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<pubnumber>600786019</pubnumber>
<title>Assessment of Solid Waste Characteristics and Control Technology for Oil Shale Retorting</title>
<pages>354</pages>
<pubyear>1986</pubyear>
<provider>NEPIS</provider>
<access>online</access>
<operator>dwu</operator>
<scandate>03/03/03</scandate>
<origin>hardcopy</origin>
<type>single page tiff</type>
<keyword>shale oil tosco retorted shales spent retorting retort water raw paraho gas material lurgi processed table coal process peak source</keyword>

                                 600
  ASSESSMENT OF SOLID WASTE CHARACTERISTICS AND
   CONTROL TECHNOLOGY FOR OIL SHALE RETORTING  ;
                       by


                Ashok K. Agarwal
                Monsanto Company
               1515 Nicholas Road
               Dayton,  Ohio  45418
           Contract No.  EPA 68-01-6487
                Project Officer
                Edward R. Bates                ]
Hazardous Waste Engineering Research Laboratory-
            Cincinnati, Ohio  45268
                  March 1986
Air and Energy Engineering Research Laboratory
      Office of Research and Development
     U.S. Environmental Protection Agency
 Research Triangle Park, North Carolina  27711
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                             NOTICE

The  information in  this  document: has  been funded wholly  or  in
part by  the United  States  Environmental  Protection Agency under
Contract  68-01-6487  to Monsanto  Company.   It  has been  subject
to the  Agency's peer and administrative  review,  and  it has been
approved for publication as an EPA>document.
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                             FOREWORD
                                                        I
When  energy  and  material  resources  are  extracted,  processed,
converted,  and  used,  the  related pollutional  impapts  on  our
environment  and even on  our  health  often require that new  and
increasingly  more  efficient  pollution  control  methods  be  used.
The  Air  and  Energy  Engineering  Research  Laboratory,  Research
TriailOle  PaT~l? .  asc'l e1"C  in  HOTT-OT /-vr\-iT-i/-r =si->^  ^^w./->»-.r-i4--v--,-t-T -^-^ ~.-.,,  __j
I         me  Air  and  Energy  Engineering  Research  Laboratory,  Research
         Triangle Park,  assists  in developing  and  demonstrating new  and
         improved  methodologies  that  will  meet  these needs i both  effi-
         ciently and economically.                              .


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                    Frank Princiotta                   i
                    Director                            :
                    Air and Energy Engineering Research Laboratory
                                111
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                            ABSTRACT
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                                  i                          (            •_
This  report  is  a  comprehensive  study  of the  characteristics  of      •
solid and  liquid wastes produced from various  oil  shale process-      H
ing  technologies,  and  control methods  for environmentally  safe
disposal of  solid  wastes.  It  also includes the results  from an      m
experimental  study  to   construct  liners  and  covers  for  proper      ||
disposal of  spent  shales.  In  addition the auto ignition potential
of raw and spent shales has been evaluated.                             «

Considerable effort  is  currently  being  directed to commercializa-      •
tion of processes  to produce  liquid fuels from oil shale deposits
in the United  States.   When financing uncertainties are resolved,      •
construction of  large-scale plants  could begin.  The retorting of      |
oil shale produces large quantities of solid wastes.  These wastes
include raw mined oil shale (which does not contain enough kerogen      «
for  economical recovery),  spent  oil shale  (mineral matter  from      |
which the  kerogen  has been thermally removed by retorting), over-
burden material  (which  must  be  removed before the shale  can be
mined),  shale   fines   from  processing  operations  (e.g.,  dust      •
collected  in  fabric  filters)  and process  wastes (e.g.,  spent      •
catalysts, wastewater treatment sludges).

Oil  shale  deposits in the eastern  and western parts of the United      f|
States, their  geological subdivisions,   their  locations,  tonnage,
and   their  physical  and  chemical   characteristics   have  been      _
described.  The  solid and liquid wastes  generated from the various      •
oil  shale  technologies have been compiled.   Amounts of solid and
liquid wastes  generated and their composition depend, among other
things, on the particular technology used  and on the type of shale      •
processed.   Some of the wastes may also be site specific.  Avail-      •
able  field and laboratory leachate  data  are also presented.

If only one-half of  the planned production comes on  line, it would      |
eventually  amount  to approximately  600,000  barrels  per  day of
shale  oil.   This  would  lead  to approximately 740,000 tons/day or      _
270 million  tons per year of retorted oil  shale, along with lesser      •
quantities  of  other  solid  wastes,  which will require environmen-      "
tally safe disposal.   If not  properly  managed, these high volume
wastes  are capable  of  producing  leachates that could contaminate      •
the  water supply  for millions  of people.  Surface disposal sites      •
covering  many  square miles in  area and  hundreds  of feet in depth
would do  extensive  property  damage and threaten  lives  should      •
they ever suffer  sudden mass  failure.    An  experimental program      |



                                                                        I
                                 IV
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was undertaken  to establish the  best combination of  spent shale
with materials readily available at the disposal site to construct
liners and covers for the spent shale disposal.        i

Also  in  this report available information has been  pompiled in
order  to  evaluate  the  auto ignition  potential of raw  and spent
shales from  various  oil  shale processes.   The results  indicate
that  raw  shale  fines have  a  potential for  spontaneous  ignition
similar to bituminous  coals  while such  potential for  retorted
shales appear to be less.  Hence,  there is a potential jthat if oil
shale  disposal  sites are  not properly  designed they i could auto
ignite.  It  appears probably  that  control  technology  employed by
the  coal   industry  can  be  modified  and  applied  toi oil  shale
disposal sites to mitigate this hazard.                j

Control technologies  to prevent serious  adverse impacts from dis-
posal  of billions of tons of  oil shale wastes  have  bejsn proposed
but their  application to oil  shale waste materials oh the scale
required for commercial plants has not been demonstrate^.   Further-
more,  to be  effective, these control technologies must be applied
to highly technical  and  integrated  disposal designs that are site
and process specific.  There is no  current experience an disposal
of wastes  of similar composition or of volumes  approaching that
which will result from the oil shale industry.         i
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                            CONTENTS

Foreword	
Abstract
Figures
Tables.	
Acknowledgment	     xxii
   1.  Introduction	; .

       1.1  Sources and volumes of solid waste, including
               an overview of the oil shale industry .  .  .
   1                                                   i
       1.2   Potential dangers to human health and the  ',
               environment from the disposal and reuse  of
               the wastes.	        5
       1.3   Present/proposed disposal approaches. .  .  i  .       17
       1.4   Conclusions and additional research needed i.  .       21
                                                       i
   2.  Characteristics Of U.S. Oil Shale	!.        23

       2.1  Introduction	' .        23
       2.2   Location	j  .       23
       2.3   Geology	.  1  .       28
       2.4   Composition	;  .       41
       2.5   Physical properties	  .       52

   3.  Solid Wastes and Their Characteristics for      •
         Oil Shale Retorting Processes	  .       69

       3.1   Lurgi-Ruhrgas  oil shale retorting ....;.       69
       3.2   TOSCO II oil shale retorting,	j  .       85
       3.3   Paraho direct  heating mode oil shale      i
               retorting	J  .  .    105
       3.4   Paraho indirect heating mode oil shale
               retorting	.:  .      127
       3.5   Occidental modified in situ oil shale     j
               retorting	j  .      135
       3.6   T? oil shale retorting	.;  .      151
       3.7   Hytort oil shale retorting.	j  .      155
       3.8   Geokinetics horizontal in situ oil shale   i
               retorting	:  .      164
       3.9   Superior circular grate oil shale retorting  .      168
       3.10   Union Oil A oil  shale retorting	       177
       3.11   Union Oil B oil  shale retorting	i.       182
       3.12   Union Oil SGR  oil shale retorting	;.       191
       3.13   Chevron STB oil  shale retorting	:.       202
       3.14   Allis-Chalmers oil shale retorting .  .  . . ;.       210
       3.15   Dravo oil shale  retorting	i.       216
                              vi i
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CONTENTS (continued)
                                                                        I
                                                                        I
   4.  Environmental Control Technologies ....... .       219
       4.1   Environmental impacts ........... .       219
       4.2   Disposal alternatives ......... ...       222
       4.3   Control technologies ............       227
                                                  »
                                                  gj
References ............ ........... •       255
Appendix ............. ............       A~!
   A.  Auto-oxidation potential of raw and spent shale
         and the suggested design of piles to avoid the                 •
         auto-ignition of shales. . . ..........       A-l      gj
   B.  Use of spent oil shale as a liner material at
         spent shale disposal sites ...........       B-i      _
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                              FIGURES
  Number
 2.2-1      Principal United  States  oil  shale  deposits.  .1 .    24

 2.2-2      Green River  formation  oil  shales-Utah,        !
             Colorado,  and Wyoming	] .    25

 2.2-3      Distribution of upper  Devonian and lower      |
             Mississippian Black  Shales in the Eastern
             United States	|     27

 2.3-1      Schematic North-South  cross  section of Piceanjse
             Creek showing relationship of oil shale     >l
             bearing members of the Green River formation
             and surrounding strata	j     32

 2.3-2      Schematic cross section of Uinta Basin showing
             relationship of oil  shale bearing Green River
             formation  with surrounding strata .....;.    34

 2.3-3      Schematic cross section showing relationship of
             Green River formation with surrounding strata    37

 2.3-4      Oil yield of Tipton shale member.  ..... .:.    38
                                                        i
                                                        i
 2.3-5      Oil yield of Wilkins peak member	    39

 2.3-6      oil yield of Laney shale member	' .    40

 2.4-1      Organic matter content of Green River oil     i
             shales	 .    44

 2.5-1      Specific gravity and oil yield of Colorado oil
             shales	    54

 2.5-2      Compressive  strength of oil shales	    60

 2.5-3      Compressive  strength-versus Fischer assay of''
            Colorado oil shale,  Anvil Points Mine .  . .  i.    62
                                                        i
 3.1-1     Lurgi-Ruhrgas oil  shale retorting process . .I.    70

3.1-2     Lurgi-Ruhrgas Process  operations  and
            waste streams	    72
                               IX
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Number
39 — 1
. .& — X
3.2-2


3.3-1


30_0
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3.4-1
3.5-1


3.5-2


•3 fi-l
*J * U JL
3.7-1


3.7-2
O O *|
3.8-2

3.9-1

3Q — 9
. ;? <£
3.9-3


31 0—1
• X U X
3.11-1


3.11-2

3.12-1
3.13-1



FIGURES (continued)


Process block flow diagram for sand wash


Schematic of Paraho direct heating




Paraho indirect mode process flow diagram . . .
Schematic of the Occidental modified in situ


Occidental MIS retorting, oil/water separation




Diagram of IGT oil shale gasification process


Hytort commercial plant conceptual design . . .

Electrical conductivity breakthrough curve
for Leachate from Geokinetics spent shale . .
Superior retorting process retort showing
movement of charge through various zones. . .


Superior process flow diagram and major waste




Flow diagram for retort! system in Union oil


Block flow diagram for Union oil Retort B

Diagram of Union Oil SGR-3 retorting process. .
Process flow scheme of Chevron STB retort . . .

X


Page
86

88


106

107

128

136


137

152


156

158
163

167

170
171


172

178


183

185

192
203


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                        FIGURES (continued)
  Number
 3.13-2    Block flow diagram of Chevron semiworks  oil  !
             shale plant	'.      206

 3.14-1    Allis-Chalmers  oil shale  process  flowsheet.  .  .    213

 3.14-2    Allis-Chalmers  oil shale  retorting and combustion
           process development unit  flow schematic  ....    214
                                                       i
 3.15-1    Dravo retorting process  .	,  .    216

 3.15-2    Dravo pilot plant  flowsheet schematic .-..]..    218

 4.3-1      Surface hydrology  control  technologies. ..  .  1  .    228

 4.3-2      Runon diversion costs	1      231

 4.3-3      Runoff collection  costs 	  [      233

 4.3-4      Runoff/leachate pond costs	:      235

 4.3-5      Runoff/leachate pond liner costs	      236

 4.3-6      Subsurface hydrology control technologies  .  j  .    237

 4.3-7      Liner  costs	j      240

 4.3-8      Leachate collection costs  -.	!     242

 4.3-9      Groundwater collection costs	!  . '  244

4.3-10    Surface stabilization technologies	j     245

4.3-11    Dust control costs	;     248

4.3-12    Reclamation and revegetation costs	!  .   250
                                XI
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Number

1 1-1
JL. * J. JL
1 1 — 9
J. * J."*j£
1 1 — ^
J. * JL *>
1.1-4

1.2-1



1.2-2
1.2-3

1.2-4


1.2-5


1.2-6


1.2-7


1.2-8




1.3-1
2.2-1







TABLES
; Page




Antrrnx n matp Solid Waste Relationships 	 6

Major Waste Produced Over a Period of 20 Years
(TOSCO II 47,000 bbl/day plant with upgrading) 7
Summary of Results from Differential Scanning
Calorimetry and Nonadiabatic Oxygen


Chemical Properties of Union B Retorted Shale . 9
Estimated Composition of Process Water for
P(=t"OT~"t"(=f^ ^Vial*3 Pool "i ncr/Wp't'T'i ncr ...... 10

RCRA Testing of Simulated Shale Plant Wastes


Chemical Composition of Leachates from Union B


Retorted Shale Leachates by Leaching Method
(ma/L) 	 	 13

Raw Mined Oil Shales Leachates (Maximum


Estimated Quantities of Some Major Constituents
Leachable from Oil Shale (Assuming
Permeability and Water Availability are not


Key Features of Solid Waste Disposal Approaches 18
Total In-Place Shale Oil Resources of the



xii

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                        TABLES (continued)

  Number
                                                       !      Page

 2.4-1     Mineral Content bf Green River Oil Shale    !
             Versus Grade. ,	       41

 2.4-2     Average Mineral Composition of Mahogany Zone1
             Shale, Colorado and Utah	j       41

 2.4-3     Fischer Assay Data of the Inorganic Mineral  '
             Portions of 16 Samples of Green River Oil
             Shale Ranging From 10.5 To 75.0 gal/ton Oil
             Shale .........                    !
                                                             42
 2.4-4     Chemical  Composition of the  Inorganic Portiori
             of Various  Grades  of Green River Oil  Shale '
             and of  The  Spent Shale Products	;      43

 2.4-5     Typical Mineralogical Composition of Devoniari
             Black Shale	!      43
                                                       !

 2.4-6     Probable  Composition of Mahogany-Zone Organic
             Matter	  . .'  .    45

 2.4-7     Elemental Composition of New Albany Shale    ;
             Organic Matter	:      45

 2.4-8     Approximate Carbon/Hydrogen  Ratios in Various
             Organic Materials  	    45

 2.4-9     Authigenic Sodium Minerals In The Green River'
             Formation	j      48
                                                       !
 2.4-10     Average Distribution  of  Sulfur and Nitrogen In
             Oil Shale	! . .: .    50

 2.4-11     Distribution of Sulfur and Nitrogen in       ;
             Colorado Oil Shale	    50

 2.4-12     Levels of Trace Elements in Green River Oil  I
             Shale	, ^    51

 2.5-1     Visual Features of Green River Oil Shale.  . .I.    53

 2.5-2     Weight (Inplace) and Weight (Broken)  for Green
            River Oil Shale'	:.     55

2.5-3     Porosities of Raw and Thermally Treated  Oil  '
            Shales  (Percent of Bulk Volumes)	;.     57
                               Kill
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                                                                        I
                       TABLES (continued)                               "

 Number                                                     Z^ge        ffi

2.5-4     Shear Strengths of Lean Oil Shale Specimens
            from Roof Material of USBM Experimental Mine                n
            (Anvil Points).	     58         p

2.5-5     Compressive Strengths of Raw and Thermally-
            Treated Oil Shales (Kilograms Per Square                    •
            Centimeter)	     59         ™

2.5-6     Compressive Strength of Green River Oil Shale                 en
            Samples Cut Perpendicular to Bedding (Samples                H
            from USBM Experimental Mine, Anvil Points,
            Colorado)	     61         _
                                                                        1
2.5-7     Summary of the Range of Concentrations in                     m
            Leachate Samples. . . j	     63

2.5-8     Comparison of Trace Element Concentrations from               B
            Raw Mined Shale with those from Soils and
            Previously Exposed Shales 	     64         am

2.5-9     Mean Values for Major Ion Composition of C-a
            Leachate	     65

2.5-10    Mean Values for Major Ion Composition of C-b                  •
            Leachate	     65

2.5-11    Mean Values of Trace Element Concentrations of                |
            C-a Leachate	;	     67

2.5-12    Mean Values of Trace Element Concentrations of                J|
            C-b Leachate	     67

2.5-13    Maximum Observed Concentrations  in Raw Shale                  •
            Leachates	     68         V

3.1-1     Inventory of  Streams to be Disposed of as                     «
            Solid Waste in the Lurgi-Ruhrgas Process.  . .    75         g

3.1-2     Physical  Properties of Lurgi Processed Shale. .    77

3.1-3     Summary of Hydraulic Conductivity Measurements                •
            for Various Compaction  and  Loadings  for  Lurgi
            Retorted Shale.	    78         •

3.1-4     Water Holding Capacity of Lurgi  Processed
            Shales  at Various Pressures  and Bulk                       m
            Densities	    78         I
                                xiv
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                        TABLES (continued)             ;

  Number                                               |      Paqe
 3.1-5     Composition of Lurgi Processed Moisturized  i
             Shale .  .................  :       79

 3.1-6     Inorganic  Analysis of the Lurgi             '< •
             Processed Shale ..........  .....     79
                                                       i

 3.1-7     Major Ion  Composition of Column Leachate-Lurgi
             Retorted Shale ..............  j       go

 3.1-8     Concentration of  Selected Trace Elements  in  i
             Column Leachate of Lurgi Retorted  Shale .  J .     81

 3.1-9     Concentrations in ASTM Water Shake Test      i
             Extracts -  Lurgi Spent Shales .........     82

 3.1-10     Concentrations in RCRA Test Extracts - Lurgi !
             Spent Shales ................ j .     33

 3.1-11     Leachable  Mass as Indicated by  the ASTM      ;
             Proposed Water  Shake Test for Lurgi Spent  i
             Shales - mg/g .  .............. j       34

 3.1-1.2     Leachable  Mass as Indicated by  the RCRA      I
             Extraction  Test for  Lurgi Spent Shales  - mg/g     84

 3.2-1      Summary of Solid  Wastes  Generated at Sand Wash
             Processing  Facility  ............ j       go

 3.2-2     Major Waste Produced Over  a Period of 20 Years
             for TOSCO II  47,000 bbl/day Plant with
             Upgrading
3.2-3     Physical Properties of TOSCO II Processed Shale    92

3.2-4     Sieve Analysis of TOSCO II Spent Oil Shale   !
            Residue .................. !      92

3.2-5     Hydraulic Conductivity Measurements of TOSCO II
            Retorted Shale ............... :      93

3.2-6     Water Holding Capacity of TOSCO II Processed !
            Shales at Various Pressures and Bulk       ',
            Densities ................. i      93

3.2-7     Reported Analysis of TOSCO II Processed Shale! -    94

3.2-8     Selected Elemental Concentrations in Raw and '
            Retorted TOSCO II Oil Shales ........ i.    94
                               xv
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 Number
                                                                        1

                       TABLES (continued)                               **
                                                                        B
Page
3.2-9     Some Polycyclic Aromatic:Hydrocarbons that have
            been Detected in the Benzene Extract of TOSCO               m
            II Spent Shales	•  •    95         |j

3.2-10    Approximate Composition of TOSCO II Combined
            Process Wastewater (50,000 bbl/day upgraded                 •
            shale oil production)	    96         •

3.2-11    Organic Content of Gas Condensate (Foul Water)                ffl
            For TOSCO II	    97         V

3.2-12    Composition of Foul Water for TOSCO II	    97         _

3.2-13    Inorganic Species in TOSCO II Foul Water.  ...    98         •

3.2-14    Concentrations in ASTM Water Shake and RCRA                   •
            Extracts - TOSCO II Spent Shales	    99         m

3.2-15    Leachable Mass as Indicated by RCRA and ASTM                  m
            Water Shake Extraction Test for TOSCO II                    (
            Spent Shales	   100

3.2-16    Effluent Concentrations - (TOSCO II) Spent                    I
            Shales.  Constant Rate Injection into a                     *
            Dry Column	   1°1

3.2-17    Levels of Trace Elements Measured in Runoff and               1
            Leachates from Field Test Plots of TOSCO II
            Retorted Shale (ppm). :	   102         «

3.2-18    Inorganic Composition of TOSCO II Leachates
            Produced During Laboratory and Field
            Lysimeter Studies  (mg/L)	   103         •

3.3-1     Paraho Direct Solid Wastes:  Types and
            Quantities	 •	   HO         m

3.3-2     Paraho Direct Retorted Shale Characteristics.  .   Ill

3.3-3     Paraho Direct Retorted Shale Major Elements                   •


3.3-4     Paraho Direct Retorted Shale Trace Elements                   A
             (ppm)	   1]-3         •
 3.3-5      Paraho  Direct Product Water Bulk
             Properties  (wt.  %).  .  ............   H5
                                xvi
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                        TABLES (continued)

  Number
 3.3-6     Paraho Direct Product Water Major  Species/Gross
             Salinity (ppm)
 3.3-7     Paraho  Direct Product Water  Trace
             Elements  (ppm)
 3.3-8      Compounds  Identified  in Paraho Direct Oil
             Shale Wastewaters
116
118
 3.3-9      Paraho Direct Recycle Gas Line Drain  (ppm).  .!  .   121

 3.3-10     Concentrations  in RCRA  and Water Shake Test  I
            Extracts - Paraho Direct Spent Shales  .  .  .,  .   122

 3.3-11     Leachable Mass  as Indicated by the ASTM      |
            Proposed Water Shake  Extraction Test for   i
            Paraho Direct Spent Shales - mg/g ..... ;  .   123

 3.3-12     Column Leaching Effluent Concentrations  for  i
            Paraho Direct Spent Shales ........ ',.    124

 3.3-13     Inorganic Composition of Paraho Direct Spent ;
            Shale Leachates Produced During Field      •
            Lysimeter Studies, (mg/L) ......... ;  .   125
                                                       !
 3.4-1    .  Paraho Indirect Retorted Shale Characteristics    130
                                                       !
 3.4-2      Paraho Indirect Retorted Shale Chemical      ;
            Composition ........... ..... |     131

 3.4-3      Composition of  Paraho Indirect Spent Oil Shales   132

 3.4-4      Paraho Indirect Process Water Composition . . j  .   133

 3.4-5      Inorganic Analysis of Condensate Streams from'
            the Paraho Indirect Process ........ ;  .   134

 3.4-6      Composition of Batch Generated Leachate from !
            Paraho Indirect Retorted Shale ....... j  .   135

 3.5-1      Inventory of Solid and Liquid Waste Streams  ;
            for Occidental MIS Process ......... \  .   140

 3.5-2     Compositions of Solid and Waste Streams for  !
            Occidental MIS Process ........... j  .   141
                                                       i
3.5-3     Composition of MIS Occidental Processed Shale!  .   142
                               xvi i
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                                                                       I
                                                                       I
                       TABLES (continued)                              •"
 Number
                                  ''        .....            " ' '
3.5-4     Boron and Fluoride in Oxy Retort 3E Spent Shale   142

3.5-5     Mineralogical Analyses for Selected Samples of                ||
            Oxy Retort 3E Spent Shale Core ........   142

3.5-6     Analysis of Core Samples^ from Oxy Retort 3E                   I
            Preliminary Data. . .  ......... ...   143         *

3.5-7     Oxy Retort 6 Steam Boiler Blowdown Collected -
            March 6, 1979 (in ppm except as noted). . .  .   144

3.5-8     Compounds Identified in Occidental Oil Shale                  g
            Retort Wastewaters. .  ............   145         B

3.5-9     Oxy Retort 6 Product Water Analysis Results .  .   147

3.5-10    Concentrations of Dissolved Species in the                    v
            Leachate from Occidental MIS Processed Shale.   148

3.5-11    Concentration Range of Macro Ions Found in the                g
            First Fraction of Leachates from Occidental
            MIS Retorted Shale. .  , ............   148         —

3.5-12    Inorganic Composition of Leachates from                       ™
            Occidental's Retort 3E, Logan Wash, Colorado
            (mg/L) ........  ............   149         M

3.7-1     Water Holding Capacity of Hytrot Processed
            Shales at Various Pressures and Bulk
            Densities ......  ............   159
3.7-2     Concentrations in ASTM Water Shake and RCRA
            Tests Extracts - Hytort Spent Shales .....   160         •

3.7-3     Leachable Mass from Hytort Shale as Indicated
            by the ASTM Proposed Water Shake Test and
            RCRA Extraction Test - mg/g .........   161

3.8-1     Inorganic Composition of Leachates from
            Geokinetics Spent Shale (mg/L) ........   164

3,8-2     Major Ion Composition of Effluent (Geokinetics
            6) ......................   165

3.8-3     Concentration (mg/L) of Trace Elements for
            Selected Pore Volumes (Geokinetics 6) ....   166         m
                               xvi 11
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                       TABLES  (continued)              j

 Number                                                I     Page
 3.9-1     General Water Quality Parameters of Superior!
            Oil Shale Process Water	j  .   173

 3.9-2     Inorganic Composition of Superior Leachate   i
            Produced by the ASTM Test Method D3987. .  .'  .   174

 3.9-3     The Effect of Coproducted Retort Waters on tne
            Quality of Superior Leachates from Spent
            Shales	j  .   175

 3.9-4     Effect of Distilled Water, and Time on the   !
            Leachate Quality of Moistened, Compacted
            Superior Spent Shales	!  .   175

 3.9-5     Concentration of Metals in Leachates from    '••
            Superior Retorted Shales	'',  .   175

 3.10-1    Physical Properties of Union A Spent Shale.   .:  .   180

 3.10-2    Chemical Properties of Union A Retorted Shale  .   180

 3.10-3    Analysis of Leachate Obtained in Laboratory  '
            Tests of Union A Raw and Retorted Shale .   .!  .   181

 3.10-4    Inorganic Composition of Leachates from Union| A
            Spent Shale	•  .   isi

 3.11-1    Inventory of Streams to be Disposed of as    :
            Solid Wastes in Union B Process	[ .   186
                                                       i
 3.11-2    Physical Properties of Union B Spent Shale.   .! .   187
                                                       ]
 3.11-3    Chemical Properties of Union B Retorted Shale! .   187

3.11-4    Estimated Composition of Union B Process Water
            In the Active Basin and the Reuse Water Sump.   188

3.11-5    Inorganic Composition of Leachates from UnioniB
            Spent Shale,  mg/L	j .   189

3.11-6    RCRA Testing Of Simulated Union B Oil  Shale   :
            Plant Wastes	; .   190
                                                       i
3.12-1    Physical Properties of Union SGR Spent Shale.i .   193

3.12-2    Particle Size,  pH,  and Electrical Conductivity
            of Spent Oil Shales Produced by Union SGR
            Retorting Process 	 .   193
                               xix
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                                                                       1
                       TABLES (continued)

 Number                                                     Page        •
3.12-3    Chemical Properties of Union SGR Retorted Shale   194

3.12-4    Amounts and Quality of Surface Runoff from                    ff
            Union SGR Decarbonized Shale Lysimeter Study.   195

3.12-5    Water Quality of Percolate from Union SGR                     •
            Decarbonized Shale Lysimeters 	   196

3.12-6    Analysis of Spring Snowmelt Runoff and                        •
            Percolate from Union SGR Decarbonized                       •
            Shale Lysimeter Study.  April 21,  1976. .  .  .   197
                                xx
                                                                        I
3.12-7    Analysis of Runoff and Percolate Samples
            Collected August 5, 1976 from Union SGR
            Decarbonized Shale Lysimeter Study	    198

3.12-8    Analysis of Spring Snowmelt Runoff and
            Percolate from Union SGR Decarbonized
            Shale Lysimeter Study.'  April 21, 1976. .  .  .    199         jfl

3.12-9    Analysis of Runoff and Percolate Samples
            Collected August 30, 1977 from Union SGR
            Decarbonized Shale Lysimeter Study	    200
3.12-10   Analysis of Spring Snowmelt Runoff and
            Percolate from Union SGR Decarbonize
            Shale Lysimeter Study.  May 3, 1978	    201
            Percolate from Union SGR Decarbonized                       •
                                                                        •
            Chevron STB Retort. ... ..........    205         J§
3.13-1    Nominal Process Operating Conditions for the
            Chevron STB Retort. ...

3.13-2    Preliminary Results:  Chevron STB Pilot Plant                 «
            Spent Shale Properties ............    208         9

3.13-3    Chevron STB Spent Shale : Leach Test Results. . .    209

3.14-1    Allis-Chalmers Western Shale Tests ..... . .    215         •
            Technologies	   229         ||
4.3-1     Key Features of Surface Hydrology Control
            Technologies ..... .........

4.3-2     Key Features of Subsurface Hydrology Control                  —
            Technologies ..... ............   238         •

4.3-3     Key Features of Surface Stabilization
            Technologies ..... ; ............   246         0



                                                                        I
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                       TABLES  (continued)

  Number
4.3-4     Engineering Costs and Timing of Solid Waste
              Management Activities for a 47,000 bbl/day
              Facility  (Thousands of Dollars)  . .  .  .  j .   252

A-!       Description of Samples Tested by RTI. .  .  .  J .   A-7

A-2       Mean Heat Capacity of Coal and Shale
            Materials Based on Initial Sample
            Weight (J/G, -325 Mesh)	i .   A-7

A~3       Exothermic Onset Temperature in Oxidation    •
            of Coal, Oil Shale and Retorted Oil Shale
            (2°C/minute heating ramp,  -325 Mesh)	   A-9

A-4       Magnitude of Exothermic Reaction of Coal, oil|
            Shale and Retorted Oil Shale (2°C/minute   i
            heating ramp, -325 Mesh)	\ .   A-10

A-5       Spontaneous Combustion Index and Calculation i
            Parameters of Materials Subjected to       l
            Nonadiabatic Test (Tested Dry)	; .   A-12
                                                       !
A-6       Summary of Results From Differential Scanning
            Calorimetry and Nonadiabatic Oxygen        i
            Absorption Testing	!    A-16

A-7       Effect of Compaction in Reducing the Volume  !
            of Air Entering or Leaving a Coal Mass in
            Response to Barometric Pressure Change. . .•- .   A-18
                               xxx
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                         ACKNOWLEDGMENT
1
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This  study  and  the  preparation  of  this  report has  involved       «
participation  of  professionals from  Monsanto  and  independent       •
consultants.   Dr. Shib C. Chattoraj's  work  in  developing  this       m
report is very much appreciated.  The contributions of Dr.  Arthur
D. Snyder and Mr. Duane R. Day are acknowledged.   Also Mr.  Robert       H
N. Heistand provided  valuable  review comments.  The  liner study       m
was performed by Denver Research Institute.

