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P<3 W-f97
ASSESSMENT OF OIL SHALE RETORT WASTEWATER TREATMENT
AND CONTROL TECHNOLOGY: PHASES I AND II
J. R. Klieve, G. D. Rawlings, and J. R. Hoeflein
Monsanto Research Corporation
Dayton, Ohio 45407
Final. Report
Contract No. 68-03-2801
March 1981
Project Officer
W. w. Liberick, Jr.
Energy Pollution Control Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45213
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
. CINCINNATI, OHIO 45268
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DISCLAIMER
This document is a preliminary draft. It has not been formally
released by the U.S. Environmental Protection Agency and should
not be construed to represent Agency policy. It is being
circulated for comments on its technical merit and policy,
implications.
ii
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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 pollution 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 must be character-
ized prior to commercialization so that pollution control needs
are identified and control methods can be integrated with process
designs. Shale oil recovery processes are expected to have some
unique air, water, and solid waste control requirements. This
document briefly- reviews oil shale retorting technologies,
summarizes anticipated characteristics of wastewater streams,
discusses concluded and ongoing research activities in the area
of retort wastewater treatability, identifies research needs,
and recommends a program to fill those needs.
Further information on the environmental aspects of shale oil
processing can be obtained from the lERL-Ci Fuels Technology
Branch.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
111
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CONTENTS
Foreword iii
Figures vi
Tables ...... viii
1. Introduction 1
2 . Summary . • : 3
3. Wastewater Characterization. ............... 6
4. Treatment of Oil Shale Wastewaters 16
Introduction 16
Mine Water . . . 16
Retort Water 19
Gas Condensate 27
Leachate 27
Discussion . . ......... 27
References ........' 33
Appendix A. Oil Shale Retorting Processes . . 39
v
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FIGURES ;
Number , Page
1 Classification of retorting process ...... I. . 7
2 Mine water treatment steps and reuse potential, i. . 12
3 Retort wastewater treatment steps and reuse
potential ....... 13
4 Gas condensate wastewater treatment steps and
reuse potential . . 14
5 Leachate treatment steps and reuse potential. .. ,. . 15
6 Mine water treatability options .......... 28
7 Retort wastewater treatability options. ...... 29
8 Gas condensate wastewater treatability options. . . 30
A-l Schematic, of Paraho direct mode gas combustion
retorting process .. . 40
A-2 Schematic of Paraho indirect mode hot inert
gas retorting ....!..• 41
A-3 The Paraho retort ........ 44
A-4 Major water streams for Paraho direct heated
process producing 15,900 m3/day "(99/170 BPSD)
crude shale oil 46
A-5 Schematic of the TOSCO II Retorting Process .... 51
A-6 Major water streams for TOSCO II process producing
7,500 ms/day (47,000 BPSD) of upgraded shale oil,
and 680 m3/day (4,300; BPSD) LPG . 55
A-7 Schematic diagram of Superior's commercial
circular grate retort (direct-heated mode). .'•... 60
A-8 Functional Design of Superior retort 60
A-9 Cross sectional view of Superior retort ....... 61
A-10 Overall water requirements for Superior's
100,000 BPD plant . . 62
A-ll Flow diagram for Union B retorting process. . . ;. . 63
A-12 Lurgi-Ruhrgas retorting process .......... 66
A-13 Schematic of the Occidental modified in-situ i
process . 68
vi
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FIGURES (continued)
Number
A-^14 Flame front movement in the Occidental modified
in-situ process ...... 69
A--15 Flow diagram of proposed commercial operation
on tract C-b, 71
A-16 Major water streams for modified in-situ shale
oil plant producing 9,000 ms/day (57,000 bbl/day)
crude shale oil • 74
A-17 Modified sublevel caving mining technique
proposed for use in the RISE process. ...... 75
A-18 Water flow - commercial phase '- GPM . . . . , . . . 77
A-19 Major water streams for modified in-situ Lurgi-
Ruhrgas shale oil plant producing 81,000 bbl/day
crude shale oil. Minewater rate of 7,656 gpm
from MIS scheme with no surface retorting .... 79
A-20 Flow diagram for Equity's BX In-Situ Oil :
Shale Project 81
A-21 Sectional view of Geokinetics horizontal in-situ
oil shale retort. 86
VI1
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TABLES
Number
Page
1 Maximum Observed Concentration of Major Con-
stituents in Oil Shale Wastewater Streams .... 9
2 Status of Research Studies Focusing on the
Treatability of Retort Water 20
A-l Characterization of Source Water Streams -
Paraho Process 47
A-2 Characteristics of Wastewater Streams -
Paraho Process. 48
A-3 Characteristics of Other Wastewater Streams -
Paraho Process. . . . < 50
A-4 Characteristics of Treated Wastewater Streams -
Paraho Process. . 51
A-5 Characteristics of Source Waters - Tosco Process. . 56
A-6 Characteristics of Wastewaters - Tosco Process. . . 57
A-7 Characteristics of Treated Wastewater and Spent
Shale Leachate - Tosco Process. 58
A-8 Characteristics of Various Water Streams in the
Union B Process . . „.„... 66
A-9 Properties of Lurgi-Ruhrgas Gas Condensate
Wastewater. 67
A-10 Characteristics of Wastewaters -
Occidental Process. . 73
A-ll Characteristics of Wastewater - Rise Process. . :. . 78
A-12 Summary of Equity Process Wastewater Component
Concentrations. 82
A-13 10-Ton Retort Water Analyses on Antrim Shales . . . 84
A-14 Trace Element Composition for Michigan Shale
Wastewater ., . 85
A-15 Characteristics of Wastewaters - Geokinetics. . ;. . 88
A-16 Trace Metals in Geokinetics' Wastewaters. ...;.. 89
A-17 Organic Priority Pollutants in Geokinetics
Wastewaters ;. . 90
A-18; Detection Limits for Organic Priority Pollutants. . 91
viii
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SECTION 1
INTRODUCTION
Oil shale has been recognized as a potentially substantial energy
resource in the United States for more than 100 years.; Recently,
increasing dependence on foreign oil supplies with rapidly escal-
ating prices has provided new incentive for shale oil recovery
from deposits in Colorado, Michigan, Utah, and Wyoming. As a
result, a number of domestic companies have completed preliminary
process research and development and are now seeking necessary
governmental approvals to practice commercial-scale oil shale
retorting.
Despite the benefits of oil shale processing as an alternative
energy source, its water effluent, air emissions, and solid
wastes could have an adverse impact on the environment if dis-
charged untreated. Consequently, pollution control methods
capable of adequately controlling environmentally harmful dis-
charges must be available to assure the oil shale industry's
compliance with future standards and to avoid potential problems
in retrofitting full-scale plants with the necessary technologies.
Prior studies by the U.S. Department of Energy, the U.S. Environ-
mental Protection Agency, and industry, have provided some charac-
terization of the environmental effects of this developing
technology. However, specific pollution control needs have not
been adequately addressed.
The objectives of this 36-month, five-phased study, which began
in May 1979, are:
(1) To summarize known information concerning oil shale retort
wastewater sources and characteristics;
(2) To identify potentially applicable control technologies
capable of treating the identified wastewater streams;
(3) To design operational pilot-plant facilities to evaluate the
selected technologies;
(4) To construct the pilot-plant facilities; and
(5) To operate the facilities for one year at three oil shale
retorts.
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The results of Phases I and II, ;which were completed as of February
1980 and are presented in this report, consist of:
(1) A survey of pertinent characteristics of oil shale retorting
processes and water effluents for use in selecting
potentially applicable treatment technologies; :
(2) A survey of concluded and ongoing research activities in the
area of oil shale retort wastewater treatability; and
(3) Identification of research needs and a recommended research
program to meet those needs. >
I
The report concludes with the recommendation that additional
bench-scale testing be conducted prior to the selection of an
optimum wastewater treatment system and the design of pilot scale
testing equipment. Section 3 provides a brief overview of oil
shale retorting, summarizes known oil shale wastewater character-
istics, and summarizes anticipated water use plans of industry and
government contractors outside of industry. Section 4 provides
descriptions of known research activities in the area of oil
shale wastewater treatability, identifies research needs,: and
recommends a program to meet those needs. Brief descriptions of
oil shale retorting processes and known wastewater characteristics
associated with each process are presented in the Appendix.
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SECTION 2
SUMMARY
Oil shale retorting is a synthetic fuel production technology on
the verge of commercialization in the United States. In order to
ensure that the emerging oil shale industry will have minimal
adverse effects upon surface and/or ground water where recover-
able reserves of oil shale are found, demonstrated technologies
to upgrade oil shale wastewaters must be available to developers.
To this end, the U.S. Environmental Protection Agency'has con-
tracted with Monsanto Research Corporation to conduct a three-
year, five-phased study to: 1) summarize known information
concerning oil shale retort wastewater sources and character-
istics; 2) identify potentially applicable control technologies
capable of treating the identified wastewater streams; and
3) design, construct, and operate pilot-plant facilities to
evaluate the selected technologies. This report presents results
of Phases I and II, in which literature and other information
sources were surveyed to obtain relevant data about oil shale
retorting technologies, wastewater sources and characteristics,
potential wastewater uses, and potentially applicable treatment
technologies. As a result of the study, data gaps were identi-
fied, and recommendations for bench-scale treatability studies
were made.
Xrt-Situ retorting, which consists of heating shale underground
after modification of the permeability of the rock formation, is
being investigated by Dow Chemical Co., Equity Oil Co.,
Geokinetics, Inc., Occidental Oil Shale, Inc., and Rio Blanco Oil
Shale Co., all of which are now conducting process development
efforts. Processes being developed by Paraho Development Corp.,
Superior Oil Co., TOSCO Corp., and Union Oil Co. are classified
as surface retorting, in which mined, crushed shale is heated in
aboveground metal vessels to produce crude oil. Although many
process variations exist within the two major retorting process
categories, in-situ and surface, distinct wastewater streams are
common to most processes within each category. From in-situ
retorting, three major streams emanate: mine water, retort
water, and gas condensate. Mine water is that water pumped from
a shale formation prior to ignition. Retort water is formed when
water vapor condenses in cool, rubblized shale ahead of the flame
front during retorting. Gas condensate is that water which
leaves the retort as a gas and is recovered when gas from the
in~situ retort is cooled.
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From surface retorting, three major streams are envisioned: gas
condensate, product water, and spent shale pile leachate. Water
normally leaves the surface retort in the vapor phase and is
recovered as gas condensate when the retort gas is cooled prior
to purification. In addition, water separates from the product
oil following oil/gas separation and is termed product water.
Since spent shale from surface retorting is expected to be dis-
posed of above ground, leachate through the shale pile is another
potential wastewater stream, though the existence of this stream
is open to question.
Mine water has been found to exhibit high levels of alkalinity,
chemical oxygen demand (GOD), chloride, fluoride, sulfate,, boron
and sodium. Existence of trace metals are of particular concern
since some mine water will most likely be discharged to the
environment. . . ;
Retort wastewater and product wastewater contain high levels of
most pollutants identified. Gas condensate wastewaters exhibit
high levels of ammonia, alkalinity, and organics; however, concen-
trations of trace metals are significantly lower in gas cbndensate
than in retort wastewater. Limited data are available to, char-
acterize leachate; however, high levels of organics, total dis-
solved solids (TDS), sulfate and sodium have been exhibited.
Water use schemes developed by industry and government contractors
have been reviewed. Most water use schemes suggest use of waste-
water within the retorting facility; however, there appears to be
little technical information to support this approach. Available
information relating to the treatability of individual retort
streams were summarized and significant data were only for the
treatability of mine water and- combined retort/product water.
In the case of mine water, activated alumina absorption, precipi-
tation with phosphoric acid and lime, and ion exchange have been
demonstrated in bench-scale screening tests to be able to remove
fluoride and/or boron. It is suggested that additional technol-
ogies be used for dissolved gas removal, suspended solids removal,
TDS removal, and disinfection particularly if the water is
discharged or used for potable needs.
Many research studies have focused on the treatment of retort/
product water. There remain, howeyer, key technical questions in
the area of emulsified oil separation and organics removal.
Steam stripping has been identified as a promising technology for
dissolved gases removal. Granular activated carbon and polymeric
resins have been demonstrated for gross organics removal; however,
for cost considerations it is recommended that aerobic biological
treatment be focused on for gross organics removal, with carbon
and polymeric resins used to remove refractory organics.
4
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No research activity in the area of gas condensate treatment was
identified; however, steam stripping should adequately treat gas
condensate for in-^plant use.
In the case of leachate, it is recommended that funds be used to
identify leachate as a major wastewater stream and characterize
it, rather than investigate treatment alternatives. If leachate
is found to be a significant wastewater stream, serious questions
regarding leachate collection arise.
In summary, several technical questions regarding oil shale
wastewater treatability exist and should be answered prior to
pilot-scale testing. Four sources of mine water, retort water
and/or gas condensate for immediate use in bench-scale testing
were also identified.
This report was submitted in partial fulfillment of Contract No.
6S-03-2801 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. This report
covers the period May 1979 to March 1980; work was completed as
of February 1980.
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SECTION 3
WASTEWATER CHARACTERIZATION
In order to select appropriate strategies for treating wastewater
discharges from oil shale retorting operations, the sources of
wastewater from these operations must be identified, and char-
acterized, and the potential for in-plant reuse must be invest-
igated. To this end, MRC has conducted an industry-wide 'analysis
based on a search of the open literature, industry contacts, and
private and government research laboratories. Since no commercial-
scale oil shale retort is in operation and no commercial-scale
operations are planned before 1982, the resulting industry anal-
ysis was based on pilot-plant data, industry plans for full-scale
operation, and predictions generated by government contractors
outside of industry. Thus, the fact that the oil shale retorting
industry is emerging, makes the result of the industry analysis no
more than a researched prediction. '
Presented in this section is a brief discussion of the emerging
oil shale industry, expected wastewater sources and characteris-
tics, and a discussion of water use as seen by industry and by
national laboratories and government contractors outside of the
oil shale industry. A more complete analysis of specific retort-
ing technologies on which discussions in this section are based
is presented in Appendix A.
Oil_shale retorting technologies1 can be divided into two cate-
gories: surface retorting and in-situ retorting (see Figure 1)
Surface retorting.involves the mining, crushing, and subsequent'
heating of_oil shale in metal vessels aboveground. In-situ
retorting is a batch operation in which an underground shale
formation is heated in place, often modifying the permeability of
the rock by fracturing and/or partial mining. If the formation
is partially mined before retorting begins, retorting is
referred to as modified in-situ retorting, in surface retorting,
heat to the oil shale can be transferred by either a gas or
solid medium. In addition, combustion for heat production can be
generated within the surface retort or outside of the retort,
Several different sources of wastewater are associated with each
individual retorting technology, and there are several types of
wastewater characteristics for both major retorting types;
surface and in-situ. In the case of surface retortingT water
normally leaves the retort in the vapor phase and is recovered
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OIL SHALE
RETORTING
SURF ACE RETORTING
GAS: SOLID
HEAT TRANSFER
INTERNAL GAS
COMBUSTION
IN-SITU RETORTING
SOLID: SOLID
HE AT TRANSFER
TRUE IN-SITU
MODIFIED IN-SITU
EXTERNAL
HEAT EXCHANGE
TOSCO 11 EQUITY
LURGI-RUHRGAS DOW
GEOKINETICS
'OCCIDENTAL
RISE
PARAHO DIRECT MODE
PARAHO INDIRECT MODE
UNION OIL B
SUPERIOR
Figure 1. Classification of retorting process.
as gas condensate when the retort gas is cooled prior to purifi-
cation. In addition, some water separates from the product oil
following oil/gas separation. Since spent shale from surface
retorting is expected to be disposed of above ground, leachate
from the spent shale piles may be another wastewater stream
unique to surface retorting of shale oil. Thus, the major
categories of wastewaters expected from surface retorting are:
Gas condensate
Water separated from the product oil (product water)
Retort water (Union Oil B process only)
Leachate
If water is encountered during shale excavation for surface re-
toring, a mine water waste stream can also be expected.
In the case of in-situ retorting, water vapor produced in the
retorting zone normally condenses in the oil shale ahead of the
retorting zone, and continues to move through the unretorted
rubblized shale as a liquid. This water is recovered as a
liquid with the product oil and is normally termed retort conden-
sate or retort water. As with surface retorting, some water
remains as a vapor and is recovered as gas condensate when the
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gas recovered from the in-situ retort is cooled. Since in-situ
retorts must be dewatered prior to igniting, in-situ retorting
results in an additional wastewater stream—mine water. Thus,
three major categories of wastewaters are expected from in-situ
retorting:
Retort water . .. •
Mine water \ •
Gas condensate. ,
In order to characterize expected oil shale retorting wastewaters
to the degree necessary to select.potential treatment technol-
ogies, MRC has gathered analytical data, where it exists,1 for
each wastewater stream from each oil shale retorting technology.
As has been noted by other investigators [1] who have analyzed
oil shale wastewaters, interferences often occur when state-of-
the-art techniques are used to analyze certain constituents, e.g.,
chlorides and sulfates, in oil shale wastewaters. Most of the
data listed in Appendix A were obtained via state-of-the-art tech-
niques and these data should be carefully interpreted in accordance
with the analytical method used., The data does serve, however,
to identify major groups of pollutants associated with each oil
shale wastewater and errors in the absolute concentration of the
pollutants; that is, gross pollutants can be identified, but the
absolute concentration may be inaccurate by an order of magnitude.
Based on the literature search, maximum observed concentrations
of major constitutents in each retort wastewater stream are listed
in Table 1. The mine water characterization data listed in
Table 1 is based on data gathered at the retort sites of four
developers: Occidental, Geokinetics, Rio Blanco, and Equity.
For most pollutant categories, data obtained at Geokinetics'
Kamp Kerogen site provided the highest observed concentrations.
As can be seen in Table 1, mine water can potentially exhibit high
levels of alkalinity, COD, chloride, fluoride, sulfate, boron and
sodium, which are of primary concern because, unlike other re-
torting wastewaters, some mine water will most likely be discharged
in some degree to the environment.
