
Figure 7. Impinger sampling train mounted in position.
-------
Product Oil
The product oil samples, together with bound water, were taken at the
collection sump of the oil recovery equipment. The samples were taken in
glass jugs and immediately capped.
Quality Assurance
During sample collection a data sheet was kept on each gas and water
sample. A test number was assigned to each sample, and the time, date, samp-
ling location, and volume of sample were recorded. Supporting information
and any special sampling procedures were noted on the data sheets. All im-
pingers and sample bottles were thoroughly washed with glassware cleaner,
and rinsed with distilled water before each test.
After the samples were collected they were taken to the field laboratory
(Figure 8) where they were preserved and transferred to sample containers as
necessary. Sample containers were stored in ice chests with dry ice.
Gas absorption and water samples were preserved and then stored in ice
chests with dry ice. The samples were shipped to the TRW and DRI labora-
tories by air freight, and were refrigerated until they could be analyzed.
LABORATORY ANALYSIS METHODS
Analysis Rationale
The general analytical plan for the Paraho samples is illustrated in
Appendix Section B. Inorganic, organic, and trace element analyses were
done. Most inorganic analyses are standard procedures, using either wet
chemistry or atomic absorption techniques. Spark source mass spectrometry
(SSMS) was chosen as the most efficient method for trace element analysis,
since over 80 different elements can be detected in a single scan.
Organic analyses present a more difficult choice of methods. In addi-
tion, qualitative measurements may be the only information obtainable for
some constituents.
Based on work carried out at the Denver Research Institute, the use of
three interconnected approaches proved to be feasible for the preseparation
and analysis of the organic mixtures extracted either from retorted shale or
from process water, and the volatile components.
0) The combination of Gas Chromatography and Mass Spectrometry (GC/MS)
This approach is feasible if (a) the boiling points of the components
are not too high; (b) the individual components in the GC contain suf-
ficient material to yield a useful mass spectrum; and (c) structural
isomers have distinct fragmentation patterns. These requirements re-
strict, of course, the use of GC-MS in particular in evaluating higher
molecular weight compounds and compounds present in the subnanogram
range.
18
-------
Figure 8. Mobile chemical laboratory on site.
-------
(2) The combination of Thin Layer Chromatography (TLC) and/or High
Pressure Liquid Chromatography (HPLC) with Mass Spectrometry. In this
case the eluted bands or spots from the TLC and/or the collected frac-
tions from repeated separation runs can be used in conjunction with
the mass spectrometer using the direct probe method. This method will
allow the investigation of the higher molecular weight compounds. If
the compounds are (or can be made) ultraviolet absorbent and/or fluor-
escent the method is quite sensitive.
(3) The combination of TLC and/or HPLC with Spectrophotofluoremetry
(SPF). While this method is limited to fluorescent compounds it is
very sensitive and can be frequently utilized for good quantitative
evaluation of very small quantities of material.
A very useful and effective preseparation method which can be used in
combination with the above mentioned analytical methods is gel permeation
Chromatography (GPC). This method (when applicable) is to be preferred
over that of the TLC or LC preseparation procedure because of a much higher
efficiency in recovery.
Gaseous Samples
Inorganic constituents in gaseous samples from the recycle gas streams
were captured in impinger solutions, and analyzed by standard methods. Ana-
lyses were done for S09, SCL, NO , AsH-,, HCN, NHq, CS9, COS and H9S as des-
• i_ j • ft _j * n ^ 3 A 0 O L- L-
cnbed in Appendix A.
Organic components were collected on site in gas bottles and adsorp-
tion tubes and later desorbed in the laboratory for subsequent gas Chroma-
tography separation and mass spectrum analysis. Volatiles were stripped
from condensate samples and analyzed in the same fashion. Representative
traces from GC and MS analyses are included in Appendix B. Most of the
information obtained was qualitative.
Water Samples
These samples included recycle gas condensate (hot) taken from the
bottom gas cooler, condensate (cold) obtained from a gaseous sample stream
condenser, and process water separated from the product oil. Hot conden-
sate was analyzed directly for non-specifics (total organic carbon, BOD,
etc.) and major inorganic constituents by standard wet chemistry and atomic
absorption methods, referenced in the Appendix B. Trace element analysis
was performed on condensates and process water by spark source mass spec-
trometry, following solvent extraction to remove interfering constituents.
The liquid phases (condensate water and process water) contain organic
constituents consisting of water soluble acids, neutrals and bases. The
determination of these fractions can be accomplished in a number of ways.
An extraction method was used, backed up by total organic carbon analysis
(TOC), a straightforward gravimetric method.
20
-------
Note that the analysis of the recycle condensates and process water
requires that the oil-water separation be carried out under identical phy-
sical conditions and for the same length of time after sampling, to obtain
reproducible results. This is because the amount of organic material dis-
tributed between the oil phase and aqueous phase will vary with time and
physical conditions.
Following the organic separations, high pressure liquid chromatography
(HPLC) and thin layer chromatography (TLC) analyses were conducted. The
TLC analytical scheme was used primarily to separate polynuclear aromatic
hydrocarbons (PAH), followed by identification and quantification by spec-
trophotofluorometric (SPF) analyses. Typical TLC and SPF patterns are in-
cluded in Appendix B.
Solid Samples
The analysis scheme for retorted shale and high-vol collected extrac-
tables, trace elements, and volatiles were done in a manner similar to
water sample procedures. Although most organic analyses were qualitative,
one PAH compound (benzo(a)pyrene) was determined quantitatively by spec-
trophotofluorometry. This compound was chosen because of data available
from other types of retorted shales.
Water extractions of the retorted shale were done to provide an esti-
mate of the total amount of water soluble inorganics present and thus the
potential maximum Teachability of the material.
Particle size determinations of low-vol collected particulates were
done with a scanning electron microscope. Larger particles were deter-
mined on site with cascade impaction collector.
21
-------
SECTION 4
SUMMARY OF ANALYSIS RESULTS
GASEOUS SAMPLES
The analysis results for recycle gas (pilot plant and semi-works) are
summarized in Table 1.
The measured values appear to be within expected ranges, as compared
to some earlier measurements made at the Paraho site during direct mode
operations of the semi-works retort in 1975. It can be seen that NhL con-
centrations in the recycle gas are higher in the indirect mode. Arsfne,
carbon disulfide, and carbonyl sulfide were not detected in the recycle
gas stream from direct-mode pilot plant operations, within the sensitiv-
ity of the measurement techniques. A data dispersion and error analysis
of these measurements is included in Appendix A.
The trace organic components in the recycle gas stream posed a number
of problems both with respect to sampling methods and analysis. A large
number of samples were analyzed, and some typical instrument traces are
included in Appendix B. In general, all gaseous samples for organic analy-
sis were subjected to GC-MS tests whenever feasible. The GC column used
for these separations had a CB cutoff. Typical C, and lighter composi-
tions of retort gases have been reported elsewhere.*
Qualitatively, the chromatograms from the various samples collected
during the direct and indirect modes of operations were about the same.
The ratio of the components differed. Quantitative data for the indivi-
dual components were not obtained since this would have required a cali-
bration of the flame ionization detector response for a wide variety of
various reference compounds. In addition, the Tenax sampling tubes were
saturated with sample, consisting primarily of aerosols. Quantification
of such samples would inevitably contain error. These observations point
to the need for more sophisticated approaches to process stream sampling
in future test work, and particularly a need for separation of light and
heavy components during sample collection.
Table 2 presents a summary of the compounds identified in the recy-
cle gas streams. These compounds are essentially identical to those
collected from the water samples headspace analysis and the supernatant
oily layer except for relative intensities (concentration) in the mixture.
Various GC compounds were identified by mass spectral analysis.
*Jones, John B., "The Paraho Oil Shale Retort," 81st National Meeting,
A.I.Ch.E., Kansas City, Mo., April 1976.