The  project  is  deeply   indebted  to  the  EPA Project  Officer,
Mr.  Edward R. Bates  for  his  continuing  advice  and  guidance
during the course of this effort. ;
                               XXI1
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                              SECTION 1

                            INTRODUCTION


 1.1  SOURCES  AND VOLUMES  OF SOLID WASTE,  INCLUDING    !
      AN OVERVIEW OF THE OIL SHALE INDUSTRY            j

 1985  makes the  start  of the commercial  U.S.  oil shale  industry
 with  the first  commercial  plant (Union Oil's 10,000 bbl/day  Long
 Ridge facility)  coming on  line.  Many  additional and often  much
 larger  plants are  scheduled to  start production between  1987  and
 1994  with many of the  early plants being subsidized by jthe Federal
 Government  through  the U.S.  Synthetic  Fuels Corp;  (Tables 1.1-1
 and 1.1-2).   If only  one half of the planned production  comes on
 line, it would eventually amount to  approximately 600,000 barrels
 per day of shale oil.  Assuming  an  average  shale  grade of 30  gal/
 ton and that  88% of the raw shale  retorted will remain  as spent
 shale to be disposed,  then about 740,000 tons/day or i270 million
 tons  per year of retorted oil shale,  along  with lesser quantities
 of  other solid wastes,  will  require  environmentally safe disposal.
 In  addition to retorted oil  shale other  solid wastes produced will
 include  waste overburden,  raw shale  fines, shale oil  coke,   API
 separator sludges,  wastewater treatment sludges,  elemental sulfur
 or  sulfur containing wastes from air  pollution control equipment,
 and spent catalysts which may contain  highly toxic substances such
 as  arsenic. .                                           ;
                                                       !
                                                       I
 The types and quantities of solid  wastes  that will  be produced
 from  proposed oil shale  facilities  are not well  defiited at this
 time.  Detailed  information prepared as supplements to' the Uintah
 Basin Synfuel  Development FEIS  [BLM,  1983], lists the  types  and
 quantities  of  solid  wastes  estimated  for the  Sand  Wash  and
 Paraho-Ute projects  [TOSCO,  1982; Paraho, 1982].

 Although  these projects are  quite  different in that  they employ
 different retorting  technologies,  mine  different  grades  of shale
 at  different  rates,  produce  differing amounts  and types  of final
products, and,  at  times,  employ differing  control  technologies,
 the rates of  solid wastes can  be  compared when examined on a
 common  basis   [Heistand, September  1984].   The common !bases  used
 are mined shale  (tons  of  wastes  per thousand tons of mined shale,
T/MT)  and hydrotreated oil  (tons  of waste per  million  barrels
of., oil,  T/MMBbl).                                      i
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Factors  were  determined  on the  basis  of shale  minied  and oil
produced  for sixteen  solid wastes, grouped  into two Categories,
as shown in Table 1.1-3  [Heistand,  September 1984].    '

Using  the  factors  presented  in Table 1.1-3,  it is  possible to
calculate  probable  rates  of various solid wastes  produced based
upon  projected mining  rates and  product oil  production for the
above-ground oil shale retorting facilities.           :

A surface retorting plant, such as  a TOSCO II processing  facility,
will be  a source of large quanitities  of plant wastes' which will
require  disposal.   Table 1.1-4 indicates  the  makeup of the waste
material that will be discarded .from a small TOSCO II plant over a
period of 20 years.                                    !

1.2  POTENTIAL DANGERS TO HUMAN HEALTH AND THE ENVIRONMENT
     FROM THE DISPOSAL AND REUSE OF THE WASTES         i

Although  oil  shale  facilities will produce huge volumes of solid
wastes,  the potential  for reuse  of the  wastes is  small.   Some
wastes such  as  spent  catalysts could potentially be reclaimed and
recycled back into the process.  Elemental sulfur, remojved by some
air pollution  control technologies,  has  a limited  market poten-
tial;  however  it remains to be demonstrated on a commercial scale
that there  are no  trace impurities that  would constrain its use.
It is  expected that hazardous wastes such as  spent catalysts and
some sludges will be  disposed in licensed hazardous wa|ste facili-
ties.   However,  one catalyst unique to shale  oil upgrading is of
particular  concern.   The arsenic  guard bed catalyst will contain
20% or more  arsenic.   No facilities exist to reprocess, this spent
catalyst  and environmentally  safe disposal may be  difficult to
achieve.    Other than  the  arsenic  guard  bed catalyst,:  the major
unique dangers  to  health  or the  environment posed by  oil shale
facilities may  be  from the long term effects  of on site disposal
of millions  of tons of  retorted oil shale, raw oil shale waste,
and other  process  wastes.  Principal concerns  in thisiregard may
be summarized as follows:                              ;

1.  A.uto  oxidation/auto  ignition  may  be  a  serious ;problem  if
    disposal of  raw shale fines  and/or carbonaceous spent shales
    are not done in a manner to minimize this  risk.     !
                                                       i
2.  High  inorganic  salt loading  and possibly organics  in leach-
    ates  from  raw  shale fines or spent  shale  could potentially
    have significant  impacts on groundwater supplies  in the area
    and on  surface  waters that supply millions  of  people (Color-
    ado River).  A  related issue  is to what extent should process
    wastewaters be  treated prior to codisposal  with the retorted
    shale.   Codisposal  of spent  catalysts and  treatment sludges
    may  also  significantly  impact the nature  of leachates  from
    disposal sites.                                     ]
 image: 








       TABLE 1.1-3.  APPROXIMATE SOLID WASTE RELATIONSHIPS
           Type of waste
Mined shale
   basis,
   T/MT
Hydrotreated
 oil basis,
  T/MMBbl
     Ma j or
       Retorted shale
      fRaw fines, dust, subore
       Off-spec sulfur
       Oily particles
       WWT sludge
       Scrap and garbage
  834.5
  784.4
   58.8
    1.3
    0.49
    0.14
    0.10
Catalysts and other wastes
Methanator
Reformer
Hydro treater (HDN, HDS) •
Lo-temp CO shift
Alumina
DEA sludge '
API sep. btms. i
API float
Hi-temp CO shift (FeCr)
Arsenic guard bed 1
27.76
0.48
1.10
17.22
2.29
5.04
0.95
24.44
2.12
1.26
36.31

I
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1
1
I
     aThese factors will give values which may range +100%
      to -£
      Based on solids content.
      Source:  Heistand, September 1984.


3.  Infiltration of  moisture into disposal  sites from precipita-
    tion  or  from surface  or groundwater intrusion could  lead to
    sudden  pile  failure.    Such  failure  could  cause  extensive
    property damage, threaten lives,  and contaminate the drinking
    water supply for millions of people.

Auto-Oxidation/Auto-Ignition

Auto  oxidation leading  to auto ignition  of some coals  and coal
wastes has been  known  to be a problem  for many years.   Some coal
wastes piles  in the east  are believed to  haye ignited  in this
manner while the phenomenon is fairly common with western lignite
coals.  Since  raw  oil  shales and some retorted oil shales possess
carbonaceous material  and are capable  of  being  ignited,  EPA has
recently  conducted  several  tests  to  assess  the  potential  for
auto-ignition of raw oil shale fines and retorted oil shales. The
results indicate that  raw  shale  fines have a potential similar to
bituminous coals while  retorted  shales  appear to be less reactive
(Table 1.2-1).  Hence there is a potential that if oil shale
                                      1
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   TABLE  1.1-4.
MAJOR WASTE PRODUCED OVER A PERIOD  OF
(TOSCO II 47,000 bbl/day plant with
  20 YEARS
upgrading)
Stream description
Raw shale runoff and leachate
Raw shale sludge - preheat system
Processed shale sludge - ball elutriator
.Processed shale sludge - moisturizer
Processed shale
Stripped foul water
Compression condensate - Wellman-Lord Unit
Cokeb
Stripped sour water purge stream
Revegetation water
Dust suppression water
Boiler blowdown
Boiler feedwater treatment concentrate
Cooling tower blowdown
Storm runoff
Processed shale leachate
Spent catalysts
Treated sanitary water
Sanitary water treatment sludge
Service and fire water runoff
Source water clarifier sludge
Trash, construction debris, etc.
TOTAL
Mater
Quantity, as a
106 tons total ^
N.D.a
11.31
0.85
0.57
350.84
18.49
ial quantity
percent of
tfaste quantity
N.D.
2.27
0.17
0.11
70.43
3.71
1.73 0.35
5.26
1.06
0.75 0.15
14.59 2.93
9.70 1.95
11-04 2.22
4.81 0.97
60.31 12.11
4.34 0.87
N.D. N.D.
0.005 0.001
0.55 0.11
N.D. ' N.D.
0.63 0.13
2.37 0.48
N.D. ' N.D.
498.15 99.93
 N.D. - Not determined.                                     i

 Most of the coke can be sold as a by-product.                 [
 Source:  EPA 600/8-83-003, April 1983                        i
                                                        i
disposal  sites  are  not properly  designed they could  iauto-ignite
producing huge quanities of pollutants  such  as S02,  NQ ,  H2S, C02
and  hydrocarbons.   Such combustion could impair pile^ stability
leading  to  failure  of  the disposal pile  and/or  substantially
accelerate  the  leaching process.   Since oil shale disposal sites
will occupy several square  miles and be hundreds of  feet thick,
there  is no known  method for  extinguishing  combustion should it
get started.   Hence, the key to  controlling ignition  must be the
design and incorporation of  appropriate  controls when tlhe  disposal
site is  constructed.   It appears probably  that control1 technology
employed by the  coal industry  can be modified and applied to oil
shale disposal sites to  mitigate  this hazard.           :
 image: 








       TABLE 1.2-1.   SUMMARY OF RESULTS  FROM DIFFERENTIAL
                      DIFFERENTIAL SCANNING CALORIMETRY  AND
                      NONADIABATIC OXYGEN ABSORPTION  TESTING

                                         -—e
Paraho Retorted Shale                 300         480           0.27

TOSCO II Retorted Shale                306         560           1.4

Union Shale Mixture                   321         860           4.6

Hytort Retorted Shale                 357       1,340           3.8
I
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I
                                   Onset,    Exotherm,    Nonadiabatic test
	Materal	°C	J/g	S index

Wyoming Subbituminous Coal             190       10,900          165               I

Western Kentucky #9 Bituminous Coal     193       13,800          60

Utah Raw Shale (66 GPT)                211       8,320          86               ™

C-a Raw Shale                        226         920           5.6             A

Utah Raw Shale (28 GPT)                227       2,990          44

Pocahontas #3 Bituminous Coal          230       15,700          42               B



                                                                             1


                                                                             I


Lurgi Retorted Shale                    -          M3           0.00            11


 Lower onset temperature means more reactive.                                     A

 Higher S index means more reactive.                                             ™

 Test in dry air, particle size:  -325 mesh.                                      m

 wo exotherm observed to 550°C.                                                 H
 Source:  EPA 600/2-84-153, 1984.

Leaching                                                                    ||

The  composition of  retorted  oil  shales  vary principally  in re-       —
sponse  to  the  properties  of the  raw shale feed  and the retorting       B
process.    The  composition  of any  leachates  from  retorted shale       *»
disposal sites  will  vary  depending upon  the properties  of the re-
torted  shale,  and other wastes codiposed with the retorted shale,       ||
such as  wastewaters   for cooling/wetting  and treatment  sludges.       fl
Anticipated composition for Union B retorted shale is provided in
Table 1.2-2, process  water  for  cooling  and  wetting  the shale in       an
Table 1.2-3, and properties  of Unisulf  solution,  Unisulf  sulfur       •
byproduct,   and  moistened  retorted shale  are  provided in Table
1.2-4.   Some leaching  test  results  on Union B  retorted shale are

                                                                             I
                                8
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 image: 








TABLE 1.2-2.  CHEMICAL PROPERTIES OF UNION B RETORTED SHALE


        	Components5	Weight, %
                                                    I
        Major elements as oxides                    ;
          SiO2                               31.5   ;

          CaO                                19.6   :

          MgO                                 5.7   |

          A1203                               6.9
                                                    i
          Fe20                                2.8   ;

          Na20                                2.2   !

          K20                                 1.6   !

          S03                                 1.9   |
                                                    i
          P20§                       •         0.4   |

        Other properties                            '
          Mineral CO2                        22.9   |
                                                    i
          Organic C                           4.3   ;

          Nitrogen, Kjeldahl                  0.2   i

          Free silica (quartz)                8.0   i

          pH of slurry                        8.7   '•


        aAnalyses determined by heating sample to   ;
         950°C for pH measurement.  Analyses by
         Union Research Department.                 |
         Source:  Battelle PNL 3830, 1981           !
 image: 












TABLE 1.2-3. ESTIMATED3 COMPOSITION OF PROCESS WATER
FOR RETORTED SHALE COOLING/WETTING


Parameter
Alkalinity (as CaC03 )
Carbonate ( as CO3 )
Bicarbonate ( as HC03 )
Chemical oxygen demand
Total organic carbon
Total dissolved solids

Total solids
Hardness (as CaCO3 )
Ammonia
Sulfides (as H2S)
Phenols
Cyanide (CN) - [
Oil and grease
Sulfate
Sodium
Arsenic :
Chromium '•
pH units '


Reuse
water sump,
mg/L
2,000
400
1,700
5,500
1,350
2,600

3,100
900
35
100
125
20
1,300
500
1,500
6.5
0.5
8-10

aThese values are maximum design case
levels based on preliminary bench-scale
tests and engineering1 calculations.
Source: Union Oil Company,


10 ;
January 1984.



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            TABLE 1.2-4.
RCRA TESTING OF  SIMULATED SHALE
PLANT WASTES (UNION B  PROCESS)
                                Unisulf
                                sulfur
                                            Moistened
              retorted shale
               plus  fines5
 Ignitability

 Causes fire through friction     No

 Oxidation                        0°F

 Corrosivity

 a) pH
 b) Steel corrosion (in/yr)

 Reactivity

 Yield gases,  vapors or  flames
  when exposed to water          No

 Yields H2S or HCN when
  exposed to  pH 2 buffer          No

 Reacts explosively
 a) When subjected to burner
   flame                         No

b) When under heated
   confinement                   No

HP Toxicity,  mq/L
                  No

                  0°F
                  No
                  No
                  No
                  No
 noistened with simulated process  water.
 Source:  Union Oil Company,  January  1984.
Maximum
allowed
                                 12.5
                                  0.25
Minimum
allowed
            2.0
Arsenic
Barium
Cadmium
Lead
Mercury
Selenium
Silver
<0.01
0.2
<0.01
<0.05
0.002
<0.0005
<0.02
0.07
<2.7
<0.01
<0.05
<0.0005
<0.0005
<0.02
5.0
100.0
1.0
5.0
0.2
1.0
5.0
                                  11
 image: 









TABLE



Compound
Ag
Al
As
B
Ba
Be
Ca
Cd
Cl
CN
Co
Cr
Cu
F
Fe
HC03
Hg
K
Li
Mg
Mn
Mo
Na
Ni
NH3-N
N03-N
Oil and grease
Pb
Phenols
PO4
Se
Si
SO4
Sr
IDS
TOG
Zn
pH, units
Source : Union




'
1.2-5. CHEMICAL COMPOSITION
FROM UNION

Union Oil
Company
1982c
<0.3 - 0.12
0.005 - 0.022
0.22 - 17.0
0.09 - 0.11
<0.05
46 - 460
<0.01 - 0.03
7 - 120
0.003 - 0.009
<0.03 - 0.05
0.003 - 0.012
<0.02 - 0.2
5.6 - 11.4
<0.5 - 6.5
92 - 257
<0.0005 - 0.001
4.6 - 48
0.1 - 0.6
29 - 1,400
0.2 - 6.7
0.8 - 4.0
11 - 4,800
<0.02 - 0.12
<1 - 4
<10 - 100
<2 - 5
0.05 - 0.5
<0.001 - 0.0086
<200
<0.005 - 0.018
1-4
115 - 19,100
1.1 - 7.6
327 - 25,000
0-31
0.04 - 0.26
7.5 - 7.9
B RETORTED

S teams -
Rogers
• 1976
'
! 0.066
' 8
0.03
• -
17
<0.02
210
<0.005
0.01
-
_
-
2,370
-
14
50
27
5,040
—
2.4
2.0
25
! <0.2
<0.005
—
—
-
7,090
—
16,000
240
-
7.6


OF LE ACHATES
SHALE

Cleave
et al.
1979
<0.009
<0.001
0.97
<0.078
-
243
0.016
7.0
-
<0.011
<0 . Oil
—
<0.025
172
-
7.4
58
<0.007
109
—
—
—
0.009
—
<0.001
-
878
—
1.518
11.3
0.025
8.33
(mg/L)

Woodward-
Clyde
1975
<0.009
<0.05 - 0.27
—
—
-
-
69 - 424
8-91
-
_
-
-
<0.05 - 20
4-32
-
3-85
5-55
mm
45 - 750
—
2-5
31 - 111
—
—
-
0.5 - 4
230 - 2,400
—
410 - 4,860
-
3.1 - 6.9
Oil Company, Januairy 1984.


12

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TABLE 1.2-6. RETORTED SHALE LEACHATES BY !
LEACHING METHOD (mg/L)

Shale
Paraho










TOSCO II










Lurgi










Paraho -
Several
Example
Source :

Parameter
pore volume
pH
EC ()jS/cm at 25°C)
HC03
C03
S04
Cl
F
Mg
Na
Ca
K
PH
EC (pS/cm at 25°C)
HC03
C03
S04
Cl
F
Mg
Na
Ca
K
PH
EC ((jS/cm at 25°C)
HC03
C03
S04
Cl
F
Mg
Na
Ca
K
0.198; TOSCO II - 1.03
Lurgi shales have been
provided is Lurgi shale

Field
9.57
21.100
-
-
12,350
526
11.9
7.7
5,591
421
834
8.9
10,000
-
-
30,270
-
13
156
10,270
463
110
_
-
-
-
-
-
-
-
-
-
~
; Lurgi -

RCRA
9.27
4,600
2,723
217
226
29
-
484
37
724
6.5
7.72
5,710
3,325
-
229
22
-
81
131
1,872
3.9
8.67
5,650
2,940
59
880
19
-
430
55
1,479
11
0.621.

ASTM
12.05
2,800
5
236
536
7
13.5
0.5
145
266
31
8.69
2,650
191
-
1,130
10
20.2
35
545
31
8
11.85
4,270
6.9
210
2,290
17
6.3
0.4
275
713
64

Column
initial
11.55!
9,230
15.3;
232|
3,840:
49 1
21:
1.6!
1,500
610;
140;
9.24^
35,080 ;
619 :
46 '
25,000
178 |
27 ,
628 ;
10,095 -
545 .
89 ;
12.24 i
59,500 ;
10.5 ;
775
34,000 ,
2,250 |
26.4 1
3.5 :
18,770 :
535 |
1,464 :
i
	
Column3
12.35
6,250
4.8
463
2,045
14
11.4
1.7
285
670
38
9.21
5,180
188
13
2,470
13
29.5
60
945
83
11
11.93
4,250
7
203
2,070
15
7.6
0.3
325
575
150

i
tested and results differ slightly.
provided by Rio Blanco Oil Shale.
EPA-600/D-84-036, March 1984.

13




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TABLE

Species
HC03
C03
TDS
F
Cl
P04
N03
S04
Zn
Fe
Co
Li
NH3
B
Cd
Be
Mg
P
Si
Mo
Mn
Ni
Na
Cu
Al
Ca
Ba
K
Cr
Sr
Pb
Ag

Se
As
Hg


1.2-7. RAW MINED
(MAXIMUM
Concentration ,
mg/L
579
5.68
72,660
113
366
0.28
2,564
45,900
0.597
2.02
1.17
0.339
2.55
1.97
0.168
0.300
12,830
7.0
13.2
1.5
2.34
1.12
2,030
0.073
5.28
505
0.822
16.4
0.290
15.4
1.036
0.012
0.007
0.013
0.007
0.003
i

OIL SHALES LEACHATES



OBSERVED CONCENTRATIONS )
Locationa
C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
C-b, 20 ft
C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
: C-a, 15 ft
C-b, 10 ft
C-a, 5 ft
C-b, 15 ft
C-a, 15 ft
C-b, 10 ft
C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
C-b, 10 ft
C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
; C-b, 10 ft
C-a, 5 ft
; C-a, 15 ft
! C-b, 10 ft
'• C-a, 15 ft
C-a, 15 ft
I C-a, 15 ft
; C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
C-a, 15 ft
C-b, 20 ft
C-b, 20 ft
Date
9/21/82
7/19/82
8/16/82
7/26/82
7/01/82
2/25/82
7/26/82
5/10/82
8/16/82
8/11/82
8/23/82
7/26/82
8/30/82
7/26/82
7/26/82
7/06/82
9/06/82
8/04/82
6/02/82
7/06/82
6/02/82
6/02/82
8/02/82
7/06/82
7/01/82
3/22/82
9/23/82
7/19/82
6/02/82
7/19/82
8/11/82
3/17/82
4/12/82
7/01/82
8/04/82
2/25/82
1
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.


•«r
a5, 10, 15, and 20 foot deep Lysimeters on Federal lease
 tracts Ca and Cb.
 Source:  EPA-600/D-84-228, 1984.
                         14  i
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                                                       I
provided  in  Table 1.2-5 while  results  on several  other  retorted
shales  (all  without  codisposed  wastes)  are  presented  in  Table
1.2-6.  Some  raw mined oil  shales  have been  leached (under  field
conditions and the results are in Table 1.2-7.          j

A significant volume of data such as that above exists.;  This data
indicates that  even if raw and retorted shale wastes are not de-
fined as  hazardous,  the leachates  from these wastes  are high in
dissolved salts  as  well  as other contaminents and could seriously
impact  surface  or  groundwater  supplies,   provided  (Significant
amounts of leachate are produced.  The amount of leachate produced
will  depend  to  large extent on site  specific  characteristics and
the disposal controls employed.  Since billions of tons of retort-
ed oil shale may eventially be produced, the cummulatiye impact on
water quality could be very great.  Table 1.2-8 indicates the quan-
tity  of some constituents leachable  from  oil shale pastes.   As
previously discussed a 600,000 bbl/day oil shale  industry  would
produce about  270 million tons/per year of  retorted Shale,  which
would accumulate to nearly 8 billion tons after 30 years of opera-
tion.   Such  a  quantity of waste will possess the  potential for
leaching  hugh  quanitities of  contaminents.   For  example assuming
8 billion tons of TOSCO II retorted shale,  then 58 million tons of
sulfate are  leachable along with 100 million tons  of total dis-
solved  solids and lessor  amounts of many other contaminents._  The
key  to  preventing  serious environmental impact  does\ not  lie in
preventing the  leaching (since  erosion of the disposal  sites and
leaching  will  eventually occur)  but  rather  in employing controls
to assure that  the rate of release of contaminents is,slow enough
to be accomodated without substantial environmental damage.  These
controls  must  be designed and  built  into the  disposal sites from
the beginning since the huge size of the disposal sites will make
any retrofit operations extremely expensive and likely;impossible.

Mass  Failure                                           !

Retorted  oil  shale disposal sites will be the largest;solid waste
disposal  sites ever constructed.  A typical 50,000 bbl/day surface
retorting plant will produce about 450 million cubic  feet/year of
solid waste,  which over an operating plant life of 30;years would
cover an  area of  about 3.5 square miles to  a depth Of 150 feet-
 [EPA  600/2-80-205a,  1980].   Most disposals  will be head of hollow
or cross  canyon fills, miles in  length and hundreds  of feet deep.
Mass  failure  of one of these  fills could have major  impacts caus-
ing  extensive property damage  and threatening lives, j Failure of
one  of several  disposal  piles  proposed could destroy downstream
reservoirs,  shale oil upgrading, storage,  and loading; facilities,
and  deposit  millions  of  tons  of leachable  retorted shale in the
Colorado  River.                                        j

The  most  likely cause of  a disposal pile failure would be satura-
tion  of  the  waste  pile  and/or  liquefaction  of the ipile bottom
leading to  slippage.  Moisture contributing to this  problem could
                                15
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come  from codisposed wastewaters, precipitation and  infiltration,
groundwater  intrusion  into  the  pile,  or  surface  streams  routed
over  or  through the  disposal  site.   The principal approach  to
prevent  these problems is  therefore  to  control  the Movement  of
moisture  into or through  the disposal pile.   To  accomplish  this
requires  the incorporation  of  a number  of  control  technologies
into  a complex  site  and material specific design.   Although the
basic  technologies  to  be  employed are well  known (i.;e., drains,
liners,  covers,  earth  fill  dams, benching) their construction  on
the scale required  and application to oil shale wastes have never
been demonstrated.                                     I
                                                       i
1.3  PRESENT/PROPOSED DISPOSAL APPROACHES              I

Due to the high volumes of  solid wastes  produced  by all oil shale
facility,  the environmentally safe  disposal  of these jwastes must
be engineered on a  site and process specific basis.  The slate  of
solid wastes  to be disposed  and  their chemical nature will vary  in
response  to  the nature of the raw shale  feed,  the particular re-
torting process employed, the specific plant design including pol-
lution control technologies, and whether raw shale oil as upgraded
on site.   The design of the solid waste  disposal  site! as well  as
the selection and application of appropriate control technologies
must be  tailored to  accomodate not only the quantities and  nature
of the  wastes but also the characteristics  of  the specific dis-
posal site.   Alternative  disposal practices and contrdl technolo-
gies are  generally well known.   All have  been proposed or consid-
ered by  one  developer or another though no developer has yet pro-
posed a  plan incorporating all the control features  that might be
desired into  a specific design for solid waste disposal.

Disposal Approaches                                    '
	 	t-A	                                    |
                                                       !
The following discussion applies  to the basic methods for handling
solid  wastes produced  by a  surface retorting process.   The  key
features  of  each  approach  are  summarized  in  Table 1.3-1.   A
discussion   of   the   control  technologies  applicable1  to  these
disposal alternatives is presented.                    |

Landfills

A landfill basically  entails placing the waste material as  a com-
pacted fill  in  a suitable location.   The wastes from the process-
ing facility  are  transported to  the disposal site by conveyors or
trucks and then  hauled to  the   active portion  of  the  landfill.
Preferably,  the  solid wastes are then laid down in  lifts of 9-18
inches  and   compacted   to   a  suitable  in-place  denisity.    The
compacted  fill  may be  built with a proper  slope to i a  vertical
height of 40-50  feet  and then flattened,  or benched, to provide a
passageway for  the disposal equipment and to facilitate  runoff
collection.  The  overall  landfill can be constructed gradually in
this fashion, using a multiple-bench arrangement.       '<
                              17
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Depending upon  the geography of  the disposal site,  the landfill
may be built  on a level or nearly level surface, in the head of a
valley, or  across a valley.  The applicable control technologies
will vary somewhat with site topography but still will jbe designed
to protect  the  surface  and subsurface waters.  Applicable control
technologies include runon and runoff catchment ponds, 'embankments
and diversion systems,  liners and cover, and revegetation.  Provi-
sion  for  structural  stability  of  the  fill  is   also  a  major
consideration.                                         !
                                                       I
A surface landfill  of  some type will need to  be included in most
oil shale developments.  This  results from the shale undergoing a
volume expansion upon mining, crushing, and processing,1 which pre-
cludes all of the shale being returned to the mine.     j

Underground Mine Backfill                              ;
     11 *	       •  ' • "                              _     i

In this disposal approach,  the waste material is placed in the in-
active portion  of  the  underground mine  (e.g.,  a room-and-pillar
mine), while production continues in other parts of the mine. This
approach  is  attractive from  several  viewpoints.    By  returning
the wastes  to the  mine, the size of  a  surface  landfill would be
greatly reduced.   The  potential  for mine  subsidence would be di-
minished.    Backfilling  the mine  may enhance resource recovery by
increasing  the  amount  of shale that  can  be  mined safely.  Disad-
vantages include  possible  release of volatiles underground in the
workplace and possible groundwater contamination.      j

The major considerations in backfilling involve developing logis-
tics for carrying out  simultaneous mining and disposal operations
while  providing protection for workers  and  the groundwater.  For
fine  processed  shales,  like  the TOSCO  II,  hydraulic  or slurry
backfilling may be  practical.   However,  additional water,  above
the moistening  needs, would be required and a drainage collection
system would be needed.  The wastes may be transported :to the mine
by  conveyors  or  trucks,  then  compacted  in  place,   but  the space
limitations reduce  the  practicability of this approach.  Alterna-
tively, the wastes may be  backfilled pneumatically,  but this ap-
proach may be difficult to implement at the scale required.