Retort water, or water which has: condensed in an in-situ retort,
will most likely be the most difficult wastewater to treat and
will probably not be directly discharged to the environment. As
can be seen in Table 1, retort water contains high levels of
most pollutants identified. Again, recent data obtained by MRC
at Geokinetics' Kamp Kerogen sitfe accounts for the highest
observed pollutant levels in most categories. ;
[1] Fox, J. P., D. S. Farrier, and R. E. Poulson. Chemical
Characterization and Analytical Considerations for an In-
Sztu Oil Shale Process Water. Report LETC/R1/78/7. • Laramie
Energy Technology Center. U.S. Department of Energy,
November 1978.
8 :
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TABLE 1. MAXIMUM OBSERVED CONCENTRATION OF MAJOR CONSTITUENTS
IN OIL SHALE WASTEWATER STREAMS
mg/L ' "
Alkalinity
(as CaC03)
pH
BOD
COD
TOC
TKN
TSS
TDS
Oil and
grease
Phenols
HC03-
cia
CN~
Fl"
N03-
N02-
Fhosphate
Sulfate
Sulfite
Sulfide
Sulfur
NH3
Al"
As
Ba
B
Ca
Cu
Fe
Pb
Li
Mg
Ho
**y
Mo
Ni
Se
si
Na
Sr
Zn
C12
Fla
p
Hardness
MinS,c
water '
25,200
7.7-9.3
ND
6,090
11
5.8
1,970
37,600
3
<1
26,000
2,380
2,200
93
6.2
5
11,100
ND
17
ND
25
ND
<^
^
88
95
<1
13
<2_
43
<1
^^
54
13
10,455
<1
cl
HD
ND
417
Retortd
water5 >1 mg/L.
cPrimary wastewater stream in in-situ retorting.
dAg, Be, Bi, Br, Cd, Co, Cr, Cs, Ge, Mn, Ti, Tl, Sn, and v were also
analyzed in one or more samples, however, none were found in
concentrations >1 mg/L.
eAg Cd, Co, Cr, Cs, Ga, La, Mn, Pr, RJ>, Sc, Sn, Ti, U, V, Y, and Zr
were analyzed in one or more samples, however, none were found in
concentrations >1 mg/L.
^Wastewater stream common to both surface and in-situ retorting.
9Ag, Be, Cr, Mn, and V were also analyzed in one or more samples,
however, none were found in concentrations >1 mg/L.
primary wastewater stream in surface retorting. •
^•Ag Cd, Co, Cr, Cs, Ga, Ge, Mn, Sb, Sc, Sn, Ti, and V were also
analyzed in one or more samples, however, none were found in
concentrations >1 mg/L.
-'NO data.
'Sjote that reported concentrations are not representative of
anticipated commercial scale retorting streams.
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Gas condensate is a wastewater stream which will emanate from
both in-situ and surface retorting; however, data presented in
Table 1 are largely based on analysis of gas condensate from two
surface retorting technologies: Paraho and Tosco. As with retort
water, gas condensate exhibits high levels of organics, bicarbon-
ate, and ammonia; however, concentrations Of dissolved trace
metals and other inorganics are significantly lower in gas conden-
sate than in retort water.
Investigators in oil shale wastewater research are undecided as
to whether leachate from spent shale piles characteristic^ of
surface retorting will be a major wastewater stream. Since
leachate may potentially be a major wastewater stream from in-situ
retorting, it has been considered in Table 1, and will be;
addressed when control technologies are discussed. As seen in
Table 1, no data is available to predict concentrations of many
pollutants, particularly organics, nitrogen compounds, and sulfur
compounds. Based on available data, high levels of TOC, TDS,
sulfate, and sodium can be expected in spent shale pile leachates.
Product water, or water which separates from product oil, will be
difficult to treat. Organics, probably originating from oil emul-
sions, are more prominent in product water than in retort water.
In reviewing industry development plans, and in conversations .
with several oil shale developers, it is quite apparent that many
developers do not have firm plans for either reusing or discharg-
ing oil shale wastewaters. Even more undefined at this time are
the wastewater treatment systems which will be used to upgrade a
wastewater for a particular reuse application or for discharge.
General statements regarding no planned discharge have been
made; however, there appears to be no information in the litera-
ture to support this approach. For example, the development plans
of some surface retorting developers indicate use of all retort
waters for spent shale moisturization and compaction. This may or
may not be feasible, as some data indicates that retort water
produced may be nearly three times the volume of that needed for
standard shale moisturization to 14% weight.
Some water reuse diagrams have been suggested by government
contractors outside of industry, particularly for the Paraho
direct heated process, the Tosco,11 process, the Occidental
process, and the RISE/Lurgi-Ruhrgas process. These diagrams
provide closed loop (complete recycle) water reuse schemes,
though many assumptions regarding wastewater treatment technology
performance and water quality needs are made. These diagrams, as
well as available information from developers concerning water use
schemes can be found in Appendix'A.
Indecisiveness on the part of industry to commit themselves to a
particular water reuse scheme and particular wastewater treatment
10
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technologies is the result of several deficiencies in the oil
shale wastewater data base. These include:
Lack of data in the.areas of wastewater characterization
and wastewater flow rates. In part, this deficiency derives
from the fact that much of this data can only be obtained
from full-scale operations, which do not exist; ,
Lack of data in the area of water quality needs for
various retorting process components; and
Lack of data in the area of wastewater treatability.
As data is provided, in part by government research activities, :
industry will begin to make commitments to water use schemes
based on economic considerations.
For the purposes of this contract (providing wastewater treat- ••
ability data for oil, shale wastewaters), MRC has summarized '.
industry and government contractor water use ideas into four
diagrams shown in Figures 2 through 5. These diagrams provide
a frame work of treatment steps which must be provided before a
particular wastewater can be used for one of many potential
applications. Once specific technologies are pilot-tested,
economic data on which water reuse decisions can be based will
be provided.
Mine water from dewatering of the in-situ retort prior to ignition
could be an important water resource in the water-short Colorado
River basin. Therefore, cooling tower makeup, boiler feed water, ,
and drinking water are included as potential uses of mine water
as shown in Figure 2. Due to potentially unsatisfactory concen- ;
trations of H2S, volatile organics, Fl~, B, and TDS, mine water
will have to be treated prior to discharge for removal of these
species. ' <
Extensive treatment will be necessary if retort water and product
water are to be discharged, as shown in Figure 3. More realis-
tically, these wastewaters will be treated to the degree necessary
for use in a thermal sludge oxidizer, for dust control for spent ;
shale moistening from a surface retort associated with a modified :
in-situ retort and/or for cooling water makeup. • \
Similarly, there are several realistic uses for gas condensate
at the retorting site as shown in Figure 4.
As mentioned, leachate may or may not be a primary wastewater
stream. Based on current analytical data, it appears TDS and trace
metal removal will be necessary before leachate can be discharged ,
to surface waters; however, there are several potential in-plant
uses for leachate requiring a lesser degree of treatment as shown >
in Figure 5. :
11
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POTENTIAL END USE
TREATMENT STEPS
REINJECTION
COOLING TOWER
MAKEUP
DISCHARGE
BOILER FEED
• POTABLE USE
MINE WATER
DISSOLVED GASES
REMOVAL
CLARIFICATION
FINES.S.
REMOVAL
IDS/TRACE METALS
REMOVAL
RESIDUAL
INORGANICS
REMOVAL
DISINFECTION
Figure 2. Mine water treatment steps and reuse potential.
12
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POTENTIAL END USE
TREATMENT STEPS
« STEAM GENERATION
VIA THERMAL
SLUDGEOXIDIZER
• DUST CONTROL
SHALE MOISTENING
• COOLING TOWER
MAKEUP
• DISCHARGE
RETORT WATER, PRODUCT WATER
EMULSIFIED!?) OIL
SEPARATION
DISSOLVED GASES
REMOVAL
ORGAMCS
REMOVAL
FINES.S.
REMOVAL
SCALE CONTROL
TRACEORGANICS
REMOVAL
TDS/TRACE METALS
REMOVAL
Figure 3. Retort wastewater treatment steps and reuse potential.
13
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POTENTIAL END USE
TREATMENT STEPS
• COOLING TOWER
MAKEUP
• DUST CONTROL
• SHALE MOISTENING
• DISCHARGE
GAS CONDENSATES
EMULSIFIED(?)OIL
SEPARATION
DISSOLVED GASES
REMOVAL
ORGANICS
REMOVAL
FINES.S.
REMOVAL
TRACE ORGANICS
REMOVAL
Figure 4. Gas condensate wastewater treatment
steps and reuse potential.
14'
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POTENTIAL END USE
TREATMENT STEPS
• DUST CONTROL
• SHALE MOISTEN ING
COOLING TOWER
MAKEUP
« DISCHARGE
LEACHATE
SCALE CONTROL
IDS/TRACE METALS
REMOVAL
Figure 5. Leachate treatment steps and reuse potential.
15
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SECTION 4
TREATMENT OF OIL SHALE WASTEWATERS
INTRODUCTION
In an effort to identify potential technologies for use in pilot-
scale oil shale wastewater treatment systems, MRC conducted a
second literature search to identify bench-scale research work
dealing with the treatability of oil shale wastewaters. jit was
hoped that an adequate data base would exist for identification
of potential technologies which could be pilot-tested; however,
it is now apparent that the existing data base is limited. Of
the four wastewaters identified in Section 3, treatability data
exists for mine water and retort water, though, as will be seen
in this section, the results of these studies are largely incon-
clusive since the studies were preliminary. It was also found
that several key studies on the treatability of retort water are
either now ongoing, or have been completed though a published
report not yet available. This section, therefore, presents
summaries of concluded and published research studies as they
relate to the four wastewater streams identified in Section 3:
mine water, retort wastewater, gas condensate, and leachate.
Where published data do not exist for a particular study,! a summary
based on project status report or personal communications, will be
presented. Following the subsections covering the treatability of
individual wastewater streams, a discussion leading to recommenda-
tions for further study will be -presented.
MINE WATER '
As discussed in Section 3, water pumped from in-situ retorts
prior to ignition may contain unacceptable levels of fluoride,
phenols, boron, and TDS if the water is to be discharged ;or used
for potable purposes.
Treatability studies have been conducted by Battelle N.W.; [2] to
evaluate methods for removing fluoride and boron from minewater.
[2] Mercer, B. W., W. Wakamiya, R. R. Spencer and M. J.!Mason.
Assessment of Control Technology for Shale Oil Wastewaters.
Paper presented at DOE Environmental Control Technology
Symposium, November 1978.
-------
The results of bench-scale experiments with groundwater taken
from a site in Colorado show a 50% breakthrough capacity of 350
bed volumes for fluoride removal by activated alumina adsorption.
The groundwater fluoride concentration was 20 mg/L; therefore,
the fluoride capacity was approximately 7 g/L of activated
alumina. In order to achieve effective fluoride removal, the
feed was adjusted to pH 2.5 for the initial 100 bed volumes to
reduce the effluent pH to about 9. Thereafter, the feed pH was
adjusted to pH 5.5, which is the optimum level for fluoride
removal. Since the alumina bed was regenerated with dilute
sodium hydroxide, it was necessary to add additional acid to the
feed at the beginning of the exhaustion cycle to neutralize the
residual caustic regenerant in the bed. The acid addition for pH
adjustment of the feed is expected to represent a substantial
portion of the chemical cost of treatment for fluoride removal by
activated alumina adsorption. Battelle N.W. estimated that 13%
per thousand gallons of groundwater would be required to adjust
the pH with sulfuric acid priced at $50 per ton of acid. Regen-
erant costs were estimated to be 16% per thousand gallons of
groundwater treated based on sodium hydroxide priced at $280 per
ton.
Results of Battelle's precipitation experiments with simulated
groundwater indicate 90% fluoride removal with phosphoric acid
and lime addition. Approximately 9 moles of phosphorus and 10
moles of calcium per mole of fluoride were required to achieve a
level of fluoride removal needed to allow discharge to nearby
surface receiving waters. The precipitation formed was basically
a mixture of fluorapatite, CasFfPCu), and hydroxy apatite, Ca5(OH)
(P04)3. The cost of phosphoric acid and lime to treat the ground-
water was estimated by Battelle to be about $2 per thousand
gallons, which was found to be excessive, relative to other
treatment methods.
Ion exchange with a weak base anion exchange resin was also
investigated by Battelle as a unique process which showed some
potential because of the low selectivity of this resin for bicar-
bonate, the principal ion competing with the fluoride. Laboratory
results showed a correspondingly low selectivity for fluoride
which negates possible advantages this process may have over other
ion exchange processes.
Battelle also found that boron removal from the groundwater was
not effected by either activated alumina or lime and phosphate
treatment. Bench-scale studies with a boron selective ion
exchange resin indicated good boron removal from 2,000 bed
volumes of groundwater containing 0.6 mg/L. Boron removal to
less than 0.3 mg/L is required for discharge.
17
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Reverse osmosis or electrodialysis are discussed by WPA [3] as
candidate processes which may be commercially viable in treating
mine drainage waters. It was pointed out that electrodialysis
will only separate those molecules which are in ionic form in
solution. Boron, for example, requires that the solution pH be
about 8.5 to 9 to become ionic. In general, electrodialysis also
does not have a capability for separating soluble organic mole-
cules which may exist in minewater. Reverse osmosis, on the
other hand, has a moderate capability for separating boron from
acidic waters, and it is only at; a quite high pH (-^N 9.5-10)
that a 75% rejection of boron is attained. Phenol rejection is
significant only at high pH as well and fluoride rejection is
typically about 90%. Both reverse osmosis and electrodialysis
require a moderate to good level of prefiltration to remove
suspended solids which will be contained in the mine water.
Since mine water is alkaline, electrodialysis would require
pretreatment with sulfuric acid to prevent scaling on the:
membranes. Acid addition or chelating agents may also be;
required to prevent precipitation of salts, if the reverse
osmosis is used. WPA emphasizes that both reverse osmosis and
electrodialysis would provide a product with a lower total
dissolved solids than required for discharge. As a rule, reverse
osmosis would give the lowest IDS product with a typical value
for the mine water considered of from 100 to 200 mg/L, while the
electrodialysis product might range from 200 to 400 mg/L.
WPA previously made study cost estimates for both membrane proc-
esses without disposal of the concentrated solutions and without
boron and phenol removal. The costs for the two processes are
similar, although electrodialysis would become less attractive
at the higher end of the IDS range. Reverse osmosis costs are
not significantly dependent on influent TDS and have the added
advantage that the system can be operated to remove boron,
phenol, and ammonia. • . -
Concentrate streams will be generated by both reverse osmosis
and electrodialysis. If it is assumed that an 85% recovery and
90% separation of the dissolved solids is attained, then the
concentrate stream would have about 6 times the concentration of
the mine water and about one-seventh its volume. WPA points
out that the cost of disposal of; this stream, ranging from
about 0.3 to 2.0 million gallons; per day, could be a major part
of the treatment cost. Concentrate disposal could be either by
evaporation in ponds or preferably in a vapor compression (RCC)
evaporator. If a "thermal sludge" or similar type unit is used
[3] Water Purification Associates Quarterly Status Report, May
1, 1979 - August 31, 1979. A Study of Aerobic Oxidation and
Allied Treatments for Upgrading In-Situ Retort Waters.
Submitted to U.S. Department of Energy, Laramie Energy
Technical Center.
18
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on site for steam raising, it may prove possible to blend the
concentrate with the feed to this unit. The concentrate would
contain sodium bicarbonate, possibly near its solubility limit
and it may prove possible to recover this material for sale,
particularly as both C02 and excess heat are readily available
at an oil shale plant.
Removal of dissolved gases (HgS, CH4, G02) and oxidation and
removal of dissolved iron from mine water may be necessary before
reverse osmosis, electrodialysis, or ion exchange can be used to
remove boron and fluoride. Simple aeration has been quite
successful for these purposes [4]. Gravity aerators such as
cascades or stacks of perforated pans or troughs are commonly
used in water purification plants. Other forms of aerators are
spray aerators, diffusers, and mechanical aerators.
RETORT WATER
Of the wastewater streams identified in Section 3, retort water
treatability has drawn the most attention from researchers
because of its unique and complex character. As can be seen in
Table 2, many attempts have been made or are being made with a
variety of techniques to treat retort water. Some studies have
been completed resulting in published, public reports (indicated
by "A"); however, the results of many studies are unavailable to
the public (indicated by "B", "C", or "D") for various reasons.
In one series of studies, Harding and Associates at the Univer-
sity of Colorado conducted "preliminary bench-scale treatment
evaluations" of activated carbon adsorption, polymeric adsorption,
thermal stripping, and weak acid ion exchange [5, 6]. They have
also conducted evaluations of the wet air oxidation process,
though results have not yet been published (personal communica- '
tion, E. R. Bennett, University of Colorado, to G. D. Rawlings,
Monsanto Research Corporation, November 8, 1979).
In studies of activated carbon adsorption, raw retort water was
passed through six columns in series filled with an unspecified
activated carbon at a flow rate of about 1 BV/hr. Over a 17 hr
period, COD removals better than 75% -were consistently observed
(influent COD = 12,500 mg/L). In addition, phenol removal was
100% (influent phenol = 31 mg/L) during a single observation
after 2 hr of operation. The investigators noted fouling of the
carbon surface was occurring since breakthrough curves for COD
removal showed no sharp inflection, and head losses through the
column developed rapidly. They suggest that pretreatment for
removal of oil and suspended material may yield better perfor-
mance of activated carbon adsorption.
[4] Fair, G. H., J. C. Geyer, and D. A. Okun. Water'and Waste-
water Engineering: Volume 2. John Wiley & Sons, Inc., 1968.
19
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Harding also investigated the use of synthetic polymeric adsorb-
ents. Four Rohm & Haas resins (XAD-2, XAD-4, XAD-^7, and XAD-8)
were screened in preliminary column tests, while only XAD-4
which demonstrated the best performance in the screening study
was evaluated in longer=ter,m tests. to-the XAD-4 test, 20 BV of
filtered retort water was applied at a r*te of 6 BV/hf.
Initially, COD removal was 84% (initial COD = 12,400 mg/L);
however, performance worsened with time, so that only 24% of the
COD was removed at the end of the test. The authors stated that
low polarity resins out performed higher polarity resins in the
removal of COD. They suggest that coupling polar and,nonpolar
resins may yield an effluent with more acceptable COD levels.