22
-------
TABLE 1. RECYCLE GAS ANALYSIS FROM SELECTIVE ABSORPTION
Component
Date/Time
3/9, 13:30-14:45
3/9, 15:00-15:45
3/10, 10:00-14:00
3/11, 10:00-14:00
3/11, 15:00
3/11, 16:00
3/12, 16:00
so2
ppmv
14
4
NH3
ppmv
1614
2689
N0x
ppmv
9
16
AsH3
ppmv
ND**
NO
cos/cs2
ppmv
ND
H2S
ppmv
2600
(Bendix
tube)
co2
vol. %
24.5
CO
vol. %
2.1
°2
vol. %
ND
Pilot Plant (Direct Mode) March 9-12, 1976
Shale feedrate: 0.91 tonne/hr (1 ton/hr)
Average Fischer assay:
Recycle gas rate:
116 liter/tonne (28 gal/ton)
493 std cu rneters/hr (290 SCFM)
Component
Date/Time
3/14, 15:00
3/14, 17:00
3/15, 12:00
3/15, 16:00
3/15, 17:00
3/15, 17:15
3/15, 17:30
so2
ppmv
773
328
NH3
ppmv
25,945
27,642
NOX
ppmv
30
37
49
Semi-Works (Indirect Mode) March 14-15, 1976
Shale feedrate: 10.2 tonne/hr (11.2 ton/hr)
Average Fischer assay: 116 liter/tonne (28 gal/ton)
Recycle gas rate: 6230 std cu meters/hr (3650 SCFM)
*1 tonne » 1000 Kg
**ND = Not Detected
-------
TABLE 2. TRACE ORGANICS IDENTIFIED BY GC/MS IN THE RECYCLE GAS STREAM
(DIRECT AND INDIRECT MODE) SUMMARY OF ALL SAMPLES
Peak
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Boiling Point
( C at 760 mm)
36
69
80.1
93-98
98.5
110.6
121-129
125.6
136.2
138.3
139.1
140.6
144.5
145-146
150.8
161-165
163.4
164.7
169.4
170.6
174.1
178
181
182.6
192.7
195.6
213.4
216.3
218
Molecular
Compound Weight
Pentane 72
Hexane 86
Benzene 78
Heptenes 98
Heptane 100
Toluene 92
Octenes 112
Octane 114
Ethyl benzene 106
p-Xylene 106
m-Xylene 106
Cyclooctatetraene 104
o-Xylene 106
Styrene 104
Nonane 128
Methyl ethyl benzene 120
a-Methyl styrene 118
1 ,3,5-Trimethyl benzene 120
1,2,4-Trimethyl benzene 120
1-Decene 140
Decane 142
Indan 118
1,3-Diethyl benzene 134
Indene 116
Undecene 154
Undecane 156
Dodecene 168
Dodecane 170
Naphthalene 128
24
-------
LIQUID SAMPLES
Three types of liquid samples were collected: (a) cold condensate (from
sample condenser), (b) hot condensate (from bottom gas cooler of semi-works
retort), and (c) process water separated from the crude shale oil. The con-
densates contained an oily component which separated out upon standing.
Inorganic analysis results for both semi-works and pilot plant conden-
sates are presented in Table 3. Trace element analyses for cold condensates
and process water are included in Table 4.
For clarity of presentation, the results of the inorganic analyses for
both the pilot plant and semi-works unit are classified into five different
groups in Table 3: cations, anions, nutrients, gross parameters and trace
elements. Under each group or category of cations and anions, only the more
significant constituents are identified and quantified. Ammonia nitrogen,
total Kjeldahl nitrogen (TKN) and phosphorus are classified under the nutri-
ent category because of their eutrophication potential in receiving waters.
Gross parameters include constituents that are not readily identified singly
but are quantified under group categories. Gross parameters are useful as
quality control parameters because of their relative ease of determination.
Trace elements included in Table 4 cover those elements that may be subject to
water quality regulation.
In general, results of the water analyses from both the pilot plant re-
cycle gas condensate (direct mode) and the semi-works recycle gas condensate
(indirect mode) are comparable to those reported in the literature for other
retorting operations. As seen in Table 3, the predominant inorganic consti-
tuents present appear to be ammonium carbonate and bicarbonates. The presence
of a high concentration of ammonia interferes with the standard titrimetric
determination for carbonate and bicarbonate alkalinity. Consequently, the
carbonate and bicarbonate ions reported in this table are computed values
based on the total inorganic carbon (TIC was determined by infrared analysis)
and the second ionization constant of carbonic acid at 0.1M ionic strength
(Appendix B). The amount of ammonium ion present in the condensates was also
computed, based on the ammonia concentration determined by distillation and
on the equilibrium constant of ammonia in water. To ensure consistency of
data presentation, the equilibrium constant for ammonia was adjusted to 0.1F1
ionic strength (Appendix B).
An overview of the data from Table 3 shows that there is definite mass im-
balance of cations for the pilot plant and of anions for the semi-works plant.
To maintain electron neutrality, approximately 840 milliequivalents of cations
must be accounted for in the pilot plant and approximately 560 milliequivalents
of anions for the semi-works plant. Based on related condensate analyses,
it is postulated that organic amines (R-NH3+) may be the undetermined
anions. Similarly, the presence or organic acids in the semi-works conden-
sate could be a possibility based on the conversion of TOC to equivalent
organic acids.
25
-------
TABLE 3. INORGANIC ANALYSIS OF-CONDEWSAIES
(MEASURED AND CALCULATED VALUES)
CATIONS
Calcium
Magnesium
Sodi urn
Potassium +
Ammonium (Nh. )
ANIOHS
Carbonates
Bicarbonates
Sulfate
Sulfide
Chloride
Fl uoride
Nitrate
Nitrite
NUTRIENTS
NH3-N
TKN
Phosphate (Total )
GROSS PARAMETERS
BOD
COD
TOC
TIC
Oil & Grease
Solids, Total
Solids (upon evaporation)
Solids, Suspended
Total , Alkalinity
Hardness
Phenols
PH
Pilot Plant Recycle Gas Cold
Condensate (Direct Mode)
3/11/76 - 0800 - 1800 Mrs
(mg/D
60.74
<0.1
0.20
0.03
5652-calc.
30500-calc.
31265-calc.
113.6
<0.1
TR
0.35
118
0.02
14060-calc.
31,400
0.58
12,000
19,400
29,200
9,800
502
22,000
21,800
200
68,550
152-calc.
46
9.8
(meq/1 )
3.03
0.009
0.002
312-calc.
610-calc.
512-calc.
2.37
0.018
3.03
<0.001
827-calc.
2243
Semi-Works Recycle Gas Hot
Condensate (Indirect flode)
3/14/76 - 0800 - 1800 Hrs
(mg/1)
39.16
<0.1
0.29
0.18
13540-calc.
3030-calc.
6280-calc.
1.65
390
TR
0.10
1.0
<0.002
16800-calc.
0.75
4,850
17,100
9,800*
1,600
33.3
429
406
12,900
98-calc.
42
9.5
(meq/1 )
1.95
0.013
0.005
752-calc.
61-calc.
103-calc.
0.034
24.38
0.005
0.016
989-calc.
*Semi-works process water total organic carbon (TOC) was 36900 mg/1 on 3/15 @ 1500 hrs.
(Note: Blank entries indicate that no calculation or measurement was done)
Operating Parameters for Water Data
Plant Feed Rate,
Tonne/hr (TPH)
Semi-Works Hot
Condensate (3/14/76),
0800-1800 hrs
and Process Water
(3/15/76, 1500 hrs)**
Pilot Plant Cold
Condensate
(3/18/76, 1130-1330 hrs)
(3/10/76, 0800-1700 hrs)J
10.2 (11.2)
0.91 (1.0)
Recycle Gas Rate,
Std.Cu.Meters/hr (SCFM)
6320 (3650)
493 (290)
**These operating parameters also apply to Table 4, following.
26
-------
Biochemical oxygen demand (BOD) and chemical oxygen demand (COD) are
gross parameters that are commonly used to assess the pollution potential of
wastewater when discharged. Unacclimated seeds from a sewage treatment plant
were used, so that BOD tests were conducted with great difficulty and little
precision. Correlation with COD results was also poor. This is particularly
true for the semi-works data in which the COD was 17,100 mg/1 and BOD was only
4850 mg/1. Future BOD measurements should be done with seeds from a similar
water source such as a refinery waste treatment plant.
The conventional method for determining dissolved solids may not be
acceptable for these condensates because of the large amount of ammonium car-
bonates and bicarbonates present. These constituents break down and volati-
lize readily as NHj, C02> and H20 at the boiling point of water, Volatile
acids may also be lost upon evaporation of water. Based on the above ration-
ale the term "dissolved solids" was discarded and replaced by the term "solids
upon evaporation."
The term "total alkalinity" in Table 3 has a different meaning than the
traditional one which defines it as the amount of sulfuric acid needed to
neutralize hydroxide tons, carbonate and bicarbonate ions. Because of the
large amounts of ammonium compounds such as R-NH2 present, a major portion of
the acid is utilized in neutralizing these ammonium compounds. Also, the
possible presence of R-C02" acids reduces the acid requirements that are
normally needed for carbonate and bicarbonate neutralization. This may be an
explanation as to why there is a significant difference in alkalinity between
the pilot plant and the semi-works plant.