A study on the above backfilling techniques has been conducted for
the wastes  from the Colony  project  [Dravo Corp.,  1975].   The re-
sults  indicate  that, while theoretically  80%  of the wastes could
be  returned to the  mine,  only 60%  of  the wastes  can 'actually be
placed in  the mine  during the project life due to  a time lag of
5-10 years  between the  mining and backfilling operations.  It was
concluded  that  none of the  placement techniques wer^  developed
sufficiently to be  applied on a large scale.
                               19
 image: 








                                    I


Impacts of Disposal Alternatives gn the Use of Oil Shale and      •
Other Natural Resources
                 t'

proaucea oy an on snaie lacinty, these wastes must be disposed
on or close to the plant site.  In the  case of open pit mines,   m
such as the one proposed for federal lease tract Ca, huge amounts   B
of overburden and subgrade oil shale will also require disposal.   9
These wastes could be disposed entirely on the surface as piles or
canyon fills or could partially be returned to the mine. Either   B
way the leaching potential of these wastes must be carefully con-   m
trolled or leachates will seriously impair the quality and use of
surface and groundwater supplies. Depending upon the specific   «
placement of these wastes they could also impair future access to   V
other oil shale resources. Returning some of the retorted oil
shale to an underground mine would be expensive and technically
difficult but could actually increase the potential for resource   JB
recovery by facilitating mining of the support pillars.        "

Potential Utilization of Oil Shale Solid Waste             •

Oil shale  solid wastes having some potential for utilization in-
elude retorted oil shale, raw shale fines, spent catalysts,  ele-   m
mental sulfur and biological treatment  sludges.  Retorted oil   U
shales, particularly decarbonized shales,  have some limited poten-   *
tial for utilization on site. Decarbonized western oil shales
posses a significant capacity to cement similar to low grade com-   fft
mercial cement. Hence a very limited amount of retorted shale may   V
be used locally as a  low grade cement substitute. Raw shale
rejects and fines, from mining and raw shale preparation, could be   m
processed in specially designed retorts  or possibly formed  into   I
bricketts and processed in the regular plant facilities.  Spent
catalysts could potentially be reclaimed and reused in the upgrad-   m
ing process, though facilities to reclaim them do not presently   •
exist. Some air pollution control technologies remove elemental   "*
sulfur which, if not contaminated by impurities, should have at
least a limited market for agricultural use. Biological treatment   A
sludges may be  useful on site as  soil  conditioners  for   m
revegetation if they do not contain significant quantities of harmful
contaminents. However,  even if all the above wastes are utilized   at
to the maximum extent  possible, it will not make a significant   •
impact on the amount of solid waste to be  disposed.           ~
                20 :
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1.4  CONCLUSIONS AND ADDITIONAL RESEARCH NEEDED        i
                                                       i
                                                       i
Conclusions                            '

1.  The  oil  shale industry will  produce  unprecedented volumes of
    solid waste mostly  consisting of retorted oil shales, raw oil
    shale  fines,  overburden  and  subgrade ore,  codisppsed waste-
    water, and much  smaller  quantities of known hazardous wastes.
    Although  the  known hazardous wastes will  be sent 'to licensed
    disposal or recycling facilities, the high volume solid wastes
    will be disposed  on or close  to the plant site.  If not prop-
    erly managed these high volume wastes are capable of producing
    leachates that could contaminate the water supply for millions
    of people.  Some of the waste may also pose the hazard of auto
    ignition unless proper controls are employed.  Surface disposal
    sites covering  square miles  in  area  and hundreds; of feet in
    thickness would do extensive property damage and threaten lives
    should they ever suffer sudden mass failure.       j

2.  Control technologies  to  prevent serious adverse  impacts from
    disposal  of  billion  of  tons  of  oil  shale  wastes have  been
    proposed  but  their application  to oil shale waste materials
    and on the scale required has  not been demonstrated.  Further,
    to be effective,  these technologies, must be applied in highly
    technical and  integrated disposal designs  that are  site  and
    process specific.  There is no  current  experience in disposal
    of wastes  of similar  composition or  of volumes  'approaching
    that which will result from the oil shale industry.!

     Additional Research Needed                        |

     a.   Solid wastes (including  codisposed wastewaters)  from  oil
         shale facilities need to  be characterized.
                                                       I
     b.   The  effects  from codisposal  of  liquid and solid  wastes
         need to be  determined.   Related  question is to  what  ex-
         tent should  wastewater  be treated prior  to i codisposal
         with retorted shale.                        ,   i

     c.   Effective  means of controlling moisture  movemejit  into  and
         from   retorted  shale  disposal  site   to  achieve mass
         stability  and minimize leachate need to be developed  and
         demonstrated.   Included  are  liners  and covers made from
         retorted  shale,  drains installed above  and below liners,
         use  of vegetation to reduce  infiltration,  arid means of
         relocating surface drainage  in filled canyons.;

    d.   The  nature and quantity  of  leachate  produced from dis-
         posal  sites  employing  state-of-the-art technology needs
         to be determined.
                             21
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                                                                   I
                                                                   I
e.  A best  management practices  design manual  needs to  be      m
    developed  to  guide   developers  and  permitters  in  the
    selection  of appropriate  control  technologies  and  the      W
    integration of  these technologies  into  complex  site  and      m
    process specific disposal designs.
                                                                   I
                                                                   I
22
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                             SECTION 2

                 CHARACTERISTICS OF U.S. OIL SHALE
2.1  INTRODUCTION

This  section describes  the  location,  geology,
the  physicochemical  properties   of  oil  shale
United States.
resources
Oil shale  is commonly defined as  a  fine-grained
containing organic  matter (known  as  kerogen)  that is
insoluble  in  petroleum  solvents, but  that  yields
quantities  of  liquid   oil,   gases,   and  residual
pyrolysis [Culbertson et al., 1973].

2.2  LOCATION
 composition
       ,  and
     in  the
 sedimentary
        rock
 essentially
 substantial
carbon  upon
The principal  United States oil  shale  deposits are  presented in
Figure 2.2-1  [Duncan et  al.,  1965].   These deposits occur in four
general  locations;   (a) the Tertiary  period  (Eocene)  deposits of
the Green River  Formation  in  Colorado,  Utah, and Wyoming; (b) the
late Devonian  and early  Mississippian period marine shales of the
central  and  eastern  United States,  stretching from  Michigan and
Pennsylvania  southward  through  Indiana  and  Kentucky to  Texas;
(c) the  early  Cretaceous   and  upper  Triassic marine, shales  in
Alaska;  and   (d) the small Tertiary  shale  deposits  £>f  Montana,
Nevada, Idaho, and California [EPA-600/2-80-205a,  1980].

It has been estimated that an equivalent of seven trillion barrels
(bbl) of oil  are contained in the U.S.  reserves of shale oil, but
not all  of these deposits  are sufficiently rich in organic matter
to be  considered commercially  attractive.   Estimates place total
known U.S. oil shale resources  for oil shales  yielding 10  gal of
oil per  ton of shale at well over 2  trillion bbl  [Duncan et al.,
1965].   The Green River Formation oil  shales  in  Colorado,  Utah,
and  Wyoming  account  for an estimated  90 percent of \ this  total
resource and  are therefore regarded  as being  the  most important
commercially.                                           I

The Devonian Marine black shales of the central and eastern United
States are estimated to contain at least 400 billion bbl of equiva-
lent oil.  While they have not received as much commercial interest
as the Green  River  Shales,  there are commercial projects proposed
                              23
 image: 








                                                        EXPl.ANATION
                                                       Tertiary d»ponltn
                                                     <3repn River Formation
                                                      In Colorado, Utah, and
                                                      Wyomuiu; Monlen>y
                                                      Formation, California;
                                                      middle Torllary deposits
                                                      In Montana. Black srean
                                                      are known high-grade de-
                                                      posit.-!
                                                       Mer.oswlc deposits
                                                      Marine shale In Alaska
                                                       Permian deposits
                                                      J'hosphorla Formation,
                                                         Montana
                                                     Devonian and Mls.sln.slpplan
                                                     df>pi)nlts (resource ontl-
                                                     mati>s Included for
                                                     hanli'trod areas only).
                                                     Boundary dashed where
                                                     concealed or where
                                                     location Is uncertain
     Figure  2.2-1.  Principal United  States Oil Shale Deposits.
                     Source:   Duncan et al., 1965

 for their development.   The Institute of Gas Technology has demon-
 strated that retorting  in the presence of hydrogen  (hydroretortina)
 can increase the oil  yield  of the  Eastern Devonian Shales,  by  a
   ?*£ °f 2'-5  CTarman  et  al-  1967].   The Alaskan marine shales
 anj. .the Tertiary  shales of California  and elsewhere  have received
  iF~   attention to date  and are not  considered to be commercially
 attractive.                                                           J

 2-2.1  Green River Formation Oil Shale

 As shown  in Figure  2.2-2,  the  oil  shale  deposits  of  the  Green
 River  Formation  occur   in  a  16/988  mi2  area  in  northwestern
 Colorado,  northeastern Utah,  and southwestern  Wyoming.   The richer
 oil shales,   those of  highest commercial  interest,  are  generally
 more  centrally located in  the four  depositional  basins:  Piceance
 Creek basin,  Colorado;  Uinta  basin,  Utah;  and the Green River and
 Washakie  basins  of Wyoming.   The  Piceance  Creek basin  of Colorado
 contains  the thickest  and  richest; oil shale  deposits  within the
 United States,  and  accordingly,  the  greatest interest related to
 commercial development has  been directed to that area.

 Table  2.2-1 presents  the total in-place shale  oil  resources of the
 Green  River  Formation.    Total identified  shale  oil  resources  in
place,  which  average 15  gal/ton or more in strata up  to 2,000  ft
 thick,  are estimated  to be  179 billion tons  in Colorado's Piceance
                                                                               I
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                                24
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                                             COLORADO
     Area of 25 gal. /Ion or richer
     oil shole 10 ft or more thick
MESA

  GRAND MESA
                                                            KEY,MAP


                                                         >•—«T  WYOMING""!

                                                                  Area of
                                                                   Map
                                                               I          !

                                                          UT«H   I	COLORADO   1_
                                                            25  i 50


                                                             SCALE, MILES
                                                                        100
  Figure 2.2-2.   Green River Formation Oil  Shales-Utah,1  Colorado,
                    and Wyoming.   Source:   Baughman,  1978 I

         TABLE 2.2-1.  TOTAL IN-PLACE  SHALE  OIL RESOURCES
                         OF THE GREEN RIVER FORMATION

Type of shale (yield/ tonne)
62.6 L/ tonne
(15 gal/ ton)
or more
Location
Colorado
Utah
Wyoming
TOTAL
Billions
of
tonnes
163.2
43.7
43.7
250.6
Billions
of
equivalent
barrels
of oil
1,200
321
321
1,842
104. 3. L/ tonne
(25 gal/ton)
or more
Billions
of
tonnes
82.6
8.7
8.2
99.5
Billions
of
equivalent
barrels
of oil
607
64
60
731
125.2 L/ tonne
(30 gal/ ton)
lor more
i
i
Billions
of
tonnes
48.3 i
6.8 :
1.8 i
56.9 i
i
Billions
of
equivalent
barrles
of oil
355
50
13
418

 In beds  at  least 10 ft thick.

Source:   Ash,  1964.
                                   25
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                                                                        I
 Creek Basin,  48  billion tons  in Utah's Uinta Basin,  and 48 billion      T
 tons  in the  combined  Green River,  Washakie,  and Sand Wash basins
 of Wyoming.   The three-state  total  is thus  1,842 billion bbl.  The      jt
 total in-place resource  is not presently  recoverable, but it is      •
 estimated  by the U.S.  Geological Survey  (USGS) that approximately
 80 percent of the known  shale  that yields  25  gal/ton or more, or      •
 some  88 billion tons  of shale oil  are suitably  located and of      I
 adequate  thickness to be reasonably regarded  as  the potentially
 recoverable  resource  base.   If 50 percent of the  25 gal/ton or      m
 more  resource could  be  recovered,  it would  be large  enough to      •
 produce  2  million bbl/day,  or over one-fourth  the present daily      *
 imports, for  more than 400  years.   Table  2.2-1 shows  that 80 to 85
 percent of the in-place, 25- to 30-gal/ton oil shale resource are      •
 in Colorado's Piceance Creek  Basin,  with the  remainder divided      |
 between Utah's Uinta Basin  and  Wyoming.

 2.2.2 Devonian-Mississippian Black Shales                              n

 The black  marine shales of the Deyonian/Mississippian periods are
 located in the Eastern and Central States.  These shales, part of      •
 an original shallow inland sea,  occur over an  area of more than      B
 400,000  mi2  in  Ohio,  Kentucky,;  Tennessee,  Indiana,  Michigan,
 Alabama, and extend as  far southwest as Oklahoma  and Texas.   As      •
 shown in  Figure 2.2-3  black  shale  deposits  also  occur  in  the      I
 northern great plains  and extend into Canada.

 The Devonian shales are  lean by western  shale  standards,  with an      I
 average Fisher  assay  of only 10 gal/ton; however,  the carbon con-      *
 tent  of Devonian  shales is  typically about  14 percent, or approxi-
 mately  the same  as Green  River shale assaying 30  gal/ton.   The      ft
 difference  in Fischer  assay is due to the  higher carbon to avail-      m
 able  hydrogen weight  ratio  of thei10 gal/ton Devonian shale (11-2
 to 1) as compared with the  30 gal/ton Green River shale (7.2 to      f»
 1).   If, however, the  10  gal/ton Devonian shale is retorted in the      •
 presence  of  hydrogen  (i.e.,  hydroretorted),  oil  yield can  be
 increased  to  25  gal/ton, according to research conducted  by  the      _>
 Institute of Gas  Technology (IGT) [Tarman et al., 1977].                •

 The higher oil yields possible with hydroretorting can, of course,
 have  an  influence on  defining  the  Devonian shale  resource base.      fl
 The USGS estimate of equivalent oil in place in Devonian shales is      9
 400 billion bbl, without considering the  effect of hydrogen in
 retorting.   With  hydroretorting, this  value could  easily increase      »
 to 1  trillion bbl,  or  250 percent of  the conventional  Fischer      •
 assay.                                                                  •

 The Institute of Gas  Technology has  surveyed  the  three-principal      tf
Devonian shale basins  (Appalachian,  Illinois,  and  Michigan)  and      p
 estimated that some 423 billion bbl of oil could be recovered from
 the 6,200 mi2 of outcrops and relatively shallow deposits  in these      m
basins alone  if  hydroretorting  were employed.   Their criteria  for      jj
 a recoverable resource required that a shale deposit have  an
                              26
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     Figure 2.2-3.
Distribution of Upper Devonian and Lower
Mississippian Black Shales in the Eastern
United States.  Source:  Baughman, 1978
organic  content of more  than 10 percent  by weight, a  unit rock
thickness of  at least 10  ft,  an overburden thickness oJF less than
200  ft,  and a  stripping  ratio of less than 2.5  to  1. i  The study
assumed hydroretprting yields  of 85  percent of the organic carbon
present, and strip mining at 90 percent recovery of in-place shale.

2.2.3  Other Shale Deposits                        ,    ,
                                                       i
Among other  U.S.  shale deposits  are the  thin  strata of carbona-
ceous shales  associated with  coal beds,  particularly iti the Appa-
lachian coal  region.   It  is estimated that perhaps 60 billion bbl
of equivalent oil may be present there in high grade shales assay-
ing  from 25  to 100  gal/ton.   In California,  the Mioqene marine
shales  are  believed  to  constitute  a 70-billion bbl  resource  in
shales  varying  from  5  to  25  gal/ton.  In  southwestern Montana,
beds  of Permian black  shale,  ranging from  5  to 15  gal/ton,  may
total up to 10 billion bbl of equivalent oil in place.  As with the
Appalachian coal shales,  however, neither the Alaskan, California,
nor the Montana shale are considered to be of near-term:commercial
importance [Duncan et al., 1965].                      :
                              27
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2.3  GEOLOGY
                                                                        I
                                                                        I
The  geology of United States oil  shales  varies  with the location      fl
of  each occurrence.  The geologic  factors  which are similar from      ™
deposit  to deposit  are  related  to the  modes  of origin  for oil
shales.  The origin of oil shale involved the deposition of organ-      H
ic remains  from quiescent organic-rich waters.  The maintenance of      H
reducing conditions  during  and  after deposition and before indur-
ation was  required to prevent oxidation of deposited organic mat-      _.
ter.  The  similarities in geology appear to end at this point, as      I
evidenced by the wide differences in the mineralogical composition      *•
of  the  inorganic  fraction  of oil  shale  and the variance  of the
properties  of  kerogen (altered organic material)  from deposit to      •
deposit.                                                                |

Oil  shale   interest  to  date  has  concentrated on the  Green River      •
Formation  deposits and more recently the  Devonian-Mississippian      I
black shale deposits.  For this reason, discussions of the geology      ^
of these two major deposits are presented.

2.3.1  Green River Formation                                            •

The  Green  River  Formation oil shales were deposited 50 to 60 mil-      •
lion years  ago in two large Eocene-age lakes.  Lake Uinta occupied      H
the  northwest  part  of  Colorado  and  the  northeast part  of Utah.
Lake  Gosiute  occupied the  southwest portion of  Wyoming.   During      «
different  periods  of deposition of the Green River  Formation the      •
two  lakes  were probably connected in  the area  of northwest Colo-      m
rado and southwest Wyoming near the east end of the Uinta Mountain
Uplift.                           ;                                      M

Located within each of these ancifent lake complexes were individ-
ual  depositional basins.   Fluctuations  in  lake levels  caused by      m
tectonic and  climatic changes resulted  in  alternating deposition      g
of  oil  shales,  saline  minerals,   fluvial  sediments,  fresh water
facies,  and  mud-flat  type  deposits.   Figure 2.2-2,  discussed      u
previously, shows the individual depositonal basins.   The thicker,      9
richer  oil  shales  are   generally  located  at  the  depositional      ™
centers of these basins.

2.3.1.1  Piceance Creek Basin, Colorado                                 p

The Piceance Creek basin is a large asymmetric structural downwarp      «
[Doimell, 1961].  The axis of the basin trends northwest to south-      •
west with  the  western and southern flanks gently sloping into the
basin.  The northern and eastern  flanks  slope much  more  steeply
into the basin.  The basin is bordered on the northwest and north      •
by  the  Rangely-Skull Creek-White River anticlinal trends;  on the      m
east by the White  River Uplift;  on the southeast and south by the
Elk and West Elk Mountains and Gunnison Uplift;  and along the west
by  the  Douglas Creek arch  [Murray  et  al.,  1964].  Numerous small
                              28
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anticlines  and synclines  are  found within  the basin;  faulting
(graben)  systems  are associated with some  of  the more pronounced
structural trends.                                     I

Strata exposed in and around the margins of the basin range in age
from  late  Cretaceous  to  early  Tertiary  [Donnell,   1961].   The
oldest  rocks  are  the  late  Cretaceous Mesaverde Group which  is
composed of sandstones, shales, and some coal beds.  Fossil content
indicates  that  deposition  occurred near  standlinesj in  fresh,
brackish,  and  marine  environments.   The  Mesaverde j rocks  are
generally more resistant to erosion and form a series of prominent
benches which outcrop continuously around the southern ;and eastern
margin of the basin. Overlying the late Cretaceous is the Paleocene
series  consisting  of the Ohio  Creek Conglomerate and; an  unnamed
unit,  composed of  feldspathic  sandstones,  shales, and  thin coal
beds, which  is  considered  a  Fort Union Formation equivalent.  The
Wasatch Formation of early Eocene overlies the Paleocene rocks and
consists  of thick  sequences  of  lenticular sandstones  and  vari-
colored  shales with  some  coal beds.   Fossil  evidencfe  indicates
that) the  Wasatch was deposited in  a terrestrial fluvial environ-
ment,.  The Wasatch Formation, being less resistive to erosion than
overlying and  underlying strata,  forms lowland areas between the
cuestas  of  the more resistive adjacent  rocks.  The  Green  Riyer
Formation, containing the  oil  shales of the Piceance Greek basin,
is generally thought of as overlying the Wasatch Formation.   How-
ever,,  upper  tongues of the Wasatch  Formation  are time equivalent
to some Green River depositional sequences which represents either
fluyial depositional  encroachment into  the  lacustrine !Green River
environment  or regression  of the Green River  lacustrine environ-
ment,.   Similarly,  the  fluvial  (stream-bed)  Uinta Formation inter-
tongues,  but   generally  overlies,  the   lacustrine j (lake-bed)
deposits  of  the Green River  Formation.   The Green River Formation
in Piceance  Creek basin has been divided into three  main members
based on  lithology, but locally a fourth clastic facies is present.
Each  of the  members is discussed in ascending order with emphasis
on the Parachute Creek Member,  the main oil  shale  be'aring unit.

The  Douglas  Creek Member,  basal member of  the Green  River Forma-
tion,,  is  composed  of sandstones,  shales,  and limestones that con-
formably  overlie the varicolored  shale  and sandstone units of the
Wasatch  Formation.   This member has been recognized  only  in the
southern, western, and central parts of the basin.  Injthe eastern
part of the basin, aclastic facies replaces the Douglas Creek Mem-
ber.   To  the northwest, the  Douglas Creek Member coalesces with
shales  of the  overlying Garden Gulch Member.  Resistant strata of
the  Douglas Creek  Member  form a series of  light brpwn  benches
along the base of the Green River Formation escarpmentJ

The  Garden  Gulch Member, overlying  the Douglas Creek Member along
the  basin margins,  is  composed of  dark,  finely laminated illite
shales  and marlstone, some of which contain kerogen.   With the ex-
ception  of  the eastern part of the  basin,  where equivalent sandy
                              29
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                                                                        1
                                _
 Garden Gulch  outcrops  as  gray  steep  slopes  between  the white
 cliffs of  the  Parachute  Creek  Member  and the  brown  and buff      {•
 benches of  the Douglas Creek Member.                                    ffl

 Problems  with  the  correlation  of the  Garden Gulch  and  Douglas      «
 Creek Members,  as they were previously  described at type sections      M
 on  the  flank of the  basin,  to central  basin deposits  as they      "
 are  presently  mapped  has  been  discussed  [Roehler,  1974].  The
 two  members  at  the  type  sections have been described  as being      •
 "...largely chronologic and  lithologic equivalents."   Others  do      •
 not  differentiate the  two  members  because  they  are  partly time-
 equivalent.   The thickness  of  the  Garden Gulch-Douglas Creek      •
 (undifferentiated fresh water unit)  in the more  central  portion      •
 of the basin is  reported to be  at least 1,000 feet.   Two easily
 discernible geologic  markers  in  the  subsurface,  found  on resis-      _
 tivity logs,  exist  in  the  vicinity  of the Garden Gulch-Douglas      •
 Creek unit.  Both  markers  exhibit an extremely  low resistivity.      P
 The  uppermost marker,  the  Blue marker,  is considered the  contact
 between  the  clay  (illite)  shales  of  the  Garden Gulch  and  the      •
 dolomitic  marlstones  of the  overlying Parachute Creek  Member.      I
 The  lowermost marker,  the  Orange  marker,  has been  described  by
 some  as the  contact  between  the Garden  Gulch and Douglas Creek      m
 Members [Roehler, 1974].                                                •

 A clastic  facies equivalent to  the Douglas  Creek,  Garden Gulch,
 and(  lower  portion of  Parachute Creek  Members are  assigned to the      •
 Anvil  Points  Member.   This   member   is  composed  of  sandstones,      •
 shales, marlstones,  siltstones,  and limestones.   The Anvil Points
 Member has  been  described along outcrops  from the Parachute Creek      •
 valley around the eastern rim, to a little north of the headwaters      1
 of Piceance Creek.   The absence  of the Anvil Points Member in the
 Piceance Creek gas  field indicates that the member is confined to      H
 the  southeast and eastern parts  of the  basin.   The maximum known      B
 thickness is 1,870 feet  in the upper Piceance Creek area.  The An-      *
 vil Points  Member appears  as  a series of benches and cliffs below
 the  cliffs  of the  Parachute  Creek Member.   It  interfingers with      •
 the  overlying Parachute Creek Member and the  underlying Wasatch      I
 Formation with  both the upper and  lower contacts  conformable  and
 gradational.                                                            «

 The Parachute Creek Member which overlies the Douglas Creek-Garden
 Gulch_unit is of most  interest because it contains the majority of      _
 the oil shale resources in the Piceance Creek basin.  Although the      I
 term  oil  shale is used  extensively,  the lithology generally con-      •
 sists  of kerogenetic dolomitic marlstone and differs considerably
 from the true illite shales of the!underlying Garden Gulch Member.      •
Weathering  of the resistant Parachute Creek Member has  produced      p
precipitous and  often  spectacular1  escarpments  around the  rim  of
the basin.   The  thickness  of the  Parachute Creek Member  varies      «
 from  over  2,000  feet  in the  north central  part  of the basin  to      I
 about  500 feet along the margins.  '                                      *
                              30
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 The most consistently rich and laterally persistent oil!  shale zone
 in  the  basin  is  designated  the  Mahogany ledge  on putcrop  and
 Mahogany zone in the  subsurface  [Bradley,  1931].   Figiire  2.3-1,  a
 schematic  cross  section,   shows   the  relative  position  of  the
 Mahogany zone as well as  other members  and zones  within the  Green
 River Formation.  The very resistant-to-weathering nature of the
 Mahogany zone is  due to its  high kerogen content and!  results  in
 vertical to near-vertical outcrops.  The Mahogany zone  is bounded
 on the top and  bottom by relatively thin barren  zones'  termed the
 'A'  and  'B'  grooves,  respectively.  These  barren zones  are  less
 resistant to  erosion,  forming slopes  on  outcrops that  resemble
 grooves,  hence their designation.  In the  subsurface both the 'A'
 and ''B'  grooves produce  distinct  lows  on  resistivity >.  logs.    The
 thickness  of the Mahogany zone ranges from approximately  100  feet
 near the margins of the basin to  about  200 feet in the  north  cen-
 tral part of the basin.   Generally,  the  grade of  oil shale in the
 Mahogany zone exceeds  20  gallons per  ton  with the  richest  sequence
 comprising approximately  130  feet of 30  gallon  per [ton shale.
                                                       I
 Above  the  Mahogany  zone  there  generally  is  300   to  500  feet of
 leaner oil shale.   This  sequence  is  thickest in the southern  part
 of the  basin.  Due  to   interfingering  with the  overlying Unita
 Formation  in the northern  part  of the  basin,  the upper  sequence
 thins to less  than 300 feet.                           !

 A  sequence of oil shale below the Mahogany zone extends  from the
 top  of  the  Blue marker  to the base  of the 'B1  groove.   In the
 southeastern  part  of  the  basin  this lower oil  shale sequence is
 interfingered  with,  and  in  some  instances  replaced by;  the Anvil
 Points  Member.  In  the  extreme  northwest  part of the  basin the
 lower oil  shale  sequence is  absent and the  Mahogany zone and over-
 lying  oil  shale rests  conformably  on  the  Garden Gulch Member
 (Donnell,  1961).   Elsewhere, the  thickness  of the  lower oil shale
 sequence ranges  from a minimum of  20 feet in the southwest to over
 1,300  feet in  the north-central  part  of  the basin.  iToward the
 central  portion of  the  basin the lower  sequence ofj  oil shale
 thickens   due  to   the   increased  lacustrine   type  deposition,
 resulting  in significant  accumulations  of  dolomitic  marlstones,
 organic  material,   and  saline minerals.    The  saline'  minerals,
 depending  on  the  particular  mineral,   have  been fotmd finely
 disseminated within the oil shale,  as individual spherical crystal
 growths or rosettes and as bedded  layers and zones.    j

The lower oil shale zone was subdivided into a series of alternat-
 ing  lean and rich zones  [Cashion  and Donnell,  1974]  j   The  rich
 zones were designated R-4,  R-5,  R-6,  etc.   This  designation and
correlation was based on oil shale grade from the Modified Fischer
Assay  or  apparent  grade  from geophysical  logs.   The^  lower  oil
 shale sequence can also  be subdivided into two zones,  leached and
unleached,  on the  basis  of removal by dissolution or  leaching of
 saline minerals, mainly  consisting of minerals  such  as  nahcolite
                               31
 image: 








   »ooo'-
   •000'-
   700O%-
   6000 -
   5000'-
   4000'-
   3OOO'-
                                                      SOUTH
                                                        A1
                                                             9000'
                                                Greovt
                                                Groovt
                                                 - 8000'
                                               GRE EN RIVER
                                                F )RMATION
                                                            - TOOO'
 GREEN f
 RIVER <
FORMATION L
                Wbsotch
                  Formation
                                                             - 6000'
                                                            - 5000'
                                                            - 4000
                                                            L 3000
  Figure 2.3-1.   Schematic North-South Cross  Section of Piceance
                  Creek Showing Relationship of Oil Shale Bearing
                  Members of the Green River Formation and
                  Surrounding Strata.
                  Source:  Baughman, 1978

and halite in the upper portions of the-saline section.  Although
leaching is not confined to any one area of the basin,  the effects
of  leaching are most  pronounced in the  central part of the basin
where there was maximum saline deposition.  An unleached or saline
zone is found  below the leached zone in the central portion of the
basin.   This  zone  contains potentially recoverable deposits  of
nahcolite  and dawsonite.   From these  two minerals,  soda  ash and
alumina can be  produced.  The  thickness of  the unleached saline
zone  in the central part  of the basin  ranges  from about  500  to
over 1,000 feet.

The interface of  the  leached and unleached zone,  somewhat poorly
defined,  is termed the dissolution  surface.   In reality,  it  is
probably  a dissolution zone, as numerous  cores have shown nahco-
lite  to be present above  the  dissolution  surface while  vugs and
cavities  are  found below.   At best,  any  designated  dissolution
surface is an  approximation.
1
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 The leached zone is characterized by cavities,  vugs,  and collapsed
 breccia.  The  thickness of  the leached  zone  toward the  central
 part of  the  basin varies  from  about 400 to 1,100 feet.   Leached
 zone thickness  is  greater  around the margins of the major saline
 deposition.   Leaching of the saline  minerals has upgraded  the oil
 shale value within the leached zone by removing inorganic saline
 minerals which would have  had the  effect  of diluting the percent-
 age of  organic  material.   Leaching  has also  produced higher  po-
 rosity and permeability by removing evaporites thus producing an
 aquifer while  reducing bulk strength of the  rock.      j

 Overlying the Green River  Formation  is  the  Uinta Formation,  which
 includes sandstones and siltstones which  were  formerly  designated
 as  the Evacuation Creek Member of the Green  River Formation.   With
 the exception of  a few local unconformities described by  Donnell
 (1961),   these   formations   represent  a  continuous  depositional
 sequence.   The  outcrop of  the  Uinta  Formation  forms!  a  buff  to
 rusty brown colored rounded cap receding  from the white cliffs of
 the Parachute Creek Member.                            :

 The maximum thickness  of  the Uinta  Formation  is  unknown  because
 the top  has  been  removed by  erosion; however,  from: subsurface
 information,  it  is known to exceed  1,200  feet.  Because of inter-
 tonguing with  the  Parachute Creek Member,  the lower boundary
 varies  from location to  location.                      i

 2.3.1.2  Uinta Basin, Utah                             ;

 The Uinta basin  is  sharply  asymmetrical, the axis of which  lies  in
 the northern portion  of the basin trending east-west and parallel
 to  the Uinta Mountain uplift which borders the basin to the north
 The Wasatch Mountains border the basin to  the west and the Douglas
 Creek  Arch  borders the basin on the  East.   The  southern flank  of
 the basin is  bordered by  the  San  Rafael Swell, the  Salt Creek
 Anticline, and the  Uncomphagre Uplift.   Over 13,000 feet of sedi-
 ments  were  deposited in the basin center  during  the  Epcene time.
 Eocene  strata of the  Uinta basin  belong  to  the Wasatch Green
 River,  and Uinta Formations, consisting  of  rocks  deposited  in
 fluvial  and  lacustrine  type  environments.   The  thickest  and
 richest  oil shales  of  the Uinta  basin  are  found  in the  east
 central portion of the basin, as indicated on Figure 2.3-2.