Harding also investigated thermal stripping to remove ammonia,
alkalinity, and COD from the retort water. Retort water at 60°C
was introduced to the top of a 1010 cm x 5 cm packed column at a
rate of 250 mL/min and recirculated through the column 3 times.
Air was passed countercurrently at a rate of 90 L/min. NH3 and
C02 were removed simultaneously; however, COD was not1removed.
The authors caution against developing any rate constants from
the study, since the experimental apparatus was small, the
column was not insulated, and the temperature of the waste
dropped 20°C after passing through the column. The study is
significant though, in that it indicates simultaneous NH3 and
C02 removal without pH adjustment.
•Weak acid ion exchange was also examined for simultaneous NH3
and COa removal. First, Duolite CC-3 was placed in a;column, and
retort water was introduced to the column in an upflow mode.
The column immediately filled with 00%, however, excellent NH3
removals were observed. The investigators then conducted a
series of batch tests which demonstrated excellent simultaneous
removals of NH3 and C02. Fouling of the resins by organics,
and evaluation of C02 were identified as problems with ion
exchange.
As mentioned, studies investigating wet air oxidation of retort
water were also conducted at the University of -Colorado, though,
published results are not available. The investigators have
indicated that excellent removals of SOD were observed. The
studies were conducted at 1,500 psig, using pure oxygen, with
temperatures ranging from 100°C to 325°C. In one run, COD was
reduced from 10,000 mg/L to 200 mg/L. The concentration of
ammonia stayed about the same.
Fox and Associates have investigated spent shale adsorption as a
means to remove both inorganic and organic carbon from retort
studies [8, 9]. In batch and column tests, excellent removals
of inorganic carbon were demonstrated (up to 98%); however,
organic removal was not as significant. The investigators
suggest that spent shale adsorption of inorganic carbon and NH3
21
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removal by stripping be used as an alternative to chemical pH
adjustment prior to C02 and NH3 stripping in a retort wastewater
treatment system. , '
Fox has also investigated anaerobic fermentation of retort
water [10]. Based on four experiments, the investigators offer
the following conclusions:
1. The retort water studied had to be pretreated to remove
toxic and add deficient constituents before it could be
successfully treated with the anaerobic fermentation proc-
ess. Pretreatment included pH adjustment to 7, ammonia
reduction and nutrient addition.
2. A digested sludge from a conventional municipal sewage
treatment plant was successfully acclimated to the retort
water studied. ;
3. A major fraction of the organics in the retort water
studied was stabilized by conversion to CH4 and C02 using
the anaerobic fermentation process. BOD5 and COD removal
efficiencies were 76% to 80%. Within the limits of
experimental error, the same removal rate was obtained
for both BOD5 and COD.
4. The effluent from anaerobic fermentation of the retort
Water studied (BOD5: 530 mg/L to 580 mg/L) may be suit-
able for treatment by conventional aerobic processes.
5. The growth of the methane formers, which stabilize the
organics, was nutrient limited in the retort water studied.
6. The pretreatment of the retort water studied removed 49% of
the BODs. This was probably due to the reduction in
solubility of high molecular weight fatty acids at
neutral pHs; they drop out of solution and do not exert a
BOD.
7. A major component removed from the retort water studied
during anaerobic fermentation was fatty acids.
8. The long hydraulic residence time used in this study (50
days) would not be used in practice. Cell recycle, which
increases the cell residence and decreases the hydraulic
residence time, would be exploited to achieve hydraulic
residence times on the order of 2 to 3 days.
In-house screening studies have been conducted by Amoco utilizing
Geokinetics1 retort water which had been pretreated with alum
coagulation and sand filtration ;[!!]. Tests with weak acid
cationic exchange resins, similar to those conducted by Harding
were conducted and resulted in similar findings. As in the
22
-------
Harding tests, Amoco found that ion exchange holds some potential
for NH3 removal; however, C02 evaluation would be a problem in a
column operation.
Amoco also investigated spent shale absorption as a means to \
remove organic carbon from retort water. In batch and column
tests utilizing Lurgi spent shale, little or no organic carbon
removal was observed. ..
Several tests were conducted utilizing aerobic biological treat-
ment with limited success. Batch reactors were used to treat
three dilutions (60:1, 40:1, 20:1) of both raw retort
water and retort water which had been steam stripped. Over a
20-day period, TOC reduction never exceeded 50%, indicating
a high level of refractory organics. Removal of NHs in the
reactors only occurred with the 40:1 and 60:1 dilutions.
Amoco observed 95% removals of ammonia and carbonate in steam
stripping tests utilizing a 3 in. packed column with steam rates
of 1 to 2 Ib/gal of feed. The investigators did note a tar-like
residue on the column packing following the tests.
Solvent extraction of an acidified and a neat sample of retort
water was investigated in batch tests using light virgin naphtha. :
Only 10% of dissolved organic carbon was removed.
Color was removed completely when retort water was contacted with
ozone for 60 min. Mild ozonation (5 min) followed by activated
sludge treatment demonstrated little or no removal of organic .
carbon. . . ;•
Battelle N.W. Laboratories have also conducted a number of
treatability screening studies [3]. Steam stripping studies were
conducted using a sample of in~situ retort water from Utah and
a sample of retort water from Lawrence Livermore Laboratory.
With the Utah -retort water, ammonia removal with recycle of the
condensate averaged 90% (initial NH3 = 3,100 mg/L) for 2 runs at
a boiloff rate of 4.5% when condensate was recycled. ' Over 99%
of the ammonia was removed at a boiloff rate of 5.3% when conden-
sate was not recycled. Steam stripping also reduced the alkalinity
from 14,300 mg/L to about 4,700 mg/L and the pH of the retort
water increased from 8.8 to about 10. Excessive foaming occurred
in the reboiler requiring precise liquid level control to prevent ;
the foam from entering the column where it could have caused
flooding. .
As with the Amoco study, some fouling of the packing in the
stripping column was observed. Although settled retort water
was used, it contained about 150 mg/L of suspended solids, which i
were reduced to about 30 mg/L through the stripper. A small
volume of light oil was removed by the steam stripping operation.
Organic carbon removal by steam stripping ranges from 15% to
23
-------
A sample of retort water from the Lawrence Livermore Laboratory
(LLL) was steam stripped while operating in the condensate
recycle mode at a condensate temperature of 85.5 ± 3.5°C. The
ammonia was reduced by 99.5% from 26,500 mg/L to 135 mg/L,at
a boiloff rate of 15% of the combined feed and condensate
recycle. This boiloff rate was equal to 18% of the feed flow
alone. Approximately 1/4 of the ammonia was recycled with the
condensate stream and 3/4 was evolved from the condensate receiver
as a gas. The feed flow to the stripper column with the LLL
retort water was restricted to about half that of in-situ' test
site retort water to avoid flooding in the column. Flooding is
believed to result from a greater gas flow (C02 + NH3) up the
column with the LLL retort water.
Aerobic and anaerobic biological treatability studies were also
conducted by Battelle N.W. on five samples of retort water; one
retort water sample from the 6,000 kg simulated in-situ retort
at the Lawrence Livermore Laboratory, one from an above-ground
retort in Colorado, and three samples from an in-situ test site
in Utah. Aerobic treatment consisted of activated sludge or
combined trickling filter and activated sludge. The results of
the aerobic treatment studies indicated toxicity problems in the
treatment units as the concentration of retort water was increased
in the feed to the units. Good biological growth and organic
carbon removals were observed during the initial phases of the
acclimation period, but an apparent toxicity problem develops as
the percent actual retort water in the feed increases and;the
percent artificial retort water decreases. Analysis of the
retort water for toxicants revealed the presence of arsenic and
thiocyanate. Thiocyanate was not believed to be a problem since
the concentration of this constituent was below the threshold
value of 500 mg/L for activated sludge; however, arsenic could
have been a problem since it exceeded the threshold value; of 0.1
mg/L for activated .sludge in all samples. Results of anaerobic
digestion studies conducted with 3.5 liter digesters also
indicated toxicant problems. Gas production from the digesters
diminished steadily'as the concentration of actual retort water
was increased.
Results of studies to evaluate powdered activated carbon •,
addition to the anaerobic digesters indicated successful opera-
tion in the case of the Livermore retort water, but continued
toxicity problems with the other retort water samples. The
activated carbon is also effective in some instances for remov-
ing heavy metals from solution in addition to removing organics,
but its effect on arsenic in retbrt water is unknown at the
present time. Analysis for soluble arsenic in the digester
receiving in-situ test site retort water revealed 0.96 mg/L
which is near the toxicity threshold for anaerobic digestion.
Soluble arsenic in the digester receiving Livermore retort water
was 0.56 mg/L. Preliminary results indicate that activated
24
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carbon treatment of Utah in-situ retort water will permit aerobic
biological degradation to take place although the amount of
activated carbon needed may be relatively high.
Preliminary stripping and biological treatability tests have also
been conducted by Water Purification Associates [3]. Small scale
batch stripping tests were conducted by WPA to assist in the
design of a larger stripping unit. As with other investigators,
WPA found that ammonia and alkalinity stripped simultaneously
from a heated sample of retort water. In addition, a minor ;
amount of COD was simultaneously removed. Of significance is the
finding that ammonia was not removed after prolonged sparging
(16 hr) at an elevated pH at room temperature. Vapor^liguid
equilibrium data would predict that some stripping of ammonia
should have occurred.
Preliminary results of aerobic treatment experiments indicated
that it was possible to successfully treat stripped retort water
at pH 7.0 without any dilution. After 70 hr of aeration, 50% of
the COD (initial COD > 10,000 mg/L) had been removed; however,
the sludge was highly dispersed. WPA isolated excessive pH in ;
the retort water as a toxicant through extensive studies investi- ,
gating arsenic, cyanide, and pH toxicity. In the successful
studies, 5 mL concentrated phosphoric acid was required to bring i
1 L of stripped retort water to pH 7.
Yen and Associates have conducted numerous and diverse treatability
screening studies focusing on the degradation of organic compon-
ents in retort water [14]. The technologies investigated include
various aerobic and anaerobic biological techniques, electrolytic
techniques, and "supplementary techniques" utilizing ozone,
permanganate, and photodegradation. In studies of aerobic
activated sludge treatment, COD removals of 37% to 43% were ob-
served after 10 days of aeration. Four dilutions of retort water :
were used in the tests: neat, 4:3, 2:1, and 4:1. No significant -'
difference was observed with the four dilutions in terms of per-
cent COD removal. In order to isolate the organic fractions most
inhibitory to biodegradation, the retort water was separated into
acidic, neutral, basic, and residual fractions prior 'to activated
sludge treatment. As a result, the basic and residual fractions
were found to be most inhibitory.
Preliminary tests with anaerobic treatment of retort water
exhibited a 27% removal of COD.
In addition, Yen investigated aerobic treatment with mutant
species. In the tests, "phenobac" and "polybac" were used with
and without activated sludge. After 21 days, the TOC reduction ;
for the sample with the sludge was 55% and the TOC reduction for :
the sample without the sludge was 45%.
25
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Preliminary tests with rotating biological contactors were also
conducted. Although details of the study are unknown, the data
presented indicates poor removal of TQC. Several brief studies
with specific bacteria (Desulforibrio and Pseudomonas) were also
conducted, though details of the work are also unknown.
Yen also conducted tests with three electrolytic treatment reac-
tors: a flat-plate cell, a fluidized-bed electrode reactor, and
an extended surface electrolytic cell. With the flat-plate cell,
65% reductions in COD were observed. In addition, the effluent
supported growth on retort water-agar plates, while the influent
did not. The other two systems demonstrated similar results.
As mentioned, several "supplementary" techniques were investi-
gated by Yen. Photodegradation with a tungsten-halogen lamp was
demonstrated since peak intensities of highly polar constituents
in a liquid chromatogram decreased following treatment. A one-
hour treatment with ozone resulted in a 14% reduction in TOC, a
32% reduction in COD, and an 80% reduction in color intensity.
Excessive treatment permanganate (13 g/L) results in a 60%
reduction of TOC. : .•
The treatability of both process water and retort water with
physical/chemical techniques was investigated by Hubbard via
bench-scale screening studies [15]. Lime precipitation/stripping,
activated carbon treatment, and cationic/anionic exchange' were
used in various combinations; however, lime treatment -> activated
carbon treatment •* cationic/anionic exchange proved to be, the
best treatment scheme with both waters. This system, provided
^•100% removals of ammonium, sodium, carbonate, chloride, and
sulfate. The activated carbon step was effective in removing
essentially all organic components.
Tests with reverse osmosis were conducted by Osmonics, Inc. with
little success in removing TOC [16]. A cellulose acetate mem-
brane with a 600 MW cutoff was used to process 177 liters
(47 gallons) of retort water. The RO was operated at 150 psig,
and 92% of the retort water was recovered; however, addition of a
detergent and a dispersant was necessary to emulsify oils to pre-
vent membrane fouling. RO concentrate was recycled and TOC in the
RO permeate averaged 16% less than that of the initial RO feed.
i
As mentioned, several other key studies in retort water treat-
ability are planned, ongoing, or: completed without published
report yet available. Of particular interest is the University
of Colorado work on wet air oxidation to be published in '
Industrial Wastes, the Battelle N.W. studies to be detailed in a
final report, WPA's work which will be included" in a report to be
released in late 1980, and evaporator studies conducted by Resource
Conservation Company which has received a subcontract from
Battelle N.W. •
26
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GAS CONDENSATE ' . ••• .•-•-. i *
No studies concerning the treatability of gas eondensate were
identified in the literature search. It is expected that gas
eondensate will be much easier to treat than retort water since
no significant concentrations of inorganics other than ammonia
and carbonate species are likely to be present. Oil and grease
emulsions may be a problem in gas eondensate; however, this
phenomena has not been observed. Steam stripping for the removal
of ammonia and acid gases should be successful, since its success
has been demonstrated with retort water—a much more contaminated
stream. Steam stripping should also remove some or all organics
which may be present, though this has not been demonstrated.
Many treatment options, as discussed in Section 3 exist if
organics remain in the stripper effluent.
LEACHATE
As with gas eondensate, no studies concerning the treatability of
leachate were identified in the literature search. In addition,
it is difficult to speculate as to which treatment systems would
treat leachate since only limited characterization data is avail-
able. If leachate is a major wastewater stream from surface
retorting operations, it is expected that at least treatment for
TDS and trace metals will be required prior to leachate discharge.
DISCUSSION ;
Several treatability screening studies have been conducted to
fill many treatment step needs identified in Figures 6 through 8,
particularly in the case of mine water and retort water treatment.
Because of their design and intent, these studies have generally
been useful to screen potential technologies and eliminate others.
Many key technical questions still remain unanswered such as:
•• How should emulsified oil be separated in retort and product
water?
What is the best system for removal of organics from
retort and product water?
«. Will state-of-the-art technologies treat gas eondensate
and leachate?
To answer these questions, and to size pilot-plant equipment, MRC
recommends conducting additional bench-scale treatability studies.
Presently, there are several opportunities for MRC to obtain
27
-------
POTENTIAL END USE
TREATMENT STEPS
TREATMENT OPTIONS
REINJECTION -
COOLING TOWER
MAKEUP
DISCHARGE
• BOILER FEED
POTABLE USE
MINE WATER
DISSOLVED GASES
REMOVAL
CLARIFICATION
FINES.S.
''REMOVAL
TDS/TRACE METALS
REMOVAL
RESIDUAL
INORGANICS
REMOVAL
• AERATION
• CHEMICAL ADDITION/
FLOCCULATION/
SEDIMENTATION
MULTIMEDIA
FILTRATION
« REVERSE OSMOSIS
ION EXCHANGE
ION EXCHANGE
* CL
Figure 6. Mine water treatability options,
28
-------
POTENTIAL END USE
TREATMENT STEPS
RETORT WATER. PRODUCT WATER
• STEAM GENERATION
VIA THERMAL
SLUDGE 0X1D1ZER
« DUST CONTROL
SHALE MOISTENING
• COOLING TOWER
MAKEUP
• DISCHARGE
EMULSIFIED (?) OIL
SEPARATION
DISSOLVED GASES
REMOVAL
ORGAN!CS
REMOVAL
FINES.S.
REMOVAL
SCALE CONTROL
• GRAVITY SEPARATION
• CHEMICAL ADDITION/DAF
• CHEMICAL EMULSION
BREAKING/SEPARATION
• ULTRAF1LTRAT10N
• STEAM STRIPPING
• AEROBIC BIOLOGICAL
TREATMENT WITH ONE OR
MORE PRETREATMENTSt
- pHADJUSTMENT
- CHEMICAL COAGULATION
-WET AIR OXIDATION
- OZONATION
-PAC ADDITION ;
• WET AIR OXIDATION
• GRANULAR ACTIVATED CARBON
• MULTIMEDIA FILTRATION
• CHEMICAL ADDITION
TRACE ORGANICS
REMOVAL
TO S/TRACE METALS
REMOVAL
• GRANULAR ACTIVATED CARSON
» POLYMERIC RESINS
REVERSE OSMOSIS
ION EXCHANGE
Figure 7. Retort wastewater treatability options.
29
-------
POTENTIAL END USE
TREATMENT STEPS
TECHNOLOGY OPTIONS
GAS CONDENSATES
• COOLING TOWER
MAKEUP
• DUST CONTROL
• SHALE MOISTENING
• DISCHARGE
EMULSIFIED (?) OIL
SEPARATION
DISSOLVED GASES
REMOVAL
ORGANICS
REMOVAL
FINE.S..S.
REMOVAL
TRACE ORGANICS
REMOVAL
* GRAVITY SEPARATION
• CHEMICAL ADD ITION/DAF
• CHEMICAL EMULSION
BREAK ING/SEPARATION
• ULTRAFILTRAT10N
• STEAM STRIPPING
• AEROBIC BIOLOGICAL
TREATMENT
(SEE FIGURE 7)
MULTIMEDIA FILTRATION
• GRANULAR ACTIVATED CARBON
• POLYMERIC RESINS
Figure 8. Gas condensate wastewater treatability options.