Total hardness determination by the conventional CEDTA)* titration method
is not possible because of interference from organic substances such as organic
acids and amines. Since the major cations contributing to hardness are cal-
cium and magnesium ions, total hardness must be determined instead by computa-
tion similar to that described in Standard Methods for water analysis.**
Trace elements analyses were done by spark source mass spectrometry
following extraction of organics by benzene (Table 4).
The analysis of condensates and process water for organic constituents
included the following:
1. Headspace volatiles over the oily layer
2. The oily layer
3. Volatiles from the aqueous layer of the condensates
4. Total organic carbon (TOC) of the aqueous layers
5. HPLC of the aqueous layer of the cpndensate
Process water separated out from the product oil within 48 hours, ber
tween a denser and lighter organic layer.
Ethylenedi ami ne-Tetraceti caci d
** Standard Methods for the Examination of Water and Wastewater, American
Public Health Association, Washington, D.C.: 13th Edition, 1971.
27
-------
TABLE 4. CONDENSATE WATER AND PROCESS WATER (SSMS ANALYSIS)
Element
Uranium
Lead
Mercury
Praseodymi urn
Cesium
Lanthanum
Barium
Iodine
Tin
Molybdenum
Zirconium
Yttrium
Stronti urn
Rubidium
Bromine
Selenium
Arsenic
Gall ium
Zinc
Copper
Nickel
Cobalt
Germanium
Iron
Manganese
Chromi urn
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Sil icon
Al uminum
Magnesium
Sodi urn
Fl uorine
Boron
Lithium
Cold Condensate Water
Pilot Plant
ug/ml
3/10/76
0800-1700 Hrs
0.03
0.7
<0.01
0.008
0.01
0.04
0.1
0.008
0.05
0.3
0.05
0.007
0.1
0.4
0.02
0.04
0.09
0.04
0.2
0.1
0.1
<0.01
>10
0.2
0.07
•=0.01
0.9
0.01
8
3
0.4
3
0.2
4
0.2
3
5*
-0.1
0.06
0.02
Process Water
Semi -Works
yg/ml
3/15/76
1500 Hrs
0.2
<0.01
0.01
2.0
0.1*
3.0
0.009
0.1
1 .0
<0.02
0.4
0.2
0.2
<0.04
<0.05
5.0
0.3
0.3
0.03
0.3
<0.05
>10
>10
2.0
>10
5.0
>10
0.8
>10
>10
7
-5.0
1.0
*Heterogeneous
After extraction of organics, sample was thermally ashed @ 450°C for
4 hr in a laboratory furnace in a quartz crucible prior to analysis.
Note: See Table 3 for operating parameters.
28
-------
Organic components identified qualitatively in the condensates and the
oily layer were essentially the same as found in the recycle gases (see Table
2). Appendix B includes an example of a HPLC chromatogram for the pilot plant
recycle gas condensate after removal of the oily layer. Other HPLC chromato-
grams are on file at Denver Research Institute. In all of these samples for
HPLC analysis, the organic components were removed by passing the condensate
and process water through a column of Bondapak 18 and subsequently eluting
the organics into a reverse phase HPLC column for separation.
SOLID SAMPLES
Size Distribution
The raw shale particulates were collected by high-vol and low-vol devices
in the primary crusher building, in the secondary crusher area, and next to
the feed bins and weigh house. Size ranges for raw shale and retorted shale
process streams and particulates are given in Table 5 below.
TABLE 5. SIZE RANGES OF SOLIDS
Material
Raw Feed Shale
Fines
Raw Shale Air
Particulates
Retorted Shale
Size Range
<7.62 cm, >6 mm (-3" +%")
<6 mm (V)
>0.01 <5 mm
see below
Remarks
Includes crushing fines
For particle size distri-
bution see Table 6 and 7
Screen Sieve Analyses of Direct Mode
Retorted Shale (3/12/76, 10:00 hrs)
Height Percent
26.4
9.9
9.0
11.5
4.4
6.6
3.2
6.2
2.7
2.4
2.4
2.1
0.6
2.4
8.7
1.6
Sieve Designation Standard
(New U.S. Nos.)
>19.0 mm
19.0
13.2
9.5
4.75
3.25
1.70
1.18
600 urn
425
300
212
150
106
75
<45
29
-------
A Brink's cascade impactton sampler was used to collect participate dust
in the primary crusher building vicinity (location No. 2 on Figure 6). The
mass of particulate collected in each separation stage was plotted according
to the calibration relations for the sampler, yielding a particle size -dis-
tribution as shown in Table 6 below.
TABLE 6. MASS FRACTION OF RAW SHALE PARTICULATES
Particulate Size Range
Cumulative Weight Percent less than
stated size
<0.3 ym
2
<1 .0 ym
26
<3 ym
73
(Sample taken at 1400 hrs, 3/17/76
crushing 28 gal/ton shale)
Mean particle size (effective diameter) analysis of low-vol air particulate
samples was determined by scanning and transmission electron microscopy.
Values as percent of particle counted are given in Table 7.
TABLE 7. NUMERICAL FRACTION OF RAW SHALE PARTICULATES
Particulate Size Range
Cumulative Count Percent
less than stated size
Breakdown % <1 .0 ym
<0.01
ym
50.4
0,01-0.05
ym
33.3
0.05-1
ym
1.2
Cumulative
% <1 .0 ym
84.9
1-5
ym
10.1
>5
ym
5.0
(Sample taken at 1410 hrs, 3/15/76
handling 28 gal/ton shale)
Compositions of Solids
Particulates --
The major components of raw shale particulates of various sizes, taken
from low-vol collectors, are shown in Tables 8 and 9. The values in Table 8
are averages of individual particulates, as determined by x-ray fluorescence,
and should not be interpreted as mass fractions. These raw shale particulate
analyses should be viewed as qualitative since river rock was being crushed
prior to the period of shale crushing operation (3/14-3/17). The values in
Table 8 indicate that the inorganic constituents tend to be emphasized in
finer particulate sizes.
Elemental Analyses --
Table 9 shows an elemental analysis of the direct mode retorted shale,
the benzene extract from retorted shale, and that of the particulates from
the crushing area. As a comparison, composite analysis of the organic matter
from Green River cores is also given, as determined by Laramie Energy Research
Center. Trace element analysis of direct mode retorted shale was done by
30
-------
TABLE 8. PARTICLE SIZE VS. MEAN ELEMENTAL COMPOSITION OF RAW SHALE
AIR PARTICULATES AS DETERMINED BY X-RAY FLUORESCENCE
^^^ Size Ranges
^\^ of Particles
^%. AT A
^^^Hnct 1 j/ZGu
Elemental ^v.
Components ^\.
Detected ^\^
Si
Ca
Al
Mg
Fe
K
Na
P
S
Ti
•X
2-
Lf>
V
W/o
20
10
10
+
+
+
-
+
+
E
P.
o
V
30%
16
11
12
9
2
2
3
12
-
E
;1
LT>
V
^
A
Wo
24
10
6
5
5
3
+
+
+
E
p-
Lf>
A
^3%
22
8
8
6
6
2
+
4
+
*High background fluorescence.
+Indicates presence of element but not quantifiable
-Indicates element not found in sample at sufficient
concentration to be detected by x-ray fluorescence.
31
-------
CO
r\>
TABLE 9. ELEMENTAL ANALYSIS OF RETORTE
Benzene Extract of Direct
Mode Retorted Shale
(3/12/76, 1000 hrs)
Direct Mode Retorted
Shale
(3/12/76, 1000 hrs)
Raw Shale Collected as
Air Parti cul ate
(3/15/76 to 3/17/76)
Organic Matter in Raw
Shale (average of 10
cores from Colorado &
Utah)
C
Total
81.41
2.95
14.25
C
Org.
81 ,41
0.80
9.58
80.5
C
Inorg.