 The  Wasatch  Formation,  the basal Eocene  strata,  is composed of
 fluvial  sandstones,  shales,  mudstones,  and   siltstones.   The
Wasatch  rocks  vary in  color from  red  and  purple  to browns and
 light grays.   The formation is  divided into two parts,  the main
body of the Wasatch and the Renegade tongue which intertongue with
the overlying Green River Formation.
                              33
 image: 








The  Green River Formation is  divided into  three members in  the
Uinta  basin:  the  basal Douglas Creek Member; and  the overlying
Garden Gulch  Member,  and  the  uppermost  Parachute  Creek Member.
Figure 2.3-2 is a  schematic  cross section illustrating the Eocene
stratigraphy of the Uinta basin.   ;
             Index
             Map
              V'//////:,-'//.'.-/.Uinta  format ion •/;/////////'.y'-V/V.;=b^==7?ciastic •'" •="-


                         Mahogany Zone
               Lacustrine Facies
               Green River  Formation
                                     Clastic  Facies
                                      Green  River  Formation
   Figure  2.3-2.
Schematic Cross  Section of Uinta Basin  Showing
Relationship  of  Oil Shale Bearing Green River
Formation With Surrounding Strata.
Source:  Baughman,  1978
The  Douglas Creek Member  is compqsed  of shale,  siltstone,  sand-
stone,  and  oolitic,  algal,  and ostracodal  limestones.   Locally,
the  Douglas  Creek  Member  contains  a  few  oil  shale  beds.   The
member  conformably  intertongues  with  fluvial  sediments  of  the
Wasatch  Renegade  Member.  The  maximum thickness  of the member is
1,180 feet [Cashion, 1967].

The  Garden Gulch Member outcrop is distinctly different  from  the
Douglas  Creek  Member  outcrop,  a$  the  Garden  Gulch  forms gray
slopes  which  contrast with  the brown ledge-forming sediments  of
                               34
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 the Douglas  Creek" Member.   The  member  is  chiefly fcomposed  of
 marlstones,  oil  shales,  and siltstones.  The  Garden Gulch Member
 is thickest along the eastern outcrop of the Green River Formation
 of the Uinta  basin/  Westerly, the  Garden Gulch  thickens,  while
 the overlying Parachute Creek and  underlying Douglas Creek members
 thicken basinward.   The  maximum  thickness  of  the Garden  Gulch
 Member is  230 feet [Cashion,  1967].                    ;

 The Parachute Creek  Member of the Green River Formation contains
 the oil shales  of significant interest  in the Uinta ^basin.   The
 member is  composed mostly of  kerogenetic  marlstone  (:oil  shale),
 barren marlstone, sandstone, siltstone, and  tuff.   The  oil shales
 are for the most part finely laminated or varved.   Individual beds
 within the Parachute  Creek Member  are well  known for their lateral
 extent and relative continuity.  Many of the  mappable units of the
 Piceance  Creek basin  oil  shales  are also recognized  and mappable
 in the Uinta basin.   The thickest  and richest  sequence of  oil
 shale  in  the Uinta basin  is  found in the laterally persistent Ma-
 hogany ledge, termed  Mahogany zone  in the subsurface.!   Oil  shale
 also  exists  above and  below the  Mahogany zone,  but is  somewhat
 leaner in grade.   The maximum thickness of  the Mahogany  zone  in
 Utah  is about 100  feet.   The Parachute Creek Member is  about  750
 feet  thick in the  east  central portion of  the basin but thickens
 to the north and  west toward the  synclinal  axis of1 the basin.
 Evidence  of  a  saline zone exists  in the upper one-third of  the
 member, where crystal cavities thought to have once contained  the
 mineral nahcolite have been observed.  The leaching of the nahco-
 lite by groundwater has given the appearance  on verticjal outcrops
 that  swallows have nested there,  thus giving rise  to  the name
 "birds  nest  zone"  [Cashion,  1967].   The  upper  section  of  the
 Parachute  Creek  Member containing  the  "birds nest  zone'"  was named
 Evacuation Creek Member [Bradley,  1931 and Cashion, 1967].  How-
 ever,  the nomenclature has  since  been revised  to  place those
 sediments  within the  Parachute  Creek Member  [Cashion  et al.,
 1974].  The lacustrine  sediments  of the  Parachute Creek member
 intertongue  with  the overlying  fluvial sediments of  the Uinta
 Formation.                                             ;

 Overlying  the  Green River  Formation is the Uinta Formation, which
 consists of approximately  1,750 feet  of sandstones  and claystones.
 Colors range  from brown and greenish gray in the lower section to
 browns and reds,  in the upper section  [Cashion, 1967].   The Uinta
 Formation  covers most  of  the east  central portion of  the Uinta
 basin where the thicker and richer oil shales are found.

 2-3.1.3  Green River and Washakie Basins, Wyoming      ;

 Ancient  Lake  Gosiute  covered a  large portion of southwestern
 Wyoming.   The  large lake was bordered to the  north bys the Sweet-
 water  Uplift,  the Wind River Uplift,  and the Gros  Ventre Uplift.
 To  the west,  the lake was bordered  by highlands  created by the
Absaroka Thrust,  the  Uinta Arch,  and the White River Uplift.  The
                              35
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                                                                        I
Park Range  and Rawlins Uplift  border the lake to  the  east.   The      •
oil shales of primary interest in Wyoming are located in the Green
River and  Washakie basins, which  are contained within  the areal      H
extent of  ancient Lake Gosiute.  Other  smaller basins  within the      H
extent of  Lake Gosiute also  contain oil shale but they are thin
and lean  in comparison to  those of  the  Washakie  and Green River      tm
basins.   The  other  basins  are the  Fossil  basin. Great  Divide      •
basin, and  the Sand Wash basin, the  latter  extending into North-
western Colorado.   The Washakie and  Green  River  basins  are now
separated by the Rock Springs  Uplift, similar to  the  separation      II
of the Uinta basin and Piceance Creek basins by the Douglas Creek      •
Arch.

The  stratigraphy of  the  sediments  containing  the  oil  shales in      |
Wyoming is  similar to that containing oil shales  in Colorado and
Utah.  The Wasatch Formation underlies the oil shale bearing Green      «
River Formation.  The Wasatch in Wyoming, as in Colorado and Utah,      •
consists predominently of fluvial varicolored brown and gray sand-      m
stones, siltstones,  shales,  and mudstones.   Upper Wasatch sedi-
ments intertongue  with the overlying Green  River  Formation.   The      •
Green River Formation has been divided into four basic members, in      B
ascending  order:   Luman Tongue,  Tipton Shale,  Wilkins  Peak,  and
the  Laney Shale Member.   The fluvial Bridger  Formation overlies      m
and intertongues with the  Green River Formation.   Figure 2.3-3 is      y
a  schematic  section,  showing the  general east-west stratigraphic
relationship  of the  rocks  deposited during Eocene time  in the
Green River and Washakie basins.                                        I

Each of the  members  of the Green River Formation represents wide-
spread  deposition of  lacustrine facies of  ancient Lake Gosiute.      •
The Luman Tongue contains only lean oil shales.   The Tipton Member      H
contains oil shales considerably richer than those  of the Luman in
the Green River basin.                                                  «

The Wilkins Peak Member consists mostly of marlstones, siltstones,      ™
saline deposits, and oil shale.  The  saline section of the Wilkins
Peak Member  contains bedded  deposits of the mineral  trona,  from      H
which  soda ash is produced.   The trona  is  presently being mined      •
and  processed.  This  saline section of the Wilkins  Peak member
correlates time-wise  with the  saline section of  the  lower Para-      •
chute  Creek  Member in the Piceance  Creek basin  [Roehler,  1974].      g
The  oil shales  of the Wilkins Peak Member,  although relatively
rich,  are thin and  separated by lean or barren marlstones.  The      —
Wilkins  Peak  Member  grades  laterally  to  gray-green  marlstones      •
and  is  eventually replaced  in  section by fluvial  tongues of the      •
Wasatch Formation.

The  uppermost member of the  Greeii River Formation in Wyoming is      I
the Laney Member.   The widespread>distribution of  the Laney indi-
cates  that Lake Gosiute was  most; extensive  during Laney deposi-      m
tion.  Oil  shales  of the Laney Member in the eastern part of the      ||
Washakie basin represent the  thickest and richest oil shale
                              36
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                                 37
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deposit,  in Wyoming.  The  section of  oil  shale varies  from  about
150  to  500 feet in thickness  [Roehler,  1973].   The oil shales  of
the  Laney Member  in the  Green  River basin are  not  as thick  as
those of the Washakie basin.   The lacustrine Laney Member inter-
tongues with the overlying fluvial Bridger  Formation.

Figures 2.3-4, 2.3-5, and 2.3-6  show the areal  distribution of the
richer oil shale beds of the Green River basin  [Culbertson, 1968].
Accompanying  histograms  indicate the  grade  of oil  shale within
the  Tipton,  Wilkins  Peak,  and  Laiiey Members  of  the  Green  River
Formation.
                                       0 10 20 Tw
                                                  10 20 30
                                       Oil yield in gallons per ton——
                                                 I
                                                 1
                                                 1
                                                 I
                                                 I
                                                 1
                                                 I
        Figure 2.3-4.
Oil Yield of Tipton Shale Member.
Source:  Baughman, 1978
2.3.2  Devonian And Mississippian

Until  quite  recntly there  has  been only  limited research on  the
black  shales  of the East and Midwest  because of the emphasis  on
the richer  and thicker  oil shales of  the Green River  Formation.
The term  "black shale" refers to  dark (principally black or dark
gray)  shale  deposits which owe  their  dark color to their organic
content and which were generally deposited under marine  conditions.
                              38
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                                   Oil yield in gallons per ton
         Figure  2.3-5.   Oil  Yield of Wilkins Peak Member.
                        Source:   Baughman,  1978

 *T v,  +?'2^' 1re£ernred to previously,  indicates the areas  under
which  the  black shale of Devonian  and Mississippian are  known and
inferred to exist.  Total  land area  indicated is nearly  400 000
square  miles.  The  crosshatched areas contain  the black  shales
area bounded by the  dashed line indicates where the location of
the  black  shales  are  uncertain or where  it  is concealed  (i p
buried)  [Duncan et al.,  1965].                         I         '"

As may be noted, these black shales  are widely  distributed  between
the Rocky  Mountains  and the Appalachian Mountains, with  the  prin-
cipal  known resources contained in  zones  five  or more; feet  thick
and correlatable in  Arkansas,  Illinois, Indiana, Kentubky, Michi-
gan, Ohio,  Oklahoma,  Tennessee,  and Texas  [Conant et al., 1961].

Depending  upon  the  location,  various  formation names!  have  been
applied  to  the black   shales  of  the upper  Devonian\  and  lower
Mississippian.  They include  the Chattanooga,  Antrim, New Albany,
196 1    Mountain Glen,  Woodford, and the Lodgepole  [Conant et al.,


Figure 2.2-3  illustrates  the  depositional  conditions  existing
during the  Devonian  and Mississippian.  The figure also  shows  the
different  names applied  to the  "black shales"  deposited  durina
this time [Conant et al., 1961].                       !
                              39
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                        20 MILES
                   GREEN

                   RIVER

                   BASIN
                                      Fo«t
                                               Fwt
                                    300
                                    250 -
           200
                                             300
                                       0 10 20     0 10 20 30 40
                                      Oil yield in gallons per ton —
         Figure 2.3-6.
Oil Yield of Laney Shale Member.
Source:  Baughman, 1978
Basically, the area of deposition was  in  the  Paleozoic  Appalachian
Sea,  which covered  the Appalachian,  Ohio,  and Michigan  basins.
Circulation of marine water carrying abundant mineral organic mat-
ter was  enhanced by outlets  from the  Appalachian Sea via  the St.
Lawrence seaway  and by a southern opening into  the Mexico Mediter-
ranean.  Under  sediment loading, the basins  continued  to subside,
and correspondingly more sediments were deposited, compressing and
forcing  the  black shales  deeper  into  their  respective  basins.
Such  conditions  existed until  the  end of the Paleozoic when the
entire eastern  part of the continent  was emergent  [Conant  et al.,
1961].                            :

The black shales  of  the  Devonian and Mississippian,  in contrast
to  the  oil shales  of the Green River Formation, are  true shales
composed dominantly of the micaceous clay illite.

Other important  minerals  associated with the black  shales  include
phosphate  and uranium minerals,  with uranium  ranging in concentra-
tion from  0.001  to 0.008 weight percent.   These minerals are found
in the Chattanooga formation.
                               40
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 2.4  COMPOSITION

 2.4.1  Minerals
 The proportions  of inorganic  and organic  minerals in  oil  shale
 vary  with  the  grade  of  shale.   Typical  values  are  shown  in
 Table 2.4-1 [Stanfield,  1951].   Typical of the minerals present in
 Green River oil  shale  of commercial grade is the listing presented
 in Table 2.4-2 [Smith  et al.,  1978].                   ;

 TABLE 2.4-1.  MINERAL  CONTENT  OF GREEN RIVER OIL SHALE| VERSUS GRADE
Fischer Assay, gallon oil/ton
Inorganic minerals, wt., %
Organic minerals, wt. , %
Oil Shale
10.5
92.2
7.8
100.0
26.7
84.0
16.0
100.0
3613
so:i
19:9
100.0
57.1
67.0
33.0
100.0
 Source:   Stanfield,  1951

     TABLE  2.4-2.  AVERAGE MINERAL  COMPOSITION OF MAHOGANY
                   ZONE SHALE,  COLORADO AND UTAH


                                                 Composition
       ,„•                                          weight
       Mineral	Chemical formula
Dolomite
Calcite
Quartz
Illite
Albite
K feldspar
Pyrite
Analcime

(Mg,Fe)Ca(C03)2
CaC03
Si02
KAl2(AlSi3)Ol0(OH)2
NaAlSi308
KAlSi308
FeS2
NaAlSiO4 • 25H20
TOTAL
32
16
15
1'9
10
6
1
r-
100
      Source:  Smith et al., 1978                      i

The chemical analyses of the inorganic mineral portions; of 16 sam-
ples of Green  River oil shale varying in grade  from  10.5 to 75.0
gallons per ton were  reported  [Stanfield,  1951].   The  minimum,
maximum,  and  average  values  are  shown in  Table  2L4-3.   The
variation of inorganic chemical  composition with shale  grade is
shown   in   Table   2.4-4,   along  with  the   inorganic   chemical
composition of the spent shale.
                              41
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   TABLE 2.4-3.  FISCHER ASSAY DATA OF THE INORGANIC MINERAL
                 PORTIONS OF 16 SAMPLES OF GREEN RIVER OIL
                 SHALE  RANGING FROM 10.5 to 75.0 gal/ton
                 OIL SHALE
              Assay data, %
Minimum   Maximum    Average
Si02
Fe2C>3
A1203
CaO
MgO
S03
Na20                                :
K20                                I
    Sub Total

Mineral C(>2 in raw shale

Mineral C02 in spent shale calculated to
  raw shale

Mineral C02 in raw shale that was volatilized
  by the assay
  9.9



  9.7



  0.0
          40.9
           4.3
           9.5
          21.2
           8.7
           2.6
           2.7
           3.4
25.7



25.6



10.2
17.4
17.0
 2.3
Source:  Stanfield, 1961

Particle   size  measurements  showed  that  99.4  percent  of  the
inorganic  constituents  of the Green  River  oil shales  are  smaller
than  44 microns (325  mesh sieve),  about 80  percent  are  smaller
than  10 microns, and  about 10 percent are smaller  than 0.5 micron
[Tisot,  1963].   Table  2.3-5  presents the  typical  mineralogical
composition of Devonian black shale [Bates et  al.,  1957].

2.4.2   Kerogen

Kerogen is that portion of the organic material  in oil shale that
is  insoluble in ordinary solvents for petroleum and that, upon the
application of heat, yields gas, oil, bitumen,  and  organic residue
(mainly fixed  carbon).   Bitumen,  a benzene-soluble  material gen-
erally comprises a  small part of the total  organic  matter in oil
shale.   The  term kerogen is  often used, however, to  denote the
total organic material in oil shale.

Kerogen appears  black  in color  to  the  unaided eye.    Under the
microscope, thick sections of kerogen appear yellow in color, with
a minor portion appearing brown or black.  It has  no well defined
structure, appearing  as stringers;  masses, and irregular granules
all intermixed with the inorganic minerals in  the rock.
                               42
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  TABLE 2.4-4.   CHEMICAL COMPOSITION  OF THE INORGANIC  PORTION OF
                VARIOUS  GRADES  OF GREEN  RIVER OIL  SHALE AND  OF
                THE  SPENT SHALE  PRODUCTS              !
Chemical
constituent
Raw shale
Si02, percent
Fe203
A1203
CaO
MgO
S03
Na20
K20
Spent shale
Si02
Fe203
A1203
CaO
MgO
Very low-
grade shale
(10.5 gal/ ton)

40.9
4.3
9.4
11.0
5.4
0.1
1.8
3.4

53.27
5.64
12.28
14.82
7.00
Medium
grade shale
(26.7 gal/ ton)

26.1
2.6
6.5
17.5
5.3
0.6
2.6
1.0

41.90
4.10
10.53
28.11
8.53
High-grade
shale
(36.3 gal/ ton)

25.5
2.9
6.3
14.2
5.6
1.2
2.7
1.9

42.36
4.74
10.46
23.54
9.30
• Very high-
i grade shale
(61.8 qal/ton)

'• 26.4
3.1
! 7.0
' 8.3
4.5
! 1.4
i
1.9
: 1.0

49.19
5.87
; 13.13
• 15.40
i 8.35
Source;:  Stanfield, 1961
        TABLE 2.4-5.  TYPICAL MINERALOGICAL COMPOSITION
                      OF DEVONIAN BLACK SHALE
                    Mineral
Composition
   weight
  percent
        Quartz
        Feldspar
        Illite + minor kaolinite and
          muscovite
        Carbon
        Total organic matter
        Pyrite and marcasite
        Chlorite
        Iron oxides
        Tourmaline, zircon,  and apatite
    22
     9  :
        i
    31  ;
    13.6
  16 - 22
    11
     2
     2
     i  ;
        Source:   Bates et al.,  1957
                              43
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The  organic  matter content of oil  shale increases with  the grade
of shale.   Reported values are plotted on Figure 2.4-1  to show the
range  in organic content  of shales  varying from  10 to 75  gallons
per  ton  in  grade,  as  determined by  the Modified Fischer  Assay.
                                        DATA SOURCES •

                                        •  USBM R I No 4825
                                        o  USBM I C. No 62!6

                                        x  USBM R I No 4744
                              SHALE GRADE, GAL. OIL/TON
                             (PER MODIFIED 'FISCHER ASSAY)
                                                           I
                                                           1
                                                           I
                                                           I
                                                           1
                                                           1
                                                                             I
 Figure  2.4-1.
Organic matter content  of Green River Oil  Shales.

Source:   Baughman, j 1978
                                44
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2•4,2.1  Composition of Keroqen

Ultimate

The ultimate composition of the organic material in ten samples of
™e£V°f Mahogany zone oil  shale  from Colorado and Utah have been
s§r?k^ CSAlth/  19613*>T£f similaritY among the compositions'was
Srf11?11!?'  t   average of the ultimate  compositions of the samples
was  taken to  represent the typical  composition  of : the  organic
matter of  Mahogany zone  oil shales  of the Green River  Formation?
This average composition is  shown  in Table  2.4-6.      ;     "»i.J.on.

TABLE 2.4-6.   PROBABLE  COMPOSITION OF MAHOGANY-ZONE ORGANIC MATTER
                 Component
                   Average amount of
                   component,  wt.  %
                   of  organic  matter
                 Carbon
                 Hydrogen
                 Nitrogen
                 Sulfur
                 Oxygen
                 C/H ratio
                          80.52
                          10.30
                           2.39
                           1.04
                           5.75
                           1.42
                 Source:   Smith, 1961

                    WaS P.er.formed  °n New Albany  shale
            -.  .        — -. —..  -.—,«.**_^  WAA^-U^  |_oinxL.ii  3.HQ
       composition  determined from this investigation
-L dXy «LC ^ • ~t"~ / »
      TABLE  2.4-7.
         ELEMENTAL COMPOSITION OF NEW ALBANY
         SHALE ORGANIC MATTER
            Component
                        Average
               (weight % organic matter)
            Carbon
            Hydrogen
            Nitrogen
            Sulfur
            Oxygen
                         82.0
                          7.4
                          2.3
                          2.0
                          6.3
            Source:  Smith and Young,  1967
                             45
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                                                                        1
Carbon-hydrogen Ratio Comparisons                                       •

The approximate  ratio of carbon to hydrogen  (C/H)  in the organic      «
matter from both Green River and New Albany oil shale is compared      g)
to  the C/H  ratio  of  various  other  organic materials  in  Table
2.4-8.                                                                  «

         TABLE 2.4-8.  APPROXIMATE CARBON/HYDROGEN RATIOS               •
                        IN VARIOUS ORGANIC MATERIALS
                     Material	C/H ratio
                                                                        I
Conventional petroleum
Athabasca bitumen
Green River Kerogen ,
New Albany Organic Matter
Gilsonite
Lignitic coal
Low volatile bituminous
coal
Anthracitic coal
6.2 - 7
7.5
7.8
11.1
8.3
12.1
19.4
35.1
.5
                                                                        I
                                                                        I
             Source:  Baughman, 1978                                    H

Particle Bonding                   ;                                     «

Tests  on surface  area  led to the! conclusion that perhaps only a      •
small   amount   of  the  organic  matter   is   either  directly  or
chemically  bonded to  the  inorganic  mineral constituents.  Green      •
River  Formation  kerogen  can be  found either partly or  entirely      11
encasing  the inorganic mineral  constituents of oil shale  [Tisot,
1963].   Despite   this  conclusion^  bonding  between kerogen  and      m
inorganic  matter  is such  that  kerogen has never been isolated in      ]|
pure  form by either  mechanical or chemical  separatory processes.

Chemical Formula                                                        H

Based  on the' elemental analysis of  kerogen from Green River oil
shale   the   following   empirical  formula  was  developed  for  the      •
material:   C6H9 8N0 18S0.o400.56  fstanfield,  1951].  This  formula      fl
is  in  substantial   agreement  , with   that   reported   later:
CoisHasoOiaNsS  [Vanderborgh,  1974].  The  latter  formula  indicates      «
a molecular weight of  approximately 3200.   It should be noted that      |
these   formulas  are   based  only   on the  elemental  analysis  of
samples,  and   they  are  not  necessarily  applicable for  use in
generallized correlations relating molecular  weight  to thermal or      •
physical properties.                                                    H


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  2-4.2.2  Specific Gravity
  2.4.3   Saline Minerals                                i
                                                       i
  The  Tertiary-age sedimentary Green River Formation oil shal<=
  very complex material.   In addition to its orglnic matte? con








                                           of
                                                   in  addition  to
 5
 and
                   e
                                           mineral and
                                 •
°f 4°° tO 35°°  fee
in a 1400   uare mile area

Another 36 billion  tons  of mixed trona and halite are

                    r^o1/ ASdS °f
                 part  of  the  area.  Occurrences  of  the  mineral
                                                           ^
Eie  Nation"
                              47
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TABLE 2.4-9.


	 Mineral name 	

Carbonates
Trona
Eitelite b
Dawsonite ^
Burbankite
Shortite3 ,
Pirssonite
Gaylussite
Norsethite
(New Unnamed)
Nahcolite
Thermonatrite
Carb ona t e-pho sphate s
Bradleyite
Carbonate-chlorides
Northupite
Silicates
Albite
Analcite
Sepiolite
Loughlinite .
Labuntsovite
Acmite ,
Elpidite
Magnesioriebeckite
(crocidolite), etc.
Feldspar
Borosilicates
Re e dme r gne r i te
Searlesite
Leucosphenite

Halides
Neighborite
Cryolite
Halite


AUTHIGENIC SODIUM MINERALS IN
THE GREEN RIVER FORMATION

Chemical formula


Na2C03-NaHC03-2H20
Na2Mg(C03)2
Na3Al(C03)3-2Al(OH)3
Na2(Ca, Si, Ba, Ca)4(C03)s
Na2Ca2(C03)'3
Na2Ca(C03)2-2H20
Na2Ca(C03)2-5H20
BaMg(C03)2 (Check formula, no sodium shown)
3NaHC03 -Na2C03
NaHC03 ;
Na2C03-H20

Na3P04»MgC03

Na2C03«MgC03-NaCl

NaAlSi308
NaAlSi206-H20
H6Mg8Si1203o(OH)1o-8H20 (Check formula, no
sodium shown)
Na2Mg3Si6Ol6-8H20
(K, Ba, Na, Ca, Mn) (Ti, Nb) (Si, Al)2(0, OH)7H20
Na20'Fe203;4Si02
Na2ZrSi60!5*3H20
Na2(Mg, Fe}3(Fe, Al)2Si8022(OH)2
Variable composition

NaBSi308
NaBSi206-H20
CaBaNa3BTi3Si9029


NaMgF3
Na3AlF6
NaCl
aUnique to Green River Formation
Known elsewhere only in
Source: Jaffe, 1962


igneous or metamorphic rocks.


48 '
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 Organic  acids  of  high  molecular  weight  have  been  found  in
 dark-colored  trona  mineral  brines  from wells  drilled  in  the
 Eden-Farson  area,  approximately 40  miles north of  Rock Springs
 Wyoming.   Both  the  dissolved  trona  and the dissolved  organic
 matter are contained in the Green River Formation.

 Nahcolite occurrences are  common in Colorado and Utah oil shales
 but are not noted in Wyoming shales.  In Colorado's Piceance Creek
 /™Si™ bedded ^posits of  the water soluble  sodium salt nahcolite
 (NaHC03) were discovered from examination of core  samples drilled
 in.1964 on Marathon Oil Company  property in the north^central por-
 tion of the basin.   Subsequent  drilling disclosed  three principal
 bedded units of nahcolite which  occur at depth in a thickness from
 °ne  t? nine feet.   Nahcolite in  disseminated  form has 'even greater
 distribution.    Reserves   of  approximately  130  million  tons  of
 ?SS?     per  s<Juare  mile nave  faeen  estimated.    [Kite  et al.
 19 6 / j .                                                ;

 The   potential  exists  for recovery  of nahcolite  from oil  shale
 formations  by in situ leaching,  by  leaching from mined and crushed
 oil  shale,  or by mining directly from bedded  deposits.;

 Nahcolite may find commercial  markets as a chemical reactant  which
 removes sulfur dioxide from stack  gas  streams,  particularly  those
 streams associated  with  coal-fueled  electric power  generating
 plants   An obvious market for  nahcolite  is as the  raw material
 from which  commercial-grade  soda  ash  may be  produced.  A  minor
 market may be  for  household use  as  high-purity  sodium bicarbonate.

 The  mineral dawsonite, a  sodium-aluminum carbonate,  was noted to
 occur in great  quantities in Colorado  oil  shale  [Smith, 19631
 Dawsonite  occurrences show great vertical and areal  distribution
 in the northern  (deeper) portions of  the  Piceance Creek  basin, the
 zone  ranging from  900 feet to  1900 feet below the  surface.  In
 place reserves of 42 million tons of  alumina  (recoverable from the
 mineral  dawsonite)  per  square  mile  in  the  area  of  the  Juhan
 corehole have been reported [Kite,  1967].              i
                                                       i
 With  proper  heat treatment, avoiding temperatures  high enough to
 promote  chemical  reaction between silicon  dioxide   and  alumina
 (A120S), dawsonite  can be converted to sodium aluminate.  In this
 form,  alumina can be  extracted from  the spent  shale waste  by
 leaching with water  or with dilute  soda carbonate brine.  Alumina
may  then be precipitated from the  leachate.    This method of ob-
 taining  alumina  is attractive when compared  with the imore costly
 conventional method known as the Bayer process.        ;

2.4.4  Sulfur and Nitrogen                             !

Table 2.4-10 presents  the distribution of  sulfur and Initrogen in
samples  of  mineable  Colorado oil  shale  from  the  Mahogany  zone
 [Stanfield,  1951].  Additional  data  on  the  distribution of sulfur
                              49
 image: 








  TABLE 2.4-10.  AVERAGE DISTRIBUTION OF SULFUR AND NITROGEN IN
                 OIL SHALE
                            Weight
                            percent
                                Remarks
Type of sulfur compound           ;
  Sulfide sulfur               67

  Organic sulfur               33
  Sulfate sulfur             Trace

Type of nitrogen compound
  Organic                     100
                      As pyrite and marcasite,
                        FeS2

                      As CaS04, FeS04  and MgS04
                      No inorganic nitrogen found
Source:  Stanfield, 1951

in various grades  of  oil shale were reported in the Annual Report
of the  Secretary of  the  Interior' for 1949, Part  II.   These data
appear in Table 2.4-11.
 TABLE 2.4-11.
DISTRIBUTION  OF  SULFUR  AND NITROGEN  IN  COLORADO
OIL SHALE
   Oil yield of shale,
     gallons per ton
            Total sulfur,
            weight' percent
Total nitrogen,
weight percent
          10.5
          26.7
          36.3
          57.1
          61.8
          75.0
                 0.62
                 0;.56
                 0.73
                 1.96
                 1.99
                 1>86
     0.28
     0.54
     0.44

     0.66
   Annual Report of the Seceretary of the Interior:  Part II,
   1949

2.4.5  Moisture

There is  no  consistent relationship between field moisture of oil
shale and oil yield from shale.  Typical values for field moisture
varied from 0.38 to 2.93 percent [Stanfield, 1951].