30
-------
relevant samples of retort wastewaters with which to conduct ;
these studies, namely:
Rio Blanco - mine water and retort water
Tosco - gas condensate
Geokinetics - retort water •
- Occidental - retort water and gas condensate ;
In the case of mine water treatment, only Battelle N.W. has
conducted bench-scale treatability studies for the removal of
fluoride and boron which are of primary concern if the excess :
mine water is to be discharged or used for potable purposes. :
Activated alumina absorption and precipitation with phosphoric
acid and lime were identified as promising technologies for the
removal of boron. WPA reported that electrodialysis and
reverse osmosis could produce a more than adequate effluent; ;
however, reverse osmosis appears to be more cost-effective at '
the high TDS levels expected and has added technical advantages.
Therefore, additional research is needed to demonstrate the :
feasibility of reverse osmosis treatment of mine water and to
size pilot-plant equipment in the case of other treatment steps.
Suggested technology options to be investigated in these studies i
are listed in Figure 6.
Many more studies have been conducted with retort water; however,
key technical questions remain. For example, no studies have beei< ,
conducted to investigate emulsified oil separating from retort and :
product water. Steam stripping has been identified by several
investigators as the best technology for dissolved gases removal, .
though they have experienced fouling of column packings. Emulsi-
fied oil separation may alleviate the problem. Many studies have
been conducte-d to assess technologies for organics removal, thougfe
many questions remain. Aerobic biological treatment has classically
been the most cost-effective method of organics removal from mu-
nicipal wastes, but it has been found that various pretreatments
are required for these systems to operate with retort water. In
addition, a large portion of the organics (^50%) appear to be re-
fractory. Therefore, additional studies are needed to identify ;
methods which would enhance the ability of aerobic biological ;
treatment to remove organic compounds. The sensitivity of bio- ;
logical systems to variations in retort water composition has ser- ,
ious implications for commercial operations. If it is found that
wastewater cannot be treated biologically, it may become necessary
to test physical/chemical methods such as wet air oxidation and
granular activated carbon adsorption. It is unlikely that retort
water would be discharged from a full-scale retorting facility;
however, if discharge is necessary, treatment for trace organics,
trace metals, and TDS will become necessary. Several investiga-
tors have used granular activated carbon and polymeric resins for
31
-------
gross organics removal; however, studies are needed to assess
these technologies for their ability to remove refractory
organics present in the effluent j from the gross organics removal
treatment step. Studies of TDS and trace metals removal by re-
verse osmosis and ion exchange would also become necessary.
Suggested treatment options to treat retort water to discharge
quality are shown in Figure 7. -:
As pointed out in Section 3, treatment to discharge quality will
probably not be necessary in full scale systems since many in
plant uses for retort water are envisioned. Bench-scale studies
conducted at this time are still recommended to complete a retort
treatability data base which would be used by industry and govern-
ment in making water use decisions.
No known studies exist for the treatment of gas condensate,
though, this stream should not be difficult to treat, compared
to retort water. At this time, the extent to which emulsions are
present in gas condensate is not known. If present, they;will have
to be removed prior to subsequent treatment steps. Steam stripping
studies are necessary to assess organics removal as well as in-
organic dissolved gases removal. If organics remain follbwing
steam stripping, studies for their removal will have to be initiated.
Suggested technology options for gas condensate treatment,are listed
in Figure 8.
Since it is not known whether leachate from spent shale piles will
be present in significant quantities,'and leachate quality is
still not fully understood, research funds should be directed to
address these issues rather than: investigating treatment alterna-
tives. If spent shale piles are .found to be porous, and the
leachate from percolation through the piles is toxic or unaccept-
able for groundwater discharge, serious questions about leachate
collection in full-scale systems exist.
32
-------
REFERENCES
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Characterization and Analytical Considerations for an In-
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Energy Technology Center. U.S. Department of Energy,
November 1978.
2. Mercer, B. W., W. Wakamiya, R. R. Spencer and M. J. Mason.
Assessment of Control Technology for Shale Oil Wastewaters.
Paper presented at DOE Environmental Control Technology
Symposium, November 1978.
3. Water Purification Associates Quarterly Status Report, May
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5. Harding. B., K. D. Linstedt, E. R. Bennett, and R. E.
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6. Harding, B. L., K. D. Linstedt, E. R. Bennett, and R. E.
Poulson. Removal of Ammonia and Alkalinity from -Oil Shale
Retort Waters by the Use of Weak Acid Cation Exchange
Resins. Proceedings of the Second Pacific Chemical Engineer-
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7. Fox, P. Spent Shale as a Control Technology for Oil Shale.
. October Monthly Progress Report submitted to Charles Grua.
U.S. Department of Energy, November 1979.
8. Fox, J. P., R. N. Cenaclerio, D. E. Jackson and S. L. Lubic.
Spent Shale as a Control Technology for Oil Shale Retort
Water. Quarterly Progress Report June 1, 1978 -'September
30, 1978 submitted to U.S. Department of Energy, January
1979. :
33
-------
9. Jackson, D. E. and J. P. Fox. Spent Shale as a Control
Technology for Oil Shale Retort Water. Quarterly Progress
Report - October 1, 1978 - December 31, 1978 submitted to
U.S. Department of Energy, January 1979. ;
10. Oggio, E. A., J. P. Fox, J. F. Thomas and R. E. Poul^on.
Anaerobic Fermentation of Simulated In-Situ Oil Shale
Retort Water. Presented at the Meeting of the American
Chemical Society, March 1978.
11. Internal Amoco Report, June 1979.
12. Mercer, B. W. Analysis, Screening and Evaluation of
Control Technology for Wastewater Generated in Shale Oil
Development. Quarterly Report October - December 1978.
13. Mercer, B. W. Analysis, Screening and Evaluation of
Control Technology for Wastewater Generated in Shale Oil
Development. Quarterly Report July - September 1978.
14. Yen, T. F., et al. Degradation of the Organic Compounds in
Retort Water. Final report submitted to R. E. Poulson,
Laramie Energy Research Center, U.S. Department of Energy.
15. Hubbard, A. B. Method for Reclaiming Wastewater from Oil
Shale Processing. U.S. Department of the Interior, Bureau
of Mines, and Laramie Energy Research Center.
16. Osmonics, Inc. Application Test Report for Laramie Energy
Research Center, July 10, 1979. [
17. Crawford, et al. A Preliminary Assessment of the Environ-
mental Impacts from Oil Shale Developments. EPA-600/7-77-
069, July 1977. :
18. Energy Resource Development Systems Report, Volume III: Oil
Shale. EPA-600/7-79-060c, March 1979. - .
19. Shih, C. C., J. E. Cotter, C. EL Prien, and T. D. Nevens.
Technological Overview Reports for Eight Oil Shale Recovery
Processes. EPA-600/7-79-075, U.S. Environmental Protection
Agency, Cincinnati, Ohio. March 1979. 115 pp.
20. Baughman, G. L. Synthetic Fuels Data Handbook, Second
Edition. Cameron Engineers, Inc., Denver, Colorado, 1978.
438 pp. '. •
21. Jones, J. B., Jr. Recent Paraho Operations. In: Twelfth
Oil Shale Symposium Proceedings, Colorado School ofiMines,
Golden, Colorado, August 1979. pp. 184-194.
-------
22. Laramie Energy Research Center. ..Draft Environmental Impact
Statement: Proposed Paraho Full-size Module Project.
January 1977. 392 pp.
23. Paraho Announces Three-Phase Module Program. Synthetic
Fuels, 15(l):2-3 through 2-10, March 1978.
24. Compendium Reports on Oil Shale Technology, Slawson.& Yen,
EPA-600/7-79-039, January 1979.
25. White River Shale Project Files Detailed Development Plan;
Suspension Sought. Synthetic Fuels, 13(3):2-24 through
2-28, September 1976.
26. Court Injunction Suspends U-a/U-b Leases. Synthetic Fuels,
14(3):2-1 and 2-2, September 1977.
27. Hicks, R. E. and R. F. Probstein. Water Management in
Surface and In-Situ Oil Shale Processing. Presented at the
87th Meeting of AIChE. Boston, Massachusetts, August 1979.
28. Predicted Cost of Environmental Controls for a Commercial
Oil Shale Industry, Denver Research Institute. Prepared
under U.S. Department of Energy contract No. EPA-78-S-02--5107
29. Quality of Surface Water of the United States, Parts 9 & 10.
USGS, 1970. p. 33.
30. Cotter, J. E., C. H. Prien, J. J. Schmidt-Collerus, D. J.
Powell, R. Sung, C. Habenicht, and R. E. Pressey, Sampling •
and Analysis Research Program at the Paraho Oil Demonstra-
tion Plant, U.S. Environmental Protection Agency, contract
68-02-1881, 1977.
31. Atwood, Ro A., and R. N. Heistand. Environmental Evalua-
tions Paraho Operations. Final Technical Report, Develop-
ment Engineering, Inc., September 1978.
32. Laramie Energy Technology Center Process Effluent Evalua-
tion. Prepared by Science Applications for U.S., Environ-
mental Protection Agency under contract No. 31-109-38-3764,
May 1979.
33. Draft Environmental Impact Assessment for a Proposed Accel-
erated Paraho Oil Shale Research Project at Anvil Points,
Colorado. U.S. Bureau of Mines, May 1975.
34. White River Oil Shale Project, Detailed Development Plan,
Volume I.
35
-------
35. Harbert, Berg, and McWhorter. Lysimeter Study on the Disposal
of Paraho Retorted Oil Shale. EPA-600/7-79-188.
36. Pollution Control .Guidance for Oil Shale Development, by EPA
Oil Shale Work Group, Revised draft report and appendices,
July 1979. ;
37. Metcalf & Eddy, Inc. Water Pollution Potential from Surface
Disposal of Processed Oil Shale from the TOSCO II Process.
Colony Development Operation, Denver, Colorado, October
1975.
38. Water Management in Oil Shale Mining, Volume I. Prepared
for U.S. Bureau of Mines under contract no. J0265019.
Colder & Assoc., September 1977.
39. Colony, An Environmental Impact Analysis for a Shale Oil
Complex at Parachute Creek, Colorado, Part 1: Plant,
Complex and Service Corridor, 1974.
40. Synthetic Fuels Data Handbook, Cameron Engineers, Inc., T. A.
Hendrickson. Denver, Colorado, 1975.
41. Knight, J. H., and J. W. Fishback. Superior's Circular
Grate Oil Shale Retorting Process and Australian Rundle Oil
Shale Process Design. In: Twelfth Oil Shale Symposium
Proceedings, Colorado School of Mines, Golden, Colorado,
August 1979. pp. 1-16.
42. Draft Environmental Statement: Proposed Superior Oil
Company Land Exchange and Oil Shale Resource Development.
U.S. Bureau of Land Management. Denver, Colorado. 1979.
105 pp.
43. An Analysis of Water Requirements for Oil Shale Processing
by Surface Retorting, T.ID 27954.
44. Hopkins, J. M., H. C. Huffman, A. Kelley, and J. R. ;Pawnall.
Development of Union Oil Company Upflow Retorting Technology.
Presented at the 81st AIChE National Meeting, April 11-14,
1976, Kansas City, Missouri. :
45. Energy from the West: Energy Resource Development Systems
Report, Volume III: Oil Shale. EPA-600/7-79-060C, U.S.
Environmental Protection Agency, Washington, D.C. March
1979. 301 pp.
46. Merrow, E. W. Constraints on the Commercialization ;of Oil
Shale. R-2293-DOE, U.S. Department of Energy, Washington,
D.C. September 1978. 133 'pp.
36
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47. An Engineering Analysis Report-on the Union B Process, TRW/
Denver Research Institute, EPA Contract 68-02-1881. March
1977.
48.- An Engineering Report on the Lurgi Retorting Process for Oil
Shale. Prepared for the U.S. Environmental Protection
Agency under Contract 68-02-1881, TRW. 1977.
49. Ashland Oil, Inc., and Occidental Oil Shale, Inc. Modifica-
tions to the Detailed Development Plan for Oil Shale Tract
C-b. February 1977. Ill pp.
50. Oxy's Logan Wash Retort No. 6 Burn Continues. Synthetic
Fuels, 16(1):2-1 and 2-59, March 1979.
51. Ashland Withdraws from C-b Oil Shale Venture. Synthetic
Fuels, 16(l):2-25, March 1979.
52. News Flashes. Chemical Engineering, 86(17):89, August 13,
1979.
53. Oil Shale Tract C-b. Detailed Development Plan and Related
Materials, February 1976. :
54. Loucks, R. A. Occidental Vertical Modified In-Situ Process
for the Recovery of Oil from Oil Shale Phase I: Quarterly
Progress Report for the Period May 1, 1978 through July 31,
1978, Occidental Oil Shale, Inc.
55. Lewis, A. E., and A. J. Rothman. Rubble In-Situ Extraction
(RISE): A Proposed Program for Recovery of Oil ;from Oil
Shale. UCRL-51768. U.S. Energy Research and Development
Administration Contract No. W-7405-Eng-48. March 1975.
26 pp.
56. Gulf Oil Corporation and Standard Oil Company (Indiana).
Revised Detailed Development Plan for Oil Shale Tract C-a,
three volumes. Denver, Colorado. May 1977.
57. Detailed Development Plan, Vols, I-V, Federal Oil Shale
Lease Tract C-a (Rio Blanco Oil Shale Project), submitted to
Area Oil Shale Supervisor. March 1976. ;
58. Equity/DOE BX In-Situ Project is Progressing. Synthetic
Fuels, 16(1 ):pp. 2-6 through 2-9, March 1979.
59. CPI News Briefs. Chemical Engineering, 86(17):102, August
13, 1979.
60. Equity Oil/ERDA Sign Cooperative Agreement. Synthetic Fuels,
14(3):2-31, September 1977.
37
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61. McNamara, P. H., C. A. Peil, and L. J. Washington. Charac-
terization, Fracturing, and True In-Situ Retorting in the
Antrim Shale of Michigan. In: Twelfth Oil Shale Symposium
Proceedings, Colorado School of Mines, Golden, Colorado,
August 1979. pp. 353-365. ;
62. Horst, B. I., and E. I. Rosier. Laramie Energy Technology
Center Process Evaluation (draft report). Contract JJo. 31-
109-38-3764, U.S. Department of Energy, Laramie, Wyoming.
May 25, 1979. 313 pp. ; ;
63. Martel, R. A. and A. E. Harak. Preliminary Results from
Retorting Michigan Antrim Shale. LERC/TPR-77/1, LERC,
ERDA, Laramie, Wyoming, July 1977.
64. Lekas, M. A. Progress Repdrt on the Geokinetics Horizontal
In-Situ Retorting Process. In: Twelfth Oil Shale Symposium
Proceedings, Colorado School of Mines, Golden, Colorado,
August 1979. pp. 228-236.
65. Delaney, J. L. Sampling arid Analytical Plan for Environ-
mental Characterization of In-Situ Oil Shale Retorting at
Geokinetics, Inc., Kamp Kerogen, Retort 17. Contract No.
68-03-2550, U.S. Environmental Protection Agency, Cincinnati,
Ohio. March 1979. 78 pp. :
66. Hutchinson, D. L. Appendix D, GKI Water Quality Study.
Progress Report.
67. Preliminary data generated ;by Monsanto Research Corporation
for the U.S. Environmental iProtection Agency under contract
68-03-2550.
38
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APPENDIX A . •
OIL SHALE RETORTING PROCESSES
SURFACE RETORTING PROCESSES
Paraho Process
Process Description^[17]—
The Paraho process is a developmental outgrowth of the Gas Combus-
tion Retort, developed by the U.S. Bureau of Mines in 1951 at
Anvil Points, Colorado [17]. :
The Paraho Process may be operated in one of two modes, gas com-
bustion or hot inert gas retorting. The gas combustion mode is a
direct process and is depicted in Figure A-l. In this mode,
shale is introduced into the top of the retort through a rotating
spreader, passes through 4 zones, and is discharged through a
special, hydraulically operated discharge grate, which more
uniformly controls solids flow rates. Retort off-gases (approxi-
mately 3.8 x 106 J/cm3 or 100 Btu/SCF) are recycled to the retort
at three points. These gases, together with combustion of a por-
tion of the carbonaceous residue on the spent shale, provide the
heat for the process. The retorted shale containing a 2.3% car-
bonaceous residue, is discharged to disposal at approximately 150°C
(300°F). Retort gases, oil mist, and vapors leave the top of the
retort at approximately 150°F (65.5°C), and pass through a cyclone,
wet electrostatic precipitator, and aerial condenser to remove oil.
As previously noted, a portion of these gases are recycled to the
retort. :
The Paraho process may also be operated in hot inert gas, or
indirect mode (Figure A-2), in which case no combustion is
carried out in the retort, per se. The retort gases therefore
have a high heating value of 3.4 x 107 (900 Btu/SCF). A portion
of these gases are used to heat a recycle portion of the gas in an
external furnace, and the latter are recycled to the retort as a
heat source. The retorted shale has a carbon content; of 4.5%.
A combination of direct and indirect operating modes may also be
employed.
[17] Crawford, et al. A Preliminary Assessment of the Environ-
mental Impacts from Oil Shale Developments. EPA-600/7-77-
069, July 1977. :
39
-------
f— 1 r"
GRATE SPEED
rnwipni i CP .
RAW SHALE
Vr
MIST FORMATION
AND •-"
PREHEATING ZONE
RETORTING ZONE
COMBUSTION ZONE
RESIDUE COOLING
AND
. GAS PREHEATING .
\ ZONE /
OILMIST
SEPARATORS
I fsT^
f\ 1 /""V~
-------
RAW SHALE
GRATE SPEED
CONTROLLER:
OIL MIST
SEPARATORS
MIST FORMATION
AND
PREHEATING ZONE
RETORTING ZONE
HEATING ZONE
STACK
CRUDE SHALE
OIL
GAS
--HEAT1R
n:
ELECTROSTATIC
REC1PITATOR/
BLOWER
CRUDE
SHALE OIL
•NET PRODUCT GAS
AIR BLOWER
f RETORTED SHALE
Figure A-2.
Schematic of Paraho indirect mode hot
inert gas retorting [17].
41
-------
Various upgrading processes may also be present at the retorting
site. These include delayed coking followed by hydrogenjation of
the naphtha and gas oil fractions. The products of this: process
are a clean crude shale oil, ammonia, sulfur and coke [18].