*
2.15
4.67
D SHALE, PARTICULATES, AND ORGANIC EXTRACTS (PERCENT)
H
10.70
0.10
1.51
10.3
0
2.22
ND
ND
5.8
N
(Dumas)
2.05
0.13
0.43
2.4
S
(Free)
7.79
ND
ND
1.0
S
(S04)
NA
0.08
0.01
S
(Sx)
NA
0.74
0.04
Ash
(dry)
<0.15
92.88
70.91
* 0.5% of total C
ND = Not Determined
NA = Not Applicable
Smith, J. W., Ultimate Composition of Organic Matter in Green River Oil Shale, USBM RI5725 (1961)
-------
spark source mass spectrometry. The values for the pilot plant shale from
direct mode operation are reported in Table 10. In 1975, retorted shale samples
resulting from direct-mode operation of the semi-works plant were analyzed by
Denver Research Institute under an agreement with Paraho, as part of an NSF
contract. Trace element analysis of these samples, done by flameless atomic
absorption, are also reported in Table 10,
Organic and Inorganic Extractions and Analyses --
Retorted shale contains various percentages of organic carbon, and vari-
ous percentages of extractable residual organic matter. The amounts of total
organic carbon and benzene extractable organic matter depend on the type ot
retorting process and the efficiency of retorting. Table 11 shows the total
organics extractable by benzene from the direct mode retorted shale, as well
as raw shale particulate, and the water soluble component of the retorted
shale.
The organic extract from the direct mode retorted shale was preseparated
by TLC (Figure 9) in order to determine the ratio of polynuclear aromatic
hydrocarbon compounds (PAH) to polar compounds. An example of the TLC chro-
matogram is shown in Figure 10.
The polar components from the direct mode retorted shale benzene extract-
ables (Table 12) contain phenolics, alcohols, and acids (aliphatic and aro-
matic acids). The phenols include phenol per se, cresols, naphtols and higher
molecular weight phenols. These and the nitrogen compounds have as yet not
been separated and identified.
The PAH compounds preseparated from the benzene extract were further sep-
arated by two dimensional layer chromatography. An example of the qualitative
separation of the PAH compounds from the direct mode retorted shale is shown
in Figure 10 and Table 13.
The TLC in Figure 10 is a mixed layer two-dimensional chromatogram.
Most of the compound identification is based on Rp values:
RB = Distance (x,y) from origin to spot
Distance (x,y) from origin to BaP spot
The benzo(a)pyrene spot was confirmed in the spot No. 1 and it was deter-
mined quantitatively by spectrophotofluorometry (Figure 11). The values
for BaP for the extracts from the direct mode retorted shale are presented
in Table 14 and compared to an earlier BaP determination from a direct
mode Paraho retorted shale sample.
33
-------
TABLE 10 TRACE ELEMENT ANALYSIS OF RETORTED SHALES
(VALUES IN PPM)
Element
Uranium
Thorium
Lead
Mercury*
Terbi urn
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymi urn
Cerium
Lanthanum
Barium
Cesium
Iodine
Antimony
Tin
Molybdenum
Niobium
Zirconium
Yttri urn
Strontium
Rubidium
Bromi ne
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Manganese
Chromium
Vanadium
Scandium
Chlorine
Fluorine
Boron
Beryl 1 i urn
Lithium
Direct Mode
(Pilot Plant)
3-15-76. 1100 hrs
5
7
23
0.06
0.7
1
0.7
2
6
2
59
21
180
6
<0.2
0.7
0.2
14
7
65
40
970
110
0.2
0.5
35
0.9
17
22
57
75
19
800
230
180
26
43
>1000
48
2
85
Direct Mode
(Seml-Morks)*
3-15-76
7
4
24
0.06
0.6
0.9
0.6
1
9
5
100
33
310
10
<0.2
1
2
18
8
41
17
760
85
0.2
0.4
18
<0.2
13
17
53
20
15
700
110
no
20
42
920
82
1
370
Note: Fe, Ti, Ca, K, S, P, Si, A1, Mg, Na, 0, N, C, H are all present
in quantities greater than 1000 ppm.
All elements not reported <0.2 ppm by weight
*Flameless Atomic Absorption
-------
TABLE 11. BENZENE AND WATER EXTRACTABLES OF RETORTED SHALE, AND RAW SHALE PARTICULATES
Total Benzene
Solubles
Wt %
Benzene Solubles
Sulfur Removed
Wt %
Water Solubles
Wt %
Benzene Solubles
of Water Solubles
Wt %
CO
en
Pilot Plant
(Direct Mode)
Retorted Shale
(3/12/76, 1000 hrs)
Raw Shale Collected
as Air Particulate
in the Crushing Area
(3/15/76 to 3/17/76)
0.03
0.03
3.39
0.00
2.05
ND
ND
ND
ND = Not determined
TABLE 12. COMPARISON OF PAH TO POLAR COMPOUNDS IN SOLID SAMPLES
Sample Designation
Wt. % PAH
Wt % Polar Compounds
Pilot Plant Retorted
Shale, Direct Mode
(3/12/76, 1000 hrs)
Raw Shale Air
Particulate
(3/15/76 to 3/17/76)
43
16
57
84
-------
TABLE 13. RB VALUES FOR PAH FRACTION OF BENZENE SOLUBLES FROM DIRECT
MODE RETORTED SHALE
Spot No. on
Figure 10
1
1
(tailing)
2
3
4
5
6
7
8
9
10
11
12
13
14
Fluorescence
purple
purple
light blue
blue
yellow
purple
blue
purple
blue
purple
blue green
purple
purple
blue
blue
RR
I B II
1.00
0.79
1.02
0.93
0.87
0.95
0.83
1.08
1.19
1.36
1.24
1.38
1.27
0.31
0.00
1.00
1.02
1.25
1.27
1.45
1.64
1.89
1.95
1.84
1.91
2.18
2.34
2.80
2.41
2.34
Compound
*Benzo(a)pyrene
*Benzo(a)pyrene
**Coronene
**1 ,2 Benzanthracene
**1 ,2 Benzanthracene
**Pyrene
**Fluoranthene
^Quantitatively identified by fluorescence spectrometry and/or
high pressure liquid chromatography.
**These compounds have been qualitatively identified by RB values
only.
36
-------
TABLE 14. EVALUATION OF BENZO(A)PYRENE CONTENT IN SAMPLES OF BENZENE EXTRACTS FROM DIRECT MODE RETORTED
SHALES
CO
Sample Designation
Pilot Plant
(Direct Mode)
KcCOiLSU oil die
(3/12/76, 1000 firs)
Retorted Shale
(Direct Mode)
ocm 1 WUr Kb
(3/75)
Bz. Sol.
Quantity
Analyzed
(mg)
8.7
8.7
Ave.
Ave.
BaP/TLC
Spot
(yg)
0.050
0.038
0.044
0.189
Wt %
BaP in
Bz.
Solubles
.000
.000
.001
0.001
BaP in
Bz.Sol.
(yg/kg)
4.7xl03
3.6xl03
4.2xl03
14x!03
BaP in
Shale
Sample
(yg/kg)
2.0
1.5
1.8
1.50
BaP in
Bz. Sols.
ppm
4.7
3.6
4.2
14
BaP in
Sample
ppm
0.2x10-2
0.2x10-2
0.2x10-2
0.2xlO"2
-------
00
oo
Figure 9. Analysis of PAH compounds, using thin layer chromatography techniques,
-------
M
w
H
CO
w
O
T
l.o
2.°
SOLVENT SYSTEM n
3.0
Two dimensional mixed thin layer chromatogram
of the PAH fraction of benzene solubles from
direct mode retorted shale (3/12/76, 1000 hrs)
Layer: 40% acetylated cellulose, aluminum
oxide G, silica gel G (1:1:1). Solvents:
System I, isooctane, drying followed by
n-hexane, benzene (95:5). System II,
methanol, ether, water (4:4:1). Compounds:
1 and 1 tailing, benzo(a)pyrene.
Figure 10. Mixed layer two-dimensional chromatogram.
39
-------
-fi.
o
Figure 11. Determination of PAH compounds with spectrophotofluorometry.
-------
SECTION 5
DISCUSSION OF PROCEDURES AND RESULTS
SAMPLING PROCEDURES
Condensates
Condensates were taken out of the bottom gas cooler ("hot") or extracted
from the recycle gas stream ("cold") with an ice-cooled sample condenser.
Both samplings provide useful information, but it must be clearly understood
in all data reporting that these two types of condensate are quite different
Lighter components will be condensed out at OOQ, but may be above their dew
point at process cooler conditions. Condensates collected in future sampl-
ing programs should be quickly frozen and kept in the frozen state until
they are analyzed, as a precaution against loss or organic volatiles. No
other sample preservation requirements than those described in the report
appear to be needed.
Retorted Shale
Retorted shale grab samples were taken directly off the discharge belt,
in approximately five kilogram lots. While there are no comparative data
for sampling by other methods at Paraho, much larger composite batches should
be taken in subsequent sampling efforts. Batch sizes of 100 kg would pro-
vide better assurance of representative samples, and the same recommenda-
tions, apply to raw shale sampling.