A method for determining the moisture content of oil shale is pre-
sented in U.S.  Bureau of Mines Report of Investigations No. 4477,
which deals with the modified Fischer Assay method.
I
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2-4.6  Trace Elements
are
           A fi <?e^Ctied tra°f elements in raw  oil  shale are shown
            '    C Poulson'  et al.f  1975].  Also shown -in the table
                    mean  values  of  the trace element  contents
        Res_earch Institute,  1977].  Gold assays were also made on
            J?°Je samPles  representing  the  Mahogany , ledge.   The

                              °f °'00°56 °UnC            per  Ion
 TABLE 2.4-12.   LEVELS OF TRACE ELEMENTS IN GREEN RIVER OIL SHALE
Element
Be
Hg
Cd
Sb
Se
Mo
Ni
Pb
As
Cr
Cu
Zr
B
Zn
V
Mn
F
Concentration as
by Poulson,
Mahogany
zone
2
0.5
0.1
0.4
3.0
15
300
3
30
400
45
30
80
15
100
250
2000
reported
ppm
Saline
zone
1
-
0.4
3
1.5
30
85
15
20
100
30
50
50
30
80
250
1000
Concentration as
reported by DRI,
ppm

0.4
1
1
:i.s
10
25
20
35
34
i
37
40
65
70
100
250
1000
Source:  Poulson et  al.,  1975  and Denver  Research Institute,  1977
                              51
 image: 








                                                                        1


                                                                        1
Recent studies have confirmed the magnitude of the mercury content      •
shown in Table 2.4-13L [Donnell, 1977].  Using flameless atomic ab-
sorption, an  oil  shale  sample,  which had previously been found to      M
contain 4.0 ppm mercury, (USGS in 1959) was found to actually con-      (}
tain 0.35 ppm.   Additional  samples were tested an no relationship
between  oil  content and mercury was  apparent.   It has been shown      -g
that the majority of the mercury present in oil  shale ends up in      ||
the gaseous Fischer Assay products.

2.5  PHYSICAL PROPERTIES                                                I

2.5.1  Visual Features

The  visual features  of six  specimens  of Green  River oil shale,      Q
selected so  as to  range in grade: from 10 gallons per ton to 75
gallons  per  ton,   are presented as Table 2.5-1  [Stanfield, 1951].      ft
Shale of most interest would assay in the 15 to 30 gallon per ton      |
range.

The  color  of fragments  of  Green River  oil  shale varies with the      •
richness or  organic  content  of the material.   Rich shale  appears      0
dark in  color  due  to the  relative  abundance  of   dark-colored
organic  matter  (kerogen)  present.   The  inorganic materials pre-      .
sent,  such as clays,  carbonates,  iand silica,  are generally light      g
colored.   Some rich shale is  also  light brown in  color.

Easily visible  in Green River  oil  shale  are repetitive thin lami-      •
nations,  called varves.  Each  varve consists of thin bands, one      »
light  and one dark  in  color.   These are minute seasonal pairs of
lamina  which average between  20  and 30 microns  in thickness,  a      m
micron representing 1/1000  of  a millimeter.  The mineral  dolomite      g
predominates  in the  layer  made darker in color by higher  organic
matter  content.   The mode of  formation  of  the  varves has been      ™
described  [Smith, 1968].   In overall effect, the varves present  a      •
woodgrained  effect, a feature  which  probably has a bearing on the      *-
naming  of a persistently rich  zone of oil shale as the "Mahogany"

                                                                        I
zone .
The Green River  oil  shale often separates along bedding planes to
form slab-like fragments.  When broken across bedding planes,  the      «
fracture is generally  conchoidal.   The laminated structure of oil      g
shale has  an important effect  on measured  physical properties of
the rock, depending  upon  whether the direction of the examination
is parallel with or  perpendicular to the laminations.  Lean shale      •
has relatively uniform properties ;in both directions.                   m

2.5.2  Specific Gravity                                                 tt

There exists  a relationship  between the organic (kerogen) content
of oil shale and the specific gravity of oil shale.  Since the or-      .
ganic component  of oil shale has , a specific  gravity of about 1.1      g



                                                                        I
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and  since the mineral components  of oil shale have specific grav-
ities  ranging  from  2.2  (for  anaicime)  to  5.0  (for pyrite),  an
increase  in the organic content  of an oil shale  causes a decrease
in specific gravity of  the  oil  shale.

The  graph presented as  Figure 2.5-1 displays  average  values for
oil  shale  samples   from  the   Anvil  Points  area  in  Colorado
[Smith, 1956].
                                                                       I
                                                                       I
                                                                       1
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                                                   Reference :
                                            Industrie! ond Engineering Chemistry

                                             Vol 48 Wo. 3 fp 441-444 1956
      14
          i.5
              1.6
                  1.7
                     1.8
                    1.9   2.0   2.1  2.2  2.3  2.4
                       SPECIFIC GRAVITY, 60/60° F
                                                2.5  2.6  2.7  2.8
                                                               2.9
                                                                            I
   Figure 2.5-1.
              Specific Gravity and Oil  Yield of Colorado
              Oil  Shales.   Source:   Smith,  1956 (Reprinted
              with permission from I.&E.C.   Copyright
              American Chemical Society.)
A  basic equation for the  relationship between organic content  and
oil  shale  density was  developed  |[ Smith,  1969].   The equation  is:
                           DADB
                        A(DB-DA) -f
                                54
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             DT  =   Shale density                     j
             A   =   Weight fraction of organic matter
             B   =   Weight fraction of mineral matter ;

              A  =   Average density of organic fraction,
                     (g/cm3)                           ;

              B  =   Average density of mineral fraction,
                     (g/cm3)

 Plotted values  agree closely  with those  shown on  Figure  2 5-1
 when values in  the  range of natural occurrence in oil:  shales are
 assigned to DR(2.7 g/crn^ ) and DA(1.05  g/cm3).          ,

 Taking the  specific  gravity/organic content  correlation  one step
 lurther,  an  empirical  relationship between specific gravity and
 01i>A    m gallons  per ton,  as determined by the  Fischer Assay
 method was  also developed  [Smith,  1956].  This  relationship  is
 expressed by:                                          i       c

          Y  =   31.563 X2-205.998 X +  326.624          j
                                                       I
          Where    Y  =  oil yield in gallons  per ton     ;
                   X  =  specific  gravity of Green River
                       oil shale at 60/60 °F.

 In another  study an equation relating  the  oil  yield  of  New  Albany
                             ™  deVel°*ed  ^mith  etal.,  1964].
                      Y =  93.482 - 34.355 X
           Where    Y = oil yield in gallons per ton   <
                    X = specific gravity of New Albany oil shale

The  calculated  relationships  between grade,  specific  gravity,
weight  (in place) and weight  (broken 38 percent voids) for typical
Green  River  formation  oil  shale  are  presented  in  Table  2^5-2.

2-5.3  Porosity and Permeability                       !

The porosity of Green River oil shale before and after heating has
been reported  [Dinneen, 1972].   The data were obtained on samp] es
ranging  in  grade from  1.0 to  60  gallons  per ton.   These  shales
were heated under controlled conditions to 950 °F to remove the or-
ganic matter and further heated to 1500°F to decompose the mineral
carbonates.   During  the thermal treatment, the oil  shale samples
were in  a stress-free environment.   Table  2.5-3 presents the mea-
surable porosities of the raw and treated oil shale samples
                              55
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       TABLE 2.5-3.   POROSITIES OF RAW AND THERMALLY TREATED
                     OIL SHALES (PERCENT OF BULK VOLUMES)
Oil yield,
liters per
metric ton
4.2
27.1
56.3
1104.3
125.2
164.8
244 . 1
Measurable
porosity of
raw oil shale
10.54
5.53
0.57
0.30
0.14
0.16
0.13
Porosity after
heating to
510°C (950°F)
13.36
14.70
19.09
30.41
36.34
45.35
61.16
Porosity after
heating to
816°C (1500°F)
1 24.83
20.89
; 32.03
.. 53.85
i 51.90
62.91
70.69
 Source:  Dinneen,  1972                                 i

 The  mineral matrices of  the oil  shales  yielding less than about
 9.6  gallons of oil per ton did not undergo noticeable structural
 breakdown  upon heating to  950°F.   For richer  shales,! the struc-
 tural  breakdown becomes  more noticeable as the grade of shale in-
 creases, so that for shales  yielding more than 30 gallons per ton,
 there  is extensive fracturing and  swelling.            ;

 The  effect  of heat,  stress,   and time  on permeability  of test
 columns  of Green River oil shale samples  of  various !grades were
 determined  [Tisot  et al.,  1971].   As compressive strain increased
 with  time,  the columns'  pre-geometry,  porosity,  and permeability
 were  concurrently  undergoing change.   Permeability  was expressed
 as the amount of nitrogen (STP) which passed through the column of
 fragments  (in cubic inches per square inch of cross-seqtional area
 per minute).                                           'i

 2.5.4  Mechanical Properties                           :

 2.5.4.1  Shear Strength

 Shear strengths of lean oil shale samples cut from the roof mater-
 ial  in the  experimental  underground oil  shale mine of  the U.S.
 Bureeiu  of  Mines   at  Anvil  Points,  Colorado,  are  presented  in
 Table 2.5-4 [Agapito,  1972].
                                                       i
 2.5.4.2  Compressive Strength                          i
                                                       [
 The compressive strengths of core samples of Green River oil shale
before and after thermal  treatment have been  reported [Dinneen,
 1968 and 1972],  The untreated  samples  displayed high Gompressive
 strength values that were  about the same, whether determined per-
pendicular  to  or parallel  to  the bedding planes  of !the  shale.
                              57
 image: 








                                                                        1
                                                                        1
TABLE 2.5-4.  SHEAR STRENGTHS OF LEAN OIL SHALE SPECIMENS FROM ROOF
              MATERIAL OF USBM EXPERIMENTAL MINE (ANVIL POINTS)         •


   Direction ofShear\Standard
shearing force to      strength,  \      Number of        deviation      •
the bedding planes	Ib/sq. in.     samples tested	(percent)      •

  Perpendicular          3,490               5              4.9         •
  Perpendicular          4,640               5              3.1         J§
  Parallel               1,770               5      .       10.5
  Perpendicular          3,560      .         5              5.1         «.
  Perpendicular          3,145               5              6.0         •
  Parallel                 890               5              8.3         *
  Perpendicular          3,205               5              5.2
  Parallel                 920               5              9.1         •


Source:  Agapito, 1972                                                  w

After heating to  950°F,  the lean shales retained high compressive
strength values in both horizontal and vertical planes, indicating      _
a high degree of inorganic cementation between the mineral parti-      I
cles comprising each lamina and between adjacent laminae.  Dinneen      "*
showed the  compressive strength of rich shale  is  quite low after
removal of  the  organic matter.   Decomposition of the mineral car-      •
bonates at  1500°F apparently does not greatly affect the compres-      p
sive  strength.    The   results   are  presented  in  Table  2.5-5,
expressed  in  metric  system  units  [Dinneen,  1968  and  1972].      sa
English system unit may be derived from Figure 2.5-2.                   |

A rather comprehensive report on the compressive strength of roof
and  mine  support  pillar specimens  cut perpendicular  to  bedding      •
Planes was  prepared  [Agapito,  1972].   The specimens were obtained      »
in the room-and-piliar system underground shale mine of Mobil Oil
Company,  near Anvil  Points,  Colorado.   The data are summarized in      •
Table 2.5-6.                                                            H

That the  compressive strength of \ oil shale  varies  with the grade      «
of the shale is presented in Figure 2.5-3  [Sellers, 1971].              •

2.5.4.3  Hardness
                                                                        u
For  two  Green  River  core  samples  tested,  the hardness  of the      II
horizontal  core  was  61  (scleroscope hardness  number)  and.for the
vertical core was  55 [Matzick et al., 1956].                            m

2.5.5  Leachate Quality and Quantity

The modified in-situ method of oil shale retorting and the various      •
surface methods  require that quantities of raw  (unretorted) shale      •
                              58
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 20       40

OIL YIELD;, 6AL./TON
                                               60
         Figure 2.5-2.   Compressive Strength of Oil Shales.
                        Source:   Dinneen,  1968 and 1972

be  mined  from shafts  and  drifts that provide  access to  the  re-
torts.   Raw shale is also mined to provide a void space into which
the  shale  in the  retort expands upo;n rubblization by blasting.  The
mined shale may be stored on the ground surface for a period of at
least  a  few  years and  possibly  even permanently.   Underground
mining and surface retorting will also require large storage piles
of  raw,  mined  shale for retort feed material.   In addition lean
shale  and rejected  raw shale  fines  may  be  permanently  disposed.
The  placement of the raw mined shale on the surface places  it in
an  t environment  with  which   it  is  no   longer  in  geochemical
equilibrium.   Subsequent precipitation on  the  pile creates  the
potential  for  the  release of  leachate  containing  a variety  of
chemicals  into percolating  waters -at elevated levels  relative to
the base line  conditions.

A^econnaisance study of  leachate quality  from raw mined  oil  shale
with emphasis on shale from Federal  lease tracts C-a and  C-b  has
been  reported  [EPA-600/7-80-181, ; 1980].   The   study   employed
laboratory  leaching  columns  containing a variety  of samples of  raw
shale  and  soils  which were obtained from  the  Piceance  Basin  of
Colorado.   The purpose of   extending the  study  to selected soil
samples was  to provide a background  and perspective from which to
view raw shale leachate properties.t  Included were four raw
                              60
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TABLE; 2.5-6.
COMPRESSIVE STRENGTH OF GREEN RIVER OIL SHALE SAMPLES
CUT PERPENDICULAR TO BEDDING (SAMPLES FRtiM USBM
EXPERIMENTAL MINE, ANVIL POINTS, COLORADO)

Distance from
Mahoqany marker,
feet
31.6 above
21. 5-26. 8 above
20 above
18 . 5 above
10 above
4.2 above
2.5 below
4.5 below
7 below
10 below
12 . 5 below
14 below
14.6 below
15.5 below
17 below
17.5 below
18.5 below
20 below
20.5 below
23 below
23 below
26.6 below
27 below
31 below
33 below
37 below
39.5 below
46.5 below
Bed
designation
Roof
do
do
A
B
C
D
D
D
D
E
E
E
F
F
F
F
G
G
G
G
G
G
H
H
H
H
I
Number of
specimens
tested
2
2
3
1
2
1
1
2
2
1
1
3
5
3
1
1
8
1
1
2
2
2
3
3
1
1
2
2
Compressive
strength,
psi
15,380
14,890
12,430
17,100
1!5,000
17,100
19,000
12,650
11,730
10,700
12,520
;8,280
7,350
11,910
12,080
9,190
'8,160
14,480
14,470
10,250
,8,600
14,090
12,960
18,560
13,600
3J5,390
17,280
12,700

 Designations refer to arbitrarily-designated groups of
 minesable beds,  lettered A through I.                  j
 Source:  Agapito, 1972

shales,  two  soils,  one  sample  of naturally  leached 'outcropping
shale,  and one  sample of naturally retorted  shale  from a surface
fire of unknown age.                                   ,

Leaching was conducted by  passing deionized water through columns
of each  material.   Both  saturated and unsaturated testis were con-
ducteid.  Samples  of the  effluents were collected and s'ubjected to
chemical analyses.  The ranges of concentration variation observed
                              61
 image: 








                                  CURVE IS FROM EQUATION

                                   = J5;760-957A + 9.72A2

                                   -2B9A (H/W) Whirl H/W= I 825
                             FISCHER ASSAY, GALLONS PER TON
      Figure 2.5-3.
Compressive Strength versus Fischer Assay
of Colorado Oil Shale, Anvil Points Mine.
Source:  Sellers, 1971
 Table 2 5 7   fS"ttweac5  °f^ ^  Aerials tested are  presented in
 sSiSc: ;5~Zi   ^ /aS f°U?d  "^ the leachate  contained dissolved
 ™°Jids at elevated concentrations relative  to the background.   The
 mauor  contributors  to the dissolved solids  content  are  caicium
 magnesium, sodium, bicarbonate,  chloride and  sulfate.   I compa™-
 iS Table f I £lemS£ concentrations in  the leachates  is presented
 tL7™i™£: i    • ^.concentrations of  four  elements  of potential
 o?™C?*°gafal  significance:   Al,  B, F,  and  Zn  were  found to  be
 significantly  greater in the  leachates from some of the mined
 snaies than in the corresponding  samples from the previously  ex-

 bv th^^1^18; iThe levels of a11 other  trace  elements  produSd
 «£M     3  6d .shales  were comparable  to those observed  from  the
 soils and previously exposed shales.
                    .     maximum observed concentrations of various
       h        -, dra:nk:Ln9 water  criteria,  it was  concluded that
 even the worst leachate  from the columns did not exceed 100 times
 drinking water  standards for  measured parameters ^   However  thJ
 maximum concentrations of Cr,  F,  Fe,  Hg, Mn, NOa   Pb? IS!!' TDS
 and  Zn were found to  exceed drinking water criteria.

 As  a  result  of the  laboratory  study  [EPA-600/7-80-
The mean concentrations of  the major  ionic species  found  in the

^aC^eSnfr0mT tlfeC-a and C-b  tracts  are Presented in Table 2.5-9
and 2.5-10.   In  the case of the  C-a tract, the leachate  from the
                              62
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                                                                        I


                                                                        i
raw shale was highly saline with a mean concentration of dissolved
solids of 29,500 mg/L for the 5 ft. depth pile and 60,220 mg/L for
the 15 ft. depth pile.  These waters were found to be a magnesium-      •
sulfate type,  with these two  constituents  accounting for  87% of      •
the  total equivalent  weight  of  the  dissolved  solids.   The  pH
ranged from 6.9 to 7.9 throughout the study.        "                    •
                                                                        m
In the case  of the C-b tract the ,quantity  of dissolved  solids in
the  leachate was  lower;  averaging 6,850 mg/L and the  pH  ranged      m
from 7.4 to 8.4.  The composition of the C-b leachate is dominated      ffl
by sodium and sulfate, rather than magnesium and sulfate exhibited      ™
in the C-a  leachate.   In both cases it  appeared  that the calcium
concentration was controlled by the solubility of calcium sulfate.      it

The mean values of trace element concentrations in the C-a and C-b
tract leachates  are presented in \ Tables 2.5-11 and  2.5-12.   The      m
data  are  averaged  over  two years of sampling for  various  pile      |J
depths.   The  concentrations  of  fluoride   observed  in  the  field
generated leachates were similar to those measured in the previous      fc
laboratory column leaching  study  [EPA-600/7-80-181,   1980],  even      •
though the  shale  samples  differed.   The concentrations  of zinc,      *»
boron, and  aluminum found in  the  field study  were  significantly
less  than the  maximum values observed  in the  laboratory  column      tt
studies (compare  Tables  2.5-11  and 2.5-12  with Table 2.5-8).   The      B
differences may be due to the difference in materials used in the
two  studies.   The maximum values  of  the species  analyzed  in the      *•
field  study  are  presented  in  Table 2.5-13.    Although  the      •
concentrations  of many trace elements were sometimes observed to
be greater  than  various recommended maxima  for  particular  uses
(e.g., drinking water),  the large concentrations of the  common      m
species   is   more   likely   to   be  the    significant   quality      m
characteristic of these leachates.

The  cumulative volume  of leachate  per unit area measured  over      £
nearly three years at the C-a tract ranged from  6.26 to 13.72 cm
per year.  These volumes represent 7 and 16 percent,  respectively,      «
of the incident precipitation over the same time period.   The lar-      •
ger  value is  believed to be  more representative of the  actual      *
leachate  volume  generated in the  pile.  The  cumulative  volume of
leachate  at  the  C-b tract ranged from 11.52 to 17.02 cm per year.      jR
These volumes  represent 12  and  17 percent,  respectively,  of the      m
incident  precipitation  over  the same time  period.  Leachate vol-
umes of these magnitudes are believed to be larger than the natur-      M
al recharge  rates on undisturbed  lands  receiving similar volumes      g
of precipitation.   The raw shale  piles  were  formed  from mine-run
size material  and remained  unvegetated.  Therefore,  infiltration      ^
capacity  was high  and  both  evapotranspiration and  direct  runoff      •
capacity were low.                                                      •
                              66
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67
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TABLE 2.5-13. MAXIMUM OBSERVED CONCENTRATIONS
IN RAW SHALE LEACHATES







Concentration,
Species
HC03
C03
TDS
F
Cl
P04
N03
S04
Zn
Fe
Co
Li
NH3
B
Cd
Be
Mg
P
Si
Mo
Mn
Ni
Na
Cu
Al
Ca
Ba
K
Cr
Sr
Pb
Ag
Ti
Se
As
Hg


Source :



mg/L
579
5
72,660
113
366
0
2,564
45,900
0
2
1
0
2
I
0
0
12,830
7
13
1
2
1
2,030
0
5
505
0
16
0
15
1
0
0
0
0
0



.68


.28


.597
.02
.17
.339
.55
.97
.168
.300

.0
.2
.5
.34 ;
.12

.073
.28

.822
.4
.290
.4
.036 ;
.012
.007
.013
.007
.003 1


EPA-600/D-84-143 ,





68
Location
C-a,
C-a,
C-a,
C-a,
C-a,
C-b,
C-a,
C-a,
C-a,
C-a,
C-a,
C-b,
w"" a. /
C-b,
C-a,
C-b,
C-a,
C-a,
C-a,
C-b,
C-a,
C-a,
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C-b,
C-a,
C-a,
C-b,
V*™" Q. f
C-a,
C-a,
C-a,
C-a,
C-a,
C-a,
C-b,
C-b,


1984



15
15
15
15
15
20
15
15
15
15
15
10
5
15
15
10
15
15
15
10
15
15
15
10
5
15
10
15
15
15
15
15
15
15
20
20






ft
ft
ft
ft
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ft
ft
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ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft
ft






Date
9/21/82
7/19/82
8/16/82
7/26/82
7/01/82
2/25/82
7/26/82
5/10/82
8/16/82
8/11/82
8/23/82
7/26/82
8/30/82
7/26/82
7/26/82
7/06/82
9/06/82
8/04/82
6/02/82
7/06/82
6/02/82
6/02/82
8/02/82
7/06/82
7/01/82
3/22/82
9/23/82
7/19/82
6/02/82
7/19/82
8/11/82
3/17/82
4/12/82
7/01/82
8/04/82
2/25/82






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                             SECTION 3                 ;

              SOLID WASTES AND THEIR CHARACTERISTICS   :
                 FOR OIL SHALE RETORTING PROCESSES     .


3.1  LURGI-RUHRGAS OIL SHALE RETORTING                 j

3.1.1  Retorting Operation                             i

A  schematic  for  the  Lurgi  retorting  process [EPA-600/8-83-005,
1983]  is  shown  in  Figure 3.1-1.    Initial  crushing  !in the  pit
reduces  the  size  of  the run-of-mine  shale  to  minus  8  inches.
Secondary  and tertiary crushing further reduce the shale  size to
minus 1/4  to  1/3  inches.   The crushed  oil shale  is fed through a
feed hopper to a double screw mixer, where four to eight times its
weight of  a hot  (1,200-1,300°F)  circulating heat carrier,  such as
sand  or  processed  shale  from the collecting bin,  is thoroughly
mixed  in,  thus  heating  the  entire  mixture  to  approximately
950-1,000°F within a  few  seconds.   At this temperature, pyrolysis
of  the  kerogen  in  the  oil  shale  occurs,  resulting  in  the
production of retort gas,  shale oil vapor and water vapor.
                                                       !
The circulating heat  carrier  and the partially retorted shale are
then  dropped  from  the screw mixer  into  the  surge  vessel,  where
residual oil  components  are distilled  off.   The mixture of heat
carrier  and retorted  shale  residue is passed to the lower section
of the lift pipe,  where combustion air  (preheated to 450-900°F) is
introduced, raising  the mixture pneumatically to  the collecting
bin.  Essentially  all available  organic  carbon  contained  in the
retorted shale residue is burned  in  the  lift pipe.  Supplemental
fuel may be added to  the  bottom of the lift  pipe  to  i sustain the
combustion  of the  organic  residue  when processing  ; leaner  oil
shales.    Also,  at  the high  lift pipe  temperature,  \ a  moderate
amount of  carbonate  decomposition occurs  in  the  processed  shale.

At the top of the  lift  pipe,  the hot, burned shale is separated
from the flue gases  in the collecting bin.  Fines arejcarried out
of  the   collecting  bin with  the  flue gas  stream.   The  coarse-
grained  shale residue  accumulates  in  the lower section of  the
collecting  bin and  flows  continuously  to  the  mixer.   Partial
removal  of the  solids to prevent  accumulation in  the collecting
bin may  be required  if the  fines carry-over is not  I sufficient.
The  combustion  air  supplied to  the  lift pipe  is preheated by
counter-current heat   exchange  with  the  flue gas  stream in  the
preheat  section of  the waste heat boiler.  The  calcined minerals
                              69
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 in the burned  shale combine with  the sulfur  dioxide \produced by
 combustion of  the organic  sulfur  to  form calcium  arid  magnesium
 sulfites  and sulfates.                                 ;

 The pyrolysis products stream containing  shale fines is  withdrawn
 at the end of  the screw mixer and passed  through  two ^series-con-
 nected cyclones  to  a  product  recovery section.   The  fines  are
 separated in these  cyclones and returned  to  the  recycle  system.
 The vapor stream  then  passes  through a sequence of  three  scrubb-
 ing coolers  (not shown).  The first  scrubbing cooler removes dust
 from the gas stream  by condensation of heavier oil  fractions.   A
 dusty heavy  oil is obtained at  this  point.  In the next  scrubbing
 cooler,  further condensation of  the  oil takes place at  a  temper-
 ature above  the dew point of water to produce a water-free middle
 oil.   Final  cooling of the  gas produces  an aqueous gas condensate
 and a  light  oil fraction.  The  light oil  is separated from  the
 condensate or gas liquor in an oil/water  separator,  finally,  the
 gas is scrubbed with  a  lean  oil in  the naphtha scrubber to  recover
 naphtha and noncondensable gases, as  deemed desirable. \
                                                       i
 The flue gas  stream in  the lift  pipe is  dedusted  in  a  cyclone
 after leaving the collecting bin;  the dust is routed to the pro-
 cessed shale  mixer.   The gas stream  is then routed through a heat
 exchcinger for preheating  of  combustion air,  a  waste heat boiler  to
 produce process steam,  another cyclone,  and a humidifier  or flue
 gas conditioner.  Additional dust removed by the waste :heat boiler
 and cyclone are  routed  to the processed shale  mixer.  The flue gas
 stream is cooled  somewhat  and  conditioned in the humidifier  by
 adding steam generated during processed  shale quenching.    After
 humiclifi cation  and cooling,  residual  dust is removed  fr|om the flue '
 gas stream using an electrostatic precipitator and  discharged into
 a  processed  shale quencher/moisturizer  where  more water is  added
 to  cool the solids.  The  processed  shale residue, cooled to ~200°F,
 is  moisturized  to  a suitable moisture content  and  discarded  as
 open pit  backfill.                                     j

 3.1.2  Solid Wastes                                    i
                                                       i
 A  block flow diagram for the basic processing and pollution con-
 trol  system  for the  Lurgi process  is  presented in Figure  3.1-2.

 In  the retort off-gas discharge system, the flue gas and entrained
 processed  shale particles  are  separated  from  each other  via a
 series  of cyclones,  waste heat recovery system,  humidifier, etc.
 The  flue  gas  is then passed through  an electrostatic precipitator
 to  remove the residual particulates  and is eventually vented to
 the  atmosphere.  The  processed shale  particulates separated along
 these steps is sent to the processed  shale mixer for quenching and
proper moisturizing before final disposal.             !

The  retort gas  is cleaned for  marketing.   The gas is ; first com-
pressed to remove much of the moisture and ammonia, theri subjected
                              71
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 to  treatment by  diethanolamine  and triethylene glycoli, which  re-
 move  the acidic components and the  residual moisture,!respective-
 ly,  from the compressed gas.  The clean,  dry  gas is then sent to
 the  pipeline.  A small amount  of spent  amines  are generated  in
 this  process, which  are disposed with the processed shale.  How-
 ever, the  spent amine is less than 1%  of the processed|shale mass.

 The  acid  gas obtained  from  the diethanolamine  regeneration  is
 treated  by the Stretford  process,  which  converts  the; H^S in  the
 gas  to  elemental sulfur.   The  clean gas is  then  vented to  the
 atmosphere.   Spent Stretford liquor could be reclaimed on site or
 sent off site for reclamation.

 The gas  liquor  from the oil and  gas recovery section is subjected
 to  oil/water separation,  but  it still contains dissolved ammonia
 and sulfur compounds  and its direct discharge or use may also cre-
 ate pollution.  Therefore, the ammonia and dissolved volatile com-
 pounds from the liquor are removed by  an ammonia recovery process.
 The  treated  water is then used  for processed shale moisturizing.

 Overall  water management activities consist of satisfying the pro-
 cess  steam and cooling water needs,  as well  as efficient manage-
 ment of  the  aqueous  waste effluents.  Properly treated mine water
 is .used  as the  boiler feedwater  to produce the steam in the Lurgi
 waste heat recovery boiler.  Treated  mine water is  also used  as
 cooling  water,  process  makeup water,  cooling  tower makeup water,
 etc.  Minor wastes generated from the water treatments are equal-
 ized in  a  holding pond  and then  used  for processed shale moistur-
 izing.