Process Use
The Paraho process is intended for use at the White River project
and is presently being used by the developer, Paraho Development
Corporation at Anvil Points, Colorado. Development of the Paraho
processes began in 1972 when Development Engineering, Inc., a
subsidiary of Paraho Development Corporation, obtained a lease
from the Department of the Interior to conduct surface oil shale
retorting at Anvil Points, Colorado [19]. In late 1973, with
funds provided by 17 participating companies, two Paraho oil
shale retorts were constructed. One was a small pilot-plant to
investigate operating parameters, and the other was a 410-Mg
(450-ton)/day semiworks for large-scale testing under production
conditions [19]. The semiworks retort was operated successfully
in both the direct and indirect modes of heating by February 1976
[19]. At that time, the Office of Naval Research and the Energy
Research and Development Administration (now DOE) awarded Paraho
a $13-M_contract to produce 15,900 m3 (100,000 bbl) of shale oil
for refining tests [20]. The program was completed last year
[21]. In January 1977, a draft environmental impact statement
was submitted for Paraho's proposed full-size commercial retort-
ing facility [22], which was designed to process 11,800 Mg
(13,000 tons)/day of raw shale [19]. Paraho initiated Phase I
of the three-phase, 5-year, $92-M program at its own expense
on December 1, 1977 [23]. :
[18] Energy Resource Development Systems Report, Volume III1: Oil
Shale. EPA-600/7-79-060C, March 1979. :
[19] Shih, C. C., J. E. Cotter, C. H. Prien, and T. D. Nevens.
Technological Overview Reports for Eight Oil Shale Recovery
Processes. EPA-690/7-79-075, U.S. Environmental Protection
Agency, Cincinnati, Ohio.- March 1979. 115 pp.
[20] Baughman, G. L. Synthetic Fuels Data Handbook, Second Edi-
tion. Cameron Engineers, Inc., Denver, Colorado, 1978,.
438 pp. ;
[21] Jones, J. B., Jr. Recent Paraho Operations. In: Twelfth
Oil Shale Symposium Proceedings, Colorado School of Mines,
Golden, Colorado, August 1979. pp 184-194. ;
[22] Laramie Energy Research Center. Draft Environmental Impact
Statement: Proposed Paraho Full-size Module Project.
January 1977. 392 pp. >.
[23] Paraho Announces Three-Phase Module Program. Synthetic
Fuels, 15(1):2-3.through 2-10, March 1978.
42
-------
The present semiworks at Anvil Points is larger than a pilot-plant
but smaller than a commercial scale facility and is depicted in
Figure A-3. In addition to the retort, supportive process equip-
ment includes raw shale crushers, condensers for oil shale vapor
and product gas, a precipitator, various blowers for air, recycle
and product gas, water storage and treatment facilities and spent
shale disposal equipment [24].
The Paraho process is also intended for use at the White River
Shale project to retort coarse rubblized shale, while ; fines will
be retorted in TOSCO II retorts [10]. Planned use of the Paraho
process was indicated on July 1, 1976, when the White River Shale
Oil Corporation submitted a Detailed Development Plan calling for
the use of both types of Paraho retorting technology to process
85% of the shale mined from Tracts U-a and U-b in Uintah County,
Utah [25]. However, exactly one year later, a court injunction
suspended White River's leases due to questions of property
ownership, specifically unpatented pre-1920 oil shale placer
mining claims and an application by Peninsula Mining Company for
a Utah state lease to the same property [26]. Therefore, develop-
ment of Tracts U-a and U-b by White River will be delayed for
several years pending resolution of the legal issues [26] (personal
communication, Rees C. Madsen, White River Shale Oil Corporation,
to Gerald M. Rinaldi, Monsanto Research Corporation, August 17,
1979).
The project activities planned for Tracts U-a and U-b are expected
to occur in four phases. In Phase I a 335 meter (1,100 ft) deep
access shaft for a subsequent room-and-pillar mine will first be
established near the center of the combined tracts, in order to.
permit testing of the shale deposit. Mining will be initiated.
some six months later. Mine development will continue, and
extend throughout the following Phase II, with an expansion of
production from 1.814 x 106 kg (2,000 tons) to 9.10 x 106 kg
(10,000 tons) of raw shale per day.
[24] Compendium Reports on Oil Shale Technology, Slawson & Yen,
EPA-600/7-79-039, January 1979.
[25] White River Shale Project Files Detailed Development Plan;
Suspension Sought. Synthetic Fuels, 13(3):2-24 through
2-28, September 1976.
[26] Court Injunction Suspends U-a/U-b Leases. Synthetic Fuels
14(3):2-1 and 2-2, September 1977.
43
-------
reco SHALE
rito
•OTATHK; souos
OlSTHl«UTO«
•OTTOH —
OI1TKIBOTIO*
*from Jones, John B., "The
Paraho Oil Shale Rttort,
81Jt H«t. Mtg., AIChE,
City, Mo., April 11-14.
»ETO«T£0
MTOKAULICU.LT OPERATED
SKATE CONTROLS
MErOKTCD SHALE
Figure A-3. The Paraho retort.
44
-------
Phase II will be of four years duration, and will involve the
construction and operation of a single modular vertical retort
with a throughput capacity of up to 9.10 x 10e kg of shale (10,000
tons) per day. The retort design has not yet been selected, but
could be a Paraho direct-heat design later modified for indirect
heating, or another available vertical-type retort. At a retort
feed rate of 6.80 x 10s kg (7,500 tons) of coarse shale per day,
some 750 cubic meters (4,700 barrels) of crude oil would be pro-
duced daily.
A commercial pl-ant (Phase III), with a first "train" projected
capacity of 7.25 x 107 kg (80,000 tons) per day, will be con-
structed, for start-up some 2 1/2 years after the successful
conclusion of Phase II. This will be followed by start-up of a
second commercial train of the same capacity some 1 1/2 years
after the first, thus bringing total plant -production capacity to •
an ultimate 1.45 x 10s kg (160,000 tons) per day.
It is currently intended that the major portion (85%) of the
Phases III and IV retorting will be carried out in vertical,
gas-combustion type, direct and indirect-mode retorts, but that
the 15% of crushing fines-produced will be pyrolyzed in TOSCO
II-type retorts. It is expected that all of the 15,800 cubic
meters (100,000 barrels) of shale oil produced daily at maximum
scale-up will be upgraded in facilities similar to those to be
used for the Colony and Tract C-b projects.
Water Quality/Quantity Data—•
A conceptual water flow diagram of a Paraho surface retort oil
shale facility as designed by WPA is shown in Figure A-4. It is
envisioned that water resulting from retorting will ultimately be
used as cooling water makeup following ammonia/acid gas stripping,
organics removal, and clarification. Slowdown from the cooling
tower will then be used in spent shale moisturizing with no
treatment requirements.
Available water quality data is listed in Tables A-l through A-4.
Tosco II Process
Process Description [17]—•
The TOSCO II process originated as the Aspeco process which The
Oil Shale Corporation (TOSCO) purchased from Aspergren and Company
of Stockholm, Sweden in 1952. Under TOSCO sponsorship, initial
development work was conducted from 1955 to 1966 by the Denver
Research Institute using a 24 ton/day pilot-plant.
In the TOSCO II process, minus one-half inch crushed shale (inclu-
ding fines) is preheated by direct contact with hot flue gases
from a ball heater (see Figure A-5) used downstream in the process,
The preheated shale is then fed to a horizontal, rotating retort,
where it is heated to 482°C (900°F) by mixing with small, hot
45
-------
Flows in L/s (gpm)
COLORADO RIVER
207(3276)
Figure A-4. Major water streams for Paraho direct heated process
producing 15,900 ms/day (99,170 BPSD) .crude'shale
oil [27].
[27] Hicks, R. E. and R. F. Probstein. Water Management in Sur-
face and In-Situ Oil Shale Processing. Presented at the
87th Meeting of AIChE. Boston, Massachusetts, August 1979.
46
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-------
TABLE A-3. CHARACTERISTICS OF OTHER WASTEWATER
STREAMS - PARAHO PROCESS
mg/L
Species
TOG
BOD
COD
Oil and grease
IDS
Solids (suspended)
Phenols
Si02
Bicarbonate
Chloride
•Fluoride
Nitrate
Sulfate
Aluminum
Arsenic
Barium
Beryllium
Boron
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese.
Molybdenum
Nickel
Potassium
Selenium
Silver
Strontium
Vanadium
Sodium
_. : - • spent:
Sanitary ,. shale c
Service wastewater Slowdowns ' leachate
water* [341 [341 [34] [35]
400
50 - 500 20
100 - 2,000 '> 50
50 - 1,000 <5
500 - 2,000 1,000 - 2,000 5,000 - 10,000 37,000
30 - 500 30 100 - 500 ;
<1
: 46.7
; 29 . 4
2,300
; , 19,7
<0 . 1
20» 200
: 0.16
OT C
. 15
: 0.24
0.007
2QQ
. y y
'• '. 527
0.02
0.32
029
0*.042
202
1 O1 26
: , ' 9'!45
0.04
1,460
0 . 04
0.004
13.6
0.45
: 1.09
10,400
a
'Estimated data for White River Shale Project where Paraho Technology will
be used to retort rubblized shale, and Tosco II technology will be used to
retort fines.
^From cooling tower, steam generator and spent ion exchange reagent.
cMaximum concentrations observed in a series of tests utilizing various
soil cover thicknesses and lysimeter ^lopes.
[34] Whie River Oil Shale Project, Detailed Development Plan, Volume I.
[35] Harbert, Berg, and McWhorter. Lysimeter Study on the Disposal of
Paraho Retorted Oil Shale. EPA-600/7-79-188.
50
-------
TABLE A-4.
CHARACTERISTICS 'OF TREATED WASTE-
WATER STREAMS - PARAHO PROCESS
mg/L
Species
Foul waterTreated stripper
stripper effluent/service
effluent*'0 [34] watera'c [34]
BOD
COD
Oil and grease
TDS
Solids (suspended)
Ammonia
Phenols
Phosphate (total)
500
50
25
80
- 1,500
- 100
- 50
- 150
150
20
800
200
10
5
- 250
- 50
- 1,000
- 300
- 15
<1
- 10
Estimated data for White River Shale Project where
Paraho technology will be used to retort rubblized
shale, and Tosco II technology will be used to
retort fines. .
Stripper treating various gas and oil upgrading,
and retort wastewater streams.
GFollowing flotation and biological oxidation.
RAW SHAL£
RUE GAS TO
ATMOSPHERE
BALLS
SURGE
HOPPER
RUE GAS TO
ATMOSPHERE
8ALLRUTRIATOR
HOT PROCESSED
SHALE
COOLER
PROCESSED SHALE
TO DISPOSAL
Figure A-5. Schematic of the TOSCO II Retorting Process [17]
51
-------
ceramic balls. Shale oil vapors' are removed, fractionated, and
condensed. The cooled balls and, retorted (spent) shale are dis-
charged from the retort and screened to separate the spent shale
from the balls. The spent shale; is cooled in a rotating drum
steam generator, moistened to about 14% water content, and trans-
ported to the disposal site. As; discarded, it normally contains
about 4% to 5% residual carbonaceous matter.
The cooled balls are sent to an external ball heater, reheated,
and recycled to the retort. In a typical situation, the ball to
raw shale feed ratio to the retort is about 2:1. The ball heater
can use an outside fuel, a portion of retort off-gases, and/or
even the carbonaceous residue on the spent shale as a fuel
source(s).
The crude shale oil is fractionated into gas, naphtha, gas oil,
and bottoms oil. Subsequent hydrotreating and coking is used to
upgrade the products to plant fuel gases and LPG, low sulfur fuel
oil, diesel fuel, plus sulfur, ammonia, and petroleum coke
byproducts. •
TOSCO has presented considerable detail regarding proposed pol-
lution control technologies to be utilized throughout its various
operations (mining, retorting, upgrading). In the case of the
retorting plant, a venturi wet scrubber is to be used for dust
control in the shale preheat system, together with settling
chambers and cyclones. Hot flue gases in the preheat system
will be incinerated prior to discharge, in order to reduce trace
hydrocarbons. Warm flue gas and a high energy venturi scrubber
will remove residual dust from the ball recirculation system. A
foul water stripper is planned to remove most of the NH3, H2S,
and C02 gases from plant waters. Plant fuel gases will be treated
to reduce the sulfur and nitrogen present, prior to on-site use
for heat generation-: TOSCO has indicated H2S recovery as
elemental sulfur in a Claus Plant, with tail gas treatment for
trace S02 removal in a Wellman-I^ord unit. Arsenic is removed
from the gas oil and naphtha prior to hydrogenation by a pro-
prietary catalytic process. Emissions from the moisturizing of
spent shale are controlled by a venturi wet scrubber.
Process Use—
The TOSCO II technology is being considered for use by three shale
oil developers: the TOSCO Corporation on their TOSCO Sand Wash
Project, TOSCO and ARCO forming[the Colony Development Company,
and by Sohio Natural Resource Company at White River Shale
project. The TOSCO Corporation has leases on five tracts of land
totalling 5,949 ha (14,688 acres) at its Sand Wash Oil Shale
property about 56 k (35 miles) south of Vernal, Utah. The
company is in the second year of an eight year plan, under terms
of a Unitization Agreement with the state of Utah, to prepare
the leases for eventual commercial development. In December 1978,
the Utah Conservation Committee and the State Division of Oil,
52 ;
-------
Gas and Mining issued permits for TOSCO Corporation to sink an
experimental mine shaft on the Sand Wash properties. The experi-
mental mine shaft will have a diameter of 3.67 m (12 feet) and a
depth of 732 m (2,400 feet). Initial field work is scheduled to
begin in 1979 with the shaft estimated to be completed in 18
months to 3 years. An experimental mining program will follow
when the shaft sinking is completed. During this experimental
mining phase no on-site processing of the oil shale is planned,
but shale samples will be sent to TOSCO's Research Center near
Golden, Colorado for retorting in a .1 L/kg (25 TPD) TOSCO
II pilot-plant. Information from the experimental mining program
will be used to help prepare final design criteria for a commer-
cial facility. TOSCO recently completed a preliminary design and
updated cost estimate for eventually building a commercial-sized
plant at Sand Wash. The proposed commercial plant would use the
company's abovegrourid TOSCO II Process to extract petroleum
liquids, gases and byproducts from crushed oil shale rock. Six
1.0 x 102 kg/day (11,000 ton/day) TOSCO II retort modules would
be included, along with equipment for product storage and loading,
utilities and disposal of spent shale [36]. Site exploration,
environmental monitoring and shaft sinking is currently underway
oh the site.
In 1964 TOSCO with SOHIO and Cleveland Cliffs Iron Company formed
the Colony Development Company to demonstrate the TOSCO II proc-
ess on a semiworks scale. Ashland Oil and Shell Oil eventually
replaced SOHIO and Cliffs. Atlantic Richfield joined the Colony
group in 1969 when a second semiworks program was initiated [36].
In 1972, the Colony group (now composed of ARCO and TOSCO) com-
pleted operations on its 1,000 TPD TOSCO II semiworks, plant on
Parachute Creek, and prepared a design for a 50,000 barrel/day
commercial plant [18]. A final EIS for the project was approved
in 1977. Colony is now in the process of applying for the'
permits necessary to construct a commercial project o.n their
Davis Gulch site, definite plans to proceed with plant construc-
tion have not yet been released [36]. ; ;
Oil shale at the Davis Gulch site will be room-and-pillar mined
and retorted using TOSCO II technology [36]. •
The White River Shale Project was formed in June 1974 by Phillips
Petroleum Company and Sun Oil Company (now Sunoco Energy Develop-
ment Company), the-owners of the Federal Oil Shale Lease to U~a,
and Sohio Petroleum Company (now Sohio Natural Resources Company),
the owner of the Federal Oil Shale Lease to U-b, for the purpose
of preparing and implementing a plan for the joint development of
[36] Pollution Control Guidance for Oil Shale Development, by EPA
Oil Shale Work Group, Revised draft report and appendices,
July 1979. ;
53
-------
two lease tracts. Phillips and Sun were awarded the U-a lease in
May 1974 for a bonus bid of approximately $75.6 million. iThe
White River Shale Oil Corporation (Phillips, Sun and Sohio) was
awarded the U-b lease for a bonus bid of approximately $45.1
million, but the tract has since been fully assigned to Sohio
Natural Resources Company [36]. The project activities planned
for the tracts are expected to occur in four phases. -In Phase I
a 335 meter (1,100 ft) deep access shaft for a subsequent roorn-
and-pillar mine will first be established near the center;of the
combined tracts, in order to permit testing of the shale deposit.
Mining will be initiated some six months later. Mine development
will continue, and extend throughout the following Phase II, with
an expansion of production from 1.81 x 106 kg (2,000 tons) to
9.10 x 10s kg (10,000 tons) of raw shale per day. Phase II will
be of four years duration, and will involve the construction and
operation of a single modular vertical retort with a throughput
capacity of up to 9.10 x 106 kg of shale (10,000 tons) per day.
The retort design has not yet been selected, but could be!a
Paraho direct-heat design later modified for indirect heating,, or
another available vertical-type retort. At a retort feed rate of
6.80 x 106 (7,500 tons) of coarse shale per day, some 750 cubic
meters (4,700 barrels) of crude oil would be produced daily. A
commercial plant (Phase III), with a first "train" projected
capacity of 7.25 x 107 kg (80,000 tons) per day, will be Construc-
ted for start-up some 2 1/2 years after the successful conclusion
of Phase II. This will be followed by start-up of a second
commercial train of the same capacity some. 1 1/2 years after the
first, thus bringing total plant;production capacity to an ulti-
mate 1.45 x 10s kg (160,000 tons:) per day. It is currently
intended that the major portion '(85%) of the Phases III and IV
retorting will be carried out in vertical, gas-combustion type,
direct and indirect-mode retorts, but that the 15% of crushing
fines produced will be pyrolyzed in TOSCO 11-type retorts1. It is
expected that all of the 15,800 cubic meters (100,000 barrels) of
shale oil produced daily at maximum scale-up will be upgraded in
facilities similar to those to be used for the Colony and Tract
C-b projects. At present it is not known when, or on what basis,
future development of tracts U-a and U-b will proceed. Lease
terms were suspended in May 1977! until court resolution of land
title [36] • :
Water Quality/Quantity Data—
A conceptual water flow diagram of a TOSCO II surface retort
facility as designed by WPA is shown in Figure A-6. Water from
retorting will be used in spent shale moistening after foul water
stripping and organics removal. j
Available water quality data is listed in Tables A-5 through A-7.