Particulates
Particulates from raw shale crushing were collected by high-vol units,
although these types of collectors are intended for very low dust concentra-
tions typical of ambient conditions. In much higher dust concentrations,
high-vol units were observed to quickly load up to the point where air could
not be pulled through. Shorter collection times and more frequent sample
removals will be needed. Dust collection was also done with low-vol units
and cascade impactors, and in these cases the quantity of sample collected
was much smaller than with high-vol units. These same comments are appli-
cable to any future collection of retorted shale particulates where handl-
ing or transfer operations occur.
Gas Stream Sampling by Selective Absorption
Conventional sample trains with various absorbing solutions in glass im-
pingers were used as one means of recycle gas constituent collection. These
41
-------
methods have primarily been used in stack sampling work, where gas con-
stituents are in low concentration. Sample train absorption of recycle
gas constituents was satisfactory for the collection of NH~ and SO-; but
attempts to detect whether or not HCN was present were unsuccessful in
the presence of ammonia. Recycle gases contain high concentrations of
hydrogen and light hydrocarbons. The sample train exhaust must be vented
to a point where the gases do not pose an explosive hazard.
The standard EPA method of NO collection by the evacuated flask
technique was also satisfactory.
Gas Sample Collection on Solid Adsorbents
Samples were concentrated on charcoal and Tenax (a polymeric mater-
ial) to provide sufficient sample for GC/MS identification of trace
organics in the recycle streams. Since this type of sampling procedure
proved to be rather difficult, a more detailed discussion of the proce-
dure is appropriate.
Some considerations to keep in mind for the evaluation of the adsor-
bent properties of charcoal and Tenax can be summarized as follows:
1. Charcoal
a. It has a very high collection efficiency for solvent
vapors.
b. It is not suitable for collecting strong oxidants,
substances with high vapor pressures, or very polar
compounds.
c. MSA tubes have two charcoal sections and if any sig-
nificant amount of the sample is found in the refer-
ence section, it should be assumed that the adsorption
limit of the tube has been exceeded; therefore, the
analysis is not quantitative even though the total
volume of gas sampled is known.
d. Less than twenty solvents have been studied for quan-
titative recovery by solvent (CS2) desorption.
e. Up to 95% humidity does not cause any problem, but
the presence of water droplets can change the adsorp-
tion characteristics of the charcoal.
f. In a mixture the more polar components may displace
the less polar components.
g. Easy recovery of the organics by CS^ desorption is
the major advantage but the more volatile part of
the sample is readily lost.
42
-------
2. Tenax
a. If Tenax is to be used for quantitative analysis,
its limits with respect to trapping efficiency and
recovery need to be established.
b. Alkanes, alcohols and amines are more efficiently
trapped than aldehydes, ketones and phenols.
c. High molecular weight compounds are more easily
retained than low molecular weight substances.
d. Each substance has a specific affinity for the
adsorbent at a given temperature and the quantity
adsorbed is characteristic of each substance.
e. Rate of sampling and temperature were found to
have strong effects on displacement but the loss
of the more volatile fraction of gaseous samples
occurs regardless of the sampling rate.
f. Samples have been stored for up to 4 months with-
out any apparent change.
The charcoal from the sample tubes could not be removed because the
samples were too moist. It was necessary to pass C$2 through the tube
to desorb the sample and thus most likely the more volatile components
were lost. Tenax is readily soluble in carbon disulfide, benzene or
xylene. Therefore if any of these components (espeically the substi-
tuted benzenes) are present, there may be irreversible adsorption. When
the recycle gases were sampled, aerosols were probably present in con-
centrations several orders of magnitude higher than would be found in
an ambient air sample.
RECOMMENDATIONS FOR FUTURE SAMPLING AND ANALYSIS
The following recommendations are designed to complement the data in
order to complete Level 1 assessment of the Paraho Plant* and prepare for
a Level 2 assessment.
1. An on site survey should be made of the facility to review sam-
pling sites and changes that have been made since the previous
testing program. This should be done before the plant is in
operation to make suggested modifications in sampling ports.
These modifications include:
a. Changing sampling outlets on the recycle gas system to
allow for probe insertion.
b. Installing door-type access to the retorted shale conveyor
system at a point as close to the actual retort outlet as
possible.
Ibid, plO; also, Technical Manual for Process Sampling Strategies For
Organic Materials, EPA-600/2-76-122, April 1976.
43
-------
2. A gas chromatograph/Integrator with appropriate detectors should
be used to quantitatively measure the inorganic and low molecular
weight organic gases of interest in the field. On-site gas
chromatography permits evaluation of the sampling methods and re-
duces the possibility of sample degradation which may occur during
transportation to the laboratory. When the chromatograph is fitted
with a thermal desorption inlet, evaluation of the trapping ef-
ficiency of organics on polymers such as Tenax is possible.
3. Organic compounds extracted from Tenax, solid samples or liquid
condensates should be separated by liquid chromatography into the
fractions shown in Table 15 for subsequent analysis by infra-red
spectrometry and mass spectrometry or combined gas chromatography/
mass spectrometry. Gel permeation chromatography and high pressure
liquid chromatography are useful separatory methods which provide
fractions separated on the basis of molecular weight and functional
group.
4. Particulate sample collection should be expanded to include bag-
house inlet-outlet air streams, using highly sensitive membrane
filter/electron microscopy methods. In addition, each hi-vol
sampler location should include paper type sampler, membrane
filter assembly and gaseous adsorption tube samplers. Backup
particle sizing using gravimetric methods would be useful for ver-
ification.
5. Complete Level 1 analysis includes performance of biological
screening tests in accordance with the EPA Office of Health and
Ecological Effects recommended procedures. Such testing is designed
to determine potential health hazards by measuring toxicity, muta-
gem'city and LD50.
6. The scope of future test work should include particulate and
gaseous sample collection in the vicinity of mining operations,
and retorted shale handling and disposal areas. Upwind-downwind
particulate collection away from the immediate process areas
should also be scheduled. Raw shale feed samples should be col-
lected for analysis in conjunction with plant operation schedules
and retorted shale sampling.
44
-------
TABLE 15. CLASSES OF ORGANIC COMPOUNDS ELUTING IN EACH LIQUID
CHROMATOGRAPHY"FRACTION
Fraction
1
2
Compound Type
Aliphatic hydrocarbons
Aromatic hydrocarbons
POM
PCB
Hal ides
Esters
Ethers
Nitro compounds
Expoxides
Phenols
Esters
Ketones
Aldehydes
Phthalates
Phenols
Alcohols
Phthalates
Amines
Ami des
Sulfonates
Aliphatic acids
Carboxylic acid salts
Sulfonates
Sulfoxides
Sulfonic acids
Sulfonic acids
Solvent
60/80 petroleum ether
20% methylene chloride
in 60/80 petroleum ether
50% methylene chloride
in 60/80 petroleum ether
methylene chloride
5% methyl alcohol in
methylene chloride
20% methyl alcohol in
methylene chloride
50% methyl alcohol in
methylene chloride
methyl alcohol
45
-------
APPENDIX A
ABSORPTION TRAIN SAMPLING AND ANALYSIS METHODS
ARSINE (AsH3)
The gas sample was drawn through four impingers in series in an ice
bath. The first itnpinger was packed with glass wool impregnated with lead
acetate solution to remove h^S. The second and third impingers contained
decinormal NaOH. The fourth impinger contained silica gel.
The pilot plant recycle gas was sampled with the first impinger packed
with glass wool impregnated with lead acetate. The second and third im-
pingers contained 25 ml of 0.1 N NaOH. The last impinger contained 20 g of
silica gel. The sampling rates for the first and second tests were 0.39
liter per minute and 0.35 liter per minute, respectively.
Reference: Furman, H. Howell, Scott's Standard Methods of Chemical Analysis,
6th Ed., Princeton, 1962, p. 137.
HYDROGEN SULFIDE
Sample gas was drawn through four midget impingers in series, held in
an ice bath. The first two impingers contained alkaline CdCl2 solution (20g
CdCl2, dissolved in 900 ml of water to which was added 20 ml of 0.5 N sod-
ium hydroxide solution). The third impinger was left dry to catch carryover
droplets, and the last impinger contained silica gel.
In sampling the pilot plant recycle gas midget impingers were used.
The first two impingers each contained 20 ml of absorbing solution, the third
impinger was dry, and the fourth impinger contained 20 g of silica gel.
Samples of the pilot plant recycle gas were taken over a one hour period
at a sample flow rate of 0.4 liter per minute.
Reference: Air Pollution Control District, County of Los Angeles, Air
Pollution Source Testing Manual, 1963, pp. 87-88.