 Table 3.1-1 summarizes the final  waste streams and the iintermediate
 streams which make-up the final waste  streams.   These streams were
 identified  in Figure 3.1-2.   The  subgrade  ore, overburden,  and
processed  shale (streams 2,  3,  and 29) constitute the majority of
 the wastes (greater  than  97% of solid wastes).   Several waste-
waters,  such  as   equalization  pond  discharge,  treated  sanitary
wastewater,  clarified mine  water,  and  oil/water  separator  dis-
 charge,  are used to moisturize the processed shale.     j

Table 3.1-1  also  describes  the  general  composition  of  these
 streeims  and  component  mass  flow  rate.   Of  the  If inal -waste
 streeims,   the processed  shale represents  more  than  50% of  the
total  volume.  The   components   of  concern and the  composition
of  the  solid waste  streams  show that for all the  waste  streams
the leachable salts  are of  primary concern.   The  water  for  dust
control  and  revegetation  (streams  90 and 91) has  a  isignificant
solids concentration which may contribute to salt leaching or met-
als leaching.  Also  of  concern are the organics  in the processed
shale (generated  from both the unburned hydrocarbons  in  the  pro-
cessed shale  as well as from the moisturizing water (stream  73),
and the sludges  to be added to the solid waste  pile.   1
                              73
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                                                                        1
                                                                        I
Sanitary  wastewater treatment  and aerated pond  sludges  although      *
not determined, can be  estimated to be 0.5 Ib/hr based on 18 gpm
influent  rate,  a  typical  TSS  concentration  of  250  mg/L, and  a      •
treatment  efficiency of 75%.   Thus,  at  0.5 Ib/hr these  sludges      If
are of insignificant weight compared to the processed shale rates.
However, the solids from sanitary wastewater treatment and sludges
may pose special health risks and should not be dismissed lightly.
                                                                        1
The rate  of spent amine is difficult to estimate  as  the influent      _
rate  of rich  amine  and efficiency  of  the amine  regenerator  are      •
unnerta in.                                                              ™
uncertain.

3.1.3  Characteristics of Solid Wastes
                                                                        I
Tables 3.1-2 to  3.1-6 provide additional  information  on  the com-
position  of the  processed  moisturized shale  (stream 29).   The      •*
nominal  feed size  of  the particles  associated with the  Lurgi      •
retorting process  is less then  0.6  cm.   As seen in Tables 3.1-2      ™
and  3.1-3,  properly  moistened  and compacted processed shale  has
low  permeability;  therefore,  actual  field leaching  may not  be
represented by laboratory column leaching experiments.   The results
of column leaching and  various  other experiments performed on the
processed shale are given in Tables 3.1-7 to 3.1-12.  Some soluble
elements are reported as their oxides.
                              74
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77
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   TABLE 3.1-3.   SUMMARY OF HYDRAULIC CONDUCTIVITY MEASUREMENTS
                  FOR VARIOUS COMPACTION AND LOADINGS FOR  LURGI
                  RETORTED SHALE
   Material
      Water
      wt. %
        Density,
         g/cm3
         Permeability, cm/s at various loadings
          ; 50 psi	100 psi	200 psi
LURGI-RG-r


LURGI-ULG-I

LURGI-RBa'b
a,b
26.6
10.4

 dry

 dry
1.41
1.33

1.81

1.22
                  1.0 x 10"6
                  3.0 x 10~^

                  8.3 x 10"5

                  1.2 x 10~^
                                    6.5 x 10~?
                                    1.9 x 10"^
 6.5 x 10~?
 2.0 x 10"^
 Leaching columns.

 Various source samples.
 Source:  EPA-600/D-84-228,  1984
 TABLE 3.1-4.
      WATER HOLDING  CAPACITY  OF  LURGI PROCESSED SHALES
      AT VARIOUS  PRESSURES AND BULK DENSITIES
   Sample
14.7 psi
(1 bar)
 44.1 psi
 (3 bar)
                     Pressure
                     73.5 psi
                     (5 bar)
                                      147 psi
                                      (10 bar)
  200 psi
(13.6 bar)
No compaction
  Lurgi           27.5

Packed to  a
BDD=1.30 g/cc
  Lurgi ash      62.4

BDb=1.45 g/cc
  Lurgi ash      60.2

BDb=1.60 g/cc
  Lurgi ash      47.2
  Lurgi           20.7
                   27.6



                   62.3


                   58.7
                   46.3
                   20.2
                       26.9



                       62.2


                       56.6
                       45.8
                       19.8
                        25.3



                        62.0


                        55.5
                        44.4
                        19.8
                                             15.5



                                             61.7


                                             55.2
                                             43.7
                                             19.0
aTable entries are moisture contents (w) expressed on  a  weight %
 basis:  weight of water per unit weight of dry solids.
v\
 BD= bulk  density.                •
 Source:   EPA-600/D-84-228, 1984
                                78
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TABLE 3.1-5. COMPOSITION OF LURGI PROCESSED MOISTURIZED SHALE
Weight
Component percent
Retorted shale
(moisturized) 100.00
Moisture 18 . 70
Oxygen (organic) 0.02
Nitrogen (organic) 0.08
Carbon (organic) 0.25
Sulfur (total) 0.93
Source: EPA-600/8-83-005, 1983
Mass flow, Flow,
10s Ib/hr 103 Ib-moles/hr
9,733
1,820 101.1
2 0.1
8 0.6
24 2.0
91 2.8

TABLE 3.1-6. INORGANIC ANALYSIS OF LURGI THE PROCESSED SHALE

Component
Silicon dioxide
Iron oxides
Aluminum oxide
Calcium oxide
Magnesium oxide
Sulfate
Sodium oxide
Potassium oxide
Carbonate
Chloride
Loss on ignition
Weight
percent
46.00
4.40
12.70
22.40
4.80
3.80
3.20
2.70
4.40
0.08
4.60
Source:  EPA-600/8-83-005, 1983
              79
 image: 








TABLE 3.1-7. MAJOR ION COMPOSITION OF COLUMN
LEACHATE-LURGI RETORTED SHALE

Vt
L
0.020
0.058
0.092
0.186
0.236
0.292
0.350
0.378
0.452
0.535
0.590
0.652
0.737
0.860
1.06












mg/L
Ca
575
560
540
520
530
540
560
570
580
600
590
590
600
610
590


Mg
0.3
0.2
0.4
0.6
0.7
0.7
0.8
0.7
0.7
0.7
0.6
0.7
0.7
0.7
0.8


Average

Source :



vt
L
Na
11970
11270
10590
5410
3150
1660
1000
795
600
575
535
405
530
385
365


K
950
760
830
300
220
160
120
110
110
100
110
100
110
80
120

TCf^
-•"— .j
permeability =
Cl
1360
1300
1150
450
230
131
75
65
45
: 48
39
30
; 41
26
23

f
"K = 8
HC03
136
67
57
29
25
26
26
22
21
21
20
18
23
20
20


.3 x K
CO3
393
351
328
208
149
123
101
111
105
118
90
93
105
136
137


3~^ cm/s
S04
23900
23400
21900
12600
5590
5450
3890
3480
3180
3110
3040
2760
3180
2770
2750



1
1
1
1
PH
10
11
11
11
11
11
10
11
11
11
11
11
11
11
11



.83
.09
.13
.22
.15
.05
.96
.07
.08
.12
.02
.07
.02
.21
.20



= pore volume
EPA-600/D-84-228,









1984


80
























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TABLE 3.1-8.  CONCENTRATION OF SELECTED TRACE
              ELEMENTS IN COLUMN LEACHATE OF
              LURGI RETORTED SHALE
vt
L
0.020
0.058,
0.092
0.186
0.236
0.292
0.350
0.378
0.452
0.535
0.590
0 . 652
0.737
0.860
1.06




F
21.0
22.7
17.5
8.2
4.4
8.6
7.9
10.1
6.1
6.3
4.5
5.4
4.1
4.8
4.4

Average
17-1-

B
1.01
0.77
0.66
0.41
0.33
0.24
0.16
0.14
0.10
0.10
0.16
0.12
0.10
0.09
0.22


Si
20
11
15
11
11
11
8
8
8
8
5
9
9
9
8
Key
permeability =


mg/L
Mo
11
11
10
5.1
3.7
2.4
1.9
1.9
1.6
1.6
1.0
1.5
1.7
1.3
1.2

K = 8.3


Mn
0.037
0.023
0.022
0.018
0.017
0.019
0.015
0.013
0.013
0.010
0.016
0.024
0.019
0.012
0.015

x 10~?


' Al
29
23
18
i 5.8
4.6
' 3.8
J3.3
3.2
,2.9
2.8
1.5
!2.7
'2.9
12.5
2.3

cm/s |


Sr
7.8
7.9
16
6.9
8.4
13
13
15
16
17
19
19
19
17
22



|p = pore volume
Source :
EPA-600/D-84-228, 1984
                   81
 image: 








        TABLE 3.1-9.
CONCENTRATIONS IN ASTM WATER SHAKE
TEST EXTRACTS - LURGI SPENT SHALES

Parameter
PH
EC
ALK
H2C03
HC03
C03
TDS
F
Cl
P04
N03
S04
Zn
Fe
Co
Li
V
NH3
B
Cd
Be
Mg
P
Si
Mo
Mn
Ni
Na
Cu
Al
Ca
Ba
K
Cr
Sr
Pb
Ag
Ti
Se
As
Hg
Units
—
|jmhos/cm @ 25°
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
RG-Ia
11.43
3660
192
0.001
9.6
110.7
3700
2.0
; 23.7
0.62
8.7
2545
0.001
0.018
<0.005
0.371
0.053
8.4
0.173
<0.001
' <0.0005
0.6
0.22
5.5
<0.05
0.008
<0.005
324
<0.001
0.60
750
0.115
43
0.100
14
0.012
<0.001
<0.005
<0.020
0.016
<0.001
ULG-Ia
11.49
2650
160
0.001
7.0
92.5
2140
3.8
10.9
<0.1
1.7
1301
0.007
<0.005
<0.005
0.616
0.059
6.2
0.005
<0.001
<0.0005
0.5
0.20
3.4
<0.05
0.006
<0.005
180
0.003
<0.02
402
0.130
34
<0.005
13
<0.01
0.005
<0.005
<0.020
<0.01
0.001
RBS
11.85
4270
355
0.001
6.9
209.6
3350
6.34
17.1
0.5
2.52
2291
<0.001
<0.005
<0.005
0.887
0.082
-
0.096
<0.001
<0.0037
0.4
0.5
5.4
<0.05
0.029
<0.005
275
0.002
<0.02
713
0.157
64
0.095
20
<0.01
0.008
<0.005
<0.020
<0.01
<0.001

Various source samples.
Source:  EPA-600/D-84-228, 1984
                                                                       1

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 image: 








      TABLE 3.1-10.
CONCENTRATIONS IN RCRA TEST EXTRACTS
LURGI SPENT SHALES
Parameter
pH
EC
ALK
H2COa
HC03
C03
TDS
Cl
P04
NOS
S04
Zn
Fe
Co
Li
V
NH3
B
Cd
Be
Mq
P"
Si
Mo
Mn -
Ni
Na
Cu
Al
Ca
Ba
K
Cr
Sr
Pb
Ag
Ti
Se
As
Hg
Units
^
pmhos/cm @ 25°
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
RG-Ia
8.06
4150
1612
37.8
1948
9.5
5690
7.1
<0.01
1.53
684
0.138
<0.005
<0.005
0.173
0.008
3.28
0.520
0.004
<0.0005
290
0.4
0.6
<0.05
0.110
0.012
43
0.032
<0.02
964
0.130
3.2
<0.005
8.9
<0.01
0.002
<0.005
<0.02
0.019
<0.001
ULG-Ia
i
7.99
4236
2188
59.7
2646
11.1
6520
6.4
<0.01
0.48
420
0.082
<0.005
< 0.005
0.135
0.006
1.08
0.270
0.003,
0.0016
269
0.7
7.0!
<0.05
0.410
0.075
28
0.017-
<0.02!
1280;
0.350;
5.0
<0.005:
13,
<0.01|
<0.002;
<0.005!
0.0201
0.020:
0.001;
RBa
8.67
5650
2505
14.1
2937
58.7
8520
18.9
<0.01
0.53
880
0.010
<0.005
<0.005
0.304
0.008
1.98
1.470
0.002
0.0026
430
0.7
7.9
<0.05
0.090
<0.005
55
0.009
<0.02
1479
0.180
11.0
<0.005
13
<0.01
<0.002
< 0,005
<0.02
0..047
<0..001
Various source samples.
Source:  EPA-600/D-84-228, 1984
                             83
 image: 








 TABLE 3.1-11.
 LEACHABLE MASS AS INDICATED BY THE ASTM PROPOSED
 WATER SHAKE TEST FOR LURGI SPENT SHALES - mg/g
            Parameter
           RG-I
ULG-I
RBC
Na
Ca
Mg
S04
Cl
F
B
Mo
Al
TDS
1
3
0
10
0
0
0
0
0
14
.296
.00
.002
.18
.095
.008
.0007
.004
.002
.80
0
1
0
5
0
0

0
0
8
.720
.608
.002
.204
.044
.015
-
.002
.006
.560


0



0
0
0

^
-
.0008
—
-
-
.0002
.010
.008
~

I
I
I
t
I
I
            aVarious source samples.
             Source:  EPA-600/D--84-228, 1984
TABLE 3.1-12.
LEACHABLE MASS  AS INDICATED BY THE RCRA EXTRACTION
TEST FOR LURGI SPENT SHALES - mg/g
           Parameter
           RG-I
 ULG-I
  RBC
Na
Ca
Mg
S04
Cl
B
Mo
Al
TDS
0.860
19.28
5.80
13.68
0.142
0.010
0.016
0.050
H3.8 ;
0.560
25.60
5.38
8.40
0.128
0.005
0.008
0.038
130.4
1.100
29.58
8.60
1.760
0.378
0.029
0.020
0.038
170.4.

            Various source samples.
            Source:  EPA-600/D-84-228, 1984
                              84
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 3.2  TOSCO II OIL SHALE RETORTING                     i

 3.2.. 1  Retorting Operation                            ;

 Figure  3.2-1 shows  a  conceptual  flow  diagram  of  the  TOSCO  II
 retorting process  [EPA-600/8-83-003, April 1983].  The process is
 indirectly  heated  and  employs  a   solid-to-solid  heat  exchange
 (between hot ceramic balls and raw shale) as a means for providing
 the  heat  of retorting.   The  integral  parts  of  the TOSCO  II
 retorting   system   are:    retort   and   accumulator;   product
 ±rac:tionator; processed shale removal system;  ceramic ball system-
 and raw shale preheat system.                         ;

 The TOSCO II  retort is a slightly inclined,  rotating drum to which
 raw shale, minus 1/2-inch size,  preheated to  approximately 500°F
 is  fed.   Ceramic balls,  at 1.5 times  the shale mass flow rate,  and
 previously heated to about 1,300°F,  are  also  added toj the retort.
 The rotating, mixing  action  results in  pulverization: of  the raw
 shale.   Heat transfer  from  the  ceramic balls  raises the  shale
 temperature to  approximately 900°F,  and pyrolysis,  or retorting,
 of  the kerogen in .the  shale  occurs.  The pyrolysis vapors and the
 mixture   of  balls   and  pyrolyzed  shale are  then  taken  to   an
 accumulator  vessel.   This  accumulator  consists of  ia  rotating
 perforated screen or  trommel which  retains the  balls; but  allows
 t]2e Pulveri2ed shale to Pass  through,  thus  affording k separation
 o±  the two.  The pyrolysis vapors are  removed from the vapor dome
 at  the top of the accumulator  and  sent to a fractionator  for oil
 recovery,  while the ceramic  balls  are  sent for recycling  and the
 processed  shale  is eventually sent for  disposal.       ;

 In  the oil recovery  section (not  shown  in Figure  3.2-1),  the  pyro-
 lysis  vapors  are separated by the  fractionator into gas,  naphtha
 oil, gas oil, bottom oil, and gas condensate,  or  foul water.  Each
 stream  is  sent  to its  respective processing unit for' appropriate
 treatment.                                             ;        '

 Processed  shale dust,  contained with  the ceramic balls as they
 emerge  from the accumulator,  is removed  by  hot flue gas from the
 steam  superheater.   The  particulate  matter is subsequently con-
 verted to  a  sludge  in the venturi wet scrubber  and  sent to the
 disposal  area.   The clean  flue gas  is  emitted to the atmosphere
 through  the  scrubber  stack.   The  clean ceramic balls  are then
 transported by  a bucket  elevator to  the  ball heater if or heating
 and recycling back  to the retort.   In  the ball heater, treated
 fuel gas and  shale  oil are burned by atomizing the fuels with air
 in  a  vertical combustion chamber  at  the  top  of  the vessel.  Hot
 flue  gas thus  generated passes  downward,  concurrently  with the
balls, thereby  heating them.   The flue gas  is separated from the
balls in the gas disengagers and the hot balls are returned to the
retort.
                              85
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 The hot processed  shale  from the accumulator is taken to a rotat-
 ing drum steam  generator/cooler  where it is cooled to about 300°F
 by  indirect  heat  transfer  to  the  feedwater  to generate  some
 process  steam.   The  cooled processed  shale  is  then taken  to
 a^2 5er rotatln9  drum and processed shale moisturizing water  is
 added.  Steam incidentally produced  during the moisturizing oper-
 ation entrains  some processed shale dust which  is  removed  in"the
 venturi wet  scrubber;  the steam, along with  a little; participate
 matter,  is released to the atmosphere through the scrubber stack
 The processed shale,   cooled to below  200°F  is  moisturized  to
 approximately 14%  water  by  weight  (to aid  compaction and  dust
 control)  and then transported to  the disposal  area.   !

 The disengaged hot  flue gas is used to preheat the rawi shale feed
 thereby recovering most of the waste heat.  The preheating system
 consists  of  a series  of  three  lift pipes  (or preheat zones),  a
 thermal  oxidizer (incinerator),  cyclones  and wet  scrubbers.  The
 flue gas  is introduced at the bottom of the last lift1 pipe  (first
 preheat  zone),  where  the raw shale stream from the -second  lift
 pipe (second preheat zone) is also  received.   The solids are lift-
 ed pneumatically and heat transfer  from the gas to the shale oc-
 curs.   The preheated shale is accumulated  in  a  collecting  bin  at
 the top of  the lift pipe  and  sent to  the retort.   Residual dust  in
 the flue gas  is  separated by  a cyclone  and  added to the feed going
 to the retort.                                         \

 Since  the  flue gas temperature is  at its highest when introduced
 to the last lift pipe  (first preheat zone), it  partially retorts
 the very  fine shale,  which  results  in hydrocarbon vapor release
 into the  flue gas.  Therefore,   the  flue gas   is introduced to  a
 thermal  oxidizer (located between the first   and  second preheat
 zones)  to  burn the hydrocarbons  so that the hydrocarbon emission
 to the atmosphere is not excessive.   Some  shale oil,  !C4 liquids
 and air are also added to the oxidizer  to sustain combustion.  The
 resulting flue gas  is cooled,  and then  introduced to the bottom  of
 the other  two lift pipes.  At this point,  the temperature of the
 flue gas is low enough so that the extent of retorting!of the fine
 shale  is  less  than   in  the  first  preheat  zone.   Hydrocarbons
 released in these two lift pipes are  emitted with the flue gas,
 without incineration.

 The  flow  diagram  for  a  complete plant complex,  emphasizing the
 waste  streams produced, is presented in Figure 3.2-2 [TOSCO, 1982].
 Production-scale mining, of the oil shale is accomplished by con-
ventional underground room-and-pillar mining.

 The  acid gases (H^S, CO^ ) in  the retort gas and hydrotreated flue
 gas  are separated.by absorption  in a diethanolamine solution as a
pretreatment step.  The treated sweet gas is eventually separated
 into C4 liquids,  LPG,  and C-4  and lighter process gas.  Sulfur from
the  acid gases is  recovered  by the Claus/Wellman-Lord processes.
                               87
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 A tail gas  stream containing a small amount of  sulfut dioxide is
 eventually emitted from the  Wellman-Lord unit.   An acidic conden-
 sate is  also  obtained from the Wellman-Lord unit;  it  is neutral-
 ized with alkali and then sent for disposal.

 The naphtha and gas oils are hydrotreated to  produce upgraded syn-
 crude.   An  ammoniacal  wash water is produced from  the hydrogena-
 tion and  subjected to an  ammonia  recovery process. ;  This  latter
 process produces  a sulfurous overhead which is sent to  the Glaus
 Plant for recovery of  sulfur.   The  hydrotreatment operations con-
 sume process  gas,  thereby  generating  flue gases. >The  ammonia
 plant does not burn any fuels.   The bottoms  oil  is  coked to yield
 a gaseous  overhead,  naphtha oil,  and gas oil which are sent  to
 their respective units for treatment, and a  coke residue which is
 disposed  of with the processed  shale or marketed.   A small  amount
 of  aqueous condensate is also produced  and sent  to  the foul water
 stripper.   A gas-fired furnace  is used for heating the,  feed  to the
 coke drums.  The flue  gas from  the  furnace is emitted to  the atmos-
 phere.  Hydrogen for  the oil hydrotreating is  generated by steam
 reforming,  using the treated  process gas (C2  and  lighter  fraction).
 The  reforming  furnaces burn fuel  and  generate  a  flue  emission.
 Carbon  dioxide, generated  as a result of reforming, is  separated
 from the  hydrogen and  is also released to  the atmosphere.

 The  foul  water  condensed from the pyrolysis vapors is steam  strip-
 ped  to  remove volatile  matter which  is sent to the Glaus  plant for
 recovery  of sulfur.  Ammonia in the  stripper overheads is conver-
 ted  to  elemental nitrogen  during incineration  in the  Glaus  pro-
 cess.   The stripped water is  used in processed shale moisturizing.

 3.2.2   Solid Wastes                                   |
                                                      i
 Large quantities of solid  waste materials will be  generated  over
 the  life  of a  TOSCO Plant.    Solid wastes  are summarized  in  Tables
 3.2-1 [TOSCO, May 1982]  and 3.2-2 [EPA-600/8-83-003, April  1983].

 3.2.3  Characteristics of Solid Wastes                \

Various data on TOSCO  II processed shales are presented in Tables
3.2-3 to 3.2-9.  Table 3.2-10 presents the composition !of TOSCO II
combined process  wastewater (retort  water and other wastewaters).
m^™s 3-2~1:L to  3.2-13 depicts chemical  composition data on the
TOSCO ii  foul   water.   Lab leachate data  on retorted  shale are
shown in Tables 3.2-14 to 3.2-16.  Tables 3.2-17 and 3J2-18 depict
field leachate data for the TOSCO II retorted shale.   !
                              89
 image: 








     TABLE 3.2-1.
SUMMARY OF SOLID WASTES ESTIMATED FOR THE
TOSCO SAND WASH PROCESSING FACILITY



Waste material
Sanitary refuse
Construction debris
TOTAL


Source
Sanitary landfill
Surface mine and plant site
Surface mine and plant site


Estimated
quantity,
ton/yr
3,000
2,500
5,500
Estimated
volume ,
cubic
yards/yr
8,500
7,000
15,500
Potential hazardous wastes
Spent catalysts
Spent HDN catalyst
Guard bed catalyst
(proprietary solids)
Spent HDS catalyst
Spent ZnS catalyst

Spent FE-CR catalyst

Spent Cu-Zn catalyst

Spent reforming catalyst

Spent methanation catalyst

Spent alumina catalyst
Spent sludge (DEA
filtration)
TOTAL
Others
Separator sludge
Tank bottom sludge
Plant debris
TOTAL

Upgrading units
Upgrading units

Hydrogen unit
(hydrodesulfurizer)
Hydrogen unit
(ZnO guard bed reactor)
Hydrogen unit
(high temp Ishift converter)
Hydrogen unit
(low temp shift converter)
Hydrogen unit
(reformers)
Hydrogen unit
(methanation)
Sulfur unit
Gas recovery



API separator
Water treatment area
Mine and plant site


305
570

18.3
6.7

14.2

33.7

12.8

5.4

80

14.25
1,070.4

500
2,000
50
2,550

500
900

35.9
17.9

25.4

54.4

19.8

8.4

100

12.6
1,674.4

720
2,400
200
3,320
NOTE:   This table does not  list sedimentjproduced by treatment of the raw water
       since the sediment may be suitable  for reclamation and will be combined
       with the spent shale in the spent shale moisturization procedure.

Source:  TOSCO, May 1982
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                                  90
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   TABLE  3.2-2.
MAJOR WASTE PRODUCED OVER A PERIOD OF 20 YEARS
FOR TOSCO II 47,000 bbl/day PLANT WITH UPGRADING
         Stream description
Quantity,
    tons
                               Material quantity
                                as a percent of
                              total waste quantity
Raw shale runoff and leachate       N.D.a
Raw shale sludge - preheat system    11.31
Processed shale sludge - Ball         0.85
  elutriator
Processed shale sludge -              0.57
  moisturizer
Processed shale                     350.84
Stripped foul water                  18.49
Compression condensate -              1.73
  Wellman-Lord unit
Coke                                  5.26
Stripped sour water purge stream      0.75
Revegetation water                   14.59
Dust suppression water                9.70
Boiler blowdown                      11.04
Boiler feedwater treatment            4.81
  concentrate
Cooling tower blowdown               60.31
Storm runoff                          4.34
Processed shale leachate            N.D.
Spent catalysts                       0.005

Treated sanitary water                0.55
Sanitary water treatment sludge     N.D.
Service and fire water runoff         0.63
Source water clarifier sludge         2.37
Trash,  construction debris,  etc.    N.D.

  TOTAL                             498.15
                                     Ni.D.
                                      2.27
                                      0.17

                                      0.11

                                     7Q.43
                                      3.71
                                      0.35
                                      | "

                                      1.06
                                      0.15
                                      2.93
                                      1.95
                                      2.22
                                      0.97

                                     12.11
                                      0.87
                                     N:D.
                                      6.001

                                      0.11
                                     NiD.
                                      6.13
                                      Q. 48
                                     N;D.

                                     99.93
 N.D. - not determined.

 May be a marketable by-product.
 Source:  EPA-600/8-83-003,  April 1983
                               91
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  TABLE 3.2-3.   PHYSICAL PROPERTIES OF TOSCO II  PROCESSED SHALE
Parameter
Geometric mean size
Geometric standard deviation
Permeability
Bulk density
Solids density
Porosity
Maximum size
Minimum size
Unit
cm
—
cm2
g/cc
g/cc
-
cm
cm
_jQuantity
0.007
3.27
2.5 x 10"10
1.30
2.59
0.47
<0.476
>0. 00077

  Source:
EPA-600/8-83-003, 1983

 TABLE 3.2-4.
                          SIEVE ANALYSIS OF TOSCO II
                          SPENT OIL SHALE RESIDUE

Sieve
U.S. standard
No. 8
No. 16
No. 30
No. 50
No. 120
No. 200
Hydrometer





Summation
Opening, Weight retained Percent
mm in grams retained
2.38
1.19
0.595
0.297
0.125
0.074
0.0461
0.0346
0.0336
0.0268
0.0157
0.0077

0
567
390
588
1,170
784
1,134
1,125
2,043
2,882
287
69
11,038
0.00
5.14
3.53
15.33
10.60
7.10
10.28
10.20
18.50
26.10
2.60
0.62
100.00
Cumulative
percent
finer
100.00
94.86
91.33
86.00
75.40
68.30
58.02
47.82
29.32
3.22
0.62
0.00


Source:  Margheim, May 1975
                              92
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         TABLE 3.2-5.   HYDRAULIC CONDUCTIVITY MEASUREMENTS
                       OF TOSCO II  RETORTED  SHALE
           Moisture,   Density,
 Material     wt.  %     g/cm3
 TOSCO  II
20.8
11.0
11.4
TOSCO  IIa    Dry
                    Permeability at various loadings"
                     50 psi     100 psi   '  200 psi
1.56
1.39
1.29

1.46
     6.8  x
     5.6  x
     6.7  x

     2.8  x
                                            6.2 x  10~6
                                            4.6 x  10~§
                                            4.0 x  10~§
         5.6  x  10'
         3.9  x  10'
         2.5  x  10"
 Leaching columns.                                 •    \
                                                       \
Source:  EPA-600/D-84-228, 1984

   TABLE 3.2-6.  WATER HOLDING CAPACITY3 OF TOSCO II PROCESSED
                 SHALES AT VARIOUS PRESSURES AND BULK DENSITIES
   Sample
                       Pressure
   14.7  psi   44.1  psi   73.5  psi    147  psi
   (1  bar)    (3  bar)    (5  bar)    (10 bar)
                              200 psi
                            (13.6 bar)
No compaction

Packed to a
BDD=1.30 g/cc

BDb=1.45 g/cc

BDb=1.60 g/cc
     48.0


     42.2

     36.0

     34.6
45.8


42.0

33.8

33.5
              45.9


              41.9

              32.9

              32.1
43.8


41.6

32.1

30.8
44.7


41.4

30.5

30.5
 Table entries are moisture contents (w) expressed on a! weight 7
 basis:  weight of water per unit weight of dry solids.!
DBD = bulk density.                                    i
 Source:   EPA-600/D-84-228,  1984                       i
                              93
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TABLE 3.2-7.  REPORTED ANALYSIS OF TOSCO  II PROCESSED SHALEa
                                                        I


                                                        I


	                                   I
                        Weight
    Component	percent                          «

Hydrogen (organic)       0^44                           ™
Oxygen (organic)        NR
Nitrogen (organic)       0.35                           H
Carbon (organic)         4.49                           •
Sulfur (total)           0.76
Na20                     8.68
K20                      3.28
CaO                ,     15.80
MgO                      5.31
A1203                    6.80
Si02                    33.00
Fe2O3                    2.52
C02                     20.92                           •
Loss on ignition                                        H
  at 900°C              27.60
aDry basis.

 NR - not r
Source:  EPA-600/D-84-228, 1984
                NR - not reported.
     TABLE 3.2-8.   SELECTED ELEMENTAL CONCENTRATIONS  IN
                   RAW AND RETORTED TOSCO II  OIL SHALES                •



                                                                       I


                                                                       I


                                                                       I


                                                                       I


                                                                       I



Source:  Wildung and Zachara, 198:0.

                                                                       I
Weight, %
Raw shale Retorted
Org C
C
H
N
S
Ca
K
Mg
Na
Si
Al
Fe


_
_
_
_
_
9.
1.
2.
1.
13.
3.
1.