54
-------
COLORADCT RIVER
Flows
t29(2046)
2(35)
in L/s
22
(3L.J
— #-
(gum)
1 366(5825)
_, SOURCE WATER .
"*" CLARIFICATION ^
l.JO( 2066) """• ""
1(20)
BIOLC31CAL
OHOATION
Ot
,,,<., POTABLE t
"* — — ^ • SAM TART
gested Sludg
e 1(14)
r T
LEACHihS i SPENT SHALE OUST CONTROL
REVEGETATION DISPOSAL MINE I PLANT
,
i
..15(23<) '.39(610)
60(946)
,45(710)
RETORTING "SCJ
i
27(425)
1
•• . i
4(60) 91(1445)
BfW TRCAT>'rNT lal^
STEAM LOSS
i COhSlHEO
71(1120)1 &4(1335) 7(110)
1 T
142(2254)
3 WATER
4rhT
142(2254)
96(1520)
^-EVWOWTJON
STEA« GENERATORS COOLING TO-ER „,„
"•• ' ^ DRIFT
1(10)
f!4(215) y J46(724)
,6(100) lf5s(1669) 102(1609)
Klhu LISTENING TREATERS v
2t36) 32(510;
J29(461) LOSSES
FOUL WATER
STBIPPER
i
>"^" NH, SEPAHAUON •
Y v 28' 4 39!
SERVICE i
FIRE WATER
Rl
NOFf
1(16)
i
7(110) j,
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WASH
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.,.>_ 1 LOSSES
I'"
^ ORCAN1CS REMOVAL 2SM34! ft
01L/WATFB Y f_
"~ • SEPARATOR Jb
66(1049)
ZA1ION
! 35(560)
8(126)
Figure A-6.
Major water streams for TOSCO II process producing
7,500 m3/day (47,000 BPSD) of upgraded shale oil,
and 680 ms/day (4,300 BPSD) LPG [27].
55
-------
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-------
Superior Process
Process Description—
The Superior Oil Company has been working on a multimineral
recovery (including the extraction of shale oil) process since
1967. Different from other potential shale oil extraction proc-
esses, Superior technology recovers rahcolite and dawsonite at
the same time oil is extracted from oil shale.
Superior has developed commercial design configurations for both
direct- and indirect-heated modes of operation of a circular
grate retort adopted from commercially proven iron ore processing
applications [41]. A simplified flow diagram for direct-heated
oil shale retorting is provided in Figure A-7, and equipment
sketches are provided in Figures A-8 and A-9.
A doughnut-shaped retort is divided into five separately enclosed
sections: a loading zone, a heating zone, a residual carbon
recovery zone, a cooling zone, and, to complete the circle, an
unloading zone adjacent to the original loading sector [19]. Raw
crushed shale enters through an airlock system, which together
with circumferential water seals makes the unit gastight. The
bed of shale loaded on the travelling grate passes first into the
heating zone, where the shale is contacted by a stream of hot
neutral or reducing gases that heat the shale to retorting
temperature. The retorted shale travels from the retorting zone
to the residual carbon recovery (or combustion) zone, where it
is contacted with steam and air to form producer gas that provides
fuel for the utility plant. Next, the retorted shale travels
to the retort cooling zone where its temperature is Deduced. It
then moves to the unloading zone where it is discharged from the
retort. •
Upon leaving the heating zone of the retort, the stream of oil
mist and process gas is contacted with water sprays [41]. The
water spray serves to cool the gas and water vapor to saturation ,
temperature, scrub out sulfur compounds, and stabilize the.
ionizing electrode and grounding plates in the electrostatic
precipitator located downstream. Both wet and dry electrostatic
precipitators were used to recover shale oil during testing of a
250 ton/day pilot plant [41].
[41] Knight, J. H., and J. W. Fishback. Superior's Circular
Grate Oil Shale Retorting Process and Australian Rundle Oil
Shale Process Design. In: Twelfth Oil Shale Symposium
Proceedings, Colorado School of Mines, Golden, Colorado,
August 1979. pp. 1-16.
59
-------
COOL RECYLE GAS
HOT RECYCLE GAS
PREHEATED COMBUSTION AIR
SHALE FEED
IN
DIRECT
HEATING
LOWBTU
BURNERS
AIR IN
|- COOLING
«*"* KWWRV»Y««« I BY AIR
i i . . GAS i
GAS COMPRESSOR
01 L& WATER
OUT
-* LOW 8TU SURPLUS
RETORT GAS OUT
NOTE: THE CIRCULAR PATH OFTHE SOLIDS
BED IS PICTURED AS A STRAIGHT
PATH FOR CLARITY
Figure A-7.
Schematic diagram of Superior's commercial
circular grate retort (direct-heated mode) [41]
CIRCULAR GRATE
RETORT
Residua^
Figure A-8. Functional Design of Superior retort [IB]
60
-------
-HOOD
WATER
SEALS
SUPPORTING
IDLER WHEEL
Figure A-9. Cross sectional view of Superior retort [18].
Process Use—
The Superior process has not been called for by any developer
other than Superior Oil Company. Superior Oil Company has owned
about 26 km2 (6,500 acres) of land in the northern portion of
Colorado's Piceance Creek basin for nearly 40 years :[36]. In
1967, Superior initiated a research program for integrated
recovery of oil shale and.also saline minerals, dawsonite
(NaAl(OH)?C03), and nacolite (NaHCOs), found at that :site.
However, in 1973, in order to block up a .more manageable tract
for commercial development using underground mining, Superior
applied to the Bureau of Land Management of the Department of the
Interior for a land exchange; a draft environmental impact state-
ment regarding this action is currently under review'[42]. Supe-
rior anticipates approval of the environmental impact statement
by the end of this year, to be followed by a decision on the land
exchange request by mid-1980; after that time, it will take three
to five years to design, construct, and initiate operation of a
commercial oil shale production facility (personal communication,
J. William Fishback, Superior Oil Company, to Gerald m Rinaldi,
Monsanto Research Corporation, August 17, 1979).
[42] Draft Environmental Statement: Proposed Superior Oil Company
Land Exchange and Oil Shale Resource Development. U.S.
Bureau of Land Management. Denver, Colorado. 1979. 105 pp.
61
-------
Water Quality Data— . '
Water quality data from the Superior process is unavailable. it
is expected that in addition to control of normal shale oil plant
emissions and effluents, control: of brines and wastes from the
leaching plant and associated mineral recovery activities will be
necessary [17]. In a second report [43], it is anticipated that
fresh water will be recovered from the process, _and the remainder
will be used in spent shale moisturizing (see Figure A-10).
I LOSSES
;2728
RAW WATER
PRIMARY MINE WATER
TOTAL PLANT REQUIREMENTS
• DUST CONTROL
• RETORTING &PREREFINING
• MULTIMINERAL RECOVERY
NO POWER GENERATION
RECOVERY OF
FRESH WATER
3081
j»
SPENT SHALE
MOISTURIZATION
Multimineral Recovery
All flows in gallons per minute
Figure A-10.
Overall water requirements for
Superior's 100,000 BPD plant.
Union Process
Process Description [17]— ; _ ,
in the Retort B process, shown in Figure A-ll, crushed oil snaie
in the size range of .32 to 5.0; cm flows through two feed chutes
to a solids pump. The solids pump consists of two piston and
cylinder assemblies which alternately feed shale to the retort;
the pump is mounted on a movable carriage and is completely
enclosed within the feeder housing and immersed in oil. As shale
is moved upward through the retort by the upstroke of the piston,
it is met by a stream of 510 to! 540°C recycle gas from the _
recycle gas heater flowing downward. The rising oil shale bed is
heated to retorting temperature by countercurrent contact with
the hot recycle gas, resulting in the evolution of shale oil vapor
and make gas. This mixture of .shale oil vapor and make gas is
forced downward by the recycle 'gas, and cooled by contact with
the cold incoming shale in the lower section of the retort c?ne:
In the disengaging section surrounding the lower cone, the liquid
level is controlled by withdrawing the oil product, and ;the
[43] An Analysis of Water Requirements for Oil Shale Processing
by Surface Retorting, TID 27954.
'62
-------
RECYCLE GAS
HEATER
RETORT MAKE GAS TO
GAS TREATING
RETORTED SHALE
TO DISPOSAL
— RUNDOWN OIL PRODUCT
Figure A-ll. Flow diagram for Union B retorting process [44].
recycle and make gas is removed from the space above the liquid
level. As shown in Figure A-ll, the make gas is first sent to
a venturi scrubber for cooling and heavy ends removed by oil
scrubbing. That portion of the 3.0 x 107 J/cm3 (800 Btu/SCF) gas
recycled is then processed by compression and oil scrubbing to re-
move 'additional naphtha and heavy ends, followed by hydrogen sul-
fide removal in a Stretford unit. The sweetened make gas is used
as plant fuel.
The product oil withdrawn from the retort is treated sequentially
for solids, arsenic, and light ends naphtha removal. The solids
removal is accomplished by two stages of water washing. The
shale fines are collected in the water phase which is recycled
to the water seal. The water seal is a Union Oil concept shown
in Figure A-ll, in which a water level is maintained in a conveyor
system for retorted shale removal to seal the retort pressure
from atmosphere. For arsenic removal, a proprietary Union Oil_
process employing an adsorbent is utilized to reduce the arsenic
[44] Hopkins, J. M., H. C. Huffman, A. Kelley, and J. R. Pawnall.
Development of Union Oil Company Upflow Retorting Technology.
Presented at the 81st AIChE National Meeting, April 11-14,
1976, Kansas City, Missouri.
63
-------
content of the raw shale oil from 50 ppm to 2 ppm. The dearsen-
ated shale oil is then sent to a stripping column for stabiliza-
tion prior to shipment.
For the Retort B process, all the plant fuel requirements will be
met by the make gas produced. The principal pollution control
devices in the Union Oil design include the Stretford process
for hydrogen sulfide removal froft the retort make gas and oil/
water separation and sour water stripping for wastewater treat-
ment. The treated wastewater is used in the cooling and moisten-
ing of retorted shale to provide for dust control and compaction.
Process Use—
Union Oil Company began development of its oil shale retorting
technology in the early 1940s [45, 46]. The Union Retort A proc-
ess was demonstrated at Brea, California, with 1,800-kg (2-ton)/
day and 45,000-kg (50-ton)/day pilot-scale units. A 320-Mg
(350-ton)/day semiworks was then operated near Grand Valley,
Colorado, in the 1950s, achieving a throughput of 1,090-Mg
(l,200-tons)/day when operations were suspended in 1958.
Two improved versions of this original process — the Union Retort
B process and the Steam Gas Recirculation (SGR) System — were
developed in the 1970s [36, 45, 46]. The Union Retort B process,
although similar to A, uses external heating and recycling of the
gaseous products. The Retort B process has been studied at the
Union research facility but has mot undergone large-scale testing.
The SGR retorting system uses the "B" Retort to extract oil and
gas from shale. The hot spent sjhale is then brought into contact
with oxygen and steam, yielding low- or high-Btu fuel gas, depend-
ing on the nature of the oxygen Isource.
In 1978, Union announced plans for construction of a 9,070-Mg
(10,000-ton)/day commercial module using the Retort B design at
its Long Ridge site near the location of the earlier semiworks
[36]. Union proposed a cooperative $120M venture to the DOE for
development of such a commercial oil shale retorting facility.
The prototype plant would be constructed on Union Oil property
located on Parachute Creek, north of Grand Valley, Colorado.
[45] Energy from the West: Ene;rgy Resource Development Systems
Report, Volume III: Oil Shale. EPA-600/7-79-060C, U.S.
Environmental Protection Agency, Washington, D.C. March
1979. 301 pp.
[46] Merrow, E. W. Constraints; on the Commercialization of Oil
Shale. R-2293-DOE, U.S. Department of Energy, Washington,
D.C. September 1978. 133 pp.
i
64
-------
Water Quality/Quantity Data-- -•'• -
Little hars been published regarding the characterization of water
streams other than boiler and cooling tower streams (see Table
A-8) [36, 47]. It is apparent from Figure A-ll, that the major
end use of_water in the Union B process is spent shale moisturiz-
ing as it is in many other surface retorting processes. Since
gas condensates from the retort will be used ultimately for this
purpose, it is expected that treatment of gas condensate similar
to those required in the Paraho and Tosco II process will be
necessary before the condensate can be mixed with the spent
shale. .
Lurgi-Ruhrgas Process
Process Description [36,17]—
Lurgi Company has been developing oil shale processing technology
for the past 40 years. Two kilns were designed and installed for
an Estonian Shale Oil Company in the late 1930's. Several other
oil shale retorting processes were also developed by Lurgi to
the commercial stage.
The Lurgi-Ruhrgas Process was developed in the 1950's for the low-
temperature carbonization of subbituminous coal. It has also
been used for olefin production using sand as the heat carrier.
The process was demonstrated commercially in two units built in
Yugoslavia in 1963. Tests on oil shale have been performed in
equipment processing 16 TPD. American Lurgi has proposed scale-
up to 8,000 TPD commercial-size retorts. Eight such plants can
provide capacity for the production of 50,000 BPD shale oil.
The Lurgi-Ruhrgas process features the use of heat-carrier solids
of small particle size, such as sand grains or spent shale solids
derived from the retorting process. Figure A-12 is a simplified
diagram of the process. The hot solids are mixed with finely
crushed ^0.6 cm (-1/4 inch) raw oil shale in a sealed screw-type
conveyor. The organic constituents are pyrolyzed during the
mixing which occurs in this device. Upon leaving the screw
conveyor, the effluents are separated into solid and gaseous com-
ponents in a collection bin. A portion of the spent solids is
recycled to a lift pipe and the remainder is discarded. In the
lift pipe, the hot spent shale is contacted with air at approxi-
mately 400°C (750°F), raising the material pneumatically, and
simultaneously burning the carbon residue on the shale surface.
The combustion gases and hot spent shale are separated at about
650°C (1,200°F) in a collecting bin and the solids are mixed
again with incoming oil shale in the screw conveyor. Between
six and eight pounds of he at-carry ing solids are circulated arid
mixed with each pound of raw oil shale.
[47] An Engineering Analysis Report on the Union B Process, TRW/
Denver Research Institute, EPA Contract 68-02-1881. March
1977.
65 ;
-------
TABLE A-8.
CHARACTERISTICS OF VARIOUS WATER STREAMS
IN THE UNION B PROCESS [36, 47]
TDS, mg/L
SS, mg/L
Hardness , mg/L
Chloride, mg/L
Sulfate, mg/L
Calcium, mg/L
Magnesium, mg/L
Conductivity, umhos/cm
Sodium, mg/L
Fluoride, mg/L
Chromium, mg/L
Ion exchar
regenerate
wastewatt
20,420
2,043
9,889
2,780
4,500
2,190
1,130
Ion exchange
backwash and
; rinse
i
-------
Since no air is injected into the retorting area, the gas product
from the process has a high heating value. Furthermore, the oil
yield from the process typically ranges between 95% and 110% of
Fischer Assay. Since the residual carbon on the spent shale is
mostly utilized in the process, the overall thermal efficiency
is quite high.
Process Use--
The Rio Blanco Oil Shale Company, comprised of Gulf Oil Corpora-
tion and Standard Oil Company (Indiana) presently intends to use
two types of retorting technologies: the Lurgi-Ruhrgas process
for above ground retorting, and the Rubblized In-Situ Extraction
(RISE) process for below ground retorting [28]. Rio Blanco has
leased tract C-a for oil shale retorting since March 1, 1974. In
March, 1976, a Detailed Development Plan calling for open pit
mining and surface retorting was submitted. Shortly thereafter,
a one-year lease suspension was obtained because of a: number of
environmental and operational considerations. Rio Blanco sub-
mitted a revised DDP on May 25, 1977, which called for a ten-year
Modular Development Phase to perfect modified in-situ retorting
technology. This phase would be followed by a 30-year Commercial
Development Phase at a planned capacity of 76,000 BPD [36].
Water Quality/Quantity Data—
The only data identified to characterize Lurgi-Ruhrgas wastewater
is listed in Table A-9.
TABLE A-9. PROPERTIES OF LURGI-RUHRGAS GAS
CONDENSATE WASTEWATER [36, 48]
Concentration,
Constituent mg/L
Total hydrocarbons
(including phenols) 4,000
Dust 300
Ammonia 17,000
Sulfur 500
Phenols 260
pH 9.3
[48] An Engineering Report on the Lurgi Retorting Process for
Oil Shale. Prepared for the U.S. Environmental Protection
Agency under Contract 68-02-1881, TRW. 1977.
67
-------
MODIFIED IN-SITU PROCESSES : :
Occidental Process
Process Description [17, 18, 24]—
Occidental's modified in-situ process for shale oil recovery con-
sists of retorting a rubblized column of broken shale, formed by
expansion of the oil shale into ^ previously mined out void
volume. The Occidental procces involves three basic steps. The
first step is the mining out of approximately 20% of the oil
shale deposits (preferably low grade shale or barren rock),
either at the upper and/or lower level of the shale layer. This
is followed by the drilling of vertical longholes from the mined-
out room into the shale layer, loading those holes with an
ammonium nitrate-fuel oil (ANFO): explosive, and detonating it
with appropriate time delays so that the broken shale will fill
both the volume of the room and the volume of the shale column
before blasting. Finally, connections are made to both the top
and bottom and retorting is carried out (Figure A-13).
OIL RECOVERY
RECYCLE GAS
COMPRESSOR
AIR MAKE-UP
COMPRESSOR
BARRIER
OIL SUMP AND PUMP
Figure A-13. Schematic of the Occidental modified
in-situ process [17].
68:
-------
Retorting is initiated by heating the top of the rubblized shale
column with the flame formed from compressed air and an external
heat source, such as propane or natural gas. After several
hours, the external heat source is turned off, and the compressed
air flow (now mixed with steam) is maintained, utilizing the
carbonaceous residue in the retorted shale as fuel to sustain
combustion. In this vertical retorting process", the hot gases
from the combustion zone move downwards to pyrolyze the kerogen
in the shale below that zone, producing gases, water vapor, and
shale oil mist which collects in the trenches at the bottom of
the rubblized column (Figure A-14). The crude shale oil and
byproduct water are collected in a sump and pumped to storage.