CARBONYL SULFIDE (COS)
The pilot plant recycle gas was sampled with a set of four impingers
in series kept in an ice bath. The first impinger contained glass wool im-
gnated with lead acetate, the second impinger contained 20 ml of 7.5%
2 with 1% ammonium hydroxide to capture COS, and the third contained 20
»f alcoholic KOH to collect C$2- The last impinger contained silica gel.
46
-------
Sampling was done for a twenty minute period at a sampling rate of 0.22
liter.
Reference: Jacobs, Morris B., The Chemical Analysis of Air Pollutants,
New York, 1960, p. 192.
SULFUR DIOXIDE (S02) AND NITROGEN DIOXIDE (N02)
Reference: U.S. Environmental Protection Agency, Standards of Performance
for New Stationary Sources, Federal REgister, Vol. 36, No. 247,
Part. 60.85.
AMMONIA (NH3)
Sample gas was drawn through four impingers in series, held in an ice
bath. The first impinger contained distilled water. The second impinger
contained 5% HC1 solution. The third impinger was left empty to collect
carry over droplets. The fourth impinger contained silica gel.
In sampling the semi-works recycle gas midget impingers were used con-
taining 25 ml each of distilled water and 5% HC1 in the first and second
impingers, respectively. The last impinger contained 20 g of silica gel.
The sampling rate was .2 liter per minute, and the test was run for one
hour.
The pilot plant recycle gas test was run with midget impingers in the
same way that the semi-works recycle gas test was done. The sampling rate
was- 1.27 liters per minute during the first test and 0.66 liter per minute^
during the second test.
Reference: Air Pollution Control District, County of Los Angeles, Source
Testing Manual, 5th Ed., (1972), sec. 5.4.1.
47
-------
TABLE A-l. GAS ABSORPTION SAMPLE DATA DISPERSION ANALYSIS
Test No.
NH3-SW-1
NH3-SW-2
N02-SW-4
N02-SW-5
N02--SW-6
N02-l
N02-2
N02-3
N02-4
N02-5
N02-6
Measured Value
(ppmv)
25,945
27,642
30
37
49
9
9
9
9
14
18
Arithmetic
Mean
25066
39
11
Difference
879
2576
-9
7
10
-2
-2
-2
-2
3
7
Standard Student's
Deviation "t"
5936 0.3
0.9
9 1.7
0.4
1.9
3.5 1.4
1.4
1.4
1.4
2.1
(x + 20) 4.9
Level of
Significance
0.75
0.55
0.20
0.75
0.15
0.2
0.2
0.2
0.2
0.07
0.003
-p.
oo
-------
TABLE A-2. GAS ABSORPTION SAMPLES - SYSTEMATIC ERRORS IN ANALYSIS
Test #
NH3-SW1
NH3-SW-2
NH3-1
NH3-2
NOx-SW-4
NOx-SW-5
NOx-SW-6
NOX-1
NOx-2
NOx-3
NOx-4
NOx-5
NOx-6
Analytical Accuracy
(± mg)
± 6.6 mg
± 8.6 mg
± 2.3 mg
± 4.9 mg
.003
.003
.004
.001
.001
.001
.001
.001
.001
Volume of Gas Samples
(ft3)
0.409
0.419
2.178
1.121
0.053
0.048
0.052
0.05
0.05
0.048
0.044
0.046
0.038
(± ppmv)
790
1005
52
214
1
1
1.5
0.3
0.3
0.3
0.3
0.4
0.5
Test Accuracy
(% of measured value)
3
3.6
3.2
7.8
3
3
3
3
3
3
3
3
3
49
-------
APPENDIX B
LABORATORY ANALYSIS METHODLOGY AND DATA
ANALYTICAL SCHEMES
The analytical schemes for gaseous, water, and solid samples are
Illustrated 1n Figures Bl through B-6.
Detailed descriptions of these analytical methods are continued
1n a separate report, Volume II.
TENAX»
ABSORPTION
MSA
CHARCOAL
ABSORPTION
BENDIX
DIRECT READING
GASTEC TUBES
LINGER
SOLUTIONS
WET 0€M,
ANALYSIS
CON DEN SATE
(COLD)
CONDE
(HOT)
CONDE
TA
I
AQUEOUS
PHASE
MASS
SPECTROSCOPY
H. P. L.C.
FLUORESCENCE
U. V.
ORGANIC CARBON
TOTAL CARBON
ANALYSIS
NOT USED DUE TO THE PRESENCE OF AEROSOL
Figure B-l. Analytical schematic for recycle gas stream.
-------
Process
Water
Bondapak
Absorption
of
Organics
H.P.L.C.
Phase Separation
(from product oil)
Solvent
Extraction
Pre-separatory*
(Silica)
T.L.C.
Acidification
to
pH=2
Organic
Extraction
Aqueous
Phase
Spark Source
Mass Spec.
Acid, Base
and Neutral
Organic
Extraction
Headspace
(Nitrogen stripping)
1
Tenax
Absorption
_L
Flasher
*See T.L.Co Analytical Scheme Figure
Fiaure B-2. Separation and analysis scheme for water samples,
-------
Neutrals - 1
Acids
Bases
Aqueous Sample
adjusted to pH7
I
Extract with methylene chloride.
Combine extracts, concentrate by
roto-evaporation, transfer to
weighted vial and dry under N£
stream.
I. Extract with Benzene
Combine, concentrate, transfer,
dry and weigh.
Adjust to pH 1 with
1:1 HC1
I
1. Extract with methylene chloride.
Combine, concentrate, transfer,
dry and weigh.
2. Extract with Benzene
Combine, concentrate, transfer,
dry and weigh.
Adjust to pH 12 with
IN NaOH
1. Extract with methylene chloride.
Combine, concentrate, transfer,
dry and weigh.
2. Extract with Benzene
Combine, concentrate, transfer,
dry and weigh.
Figure B-l. Flow diagram for extraction of organics from aqueous
phase of recycled gas condensates.
52
-------
DesulfunzecT
Benzene
Solubles
Preseparatory
Silica
One Dimensional
TLC
Polynuclear aromatic
Hydrocarbon (PAH) [
Bands
Dry*
Weights
Second Silica
Preseparation
Drying Under
Purified N Stream
Cyclohexane
Methanol
Solubles
(PAH)
Analytical Mixed Thin
Layer Two Dimensional
TLC
Benzene Elution
of PAH Spots
Identification and
Quantification by
Spectrophotofluorometrie
Analysis (SPF)
Figure B-4. Thin layer chronatographic (T.L.C.) analytical
scheme.
*Denotes point at which reported preseparatory dry weights were taken
53
-------
RETORTED SHALE
a
HI-VOL AIR PARTICIPATES
SPARK SOURCE
MASS SPEC.
SOLVENT
EXTRACTION
C.H.O.N.S,
ASH AND SIEVE
ANALYSIS
WATER EXTRACTION
(LEACHATE)»
DESULFURIZATION
en
-p.
T. L.C.*»
FLASHER*
(VOLATILES)
H.P. L. C.
FLUORESCENCE
U. V.
GAS
CHROMATOGRAPHY
SPECTROPHOTO-
FLUOROMETRIC
ANALYSIS
MASS
SPECTROSCOPY
* NOT PERFORMED ON AIR PARTICULATES .
« * SEE T.L.C. ANALYTICAL SCHEME FIGURE
Figure B-5. Analysis schematic for retorted shale and high-vol air
particulates.