8
25
6
43
0
4
89


5.
—
—
-
—
11.
1.
3.
1.
16.
4.
2.


shale
5




3
50
9
74
0
2
45


F
Sr
Ba
Mn
B
As
Cu
Cr
Pb
Ni
Zn
Mo
Se
Cd
PPM
Raw shale Retorted
1,020
640
1,310
271
110
70
48
36
30
29
72
28
4.1
1.05
1,490
780
1,580
334
146
82
62
42
41
34
105
36
4
0
shale












.9
.98
                             94
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TABLE 3.2-9.  SOME POLYCYCLIC AROMATIC HYDROCARBONS :THAT HAVE
              BEEN DETECTED IN THE BENZENE EXTRACT OF TOSCO
              II SPENT SHALES                       ;

         	Compound     	ppb (W/W)
         Benzo(a)pyrene (BaP)                 28-55 >
         Alkyl I (BaP)                           _    \
         Alkyl II  (BaP)                         _    I
         Benzo(ghi)fluoranthene                 _    j
         Benzo(e)pyrene                       18-29
         Perylene                               3_g   >
         Benzo(ghi)perylene                    12-24 '
         Anthanthrene                           3_5   ; -
         Pyrene                                58-1021
         Fluoranthene                          21-23
         Benz (a) anthracene.                     27-45
         Triphenylene                          13-34  ;
        Penanthrene                                 !
        7,12-DimethyIbenz(a)anthracene         -    !
                                                    i
        3-Methy1cho1anthrene
        Coronene                               5    i
        Chrysene                             30_35  ;
        Source:   Fox,  July 1983
                           95
 image: 









•
1
1
TABLE 3.2-10. APPROXIMATE COMPOSITION OF TOSCO II COMBINED
PROCESS WASTEWATER (50,000 bb I/day upgraded fl
shale oil production)
i
Component
Ca+2
Mg+2
Na"1"1
NH4+1
Zn+2
As*5
Cr+6
C03~2
HCOs"1
S04~2
S203"2
P04"3
Cl
CN"1
Phenols
Amines
Organic acids
Neutral oils
TOTALS (rounded)

NOTE: In addition
(less than 1
Cu, Ni, Co,
Concentration ; in water (mg/L
added to spent shale
280
:iOO
670
16
5
0.015-0.3
2
j 360
100
850
90
5
570
5
315
410
1
1,330
960

6,100

to above, elements present in
mg/L) are Pb, ;Ce, Ag, Mo, Zr,
Fe, Mn, V, Ti, K, P, Al, F, B,
Source: DRI No. 5269, April 1980



96
•B
xxy/ ^
1
32
204 |
1
1.8 •
0.0045-0.09 •
0.45
109 |
32 I
261 I
1
1.8
175 1
1.81

127 g
409
295 |
n
1,870

^«w^ ^~v^— . — 	
Sr, Kb, Br, Se,
Li |

1
1
 image: 








          TABLE  3.2-11.
ORGANIC CONTENT  OF GAS CONDENSATE
(FOUL WATER) FOR TOSCO II      ;
Component
Acids
Phenols
Bases
Neutrals
TOTAL
TOC
Concentration ,
mg/L
1,710
510
680
1,424
4,324
3,160
Mass % of
organics
39
12 •
16 !
33 !
100 1
73
             Source:   EPA-600/8-83-003, April 1983

      TABLE 3.2-12.   COMPOSITION OF FOUL  WATER FOR TOSCO II
Component
NH3
H2S
C02
Organic acids
Organic phenols
Organic bases
Organic neutrals
HgO
TOTAL
a
Amount in
raw shale'
Ib/ton
0.28
0.036
0.34
0.155
0.046
0.062
0.129
—

a Foul water Coker wash,
flow water flow
Ib/hr (opm) Ib/hr (qpm)
770
99 386
935 - .
426
127
170
355
213,300 (426) 36,050 (72^
216,182 36,436
Total fpul water
Ib/hr (gpm) ma/T,
770i
485:
935j
426'
mi
170;
355 j
249,350: (498)
252,618
3,088
1,945
3,749
1,710
c -i n
ftRO
1,424


Pilot plant data obtained from Metcalf & Eddy Engineers, Octoberi1975.

Estimated from material balances based on data from Colony Development
Operation, 1974, and Whitcombe and Vawter, March 1975.          '

Source EPA-600/8-83-003, April 1983                           ;
                                97
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TABLE 3.2-13.  INORGANIC SPECIES IN TOSCO II FOUL WATER
Component
                                      Concentration ,
                                           mg/L
         Ca
         „„
         Mg
         Na
         K
           ++
                                     5

                                     0.4
         C03

         Cl"
          CN

          Si
     Other components
                                     5

                                     0.3




                                     12

                                     1.3

                                 Range,  mg/L
     Fe

     B                        ;

     Ce,  Ag,  Sr,  Rb,  Br,  Se, As,
       Zn,  Cu,  Ni,  Mn, Ti, P, Al

     Pb,  Ba,  Mo,  Zr,  Co,  Cr, Li
                                    0.1-1.0


                                   0.01-0.1

                                  0.001-0.01
     Source:  EPA-600/8-83-003, April 1983
                          98
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   TABLE 3.2-14.
CONCENTRATIONS IN ASTM WATER SHAKE AND RCRA
EXTRACTS - TOSCO II SPENT SHALES    ;
Parameter
p.H
EC
ALK
H2COS
HC03
C03
TDS
F
Cl
P04
N0a
S04
Zll
T™* j«*.
Fe
Co
Li

NH3
B
Cd
Be
Mg
P"
Si.
Mo
Mn
Ni
Na
Cu
y. -1
Al
Ca
Ba
K
Cr
Sr
Pb
Ag
TL
Se
As
Hg
Units
)—
p mhos/cm @ 25°
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
ASTM
4:1
8.69
2650
164
0.88
191
4.0
1970
20.2
9.8
<0.03
16.0
1130
0.020
0.018
<0.005
0.079
0.007
0.644
2.500
<0.001
<0.0005
35
0.18
0.8
1.56
0.053
<0.005
545
<0.001
2.15
31
0.117
8
0.025
0.53
<0.010
<0.001
0.006
<0.020
0.018
<0.001

20:1
9.0l!
740
96 i
0.24:
107
4.7 i
510
7.5
1.9
<0.03 i
19.5 !
238 i
<0.005 l
<0.005
<0.005 !
0.039 i
<0.002
0.067
0.530
<o.ooi ;
<0.0005 ;
14 '•
<0.05
0.28 ;
0.35 i
0.004
0.070
116 i
0.018
3.75 !
17 ;
0.084
1.7 '
0.018 i
0.35 -
<o.oio :
<0.001
<0.005 ;
<0.020 :
0.010
0.001
RCRA
7 72
/ * / £*
5710
2737
140
3325
7.5
8180

22.2
<0.01
2.0
229
0.078
<0.005
<0.005
0.084
0.006
0.60
0.640
0.003
0.0045
81
0.6
1.2
<0.05
1.260
0.055
131
0.014
< 0 . 02
1872
0.780
3.. 9
0.007
16
<0.01
0.002
<0.005
<0.02
<0.01
0.075
Source:  EPA-600/D-84-228, 1984
                             99
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TABLE 3.2-15.  LEACHABLE MASS AS INDICATED BY RCRA AND
               ASTM WATER SHAKE SHAKE EXTRACTION TEST
               FOR TOSCO II SPENT SHALES - mg/g
Parameter
Na
Ca
Mg
S04
Cl
F
B
Mo
Al
TDS
RCRA
2.620
37.44
1.620
4.580
0.444
'•*>
10.013
0.010
.0.054
163 . 6
ASTM
2.18
0.124
0.140
4.52
0.039
0.081
0.010
0.006
0.009
7.88

            Source:   EPA-600/D-84-228,  1984
                        100
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TABLE 3.2-16.
EFFLUENT CONCENTRATIONS - (TOSCO II) SPENT SHALES

CONSTANT RATE INJECTION INTO A DRY COLUMN
vt
L
0.020
0.050
0.100
0.121
0.264
0.287
0.308
0.333
0.355
0.375
0.397
0.418
0.440
0.464
0.488
0.511
0.534
0.556
0.579
0.629
0.965
1.030
1.120
1.191
1.886
2.013
2.25
Ca
545
540
520
505
495
425
410
455
435
395
415
380
345
352
320
330
300
275
265
252
120
83
90
72
26
14
13
Na
10,095
10,060
10,540
10,570
10,520
9,815
9,355
9,440
8,590
7,965
7,420
6,705
5,770
5,490
4,885
4,185
3,744
3,425
3,075
2,605
1,280
945
1,060
715
485
375
420
Cl
mg/L
178
172
176
167
154
163
152
139
133
114
100
92
84
74
61
54
49
45
32
29
19
13
16
12
7
6
7
S04
25,000
25,200
27,400
26,700
26,800
26,800
25,500
24,100
23,400
21,500
20,500
17,000
15,900
14,400
13,500
12,100
11,200
10,300
9,400
7,920
3,210
2,470
2,820
1,820
1,010
660
840
F !
27.0
29.0 !
30.0
30.2 !
39.2
36.3
34.0 :
23.2
28.4
15.9 :
17.2 i
37.8 :
32.6 ;
33.3 !
17.7 '
17.7
18.2 i
19.7 ;
18.3 -
19.1
29.2
29.5 :
29.1
30.5 :
33.5 ;
38.5 :
31.1 ;
i
pH
9.24
9.28
9.29
9.39
9.37
9.31
9.34
9.28
9.30
9.27
9.29
9.26
9.21
9.17
9.25
9.21
9.20
9.13
9.20
9.20
9.10
9.21
9.24
9.27
9.35
9.38
9.25
           K = 2.8 x  10

          vt           ,
          ^— = pore volume
                                         cm/s
    Source:  EPA-600/D-84-228, 1984
                             101
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      TABLE 3.2-17.
LEVELS OF TRACE ELEMENTS MEASURED IN
RUNOFF AND LEACHATES FROM FIELD TEST
PLOTS OF TOSCO II RETORTED SHALE (ppm)
              Runoff  from
             typical  rain
                storms
          First leachate
           from sloping
          section of plot
Source:  EPA-600/8-83-003, 1983
First leachate
 from deepest
portion of bed
Be
Hg
~-—^y
Cd
Sb
Se
Mo
Co
Ni
Pb
As
Cr
Cu
Zr
B
Zn
Li
V
Mn
F
Ba
Fe

0.00002-0.00007
_
_
0.004-0.007
0.03-0.09
0.01
0.05
0.009
0.005-0.008
0.01-0.07
0.02
0.001
_
0.01-0.09
0.02-0.2
0.003
0.004
0.02-3
0.02-0.04
0.09-0.6
0.0006
0.0005
0.006
0.001-0.003
0.002-2
3-74
0.01
0.05-0.02
0.004
0.02
0.004-0.009
0.06-0.2
0.001
0.02-0.9
1
0.007-0.076
0.003-0.006
0.06-0.2
; 2-17
0.06-0.1
0.6-2
—
0.0003
0.003
0.002
2
5-74
0.001-0.04
0.2-0.6
0.003
0.08-0.2
0.004
0.06-0.2
0.003
0.02
1-3
0.07-0.8
0.004-0.1
0.06-0.5
0.006-12
0.1
1-3
                              102
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TABLE 3.2-18.
INORGANIC COMPOSITION OF TOSCO II LEACHATFS
DURING LABORATORY AND FIELD L?S MTER
                                                                 g/L)



Al
As

Ba
Br
Ca
Cd
Cl
Co
Cr
DOC
EC ((Jmhos/cm)
F

Fe
HC03
Hg
K
Li
Mg
Mn
Mn
11U
M =
Na
Ni
NH4
NOo
N03
Oil and grease
Pb

Rb

S
Sediment
Se
Q-i
WJ.
S04
Sn
Sr
IDS
TOC
U
V
Zn
pH (units)
Bulk density, g/cm3
Solid-to-liquid ratio
Contact time
No. of replicates

Batch
(Runnells
and
Eammaili,
1981)
7.6
<0.2
5.2
<0.02
1.6
<0.02
22
<0.02
<0.01
0.03
96


76
<0.01
<0.05
8
"0.4
0.01
3.2
815
<0.02
2
3
<0.5


<0 . 1
<:L
"*
530
<0.3
0.12
625
<0.15
0.07
2185
<0.5
0.12
<0.01
9.9
0.4 g/mL 1.
17 days 17
2 4
Ldlxadlory studl£ 	 >—
Batch
{Runnells
and
Eanmaili,
1981)
20
0.6
11.5
0.017
1.0
<0.02
52
<0.02
<0.01
<0.01


155
<0.02
<0.06
"10.6
0.2
<0.3
0.01
6.3
1865
<0.02
<2
"3
<0.5


<0 . 1
3
—
1300
<0.3
1.4
1700
<0.18
0.05
5480
<0.5
0.61
<0.01
10.3
0 g/mL
days

Column first
pore volume
(Stollenwerk,
1980 )a
<
6.02
10

1.3
470
230
0.12
0.08
73
~
26
0.24
390
77
1700
0.42
3.9
4700
<0.04
7.7
<0.2
0.1
~
<0.03
0.18
0.18

0.02
6.5
15,700
<0.06
9.8



<0.03
8.0
1.15
2.8 g/mL
46 days
4


Blender ;
(Marqheim 1975)



_
114
7.6

-
,-
1750 !

;
20 :
32 ;
27

165
5.6 •
•"
— i
_
,
_ '
,
™* ,
i
730 ;
'
1262 |
~ |

8.4
0.1 g/mL '
5 min. '
i !
                                                  (continued)
                             103
 image: 








                    TABLE 3.2-18  (continued)
Field Ivsimeter studies




Al
As
B
Ba
Br
Ca
Cd
Cl
Co
Cr
Cu
DOC
EC (jjmhos/cm)
Fe
HC03
Hg
"3
K
Li
Hg
Hn
Ho
Na
Ki
NH4
K03
N02
Oil and grease
Pb
P04
Kb
s
Sediment
Se
Si
S04
MW^
sn
Sr
TDS
TOC
U
V
Zn
pH (units)
Bulk density, g/cm3
Solid-to-liquid ratio
Contact time
No. of replicates


Runoff
(Margheim,
1975)

-
_
-
.
10-232
-
—
-
-
-
88-1415
-
20-25
-
<0. 06-16
-
_
<l-74
-
-
-
—
_
-
-
_
1300-5500
_
7-726

_
_
-
:
_
7.74-8.52
1.39
0.46-1.0
3.6 hours

Snowmelt
runoff
(Ward and
Reinecke ,
1972)

-
-
-
- '
9-83
-
I :
-
-
- •
58-572
~
13-89
<0.1-1.8
0.9-22
-
- i
0.2-11
-
-
-
—
_ '
- .
-
«-
-
-
16-239
-
-
-
-
I;
_
7.58-8.95
1.39
<0. 01-0. 08
1.4, 4.2 hrs.


Rainfall
runoff
(Metcalf and
Eddy, 1975
0.06-0.2b ,
0.005-0.008
~ V,
0.02-0.04
0.02
15-140
-
o~oib
0.01b
0.02
-
300-1800
1.5-24 .
0.1-0.3b
0. 00002-0. 00007b
4.3-33,
0.02b
13-23 b
0.004
0.03b
35-518
0.02-0.05
~
~
"
7-18
b
0.004-0.03
-
1790-27,450
0.004-0,. 007
0.3-16
-
"~ >>
0.2b
243-4518
2-10
o~oib b
0.01-0.09
7.4-8.15
1.36
0.79
20 min-48 hrs


Percolation
(Metcalf
and Eddy,
1975)
0.09-2
0.02-0.2
0.02-0.9
0.01-0.1
' 0.1-0.7
420-550
0.003-0.006
0.001-0.07
0.003-0.009
0.06-0.2
™
5.2-18
<l-8
<3xlO"6-5x!0"4
59-140
' 0.007-0.8
64-315
0.06-0.5
3-76
7820-17,825
0.05-0.6
"

™
50-163
0.003-0.004
~
0.01-0.03
~
14-120
0.4-2
4-8
29,110-31,120
0.003-0.005
4-6
28,425-57,137
284-647
0.003-0.01
0.9-3
2.5-4.8
1.36
0.79
-

aSamples collected and analyzed in quarter pore volumes.  Recorded value is
 average for four samples collected over first completed pore volume.

baverage or # range for two samples of runoff collected 16 and 48 hrs. after
 start of rainfall.  Analyses by spark source mass spectrometry,
 is by flameless atomic absorption spectrometry.
 Source:   Fox, July 1983
                                   104
except H  which
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 3.3   PARAHO DIRECT HEATING MODE OIL SHALE RETORTING

 3.3.1  Retorting Operation                            I

 The  Paraho  retort was  developed by  modifying the USBM  vertical
 kiln technology  [Shih,  1979]].   In demonstration  runs  at  Anvil
 Points,  Colorado, the Paraho direct mode  was  used to  produce more
 than 100,0000 barrels  of  shale oil  for the  U.S.  Navy.   It was
 refined to  products meeting all specifications.        i

 A schematic  diagram  of the Paraho direct  mode  is presented  in
 Figure  3.3-1.   The crushed  shale,  flowing downward,  is contacted
 with a countercurrent stream  of hot gases having sufficient heat
 content to  pryolyze the kerogen  in  the  shale.  The  oil is carried
 out  of  the  top of the retort as a stable mist  with the1 gas stream,
 and  the retorted  shale  is removed  from the bottom of the retort
 through a hydraulically-operated grate.  The process  is continuous.

 Raw  oil shale,   crushed  to a 1/4  to 3 in. size,  is spread evenly
 across  the  top of the shale  bed in the retort  where  it; is preheated
 by the  rising hot gases.  Raw  shale fines,  less  than a/4 in. are
 screened  from the retort  feed  to avoid lowering the bed porosity
 and  increasing the resistance to  the countercurrent  gas flow.  The
 shale  moves downward  by  gravity through the mist formation and
 preheating  zone  into the  retorting  zone where the  temperature  is
 increased to retorting temperatures to produce gas,  oil, and  coke.
 This  residue of  coke, or  char,  about 4.5 per cent by  weight  of
 organic  carbon,   remains  on the  shale.   As  the  shale  continues
 downward  into the combustion  zone,  much of the  heat  used for
 direct  mode retorting is  supplied by the combustion  iof the coke
 residue.  Air,  used for combustion, is  mixed  with recycle gas  to
 control   flame  temperatures  and assure  even gas  distribution.
 This  air-gas mixture is introduced  at several levels  ;in the com-
 bustion  zone.   Additional    recycle  gas  is introduced;through the
 bottom  grate to  cool the  shale  as  it passes  throughithe cooling
 zone.  The  retorted shale  leaves  the retort at approximatley  300°F.
 The  hot  gases   are cooled by  the incoming  shale  in the  mist
 formation zone to  approximately 145°F to produce a stable oil mist.
 The  oil mist is  separated from  the  offgas by  oil mist separators
 (coalescers)  and  an  electrostatic  precipitator.   The oil  yield
 from the Paraho  direct mode is about 93 percent of Fischer assay.
 Part  of  the oil-free   gas  is  recycled  to  the  retdrt   and the
 remainder is available as plant fuel.                  !

 3.3.2  Solid Waste                                     \

The  process operations  for the Paraho  direct mode  process are
presented in Figure 3.3-2.  This figure shows the block-flow dia-
 gram  for  commercial-scale  operations  designed for the Paraho-Ute
project in  Utah  [Paraho, June  1982].   Raw shale mining,  crushing,
screening,   and  stockpiling  will  generate  dusts  that  will  be
controlled  by a  variety of control devices.   The  raw  shale  dust,
                              105
 image: 












1
1
PRODUCT I
GAS
RAW SHALE
A
/

^ RETOF
MIST FORMATION ZONE
J
RETORTING ZONE
I TOP
COMBUSTION D'STRIBUT
ZONE
1 ' MID
i k DISTRIBUT

RPTCJHTCn CMAI C
nc iwn i cu OFIMI.C
COOLING ZONE

V
\ ,
y

\ ^
0 hi- GAS OIL/GAS £") *"
'T SEPARATORS ^^
1 RECYCLE GAS
PRODUCT OIL BLOWER
^ ! TOP DILUTION GAS \
TOP AIR
MID DILUTION GAS 1
OR jk
MID
AIR ** r^i AIR
AIR BLOWER
^ BOTTOM COOLING GAS 1

/
1
i
RECYCLE
, MS 1
I


I

1

1
. RETORTED SHALE •
1
Figure 3.3-1. Schematic of Paraho direct heating mode process.
Source :




DOE/EV-0086, June. 1980 1
1
1
1
106 •
 image: 








                                      to
                                      u
                                      o

                                      *!
                                      g   CS
                                      g   cb
                                      o   e^
                                     o   TTI

                                      o   d)
                                     43   C
                                      fl3   0
                                      M   *~>
                                      (0   '

                                          6


                                     ca*  I
                                     V   rt
                                     en  to
                                         ..
                                     0)  (1)
                                     M  O
                                     £j  M

                                     &>  3
                                    •H  O
                                    fa  W
107
 image: 








                                                                       I


                                                                       1
collected by these devices  will  be disposed as a solid in the raw     »
shalS fines  storage  area.  Future plans call  for  the utilization
of these  raw shale fines  for their energy value    The  total raw     |
shal? rejects  (fines plus  dust)  will be about 7,500 tons per day.     fl]

The  Paraho  direct mode  retorting operation,   designed to Produce     «,
42?300 barrels of hydrotreated  shale  oil  per day,  will produce     |
about 52,000 tons  of  retorted shale per day.   This represents  by
far, the  largest solid waste stream.   The  retorted shale will be
disposed  in  an  above-ground  site  designed  to  minimize  water     •
infiltration, runoff,  and percolation.  The retorted shale will be     •
Sansferred  from the  retort to  the disposal area using covered
conveyors, an  enclosed silo,  and covered bottom dump trucks.  The     H
bulk of tlie  shale  will be  spread in 8  to 10 in. layers,  wetted to     |
about 10% by weight on the  surface for  dust control, and subjected
to light compaction.                                   v                flj

Additional water will be used to construct special water- imperious
liners and,  in case of emergencies, to control excessive tempera-
tures   This water,  used  for retorted shale  dust control,  liner     |
construction,  and  emergency temperature control, will consist of  a     H
mixture of treated process  water  and river water.   Water usage tor
both raw  shale fines  storage  and retorted shale disposal will be     m
about 925 gal. per minute.                                             H

The  crude shale  oil,   obtained  from the oil  recovery system, is
dewatered and  subjected  to  on-site  hydrotreating  to  produce  a     •
pipeline  quality,  marketable product.  This hydrotreating  and its     W»
auxiliary processes produce  a variety of spent  catalysts  which
constitute potential  solid wastes.                                      •

The  product  gas,  hydrotreater off gas,  and wastewater _ off gas are
subjected to  ammonia  and sulfur irecovery  prior to being used as      «
plant  fuel.    Sulfur  recovery,   will  produce   additional   solid      ||
wastes .

Sour  water  from  oil   recovery,   hydrotreating,   ammonia  plant      •
and  Stretford  units  is   treated  in  a   wastewater   treater.      B
This treatment will produce additional solid wastes.

Finally,  solid wastes will be  generated from  normal construction,      §
 scrap,  and sanitary wastes.

 The amounts of these  solid waste streams and their characteristics      |
 have been  compiled  in  Table  3.3-1.  Although  these, wastes  are
 presented as average  annual rates, most of these materials are not
 processed on a daily  basis.   Detailed characterization  data  are      |
                                                                         ™
 not available.

108
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 feedstocks  on  offsite  reclamation plants.   The hazardous wastes
 will  be  transported   to   an   approved  offsite hazardous  waste
 disposal  area.                                        :

 The dusts (raw  shale, retorted  shale, surficial  soils,' overburden,
 and unit  operations) produced from the Paraho-Ute facility will be
 about 250 tons  per day  [Paraho, 1982].                i
                                                      i

 3 .3.. 3  Characteristics  of Solid Wastes                I

 The retorted shale produced by the  Paraho direct mode operations
 has been  subjected to  extensive  characterization studies.  These
 retorted  shale  physical and chemical characteristics :are compiled
 Tables 3.3-2 to 3.3-4.  Detailed physical properties are available
 in  the   literature.    Due   to  the  varied  research  operations
 performed during most  of  these  characterization  studies,  along
 with  variations  of  these  studies,   these  data  exhibit  wide
 variations and  inevitable uncertainty.                '

 Since all of the water produced during the retorting and auxiliary
 operations will be treated  and used for dust control >(co-disposed
 with  the  retorted shale),  the characteristics  of  these  process
 waters are listed in  Tables 3.3-4 to 3.3-9.  At the present time,
 there have been two types of process water that have been studied:
 the product  water (Tables  3.3-4  to  3.3-8),  co-produced with the
 crude  shale  oil  and   separated  from  oil  tank  bottoms;   gas
 condensate,   (Table 3.3-9)   water  condensed  from the iproduct  gas
 after  oil-water  separation.    The  data  in  Table 3.3-9  contain
 uncertainties   about  the  operation  and  may not  depict  actual
 commercial operations.                                '

 Tables 3.3-10 and 3.3-11  present leachate data  from the RCRA and
ASTM water shake tests.   Table 3.3-12 presents data from laboratory
 tests in  which  certain  pore volumes of water were  passed  through
 a column  of shale.   Finally Table  3.3-13 summarizes  field  data
 obtained from field lysimeter studies.                 i

 It  should  be  noted  that  various  investigators  have  studied
characteristics   of  solid  wastes  for  Paraho   Direct process.
Only  selected   data   are  presented   in  the   above   mentioned
Tables 3.3-2  to  3.3-13.
                              109
 image: 










TABLE 3.3-1. PARAHO DIRECT SOLID WASTES:
(42,300 barrel per day plant)
Quantity & design
Solids waste case rates
Construction debris 16,000 cu yd (first
and garbage 3 years)
Raw shale fines 7,385 TPSD (max)
Retorted shale 52,235 TPSD
Wastewater treatment 2,468 TPSD (wet
sludge basis, 0.6% solids)
Sulfur, crystalline 95 TPSD
cake
Scrap and garbage 4.6 T/D
Oil filter particles 64 TPSD (50% oil)
ZnO catalyst 250 cu ft/6 mo
Lo-temp CO shift 2,600 cu ft/2 yr
catalyst
Methanator catalyst 600 cu ft/2 yr
Reformer catalyst 1,500 cu ft/2 yr
Hydrotreater catalyst (Confidential)
(ICR-106)

API separator bottoms 0.9 T/D
Air floatation unit 0.09 T/D
float
High- temp CO shift 1,750 cu ft/2 yr
catalyst
Arsenic guard bed 9,600 cu ft/6 mo
catalyst
aEstimated solids
•u
Construction only.
GNot a waste; feeds taken for future use.
^Not a waste; feeds taken for reclamation.
eOff-site disposal, EPA-approved site.


TYPES AND QUANTITIES

Thousand tons/yeara
5.3b

2,450°
17,250
4.8

31.4

1.6
21. ld
18.8;;
488°
^
25d


0 .3
0.03
32. 8e
_
720






1
1
1
Ov

1
*
1







1

I




1



1
n

.
•
Source: Paraho , June 1982 and Heistand, 1984. V

i
110





1
1


 image: 








    TABLE 3.3-2.   PARAHO DIRECT RETORTED SHALE CHARACTERISTICS

A.
Size Classification
'
Unified Soil Classification System !

B.

C.

.D.


Designation
Cobble
Gravel
Sand
Silt
Clay
Density
Compactive effort
ft.-lb/cu. ft.
Light, 6,200
Std. Proctor, 12,375
Heavy, 56,250
Strength
Days curing
28
60
Permeability
Compactive effort
ft.-lb/cu. ft.
Light, 6,200
Heavy, 56,250
Size, mm Weight percent
+38.1 ! 3.9
4.76 - 38.1 ; 51.8
0.074 - 4.76 ! 21.7
0.005 - 0.074 ! 20.7
-0.005 ; 1.9
i
Water Added ;
Density, Ib/cu. ft.
None Optimum, 22 wt._%
86 88
90 93
96 9!8
i
i
Compressive strength, psi
19ti
200
;
Permeability, ft/yr
Loading No | Optimum
psi water i water
50 40 6.3
100 27 1.3
200 18 i 0.8
50 35 ; 1.0
100 30 i 0.6
200 23 0.1

Source:  Holtz,  1976.
                             Ill
 image: 








         TABLE  3.3-3.   PARAHO DIRECT  RETORTED SHALE
                         MAJOR ELEMENTS (wt. %)
 Elements
WCC
BNW1
CSM
                                      BNW2
Battelle   Paraho   DRI
Aluminum       1.27    4.7             4.6      4.83

Calcium       11.5    13.4    12.0    13.4      13.3

Carbon, min.   4.95                            3.73      4.42

Carbon, org.   1.86                            2.39      2.31

Iron           2.03    2.45    2.31     2.56     2.40

Magnesium      4.22    4.21    4.47             4.32


Nitrogen                                       0.58      0.22    0.3

Potassium      0.6     1.82    1.85             1.86

Silicon       16.1    17.7            18.0      13.2

Sodium         1.48    2.24            2.36     2.19

Sulfur                              ..           0.48      0.77    0.8

Titanium               0.22            0.22
NOTES AND SOURCES:
WCC [Holtz, 1976]
BNW1 - weighted means,  August  1977  [DOE/EV-0086, June 1980]
CSM - means, August-September  1977  [DOE/EV-0086, June 1980]
BNW2 - weighted means,  November  1977  [DOE/EV-0086, June 1980]
Battelle [Battelle  PNL  3830]
Paraho - means, 1977-1978  [DOE/EV-0086, June 1980]
DRI [DRI, June 1977]
                             112
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 image: 









TABLE 3.3-4. PARAHO DIRECT RETORTED SHALE
TRACE ELEMENTS (ppm)
Elements A B C D E F
Antimony 2.8 2.9 0.7
Arsenic 59 60 44 21 59 30
Barium 625 586 737 800
Beryllium - - - 2
Boron 120 190 96 52 107 65
Bromine 0.8 <l 0.6
Cadmium 0.9 0.6
Cerium 52
Cesium 4.7
Chromium 41 37 136 44
Cobalt 10 11 13
Copper 53 42 57 44 56
Dysprosium 2.4
Europium 0.71 0.82
Fluorine 1900 1000 1660 1000 150
Gallium 11.5 7.8 11.7
Hafnium 2.1 2.1
Holmium 0.9
Lanthanum 24
Lead 34 32 33 18 35
Lutecium 0.4


113
! ' ' '

G
i
54

-
100
















(continued)


 image: 








                    TABLE  3.3-4  (continued)

Elements
Manganese
Mercury
Molybdenum
Nickel
Niobium
Rubidium
Samarium
Scandium
Selenium
Strontium
Tantalum
Terbium
Thorium
Uranium
Ytterbium
Zinc
Zirconium


A
416
0.03
33
34
10.3
85
4.1
7.1
2.9
832
0.7
0.4
7.0
5.2
16
85
70


B CD E F G
332 411 600 396
0.02 0.07 0.04 0.06
43 33 12 31 16 28
35 35 38 32
7.0 7.0
97 87
3.6
7.0
1.6 3.3 0.3 3.3 0.5 2.0
935 877 800


7.5 :
1
14 15
68 71 16 82
68 71 42

NOTES AND SOURCES:

A - BNW, weighted means, August 1977  [DOE/EV-0086, June 1980]
B - CSM, means,  August-September 1977  [DOE/EV-0086, June 1980]
C - BNW, weighted means, November 1977 [DOE/EV-0086, June 1980]
D - TRW, May 1977
E - Battelle PNL 3830              ;
F - DRI, June 1977
G - Stollenwork and Rumell,  1981
                             114
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         TABLE 3.3-5.
PARAHO DIRECT PRODUCT WATER'
BULK PROPERTIES (wt. %)
Date
5/77
6/77
7/77
8/77
8/77
9/77
9/77
10/77
11/77
11/77
12/77
1/78
2/78
4/78
5/78
6/78
6/78
7/78
7/78
8/78
8/78
9/78
Other
H2S,
TOC,
a
Lab
PAR
PAR
PAR
BNW
PAR
PAR
CSM
PAR
BNW
PAR
PAR
PAR
PAR
PAR
PAR
CSM
PAR
CSM
PAR
PAR
BNW
PAR
C
5
.1
4.3
4
2.
3.
4.
4.
4.
2.
3.
5.
4.
7.
5.
4.
6.