AIR& STEAM
THICKNESS DEPENDENT v5"'
ON LOCATION „
OVERBURDEN
60-90
meters
'. y:/::'(vi;;- BURNEDOUT 'ZONE;. !jv:?x"'..
'
£-1 RETORTING AND_V_APORIZATION
$ VAPOR CONDENSATION ZONE
GASES, OIL, AND WATER
Mil
PILLAR
•OIL
PILLAR
A
Figure A-14.
Flame front movement in the Occidental
modified in-situ process [17].
69
-------
The off-gas consists of productsjfrom shale pyrolysis, carbon
dioxide and water vapor from the combustion of carbonaceous
residue, and carbon dioxide from1the decomposition of inorganic
carbonates (primarily dolomite arid calcite). Part of this off-
gas is recirculated to control both the oxygen level in the
incoming air and the retorting temperature. The off-gas has a
heating value of approximately 2*4 x 106 J/cm3 (65 Btu/SCF), and
the part of the off-gas not recycled is currently flared.:
Occidental envisions using the low Btu gas from a commercial
retort for generating electric power. Turbines manufactured by
Brown-Boveri of Switzerland will be investigated for this appli-
cation. According to Occidentals estimate, only 20% to 25% of
the electric power produced from the low-Btu gas is required for
operating the modified in-situ process.
Occidental has not disclosed any' information on the design of
surface oil and gas treatment plants. The minimum treatment
required for the crude shale oil! produced from the retorting
process will include phase separation of the oil from the: by-
product water and the stabilization of the oil product. The
wastewater effluent from the pha&e separator may be used for
steam generation after appropriate treatment.
Process Use—
The vertical, modified in-situ oil shale retorting process was
conceived by Occidental Petroleum's in-house research firm,
Garrett Research and Development Co., in the late 1960's [19, 49].
In May 1972, U.S. Patent 3,661, 423, "In-Situ Process for
Recovery of Carbonaceous Materials from Subterranean Deposits,"
was assigned to Occidental Petroleum. Site development for field
testing commenced in July 1972 at the head of Logan Wash, outside
of DeBeque, Colorado. In the ensuing months, three research
retorts were prepared and ignited. At the end of 1974, the
project was transferred to Occidental Oil Shale, Inc., upon its
establishment as a subsidiary of the Occidental Oil and Gas
Production Division. The first 'commercial-size retort (No. 4),
76 m (250 ft) high with a cross section of 37 m (120 ft) square,
was ignited in December 1975 and burned through June 1976 to
produce 100 m3 (27,500 gal) of crude shale oil [19]. As of
February 1979, Retort No. 6, the third commercial-size operation,
had produced nearly 5,090 m3 (32,000 bbl), and a total of
11,900 m3 (75,000 bbl) was expected to be produced before the
burn was completed in April 1979 [50]. This ongoing development
[49] Ashland Oil, Inc., and Occidental Oil Shale, Inc. Modifica-
tions to the Detailed Development Plan for Oil Shale Tract
C-b. February 1977. Ill |pp.
[50] Oxy's Logan Wash Retort No. 6 Burn Continues. Synthetic
Fuels, 16(1):2-1 and 2-59, March 1979.
70
-------
work is being conducted under a $60.5-M cost-sharing DOE contract,
signed in September 1977 [50].
In November 1976, Occidental Oil Shale formed a partnership with
Ashland Oil for the development of Federal Prototype Oil Shale
Lease Tract C-b in Rio Blanco County, Colorado [49]. Ashland
withdrew in February 1979 [51], but in August, Tenneco Oil
Company agreed to pay Occidental $110M to acquire a 50% interest
in Tract C-b [52]. One of the retort designs tested at Logan
Wash will be used to construct 40 operating retorts that are
capable of producing 9,060 m3 (57,000 bbl) of shale oil daily
by 1983, at the Tract C-b site [49].
Water Quality/Quantity Data— '
A block flow diagram of the full-scale commercial facility at
tract C-b, as envisioned by the developer, is shown in Figure A-15
Several water waste streams which appear in the diagram are:
excess mine water :
blowdowns from water treatment and steam generation
product water from oil/water separation. :
In addition, the developer has noted that sanitary wastewater
from several oil treatment units will exist.
UlNfD iHALC
41,134 T/O
MIWE WATER
ITOO P
100 TO soo at>u
TO
Flaunts
;oo,ooo LS/HR _ STMM
999.9 MUSCTO
¥
RETOfi Tl
ttf.oooa/tm
sre/sw
GENERATION
PLUS THERMAL
OMDIZER
.... (MS PRODUCT
™* 1573.2 MHSCFOC
i
STARTUP OIL
tZZ B/O
LIOUIO PRODUCT __
83,463 B/O
m>\
3454.0 HUSCFO
(TOTOLl
ao apu _
" 1370.7 UUSCFOtDftr)
GAS
TREATMENT
OIL/WATER
SEPARATION
9Z.2 LT/B ._
S&99S B/O 1 ^_
«-imurr USE
jracx
-------
Occidental has characterized the aquifer water which would be
characteristic of mine water as shown in Table A-10. Product
water from an Occidental test retort at Logan Wash is also
characterized in Table A-10 . .
Several options for disposal or reuse of waste waters are being
considered by the developer [53]. For mine water, they include
the following:
disposal by evapotranspiration ' "
disposal by reinjection ;
use as boiler feed after clarification, filtration, chemical
addition for scale control, reverse osmosis, deionization
and deaeration i
use as potable water or surface discharge after clarifica-
tion, filtration, reverse osmosis, activated alumina, and
chlorination I
use for dust control. j
The developer is also considering several options for use of
water treatment blowdowns and process wastewaters. These
include: ;
use for dust control
moisturization of spent shale from surface retorting of
shale removed from the modified in-situ retort
ponding ;
evaporating
return to spent retort
as a last resort, treatment for discharge.
Several of the above options have been included in a generalized
water reuse scheme developed by WPA and DRI for a modified
in-situ retorting facility such as Occidental's. This flow
diagram is presented in Figure A-16.
Rubblized In-Situ Extraction (RISE) Process
Process Description—
The RISE process was conceived by the Lawrence Livermore
Laboratory (at the University of California) in the early 1970's.
The RISE process is conceptually similar to Occidental's vertical,
modified in-situ retorting process. About 20% of the oil shale
[53] Oil Shale Tract C-b. Detailed Development Plan and Related
Materials, February 1976.
72 : '
-------
TABLE A-10.
CHARACTERISTICS OF WASTEWATERS
OCCIDENTAL PROCESS
mg/L
«
-------
Flows in L/s (gpm)
89(1413)
4(56)1 LOSSES LOSSES |100)
Figure A-16.
Major water streatas for modified in-situ shale oil
plant producing 9,000 m3/day (57,000 bbl/day)
crude shale oil [27].
74
-------
will be continuously mined out using a modified sublevel caving
technique described in Figure A-17 [45, 55]. The RISE process
supposedly prepares more uniformly sized rubble than Occidental's
technology [45], thus promoting better gas distribution [20].
STARTING SLOT
/
SHALE
DRIFT
DEVaOPMENT
LEVaA
D
LEVELS
DEVELOPMENT BEGINS AT TOP OF RETORT,
HORIZONTAL DRIFTS ARE DRIVEN THE.
Wl DTH OF THE BLOCK. A VERTICAL START-
ING SLOCK IS DRIVEN TO PROVIDE A FREE
BLASTING SURFACE FOR SUBSEQUENT
DRILLING AND BLASTING.
"o
SHALE
FAN DRILLING
] SUBLEVEL
STARTING SLOT
1 STA
*"
SHALE
LEVaA
DEVELOPMENT ] ]
LEVEB
2. SHALE IS LOADED AFTER EACH BLASTING
OPERATION . APPROXIMATELY 20% OF
THE BROKEN SHALE IS EXTRACTED. THE
REMAINDER FORMS THE RUBBERIZED
RETORT. ;
STARTING SLOT
I*-*
SUBLEVa
LEVELS
DEVaOPMENT
3. DEVELOPMENT PROCEEDS SIMULTANEOUSLY
ONMULTIPLESUBLEVELS.
Figure A-17.
Modified sublevel caving mining technique
proposed for use in the RISE process [45, 55^
[55] Lewis, A. E., and A. J. Rothman. Rubble Jiz-Situ Extraction
(RISE): A Proposed Program for Recovery of Oil from Oil
Shale. UCRL-51768. U.S. Energy Research and Development
Administration Contract No. W-7405-Eng-48. March 1975.
26 pp.
75
-------
The rubblized column, 46 m (150 ft) wide, 91 m (300 ft) long, and
229 m (750 ft) high on a commercial scale [56], is retorted by
using hot gas to heat the oil shale [45]. This gas can be
generated by combusting a portion of the oil shale with air, or
it could be heated by external combustion [55]. The products
from the underground retorts would be treated to remove entrained
solids, and the oil would be fraptionated into naphtha and a
heavy oil stream for blending wijth the liquid products from
surface retorting [36]. Product gas from the in-situ retorts,
after removal of sulfur compounds, would be fed to gas turbines
to generate electricity [36].:
Process Use—
The RISE process will be used by the Rio Blanco Oil Shale. Company
on tract C-a for below ground retorting, while Lurgi-Ruhrgas
retorting will be used above ground. The history of the Rio
Blanco Oil Shale Company is presented earlier in this appendix
on page 69.
Water Quality/Quantity Data—
As with the Occidental modified in-situ process, a block flow
diagram of the commercial facility at tract C-a has been provided
by the developer in Detailed Development Plans, and is shown in
Figure A-18. Rio Blanco intends to discharge only excess water
by aquifer reinjection while reusing the remaining mine water and
retort water. ;
Analysis of retort wastewater is unavailable, however, groundwater
analysis characteristic of mine idewatering water are provided in
Table A-ll. ;
DRI and WPA have analyzed the tract C-a processes and have
prepared a water reuse scheme utilizing wastewaters from the MIS
retort/ Lurgi-Ruhrgas retort, and mine water. This scheme is
presented in Figure A-19.
TRUE IN-SITU PROCESSES ',• . '
Equity Process
Process Description—
Equity's BX process is unique in that superheated steam, at 540°C
(1,000°F) and 10 MPa (1,500 psig), is used as a heat-carrying
medium to retort leached-zone oil shale, and to provide a
[56] Gulf Oil Corporation and Standard Oil Company (Indiana).
Revised Detailed Development Plan for Oil Shale Tract C-a,
three volumes. Denver, Colorado. May 1977.
76
-------
LO
PM
O
w
rB
a.
o
41
o
u
o
1—I
4H
!H
-P
m
3=
00
t—I
I
a>
O O**
-H rH
OH
o
i m
u s
-P
u •
its S-i
M O
H co
(0
rH 0)
(T3 rH
43 03
CO
rH
•H rH
O-H
O
S-l to
(!)
Q rH
•H
•a o
-------
TABLE A-ll. CHARACTERISTICS OF WASTEWATER - RISE PROCESS
Mine dewatering
[17, 57]
Upper Lower
Parameter , aquifer aquifer
TDS 1,140 1,500
Boron
Copper
Cyanide
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nitrate as N
Selenium
Silver
Fluoride
0.692 1.830
0.027 0.018
0 0,005
0.004 0.001
0 0
0.002 0.001
0.005 0
0.353 0.647
0 0
0.534 0.765
0 0
0.007 0.003
4.090 13.700
.
1
"
78
-------
Flc
19 PO
S«
MINE WATfR
MS in gi'rn vL>c«
.. r. J . . :
W I
"iBL»i«iitt -*-•-—• p«- - - {tAni'mncn '"" 551
\fl j Cfl'.UIMTC 79
I"
I ,. 18
I » .._.- „
RO.1JICHC.-I 0;SI CO'iISOt CCiiTroi.
" 1 n 'A
s*:o as j ?io
j.
as; Nit
HIV5S 1 I •" '" " "~~" ~ j
ExtwM •- c0^; :•;';':''' i
'-: "•
,
}tC-.-.!S
ei l« 5 ?M)
JT . T _. '
^ t ^ft""I'A "(
eo:it»s i STta.- CIA:-..-, TC..:>
srsi[H ( - « crtiis! — -oiirt
, . . i
il
"
71? 6407 . E'.n " T
5» lOSi!S IDSifj I 10
L7Z3 i?n? i?;r
,IS niTOa: *- «$ tJC<-i''C'.* •"" ' '.''13 HICOVIP.T •" OKOA'.TS RIP-..M. I •"
A . " 7 i f
SItAM ^ j
I »?t»»'t ,,,r
rc-io '
• „ , ; - - • .,,_.,--) «a [
1S4
f ~" " :
,. CU/Wt'tt .,
_», sr»»ic' i n?c » iip-'wic1" ^---
h«tC» fS Nc(l
-------
mechanism for the recovery of the shale oil [58]. The leached
zone is a geological formation in which the shale content has
been upgraded by natural dissolution of inorganic saline minerals
to produce higher porosity and permeability. The oil shale will
be retorted by injecting steam into the leachate zone and recover-
ing steam, water, oil, and gas through an array of production
wells. :
A sophisticated steam generating- plant, a water treatment plant,
water storage facilities, and an instrumentation system are
needed to facilitate injection of 6.0 x 1010 J (5.7 x 107 Btu) of
steam per hour [58]. Figure A-20 is a flow diagram depicting the
basic elements of the Equity oil; shale retorting process [58].
Water produced from the leached zone is held in the water storage
pit until it can be processed in! the two water treatment plants.
After treatment, the water is stored in five 64-m3 (400-bbl)
tanks. As needed, treated water is fed to two steam generators
capable of producing dry steam at 320°C (605°F) and 11 MPa
(1/600 psig), after which the stfeam is superheated to 540°C at
10 MPa (1,500 psig) [58]. From the superheater, the steam is
distributed to eight injection wells; the quantity sent to each
well is proportionately controlled by automatic valves. The
steam is injected through insulated 70-mm (2 3/8-in.) steel
tubing suspended in a 180-mm (7-in.) steel casing that is perfor-
ated at the top and bottom of the leached zone [59].
Condensed steam and retorted oil! and gas are withdrawn from the
middle of the leached zone by fijve production wells. On the
surface, oil, gas, and water from the production wells are
separated. Water is returned to' the water storage pit, and
product gas is recovered for use; as fuel for the steam
generators. !
Process Use— I
Equity Oil Company, under the Department of Energy's Cooperative
Agreement No. ET-78-F-03-1747, is conducting a demonstration of
in-situ oil shale retorting technology. The test location for
the so-called BX In-Situ Oil Shale Project is Section 6, Township
3 South, Range 98 West, near the center of the Piceance Creek
basin in Colorado [58]. At this; site the leached zone is 165 m
(540 ft) thick, the oil content ;of the shale averages about
100 m3/106 kg (24 gal/ton), and Ithe overburden thickness is
about 240 m (800 ft) [58]. The planned period of operation for
[58] Equity/DOE BX In-Situ Projiect is Progressing. Synthetic
Fuels, 16(l):pp. 2-6 through 2-9, March 1979.
[59] CPI News Briefs. Chemical Engineering, 86(17):102, August
13, 1979.
80
-------
WAITER
Figure A-20.
Flow diagram for Equity's BX In-Situ
Oil Shale Project [58].
Equity's BX project is approximately two years, during which time
1.1 x 1015 J (1.0 x 1012 Btu) of superheated steam will be
injected into the leached zone, and at least 79,500 m3 (500,000
bbl) of oil will be recovered [58]. The $6.5-M cost of the 55-
month project is to be shared by Equity (14%), and by DOE (86%)
[58, 60]. :
Water Quality/Quantity Data--
Process wastewater from the Equity process is produced along with
the shale oil pumped from the retort and as a vapor carried with
the off-gases. Process wastewater will consist of water present
in the formation, condensed injected steam, and moisture
produced from chemical reactions of the retorting process. No
information is presently available on the quantity or quality
of this wastewater; however, it has been suggested that Equity
process wastewater is similar to that from the Paraho, process
operating in the indirect mode. In addition, it has been
suggested that the retort groundwater may be similar to alluvial
water analyzed at the Equity site. Based on these assumptions;,
composition of Equity process water has been estimate'd and is
shown in Table A-12 [32].
[60] Equity Oil/ERDA Sign Cooperative Agreement.
Fuels, 14(3):2-31, September 1977.
Synthetic
81
-------
TABLE A-12.
SUMMARY OF EQUITY PROCESS
COMPONENT CONCENTRATIONS'
WASTEWATER
[32]
Parameter Groundwater
Calcium, mg/L
Magnesium, mg/L
Sodium, mg/L
Potassium, mg/L
Carbonate (as C03), mg/L
Bicarbonate, mg/L
Sulfate, mg/L
Chloride, mg/L
Nitrate (as N), mg/L
Fluoride, mg/L
Boron, mg/L
Silica, mg/L
Ammonium, mg/L
TOC, mg/L
COD, mg/L
TKN, mg/L
NH3 (as N), mg/L
pH, units
Conductance, [jfi/cm
Hardness (as CaC03), mg/L
TDS, mg/L
Alkalinity (as CaC03), mg/L
Total chromium, mg/L
Selenium, mg/L
Mercury, mg/L
Arsenic, mg/L
Iron, mg/L
Suspended solids, mg/L
Sulfide, mg/L
Oil and grease, mg/L
Cadmium, mg/L
Lead, mg/L
Molybdenum, mg/L
Cyanide, mg/L
Phenol, mg/L
94.9
43.il
65.3
1.613
0 '!
463'
57.1
1.06
1.73
0.39
0.29
0.35
i
10 J8
19.5
5.77
0.24
7.65
1,180
417
790
380
<0.1
<0.01
<0j01
<0.1
OJ05
1,970
j -
16.9
<6.l
-------
Dov Processes
Process Descriptions—
Dow Chemical Co. is currently considering three main operational
strategies for retorting Michigan Antrim oil shale [61]. Sepa-
rated Front Pyrolysis/Combustion (SFPC) represents conventional
in-situ oil shale extraction technology [62]. However, this may
not be the optimum strategy because Antrim shale produces less
gas and oil and more char during pyrolysis than do the western
shales. Therefore, more of the potentially recoverable energy
would remain in the, shale after pyrolysis. ;
The second operation strategy being considered by Dow is gasifi-
cation [61]. The gas and oil products of pyrolysis would be
burned in-situ to generate a hot char bed, which would be
gasified with air and steam. '
Combined Pyrolysis/Combustion/Gasification (CPCG) is the third
operational strategy considered by Dow [61]. CPCG seeks to
increase the efficiency of energy extraction by employing both
SFPC and gasification. Limited data supporting the possible
success of this strategy have been.obtained in horizontal,
modified in-situ trials. A strategy such as this wou;ld allow
Dow to take advantage of the tendency of Antrim shale to produce
char while still collecting pyrolysis products.