-------
NUCLEOPORE
AND
MILLIPORE
MEMBRANE
FILTERS
en
en
FILTER
SOLUBILIZATION
CARBON
PLANCHETTE
(MILLIPORE ONLY]
SCANNING
ELECTRON
MICROSCOPE
S. E.M.
PARTICLES > O.l
TRANSMISSION
ELECTRON
MICROSCOPE
T. E.M.
PARTICLES < O.ljj
X- RAY
FLUORESCENCE
ANALYSIS
COLLECTION
LOCATION
COLLECTION
TECHNIQUE
1 L1TER/MIN. FLOW RATE
0.2p TO 5.On PORE SIZE
E.M. PREPARATION
STATISTICAL
ANALYSIS OF
PARTICLE SIZE
MORPHOLOGY
AND ELEMENTAL
ANALYSIS
r1aure B-6, Collection & analysis schematic for low-vol air participates
-------
WATER ANALYSIS METHODOLOGY FOR INORGANICS AND GROSS PARAMETERS
Parameter Method of Analysis
Cations
Calcium
Magnesium
Sodium
Potassium
Ammonium
Anions
Carbonates
Bicarbonates
Sulfates
Sulfide
Chloride
Fluoride
Nitrate
Nitrite
Nutrients
NH--N
TKR
Phosphates
Gross Parameters
BOD
COD
TOC
TIC
Oil & Grease
Solids, Total
Solids, upon
evaporation
Solids,
suspended
Total
Alkalinity
Hardness
Phenols
pH
Standard methods* - permanganate titrimetric method
Standard methods - gravimetric method
Atomic absorption spectrophotometric method
Atomic absorption spectrophotometric method
Computed value based on NH^-N determination and
equilibrium constant and pH
Computed value based on total inorganic carbon (TIC)
determination and second equilibrium constant
Computed value based on TIC determination and second
equilibrium constant
Standard methods - gravimetric method with ignition
of residues
Standard methods - methylene blue color matching
method
Specific ion electrode
EPA manual** - automated complexone method
EPA manual - brucine sulfate method
Standard method - diazotization and photometric method
EPA manual - distillation and titrimetric method
EPA manual - digestion automated phenol ate method
EPA manual - digestion and stannous chloride method
Standard methods - incubation and modified winkler
method
Standard
Standard
Standard
Standard
Standard methods - evaporation at 103UC
methods - dichromate digestion method
methods - combustion-infrared method
methods - combustion-infrared method
methods - hexane extraction
Standard methods - filtration and evaporation at 103°C
Standard methods - drying of filter at 103°C
Standard
Standard
Mg cone.
Standard
pH meter
methods - titrimetric
methods - calculated value based on Ca and
method - distillation and photometric
- instrumental method
^Standard Methods for the Examination of Water and Wastewater, American
Public Health Assn., Washington, D.C.: 13th Ed., 1971.
**Methods for Chemical Analysis of Water and Waste, EPA 625-6-74-003.
56
-------
Theoretical Computation of Concentrations of Bicarbonates (HC03~), Carbonates
(C03=) and Ammonium Ions for Condensate Samples
Bicarbonates and Carbonates
K2 = 4.7 x 10"11
Total Inorganic Carbon (TIC) = 9800 mg/1 =817 millimoles
Assume 0.1M ionic strength activity coefficient yC03~ = 0.38
YHC03" = 0.77
(H+)(C03=)
(HC03~)
yH+ YCO.,
•j
YHC03"
(co?=)
HI
ui 1 1
(HC03~)
YC03=
yHC03-
K0 = conditional constant =
yHCO,
-11
= 9.5 x 10
CT = CH2C03 + CHC03" + CC03=
Since pH of wastewaters are around 9, the only significant ions are
HC03" and C03~
.'. CT = (HC03") + (C03=)
Let x = (HC03~)
. K2
- x
'• TH4T aH+
(HC03")
(i) for pilot plant (at pH = 9.8, aH+ = 1.58 x 10
,-11
-10
.. x =
9.5 x 10
1.58 x 10
817
1.594
817 x
x
= 512 Millimoles of HC03 or 31,265 mg/1
(C03 ) = 817 - 512 = 305 Millimoles or 30,500 mg/1
57
-------
( (ii) for semi-works plant (at pH - 9.5, aH+ = 3.16 x 10" )
CT = 1600 mg/1 = 133.3 Millimoles
9.5 x IP"11
^10
133.3 - x
3.16 x 10
x = [HCO,"] = 1?3:3 = 103 Millimoles or 6280 mg/1
o I • o
[C03=J = 30.3 Millimoles or 3030 mg/1
Ammonium Ions
-5
KNH3 = 1-8x10
Total Ammonia = CT 19,400 mg/1 = 1141 Millimoles
CT = 29,600 mg/1 = 1741 Millimoles
'2
Assume 0.1M ionic strength activity coefficient YNH3 = 1
NH3
(NH +)
(NHJ
(NH,
aOH"
YNH,
YNH4+ = 0.75
-5
" NH3
= 2.4 x 10
CT = (NH3) + (NH4+)
(NH/)
aOH"
YNH
yNH,
YNH
3_ , r""3 1.8 x IP"5 x 1
+ NNHo MU +
3 YNH,,
0.75
- x
aON
where x = (NH.J
(1) for pilot plant (at pH = 9.8, OH" = 6.31 x 10"5
,-5
. 2.4 x 10
1141 - x
.. x =
6.31 x 10
1141
-5
= 827 Mi
x
4,060 mg/1 = (NH3)
(NH4+) = 314 Millimoles or 5650 mg/1
58
-------
(ii) for semi-works plant (at pH 9.5, aOH" = 3.16 x 10"
. 2.4 x IP"5 = 1741 - x
3.16 x 10"5 X
x = = 989 Millimoles or 16,800 mg/1 NH~
I . /b °
(NH4+) = 752 Millimoles NH4+ or 13,540 mg/1
REPRESENTATIVE INSTRUMENT TRACES
Figure B7 - HPLC Chromatogram of Pilot Plant Cold Condensate
Figure B8 - Fluorescent Spectrum of BaP Spot for Two Dimension TLC
(refer to Figure 10)
Figure B9 - X-ray Fluorescence Spectrum of Raw Shale Parti cul ate
Figure BIO - Scanning Electron Micrograph of Air Particulate
59
-------
COLUMN HP.IC. ;. Ut.«lh.L.ff.e.te.r... Dia...l.,.6...n™..
Coating pc I; nid cc v 1 s i 1 n ne (0nln
Support Mesh
TEMP: Col: IniL °C final °C
Rale °C./min. Det °C Inj. °C
CARRIER 7OZMoOl1, 30ZI1 , Rale 1.0 „,../„,;„.
Pressures: Inlet Outlet
! Hydrogen ml./min. Air ml./min.
: DETECTOR: yy.,..J.l ; ma »olti
Scavenger , Rate ml./min.
Sens R«. range mv.
! SAMPLE ...RG-.?.,. t!i.r.ougli...Bondnpak
SoUenl £!!.2?. J..2. Concn,
: I , I
I : II-
r
i
i
i
i .
i
i
Fijure B-7.
HPLC chromatogram of bondapak adsorbed material from
pilot plant recycled gas condensate (cold) sample RG-9.
60
-------
cr>
too
90;-
SAMPLE: CSA VII (1)
SOLVENT: Benzene
CONG mg/mi 20 ng/ml
SPECT^LIM: L565K,Spot 1
MONOCHROMATOR
EXCITATION MONO
ENTRA.'iCE: 1
EXIT: 1
SLIT SLIDE:
SLIT WIDTHS mm
EMISSION MONO
ENTRANCE: 1
EXIT: 1
SLIT SLICE:
MULTIPLIER:
SENSi'TiVrY:
LAMP:
PM T'o2E' 7.5 C
or % FULL SCALE:
CELL TEWP.'C:
HIGH VOLT .
-------
en
PO
Figure B-9. Typical x-ray fluorescence spectrum of an
unretorted shale air particulate particle.
-------
Figure b-10. Typical scanning electron
micrograph of retorted
shale air participate,,
-------
APPENDIX C
SUMMARY OF COLLECTED SAMPLES
Sample Type Sampling Location
A. Gas Sampling Trains
Absorption Solution Semi works recycle
gas (suction side)
Absorption Solution Pilot plant recycle
gas (suction side)
n
"
n .
n n
Absorption Solution Semi works recycle
gas (suction side)
n n
Absorption Solution Pilot plant recycle
gas (suction side)
„
,
B. Cascade Impaction Plates
Impaction Plates Primary Crusher
Date
3-15-76
3-11-76
3-10-76
3-12-76
3-12-76
3-12-76
3-11-76
3-15-76
3-14-76
3-9-76
3-9-76
3-10-76
3-17-76
Time
12pm, 4pm
9am, 11 am
2pm
9am, 2pm
4pm
4pm
2pm, 4pm
5-5: 30pm
3pm,4:30prr
l:30pm~
3:45pm
2pm, 3pm
9am, 11 am
2pm
Test to be Performed
Kjeldahl distillation,
titration
Colorimetric
Kjeldahl distillation,
titration
Kjeldahl distillation,
titration
Titration
Colorimetric
Barium perch 1 orate
titration
Colorimetric
Gravimetric
Analysis
NH.,
j
Arsine
HCN
cs2
COS
NH3
NOX
so2
NO
S09
C-
H2S
en
-------
en
Sample
Number Sample Type
C. High Vol Filters
18 High Vol
Filter
2
22
27
32
17
12
23
28
33
16
13
24
29
34
Location
Primary crusher building S.W.
of crusher
i
11
Secondary crusher bldg. on
balcony at south end of bldg.
i
ii
M
Bins and weigh house lower level
on output end
Date
3-15-76
3-16-76
3-16-76
3-17-76
3-17-76
3-15-76
3-16-76
3-16-76
3-17-76
3-17-76
3-15-76
3-16-76
3-16-76
3-17-76
3-17-76
Time
0815 to
0830 (3-16)
0830-1635
1635 to
0915 (3-17)
0915-1530
1535 to
0830 (3-18)
0810 to
0835 (3-16)
0835-1645
1645 to
0920 (3-17)
0920-1535
1540 to
0835 (3-18)
0805 to
0845 (3-16)
1000-1645
1645 to
0930 (3-17)
0930-1530
1545 to
0840 (3-18)
Notes/Types of Analysis
*
*
*
*
*
Organic extraction &
elemental analysis
Organic extraction
*
Organic extraction
Sample ruined in
handling
Organic extraction and
x-ray fluorescence
analysis
Organic extraction
ii
II
-------
Sample
Number Sample Type
D. Low Vol Filters
M2 5 Millipore
Filter, 1 min
M4 5 Millipore
Filter, 2 min.
M7 5 Millipore
Filter, 5 min.
M5 5 Millipore
Filter, 10 min.
N4 0.2 Nucleopore
Filter, 5 min.
N5 0.2 Nucleopore
E. Bulk Samples
CSA VII Retorted Shale
(A) Bulk Sample
2 cans
CSA VII
(B)
Oil Product Oil
(Process 10 gal .
Water)
Location
Bins and weigh house
i
it
M
M
Next to dump chute out of pilot
plant before screen conveyor
(direct mode)
Semi -works (indirect mode)
Date
3-15-76
3-15-76
i
n
n
3-9-76
3-12-76
3-15-76
Time
1000
1005
1010
1025
1400
1410
1000
1000
1500
Notes/Type of Analysis
*
*
*
X-ray fluorescence analysis
*
Used for scanning electron
microscope, X-ray fluorescence
and transission electron
microscope analysis
Combined with CSA VII (B)
for organic extraction, in-
organic (leachate) extraction,
SSMS and elemental analysis
See CSA VII (A) above.
Volatiles analysis - GC-MS
Used for phase separation of
process water from oil. Trace
inorganics by spark source
mass spec. HPLC
GC-MS
-------
Or
Sample
Number Sample Type Location
F. Recycle Gas Stream Absorption Samples
MSA MSA Charcoal Pilot plant recycle gas
1 Tube Absorption
2 1 min.
3
4
5
6
MSA
15 5 min.
16
17
18
MSA " Pilot plant recycle gas blower
7 1 min. output using Teflon condenser
8
9
10
1
MSA
11 i— .
1 5 mm.
12
13
14
Bl Gastec Tube Pilot plant recycle gas blower
CO Type 1H output
B2 C02 Type 2H
B3 HCN Type 12H Pilot plant recycle gas blower
output
Date
3-10-76
3-10-76
3-10-76
3-10-76
3-10-76
3-10-76
Time
1300
1315 to
1345
1345
1400 to
1430
1430
1430
Notes/Type of Analysis
*
MSA 15 GC-MS
11 16 "
MSA 7 GC-MS
MSA 11 GC-MS
Direct indicating gas
analysis tubes used for
backup and/or
verification of other
procedures
Direct indicating gas
analysis tubes used for
backup and/or verifica-
tion of other analytical
procedures
-------
en
oo
Sample
Number Sample Type Location
F. Recycle Gas Stream Absorption Samples
B4 H^S Type 4H Pilot plant recycle gas blower
output
B5 N0-N02 Type 10
B6 NH3 Type 3M
B7 S02 Type 5L
Bendix Bendix Charcoal "
17 Flasher Tube
31 1 min. ea.
32
34
Bendix
4
10
14
21
T9 Tena* Absorption "
T6 Tubes-
T20 1 mfn. ea.
T4
T7
T15 5 min. ea.
T19
T18
Date
3-10-76
H
n
"
n
n
M
n
Time
1445
1445
1445
1445
1515
1530 to
1555
1600
1615 to
1640
Notes/Type of Analysis
Direct indicating gas
analysis tubes used for
backup and/or verifica-
tion of other analytical
procedures
n
1
n
*
Bendix 4 - GC-MS
*
*
-------
en
Sample
Number Sample Type Location
G. Gas Bottle Samples
Gl 250 ml gas Pilot plant recycle gas
G2 bottle (output side of blower)
G3 (triplicate)
H. Recycle Gas Condensate Samples
RG1 Recycle gas Pilot plant (direct mode)
cold recycle gas blower output
condensate
RG2
RG3
RG4
RG9
RG5 Recycle gas Semi -works recycle gas
condensate condensate tank
(hot)
Date
3-10-76
3-10-76
3-11-76
3-10-76
3-15-76
3-16-76
3-15-76
Time
1730
1000 to
1500
0800 to
1400
1700 to
0800
(3-11)
0800 to
1200
0800 to
1200
1000
Notes/Type of Analysis
Gl-GC-MS
Benzene preserved in field;
sent to TRW for analysis
TC - TOC analysis
Acidified to pH2 in fieldj
organics extracted used
for inorganic trace analy-
sis by spark source mass
spectroscopy.
TC - TOC analysis
GC-MS, HPLC and TC - TOC
analysis.
Benzene extracted in field.
Acidified in field.
indicates sample not used for analysis.
Note: Within any given time slot, gas stream absorption samples
in which they were collected.
SSMS - Spark Source Mass Spectroscopy
GC-MS - Gas Chromatography Couples Mass Spectroscopy
HPLC - High Pressure Liquid Chromatography
TLC - Thin Layer Chromatography
GPC - Gel-Permeation Chromatography
are listed according to the order
-------
Sample
Number
Sample Type
Water sample
Water sample
Location
Semi-Works recycle gas
condensate (hot)
Pilot plant recycle gas
(cold)
Date
3-14-76
3-11-76
Time
0800 to
1800
0800 to
1800
Notes/Type of Analysis
All inorganic and non-
specific
All inorganic and non-
specific
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-78-065
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Sampling and Analysis Research Program
at the Paraho Shale Oil Demonstration
5. REPORT DATE
April 19?8
i s s u ing date
_
6. PERFORMING O R~G AN I ZATION CODE
7. AUTHOR(S)
J. E. Cotter, C. H. Prien, J. J. Schmidt-Collerus,
D. J. Powell, R. Sung, C. Habenicht, and R. E. Presse,
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
TRW Environmental Engineering Division
Redondo Beach, California 90278
Denver Research Institute
Denver, Colorado 80210
10. PROGRAM ELEMENT NO.
EHE 624B
11. CONTRACT/GRANT NO.
68-02-1881
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory-Cin. , OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Final Report 1/76-7/77
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
^.ABSTRACT A sampling and analysis research program was conducted at the Paraho oil
shale retorting demonstration site at Anvil Points, Colorado. The overall objective
of the test program was to obtain preliminary quantitative and qualitative measure-
ments of air, water, and solid compositions, and to gain experience that would lead
to improved sampling procedures and the determination of priorities for sampling and
analysis of shale oil recovery operations. Selection of sample locations was based
on need for information on process streams relative to emissions and effluents
expected in a full-scale plant.
Samples taken included the recycle gases (F^S, S02, NOX, NH3, and trace
organics), recycle condensate, product oil/water, processed shale discharged from the
retorts, and dust in the vicinity of crushing, screening, and conveying equipment. A
variety of laboratory analysis methods were used, including wet chemical analysis,
spark source mass spectrometry, high pressure liquid chromatography, thin layer
chromatography, gel permeation chromatography, and gas chromatography/mass spec-
trometry methods (GC/MS). Condensate water inorganic analyses were done for calcium,
magnesium, sodium and potassium salts, ammonia, gross parameters, and trace elements.
Condensate and product water samples were also analyzed for organic neutrals (partic-
ularly aromatics), organic acids, and organic bases. Elemental determinations of both
retorted shale and raw shale particulates were made.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Oil shale
Chemical Engineering
Shale Oil
Roasting
Combustion Control
b.IDENTIFIERS/OPEN ENDED TERMS
Plant equipment
Apparatus
Techniques
Unit Operations
Processing
Organic properties
hemical thermodynamics
o I oraao, Retorting
c. COSATI Field/Group
99A
8. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (This page)
Unclassi fied
22. PRICE
EPA Form 2220-1 (9-73)
71
.", U. S GOVERNMENT PRINTING OFFICf. 1978-757-140/6846 Region No. 5-||
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