Process Use--
In September 1976, Dow Chemical was awarded a 4-year DOE contract
(EX-76-C-01-2346), valued at $14M, to test the technical feasi-
bility of recovering combustible gases by in-situ processing of
Michigan.Antrim oil shale [61]. The project site consists of
0.32 km2 (80 acres) located in Fremont Township, Sunilac County,
Michigan [62]. The three principal tasks of the program are:
1) the characterization and mapping of the Antrim shale resources,
2). the evaluation of three in-situ fracturing techniques, and
3) the demonstration of in-situ retorting [62]. ;
[61] McNamara, P. H., C. A. Peil, and L. J. Washington. Charac-
terization, Fracturing, and True In-Situ Retorting in the
Antrim Shale of Michigan. In: Twelfth Oil Shale Symposium
Proceedings, Colorado School of Mines, Golden, Colorado,
August 1979. pp. 353-365.
[62] Horst, B. I., and. E. I. Rosner. Laramie Energy Technology
Center Process Evaluation (draft report). Contract No. 31-
109-38-3764, U.S. Department of Energy, Laramie, Wyoming.
May 25, 1979. 313 pp.
83
-------
As of August 1979, experimentation with three fracturing methods
— hydraulic fracturing, chemical underream, and explosive under-
ream __ was complete, and a time in-situ retorting trial_had
begun [611 (personal communication, C. A. Peil, Dow Chemical
Company, to G. M. Rinaldi, Monsanto Research Corporation, _August
15 1979). Ignition conditions are considered to be critical lor
successful extraction. A sufficiently large mass of shale, with
available fractures for needed air flow, must be sufficiently
heated to produce sustained combustion. The ignition gas tempera-
ture will be controlled to about 53.0°C (990°F), and the heat
input will continue for about 10 days [61].
Water Quality/Quantity Data— : . , ,
No water flow diagram is available for the Dow experiments at
this time. In addition, no process wastewater analysis are
available; however, several experiments have been run on the DOE
10-ton experimental retort using Antrim shales. The analysis
of these retort waters is presented in Tables A-13 and A-14.
TABLE A-13. 10-TON RETORT WATER ANALYSES ON
ANTRIM SHALES* [32]
Concentration,
Parameter
Concentration,
mg/Lc
c a.±. nine u^j-
Calcium
Magnesium
Sodium
Potassium
Carbonate
Bicarbonate
Sulfate
Chloiide
Nitrate
Fluoride
Boron
Silica (SiO2)
Ammonium
7.6.
31.9
22.2
13
425
11,225
1,827
1,890
14.8
5.0
8
6,200
TOC
COD
TKN
NH3 as N
1 pH
Conductance
: Hardness (CaC03)
TDS
: Total C03
1 Cadmium
! Selenium
Mercury
1 Arsenic
1,975
17,500
4,880
,667
.4
20,890
286
,765
6,100
< 0 . OS
0.96
. 05
<0.005
aAverage of 5 values; data cited in Reference 14; however,
original source of data was not given.
bExcept pH, given in pH units.
84
-------
TABLE A-14.
TRACE ELEMENT COMPOSITION FOR MICHIGAN
SHALE WASTEWATER [32, 63]
ppm
Element
Uranium
Bismuth
Lead
Mercury
Tungsten
Tantalum
Neodymium
Praseodymium
Lanthanum
Barium
Cesium
Iodine .
Antimony
Tin
Molybdenum
Niobium
Zirconium
Strontium
Rubidium
Concentration
_a
0.001
0 . 120
0.0002
_a
0.003
_a
-a
_a
0.012
_a
0.200
0.026
0.005
0.049
0.003
0.003
0.020
0.013
Element
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Sulfur
Phosphorus
Silicon
Aluminum
Concentration
0.520
; 0.011
0.006
0.002
6.900
1.900
0.005
: 0.051
: 1.100
0.280
0.020
0.011
0.013
69
39
2.600
0.075
-
Elements not reported, <0.001 ppm.
Geokinetics Process '
Process Description—
The Geokinetics horizontal in-situ retorting process begins with
the drilling of blast holes from the surface, through up to 46 m
(150 ft) of overburden, and into the oil shale bed [64]. The
[63] Martel, R. A. and A. E. Harak. Preliminary Results from
Retorting Michigan Antrim Shale. LERC/TPR-77/1, LERC,
ERDA, Laramie, Wyoming, July 1977. \
[64] Lekas, M. A. Progress Report on the Geokinetics Horizontal
In-Situ Retorting Process. In: Twelfth Oil Shale Symposium
Proceedings, Colorado School of Mines, Golden, Colorado,,
August 1979. pp. 228-236.
85 ;
-------
holes are then loaded with explosives, which are fired to.yield
a rubblized mass of oil shale with increased permeability. During
fragmentation, the surface undergoes noticeable uplift. A slope
is created below the oil shale bed, allowing shale oil to drain
to a sump for recovery by production wells, as shown in
Figure A-21 [64].
AIR INJECTION WELL
LIQUID
PRODUCTION WELL
0-50m
-.\ \» t < ^ • - , / -- -
f-
_—!.,- * '— ~~- '• LiL" I _. '--•II™" __-_*T'—JM—1^^^ ***""*"* ^**~ ™*' I- !• • iriTTTM^^ni— ^ 1^,
"^ O
C3.0. _-^ •••- <
^i^; C-7 <3 .?*S£s"-
^^^ *-l nil __T^ .
RCfORT
-*• OFF-OASES
• OIL/WATER
. MIXniRE
SUMP
Figure A-21.
Sectional view of Geokinetics horizontal
in-situ oil sihale retort [64].
The oil shale is ignited with burning charcoal at the air injec-
tion wells, which are drilled at one end of the retort. Injected
air establishes and maintains a .horizontally moving burn front _
that occupies the entire cross section of the rubblized bed. Off-
gases containing oil mist exit through output holes at the down-
stream end of the retort. Above ground, a mixture of water and
shale oil is pumped by production wells to an oil-water separator
tank. The aqueous layer i-s separated and sent to an evaporation
pond, and the oil is pumped to product storage tanks. The
entrained oil and water in the tetort off-gases are removed by a
demister; the recovered liquid is sent to the separator tank
mentioned above. j
Process Use— : . ^
On July 22, 1977, Geokinetics, Inc., signed a contract with the
U.S. Energy Research and Development Administration (now the
Department of Energy) to develop a process for explosive frag-
mentation and horizontal in-situ retorting of oil shale deposits
that are located under shallow overburden [36]. Cooperative
Agreement No. ET-76-A-03-1787, valued at about $9.2M, is intended
to develop and improve the shale oil recovery technique studied
by Geokinetics in laboratory and field work dating back to 1973
86
-------
[36]. The project site, leased from the State of Utah in
March 1975, is located in the northeast quadrant of Section 2,
Township 14 South, Range 22 East, Uintah County [36, 64].
As of December 31, 1978, Geokinetics had blasted and burned 11
retorts at the "Kamp Kerogen" site, producing over 800 m3 (5,000
bbl) of crude shale oil [64]. During July 1979, air emissions
and water effluents from Geokinetics Retort No. 17 were sampled
by MRC personnel under EPA contract 68-03^2550 to provide addi-
tional data for environmental characterization of in-situ oil
shale retorting [65]. Geokinetics' future plans for research at
Kamp Kerogen include: (1) burning a retort with a 9-m thick oil
shale bed and blasting a full-sized retort (60 m wide, 60 m long,
and 9 m thick) during 1979, (2) blasting a cluster of three
full-sized retorts during 1980; and (3) burning the above cluster
and blasting a second three-retort cluster during 1981, the
burning of which will be completed in the first half of 1982 [64],
Water Quality/Quantity Data-^- ;
Presently, retort water is sent to an evaporation pond; longer-
term there are no known alternatives to this practice.
Geokinetics wastewaters have been extensively characterized;
available data is listed in Tables A-15 through A-18.
[65] Delaney, J. L. Sampling and Analytical Plan for Environ-
mental Characterization of In-Situ Oil Shale Retorting at
Geokinetics, Inc., Kamp Kerogen, Retort 17. Contract No.
68-03-2550, U.S. Environmental Protection Agency,
Cincinnati, Ohio. March 1979. 78 pp.
87
-------
TABLE A-15.
CHARACTERISTICS ;OF WASTEWATERS - GEOKINETICS
mg/L
Alkalinity as CaCO3
Hardness as CaCO3
Bicarbonate
Carbonate
pH
Conductivity ( pmhos/cm )
BOD
COD
TIC
TOC
Chloride
Cyanide
Phenols
Oil and grease
Surfactants as MDAS
Fluoride
Total phosphate
Ortho phosphate
TS
IDS
TVS
TDVS
Ammonia as N
Ammonium as N
Nitrate as N
Nitrite as N
TKN
Organic N
Total sulfur
Sulfate
Sulfide
Sulfite
Tetrathionate
Thiocyanate
Thiosulfate
Gross alpha (pCI/L)
Gross beta (pCI/L)
Ground
watera
166]
25,200
39
26,000
2,380
9.33
36,300
6,090
2,200
0.11!
0.19'
3.33:
4.31
93. 3;
5.02;
2.17:
37,600'
25
6.21
0.39
1
11,100
17
l
i
1
6.18
17.8
Retort
water
[66]
17,800
154
17,200
2,800
8.56
34,000
3,700
3,000
13.3
11.6
103
23.2
35.2
2.1
1.07
22,100
1,270
34.2
1.33
609
447
8.29
26.5
Retort
water
[671
16,600
34
5,380
173
8.9
11,200
2,000
7,200
1,100
2,150
1,100
95
37.8
186
15.6
4.30
1.30
10,200
9,400
1,900
2,100
870
317
9,500
0.08
1,230
355
1,230
825
0.2
400
1,080
325
<25
Evaporation
pondwater ,
[67]
22,400
122
10,800
345
8.9
20,000
10,900
2,200
2,900
3,300 '
266
24 '
648
42
1.77
1.77
29,100
28,400 ,
4,300
4,000
1,200
437
20,000
0.07
1,250
50
4,200
3,080
1.14 '
1,100
3,700
1,030
<25
aAverage of 8 values.
bAverage of 11 values; 1 from retort #15, 5 from retort #14,
5 from retort #16. i
GSingle value from retort #17. !
dsingle value. \
[66] Hutchinson, D. L. Appendix D, GKI Water Quality Study.
Progress Report. i
[67] Preliminary data generated by Monsanto Research Corporation
for the U.S. Environmental Protection Agency under contract
68-03-2550. 1
88 •
-------
TABLE A-16.
TRACE METALS IN GEOKINETICS' WASTEWATERS
mg/L
Aluminum as Al
Antimony as Sb
Arsenic as As
Barium as Ba
Beryllium as Be
Bismuth as Bi
Bromide as Br
Boron as B,
Cadmium as Cd
Calcium as Ca
Chromium as Cr
Cobalt as Co
Copper as Cu
Germanium as Ge
Iron as Fe
Lead as Pb
Lithium as Li
Magnesium as Mg
Manganese as Mn
Mercury as Hg
Molybdenum as Mo
Nickel as Ni
Potassium as K
Ssslenium as Se
Silicon as Si
Silver as Ag
Sodium as Na
Strontium as Sr
Thallium as Tl
Tin as Sn
Titanium as Ti
Vanadium as V
Zinc as Zn
Ground
water
[661
0.24
0.46
.0.71
0.009
0.30
0.152
87.85
0.14
7.11
0.10
0.28
0.20
0.009
13.18
0.17
0.24
12.79
0.383
0.0007
0.41
0.43
53.80
0.97
13.3
0.041
10,455.38
0.035
0.31
0.15
Retort
water
[66]
0.011
2.55
0.54
0.009
0.059
0.18
60.55
0.084
32.58
0.078
0.56
0.209
0.044
13 . 99
0.642
0.179
17.49
0.937
0.004
11.91
1.62
121.43
0.215
8.4
0.135
9,392
0.002
0.168
0.43
0.095
Retort
water
[67]
0.35
0.11
1.6
0.22
< 0.00004
61
0.02
6.6
0.04
0.11
0.04
0.80
0.14
8.9
0.01
0.04
0.27
0.49
29
0.02
0.31
0.05
2,800
0.69
<0.05
0.05
0.02
0.12
0.06
Evaporation
pond water
[67]
0.51
0.44
15
0.37
<0. 00004
[
186
0.02
11
0.06
0.25
0.07
9.6
0.20
31
0.03
0.03
6.9
: 0.76
57
0.28
0.96
0.13
8 , 300
0.89
<0.05
0.1
0.04
: 0.3
0.1
aAverage of 8 values.
bAverage of 11 values; 1 from retort #15, 5 from retort #14, 5
from retort #16. ;•
cSingle value from retort #17.
Single value.
89
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TABLE A-17. ORGANIC PRIORITY POLLUTANTS IN
GEOKINETICS WASTEWATERS [67]a
.Retort Evaporation MetEod"
/water pond water blank
Fluorene - - 0.4
Acenaphthylene 11 92 -
Bis(2-ethylhexyl) phthalate 0.5 3.8 9.0
Anthracene/phenanthrene : 3.6 10 1.3
Diethyl phthalate _ 3.5 13
Di-n-butyl phthalate - 0.8 0.6
Dimethyl phthalate - - 1.8
Butyl benzyl phthalate - - 0.5
Di-n-octyl phthalate '. - 1.5 0.6
Phenol ; 670 230
Methylene chloride : 11 22 0.8
Trichloroethylene 1.7 2.8 1.4
Benzene ; 370 67 0.5
Tetrachloroethylene
Toluene
Ethylbenzene
Chloroform
Acrolein
Acrylonitrile
Fluoranthene
Pyrene
0.9 0.5
280 64 3.6
45 29 0.2
2.0
360
250 1,700
8.3
3.2
Chrysene - 0.9
Nonpriority pollutants observed
Acetone ^4,000 ^900 ^50
Xylenes { ^250 -^68 ^0.5
n-Propyl benzene ; ^120 ~49
Trimethyl benzene '. ~400
aWastewaters were analyzed for;all of EPA's organic priority
pollutants, however, only those compounds which were found
above detection limits are listed. Detection limits for all
organic priority pollutants are listed in Table A-18.
90
-------
TABLE A-18. DETECTION LIMITSa FOR ORGANIC PRIORITY POLLUTANTS
Compound
Concen-
tration,
pg/liter
Compound
Concen-
tration,
ug/liter
Acids:
2-chlorophenol 0.09
. Phenol 0.07
2,4-Dichlorophenol 0.1
2-Nitrophenol 0.4
p-Chloro-ffi-cresol 0.1
2,4,6-Trichlorophenol 0.2
2,4-Dimethylphenol 0.1
2,4-Dinitrophenol . 2.0
4,6-Dinitro-o-cresol 40.0
4-Nitrophenol • 0.9
Pentachlorophenol 0.4
Volatiles:
Chloromethane 5.0
Dichlorodifluoromethane 2.0
Bromomethane 5.0
Vinyl chloride 5.0
Chloroethane 5.0
Methylene chloride 0.1
Trichlorofluoromethane 0.3
1,1-Dichloroethylene 0.5
1,1-Dichloroethane 0.4
J*rans-l,2-dichloroethylene 0.7
Chloroform 0.3
1,2-Dichloroethane 2.0
1,1,IrTriChloroethane 0.3
Carbon tetrachloride 0.4
Bromodichloromethane 0.3
Bis(chloromethyl) ether 5.0
1,2-Dichloropropane 0.8
7",rans-l,3-dichloropropane 0.7
Trichloroethylene 0.2
Dibromochloromethane 0.4
Cis-l,3-dichloropropene 1.5
1,1,2-TriChloroethane 0,5
Benzene 0.2
2-Chloroethyl vinyl ether 5.0
Bromoform 1.0
Tetrachloroethylene 0.2
1,1,2,2-Tetrachloroethane 0.3
Toluene 0.1
Chlorobenzene 0.2
Ethylbenzene 0.1
Direct injectables:
Acrolein 200
Acrylonitrile 100
Base/neutrals:
1,3-Dichlorobenzene
1,4-Dichlorobenzene :
Hexachloroethane
1,2-Dichlorobenzene
Bis(2-chloroisopropyl) ether
Hexachlorobutadiene
1,2,4-Trichlorobenzene
Naphthalene :
Bis(2-chlproethyl) ether
Hexachlorocyclopentadiene!
Nitrobenzene
Bis(2-chloroethoxy).methane
2-Chloronaphthalene
Acenaphthylene
Acenaphthene '.
Isophorone i
Fluorene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
2,4-Dinitrotoluene
N-nitrosodiphenylamine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene
Anthracene
Dimethyl phthalate
Diethyl phthalate
Fluoranthene
Pyrene
Di-n-butyl phthalate
Benzidine ;
Butyl benzyl phthalate
Chrysene !
Bis(2»ethylhexyl) phthalate
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benz o(a)pyrene
Indeno(1,2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene ;
N-nitrosodimethylamine
N-nitrosodi-n-propylamine
4-Chlorophenyl phenyl ether
3,3'-Dichlorobenzidine
Di-n*octyl phthalate
0.
0.
0.02
0.04
0.1
0.05
0.06
0.08
0.09
0.007
0.07
2
08
0.06
0.02
0.02
0.04
0.06
0.02
0.2
0.02
0.02
0.07
0.05
0.1
0.01
0.01
0.03!
0.03
0.02
0.01
0.02
0.02
0.03
0.02
0.04
0.02
0.02
0.02
02
02
02
01
0.8
0.2
0.03
1.0
0.9
0.
0.
0.
0.
Based on the lowest quantifiable area obtained from gas chromatography/mass
spectrometry.
91
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