8.
1
4
0
5
6
3
4
6
4
0
4
9
8
1

1
3
2
3
2
2
3
2
2
2
2
3
1
3
6
3
4

N
.7
.9
.1
.2
.1
.0
.9
.8
.6
.4
.0
.7
.8
.1
.9
.4

5.6
S
3
.5
4.3
5.
3.9 -
3.
1
• 5.1
5
2.7
3.
8
2.2 - 4.8
4.4
4.
4.
3.
3.
5.
2.8 -
4.
2.7 -
4.
4.

6.
5
4
9
1
7
3.1
3
2.9
3
4

5
Mm
3
CO? Alkalinity t>H
.0

3,4 1


1



2.7 !
4
3.
4
4.
3.
4.
3.
0.
4.
?
2.
3 .
3.

1.
1
o
5
9
4
5
8
7

8.8 - 8.9
8.5 - 8.6

ft R



2.6 - 7 . 8i 8.6 - 9.1
2
5 2.9 - 3.7
2
0

0
species :
<10 ppm
1.4-4.4
; so4,
Wt. %;
0.02-1
Cl, 1
.08 wt
.3-2.8
wt!
NH3, 1.4-3.6 w
<y
A>
8.5 - 8.9

8 fi


'r— %;
Product water - water CO-produced with oil in the gas-oil
separator.

Source:  DOE/EV-0086, June 1980.
                          115
 image: 











nr
p»

^•x
K
n
*3
w
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H
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H
0
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PH
B
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rrj
CO W
rH > T3
re r-H -H
4-> O i-H
O (Q O
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CO




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116
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rH > -C
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(U

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rH
U

rH


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S-4
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! -A
1 -H-H
; ^ C/3 t^ CO rfi CO Ixi t , [ t
MpnS WfeS (-HOHSx <iE-iS







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CO CO CM CM CO <* rH

O
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co"
"£ VO CO O rH «tf«
CO rH t^ r- CM
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ooo i>! t^.
C? C? v1 S

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1-1 <-i r- m CM co co
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CO
O
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S-,
3
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to
117
 image: 








TABLE 3.3-7. PARAHO DIRECT PRODUCT WATER TRACE ELEMENTS (ppm)

6/77
PARa
Sb
As 9.0

Ba <0.5
B 30
Cd 0.3
CN 8.8
Cr
Cu 0.2
F 3.8

Pb <0 . 1
Li
Mn
Hg
Mo 3
Ni

Se <1
Ag <0.2
Sr

Th
Zn 1.0

Sources:
aDOE/EV-0086

8/77 9/77
BNW GE-T

3.1- 22.2
6.9
0.8 0.4
43 13



0.5- 2.6
0.9
1.4- 43
10.0
<0.4 0.4


0.04
0.1-
0.3

1.5- 7.9
11.0




0.2- 1.5
1.1

, June 1980.

11/77 12/77
BNWa GSRI

4.9- 6
18.2
<3 0.3
16- 0.2
43
<0.2


0.5-
11.8
16- 0.8
36
<0.3 0.3

'
0.005
o.i- ; 0.3
0.5

3.9- 0.2
8.3
<0.2



0.1- 0.5
8.5



1/78 , DRIC ang
PARa Jackson Jackson
1
9 1.5- 0.01
9.0 (5.1)
<0.5 0.1
40 0.1- 3
3.6
0.1 0.1 0.5
1.6
0.14 (0.1)
2.5
0.1 6

3.5 0.1
0.4- 1
2.9
0.2
<0.01
0.7 <0.1- 0.1
0.5
0.1-
0.4
0.4- 0.1
4.4 (0.8)
0.4 <0.1
<0.1-
0.8
0.1-
1.7
0.6 (2.0)



1
1
1
1

I

1

1

1

fl
H
1

1

1

1



I

I

1
Jackson & Jackon, 1982.
CDRI, June,

1977.


118


1
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 image: 








TABLE 3.3-8.  COMPOUNDS IDENTIFIED IN PARAHO
              DIRECT OIL SHALE WAS.TEWATERS3 I
      __________^	     I
             Compounds              	

      Total Organic                         ;
        Carbon (ppm)            41,900      \

      Toluene
      Phenol                                |
      o-Cresol                              l
      m-Cresol
      p-Cresol                              '
      C2-Phenol                             i
      C3-Phenol                             '
      2,6-Dimethylphenol                    !
      3,5-Dimethylphenol                    i
      Methoxyphenol
      Naphthalene                            ;
      2-Methylnaphthalene                    '
      C2-Naphthalene
   .   2-Methylpyridine           x          i
      4-Methylpyridine           x
      2,3-Dimethylpyridine                   •,
      2,4-Dimethylpyridine        x          i
      2,5-Dimethylpyridine        x          :
      2,6-Dimethylpyridine        x          ;
      2-Ethylpyridine                        ;
      C2-Pyridines                x          ;
      2,4,6-Trimethylpyridine     x          '•.
      C3-Pyridines                x
      4-(n-propyl)pyridine                   •
      C4-Pyridines                x          ;
      4-(3-pentyl)pyridine        x          I
      C5-Pyridines                x          i
     Aniline                     x
      3-Methylaniline                        :
     N-methy1aniline             x          ;
     N,N-dimethylaniline         x          ;
     N-ethylaniline              x          i
     2,4-Diethylaniline          x          ;
     N,N-diethy1aniline          x          :
     Quinoline                   x          |
      Isoguinoline                x          '
                                           (continued)
                  119
 image: 








                                                       1
                                                       I
                                                       I
     TABLE 3.3-8 (continued)

       Compounds               	                      fl

2-Methylquinoline           x
3-Methylquinoline           x                          «
7-Methylquinoline           x                          U
2,4-Dimethylquinoline       x                          m
2, 6-Dimethylquinoline
2,7-Dimethylquinoline       x                          •
Trimethylquinoline                                     •
Acridine                    x
                                                       1
aCompounds marked with "X" were
 identified in each sample.
 Those not marked are not                              •
 necessarily absent.                                   P
 Source:  Engineering Science,
          June 1983
              120
                                                        I

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                                                        I

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                                                        1

                                                        I

                                                        I

                                                        I

                                                        I
 image: 








TABLE 3.3-9.  PARAHO DIRECT RECYCLE GAS LINE DRAIN* (ppm)
m
1
w
1"


1



.

1

1
^



1







1

I
•

1
m
I


1

Analyses

Aluminum
Arsenic
Barium
Boron
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Mercury
Molybdenum
Potassium
Selenium
Silver
Sodium
Silicon
Zinc
Alkalinity as CaCOs
Carbonates
. Carbon, total
Carbon, organic
Chemical oxygen demand
Chloride
Cyanide
Fluoride
Hydrogen, total
Nitrogen, total
Nitrogen , ammonia
Nitrogen, nitrate
PH
Phenol
Phosphate , total
, Total suspended solids.
Total dissolved solids
Sulfur, sulfate
Sulfur, sulfide
Sulfur, total

After oil separation.
CE -TEMPO
9-09-77


10.3
<0.1

13.7
<0.03
0.2
1.5
0.2
29.5

2.4
1.8
27.6

0.1





1.6



8.9


1540




GSRI
12-13-77

0.2
0.9
0.1
<0.02
<0.01
4
0.02
0.9
2
0.04
1
4.8 ppb
0.04
0.1
<0.01
3
0.6



0.5

-0.07











Values reported are for TDS after vacuum evaporation
and after evaporation at 180°C, respectively.
Source: DOE/EV-0086, June


1980

121



PAR ;
1-04-78
i
<i
<2
<0.5
<20
<0.01
2.8
o.oi
0.09
2.2
<0.5
26
<5
<0.2
6.82
2
0.7
11
<2
0.02
19,400
13,410
7,400
3,740
l,60d
750
60. Q
0.96
106,900
4,900
5,960
<0.02
8.9'
19.2
<1
9'
3.3
1,400
<1
<500


PAR
6-01-78

<1
<2
<0.5
<20
<0.05
21
0.00
<0.05
0.9
<1
30
<7
2
2.1
<1
1.0 :
60 '
7
0.03
25,000
2,514
6,970
6,280 ;
1 , 850
32
5.3
<0.04

5,910
6,985
<0.1
9.0
67
<0.1
<0.02
11.9/9.3
460
<0.01
2,570


at ambient temperature






 image: 








                                                                   I
TABLE 3.3-10,
CONCENTRATIONS IN RCRA AND WATER SHAKE TEST
EXTRACTS - PARAHO DIRECT SPENT SHALES
Parameter
pH
EC
ALK
H2C03
HC03
C03
TDS
F
Cl
P04
N03
S04
Zn
Fe
Co
Li
V
NH3
B
Cd
Be
Mg
P
Si
Mo
Mn
Ni
Na
Cu
Al
Ca
Ba
K
Cr
Sr
Pb
Ag
Ti
Se
As
Hg
Units
mm
|jmhos/cm @ 25°
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
RCRA
9.27
4600
2593
3.5
2723
217
6220
-
28.8
<0.05
1.75
220
<0.001
0.020
0.044
0.503
0.018
0.161
0.333
<0.001
<0.0005
484
0.49
4.0
<0.05
0.016
<0.05
37
0.019
3.0
724
0.915
6.5
<0.10
8.4
<0.010
<0.002
<0.005
< 0.020
0.010
<0.001
ASTM
12.05
2800
398
<0.001
5.0
236
1425
13.5
7.2
<0.1
3.5
536
0.0003
<0.005
<0.005
0.944
0.035
2.2
0.513
<0.001
<0.0005
0.5
0.3
2.3
<0.05
0.002
<0.005
145
0.002
<0.02
266
0.157
31
<0.005
5.0
<0.01
0.003
<0.005
<0.020
<0.01
<0.001

   Source:  EPA-600/D-84-228,  1984
                          122
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TABLE 3.3-11.
LEACHABLE MASS AS INDICATED BY THE ASTM
PROPOSED WATER SHAKE EXTRACTION TEST FOR
PARAHO DIRECT SPENT SHALES - mg/gI
Parameter
Na
Ca
Mg
S04
Cl
F
B
Mo
Al
TDS
Paraho
0.580
1.064
0.002
2.144
0.029
0.054
0.002
0.003
0.005
5.700

                Source:  EPA-600/D-84-228, 1984
                       123
 image: 








      TABLE  3.3-12.
            COLUMN LEACHING EFFLUENT  CONCENTRATIONS
            FOR PARAHO DIRECT SPENT SHALES
vt
L
0.022
0.032
0.047
0.070
0.088
0.105
0.128
0.151
0.167
0.178
0.190
0.202
0.220
0.244
0.263
0.275
0.294
0.312
0.353
0.367
0.412
0.423
0.473
0.483
0.606
0.644
0.726
0.836
0.918
1.642
1.978
2.177
Ca
610
605
610
625
625
640
660
635
635
610
650
605
635
670
660
670
680
620
685
665
700
655
715
710
700
730
660
680
670
560
380
390
Na
1,500
1,445
1,385
1,305
1,280
1,165
1,095
1005
955
965
935
895
875
830
785
780
760
705
640
595
565
525
490
460
430
370
340
305
285
140
100
105
Cl
mg/L
49
47
47
42
39
35
33
31
3d
27
26
26
23
24
27
32
30
23
25
24
26
21
17
19
18
14
16
13
14
9
6
6
S04
3,840
3,805
3,735
3,695
3,525
3,485
3,320
3,270
3,180
3,185
3,175
3,085
3,060
3,065
2,975
2,930
2,890
2,890
2,815
2,605
2,615
2,530
2,500
2,395
2,390
2,290
2,205
2,105
2,045
1,500
1,000
860
F
21.0
22.2
21.9
22.0
22.6
21.0
21.0
21.5
22.0
20.4
20.9
21.4
21.1
21.8
21.8
22.5
21.9
21.6
14.2
12.4
14.4
14.5
12.7
12.8
12.5
11.5
12.4
11.4
11.4
10.2
8.1
8.3
PH
11.55
11.60
11.66
11.73
11.78
11.81
11.86
11.89
11.91
11.83
11.94
11.95
11.99
12.02
12.01
12.03
12.06
11.96
12.06
12.10
12.13
12.07
12.14
12.17
12.21
12.24
12.27
12.31
12.35
12.46
12.57
12.60
Source:
EPA-600/D-84-228, 1984
                       K = 4.6 x 10~4 cm/s
                      vt = pore volume.
                      L
                             124
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TABLE 3.3-13.
INORGANIC COMPOSITION OF
i
i
l
i
PARAHO DIRECT
SPENT SHALE LEACHATES PRODUCED DURING




Al
As
B
Ba
Br
Ca
Cd
Cl
C03
Cr
Cu
DOC
EC, (.imhos/cm
F
Fe
HC03
K
Li
Mg
Mn
Mo
Na
Ni
NH4
N03
N02
Pb
P04


FIELD LYSIMETER STUDIES,
Lysimeter3 Percolate
Colorado Shale
(Garland
et al., 1979)
0,0005 - 0.1
0.007 - 0.08
0.5 - 3
0.03 - 0.55
M
,140 - 530
—
70 - 2,200
_
<0.001 - 0.02
<0.001 - 0.07
<2 - 400
'8,000 - 30,000
3-13
<0.01 - 0.3
1
320 - 1,230
6 - 20
0.2 - 140
<0.01 - 0.075
1.2 - 9.5
1,500 - 10,400
<0.005 - 0.04
<1 - 11
<0.1 - 6
0.001 - 4
_
-

125
(mg/L) ,
Lysimeter3 Runoff
Colorado Shale
; (Kilkelly
et al., 1981)
	 	 	 i 	 '

,
1

7-10

i <4
i
1
; _ •
i
.70 - 170
\ _
!
18 - 50
i 4 _ 5

: 3 - 14
i
_
1 ~
2-5

;
i
;

I
; (continued)
i
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                       TABLE  3.3-13  (continued)
                                 Lysimeter  Percolate
                                    Colorado Shale
                                       (Garland
                                    et al., 1979)
                 Lysimeter  Runoff
                   Colorado Shale
                      (Kilkelly
                   et al., 1981)
1
I
I
I
1
Rb
Se
Si
S04
Sn
Sr
TDS
TOG
U
V
Zn
pH

0.0005
i 5
3,000
<0
! 4

2
<0.0003
0.1
0.005
6.9
» —
- 0.04
-16
- 20,000 5-14
.04
-13
- -
- 429
- 0.003
- 0.45
- 1.1
- 11.5
Bulk density, g/cm3
Solid-to-liquid ratio,  g/mL
Contact time, min
Particle size, dso
Number of replicates
1.55
NA
aAnvil Points lysimet'er,  high elevation site.  Runoff values are for spring
 snowmelt.  The first reported value for runoff is from spent shale with
 20-cm soil cover and the second value  is for  runoff from preleached, bare
 spent shale.

Source:  Fox, July 1983
                                   126
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 3.4  PARAHO  INDIRECT HEATING MODE OIL SHALE RETORTING!

 3.4.1  Retorting  Operation


              in?ir? Ct m-°de  of 0Peration is  basically ' the same  as
                                                     .
 equipment.   In the  indirect mode,  the  air  blower! are
       ^16                              is eliminated
                                                       i -
 The principal  zones  within the retort are essentially! the  same  a^

     d                                                          1
 Because of changes in the nature and flows of the recycle eras  the

 ^r" fE-e%h°f  ^ th,S °f fgas  and retorted  shale Yare Sm4wha?
 ^?^er .for  the.  ^direct  mode.  Both  the retorted shale  and the
 offgas temperatures average approximately 300°F.
 rHT-^M- mn* ind^ect "L0^6 J138. not been tested as extensively as the
 direct mode.  Thus, the  indirect mode data are auite limited -mrf
 since the Paraho  retort had not been operated for extensive^ Se?l
 iods  of time,  much of the samples and data that have bet£obtained

 expensive e^What- .uns,ta^le  start-up or  shutdown ?ondi?ions   No
 extensive engineering designs have been made for a commercial-size
 facility using Paraho indirect mode retorting technology^

 3.4.2   Solid Wastes                                    ;


 Although no block-flow  diagram is available for  the  Paraho indi-

 n?S^22  ?oPr0<^SS' th,e Odla9.ram Provided  for the Paraho :direct mode

 £oreUraeteFs19pUfrepro?eLe-dn  Ulll^ ^er^d^st^ <?^ln
 commerce,1   facility   using   Paraho  indirect     -'
the o»™ieff?1?8^ fines  storage,  and dusts  will be  approximately
the same  for  both processes.  It is likely  that the  indirect mode
process  will  produce  a  slightly higher  rate  of  retorted
because  of  the  lower  carbonate decomposition  and higher

San°ni Tf^f'  £Ut the °rra^ rat-e Should not incase
shSe rate  &*  S^f-l ?^K th,1S  Sli-ght increase  in  the retorted
snale rate  and  the likelihood  of  increased  temperatures
                               127
 image: 









RAW
SHALE
A
MIST
FORMATION
AND
PREHEATING
RETORTING
ZONE
HEATING
RESIDUE
COOLING
AND
GAS
PREHEATING
•^ 	 jf.
V /
RESIDUE
Figure 3.4-1.
1
I
1
1
OIL MIST R
SEPARATORS U


~yw i ,
T W
\ *-OIL
OIL ; r- |
— STACK 	 -\
"* i rAo tLliCIHOSIAIIC— ' H
T X'SpArro PRFC-IPITATOR •
HtATcn H
< „ 	 _' i»,..-—- n(r^*vr*i c r*f\f
- . ( •* ] '' Rl OU/FR H
^ 	 i - x_>^ - •


I
1'

-• ... rnni PP _^— . __
•" V^UUl_C.r\ n*
1
Paraho indirect mode process flow diagram. •
Source: EPA-600/7-79-075, 1979.
1
1
1
128 |
 image: 








As  there  is  no  information  available   for  other  solid wastes
produced by  a  facility based  upon Paraho indirect mode technology,
a  general  estimate of these  wastes is available from information
based  upon  the  Paraho direct  mode process  (see Table  3.3-]  in
Section 3.3.2).                                       i

The product  gas  will  experience the biggest single change between
the  Paraho  indirect  mode and  the  Paraho  direct mode processes.
The offgas volume decrease is largely offset by increases in con-
centrations.   Thus,  the  overall  energy   (MBtu/hr),< the  sulfur
production,  ammonia  production and  the  estimated  rates  for
catalysts,  sludges,  non-marketable byproducts,  and 'other  solid
wastes will be essentially the same.                  ;

3.4.3  Characteristics- of Solid Wastes                !

Except for retorted shale,  the  characteristics of Parjaho indirect
process  solid  wastes should be quite similar to Paraho  direct
process solid  wastes.  Available characterization datk for Paraho
indirect retorted shale  are  presented  in  Tables 3.4-il  to  3.4-3.
Available  information  regarding  process  water  characteristics
produced from  the Paraho  indirect mode technology is presented in
Tables 3.4-4 and 3.4-5.   The limited amount of  data Ion leachate
characteristics  produced  from  experiments  using retorted  shale
produced by  the  Paraho indirect mode is presented in Table 3.4-6.
                            129
 image: 










TABLE 3.4-1.

A. Size Classification


PARAHO INDIRECT RETORTED
SHALE CHARACTERISTICS3


Unified Soil Classification System
Designation
Cobble
Gravel
Sand
Silt
Clay
B. Density

Compactive effort
ft.-lb/cu. ft.

Light, 6,200
Std. Proctor, 12,375
Heavy, 56,250
C . Strength
Days curing
28
60
120
D. Permeability

Compactive effort
ft.-lb/cu. ft.
Light, 6,200


Heavy, 56,250



ja
aHoltz, 1976.


Size, mm Weight percent
+38.1
4.76 - 38.1 52.4
0.074 - 4.76 , 31.9
0.005 - 0.074 13.3
-0.005 2.4

Water Added
Density, Ib/cu. ft.
None Optimum, 22 wt. %

89.0 93.9
94.4 98.8/99.2
102.1 105.8

Compressive strength, psi
11.8
15.3
10.8

Permeability, ft/yr
Loading No Optimum
psi water water
50 71
100 52
200 . 30
50 2 -
100 2.5
200 2.4





130
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 TABLE 3.4-2.   PARAHO INDIRECT RETORTED SHALE
               CHEMICAL COMPOSITION         '[
Major componenta
Ash
Min C02
Organic C
Si
Al
Fe
Ca
Mg
S
Na
K
Trace components
Be
Hg
Cd
Sb
Se
Mo
Co
Ni
Pb
As
Cr
Cu
Zr
B
Zn
V
Mn
F
Concentration, wt. %
79.4, 79.1 '
18.1 !
1.8
10.8 :
4.2 •
1.9
10.9 :
3.9
0.7 :
1.7 i
2.0 i
Concentration, ppm:
0.7 '
0.03 i
^ '
0.8
0.2 ;
10
16 :
14 i
11
18 ;
66
26
62 :
18
21
88
272
450
aWCC (Holtz), 1976
bTRW, 1977.
                  131
 image: 








TABLE 3.4-3.
COMPOSITION OF PARAHO INDIRECT
SPENT OIL SHALES
         Component
            Weight, %
        Si02

        CaO

        MgO

        A1203

        Fe2O3

        Na20

        K2O

        S03
        Mineral C02

        Organic C

        Inorganic C
             23.1

             15.3

              6.5

              8.0

              2.7

              2.3

              2.4

              0.7



             18.1

              1.84

              4.95
        Texture

        pH
          silty gravel

             10.9
        Source:  EPA-600/2-80-205a,
                 1980
                   132
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TABLE 3.4-4.  PARAHO INDIRECT PROCESS WATER COMPOSITION

Element
Lead
Mercury
Cesium
Barium
Molybdenum
Strontium
Bromine
Selenium
Arsenic
Gallium
Zinc
Copper
Nickel
Cobalt
Germanium
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Boron
Lithium
Mg/mL
0.2
<0.01
0.01
2.0
0.1
3.0
0.009
0.1
1.0
<0.02
0.4
0.2
0.2
<0.04
<0.05
5.0
0.3
0.3
0.03
0.3
<0.05
>10
>10
2.0
>10
5.0
>10
0.8
>10
>10
7
5.0
1.0

                 Source:  EPA-600/2-80-205a,
                          1980
                        133
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                                                                  I
	„.  	..	 „  	
              FROM THE PARAHO INDIRECT PROCESS
               Parameter	mg/L
                                                                   I
           Cations:                                                 H
             Calcium                 39.16                         I
             Magnesium                <0.1
             Sodium                   0.29                         m
             Potassium                0.18                         I
             Ammonium, NH4       13,440-calc.

           Anions:                                                 I
             Carbonates           3,030-calc.                       •
             Bicarbonates         6,280-calc.
             Sulfate                  1.65                         H
             Sulfide                   390                         I
             Chloride                   TR
             Fluoride                 0.10                         H
           Nitrate                     1.0                         •
           Nitrite                  <0.002                         •

           Nutrients:                                              ffi
             NH3-N               16,800-calc.                       H
             Phosphate, total         0.75

           Gross parameters:                                       I
             BOD                     4,850
             COD                    17,100                         _
             TOC                 9,800-36,900                       •
             TIC                     1,600                         •
             Oil and grease           33.3
             Solids, total             429                         •
             Solids, upon                                          H
               evaporation             406
             Total alkalinity       12,900                         M
             Hardness                98-calc.                       I
             Phenols                    42
             pH                        9.5                         •

           Source:  EPA-600/2-80-205a,  1980                        •



                                                                   I
                        134
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TABLE 3.4-6.
COMPOSITION OF BATCH GENERATED LEACHATE
FROM PARAHO INDIRECT RETORTED SHALE

Element
Al
Ca
Fe
K
Mg
Si
Na
S04
C03
HC03
Cl
PH


mg/L
<0.03
4.3
0.04
3.3
1.8
8.5
65
25
1.4
<0.1
44
10.9

                Source:   Holtz,  1976
                       135
 image: 








 3.5   OCCIDENTAL MODIFIED IN SITU OIL SHALE RETORTING

 3.5.1  Retorting Operation

 The  recovery of shale oil by the Occidental modified in situ (MIS)
 process involves  the underground- pyrolysis  of large  chambers  of
 rubblized shale [Fox, July  1983].   These chambers  are constructed
 by mining out about  20% of the volume  of the retort  and blasting
 the  balance  so  that the  entire chamber  is  filled  with fractured
 rock.   A  commercial-sized  retort  will  measure about 333 ft  by
 166  ft in cross  section and  400 ft high.   Oil is  recovered  from
 such a retort, shown in Figure 3.5-1,  by initiating combustion at
 the  top of the retort with an external fuel supply  and propagating
 the^  reaction zone,  which  consists  of  a  pyrolysis   zone  and  a
 trailing combustion  zone,   down the bed of  rubblized  with  input
 gas.   The  volatile hydrocarbons condense in the  cool region at the
 bottom of  the retort and are pumped to the surface.
                     INPUT GAS
                Overburden
                                   EXIT GAS
            Pillar =
                 ,V BURNED OUT ZONE •"..•• =
                 ii COMBUSTION ZONE
                  . * •• s  * .,v f '.., '..•'.
                 '-••*.:'"PYROLYSi'10N E|f
                 .•;. CONDENSATION ZONE" .' =
                             OIL
0     500    1000

  Temperature (°C)

       XBL 612-623!
       Figure 3.5-1.   Schematic of the Occidental modified
                       in situ retorting process.

       Source:   Fox,  July 1983.

Occidental  has  tested eight  experimental retorts  at Logan Wash,
Colorado.   Leaching studies have  been conducted on materials  from
Retort 3.   Retort  3  was operated  between  February and  July  of
1975 in air-recycle gas  mode.   Yield was around 60% Fischer Assay.
This retort was cored in December 1978, and the spent shales  have
been characterized  and subjected to leaching studies.

Figure 3.5-2 presents a  conceptual illustration of a rubblized MIS
retort  [EPA-600/8-83-004,  1983].    In  the  operation  of  an  MIS
retort, air and steam (streams 37 and 70) are admitted at the top
                                I
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                                                                        I
through several openings which connect the retort air level to the
top of  the rubblized shale.   The steam is  produced from process
waters,  using kettle evaporators and  Lurgi waste  heat  recovery      B
boilers.   Steam promotes  the  water/gas reaction and provides  a      •
means  of  controlling the combustion  zone temperature.   Retort
start-up  is  accomplished  through introduction of hot  inert gas.      •
When the  temperature  of  the broken rock at  the  top  of  the retort      g|
is high enough, air is introduced to initiate combustion.

An operating  retort contains four major zones.   In  the  first,  or      •
preheat zone,  the  air/steam feed gas is preheated through contact      m
with hot processed shale.  The heated  gas  then  reaches  a combus-
tion zone where oxygen is  consumed by  burning residual  carbon in      B
the processed shale.   Below the  combustion  zone is  the retorting      B
zone where hot combustion gases heat the raw  shale  rubble to ap-
proximately  900°F,  and  the retorting  process  commences.   During      m
retorting, the kerogen is  pyrolyzed  to produce  gas, oil and oil      g
vapor,  and solid  residue  with residual carbon.  The shale oil
moves  downward by  gravity and precedes the advancing  combustion
front by  six  to ten feet.  In  the  final zone,  the combustion and      •
retorting  gases  are cooled as they flow downward, condensing most      •
of the  vaporized oil.  During  the early stages  of the  burn, when
the rock is still cool, some water is also condensed.                   H

Oil, water, and retort gas exit the bottom  of the MIS  retort and
undergo separation in a three-phase separation sump located under-      «
ground.  Heavy oils (stream 39) obtained from this sump are pumped      •
to storage.   The retort  water (stream 41)  is also  pumped to the
surface  and  steam stripped  to  remove volatile compounds.   The
overhead  vapors (stream 43) are  sent to  the Phosam-W unit, while      •
the stripped  water is used in  the production of  low-quality steam      H
to be  injected back into the MIS retorts.   The retort gas mixture
(stream  38)  consists of  light hydrocarbons from shale pyrolysis,      n
carbon dioxide and water vapor  from the combustion of carbonaceous      ||
residue, water vapor  from  steam injection, carbon dioxide  from the
decomposition  of inorganic carbonate (primarily  dolomite  and cal-      _.
cite), and nitrogen from the combustion air.   In  addition, the gas      B
contains  ammonia and sulfur-bearing  gaseous products such as H2S      "
and COS.   The gases are drawn  to the surface by  large blowers and
fed to an absorption/cooling oil  recovery unit.                         •

3.5.2  Solid Wastes

Table 3.5-1  presents  an   inventory  of  solid  and  liquid waste      Q
streams.   From  a  commercial   size  development  with  229 retorts
operating  simultaneously,   each   120 ft  x 120 ft x 250 ft  and
containing oil shale with  an average Fischer  assay  of 15  gpt, the      B
Occidental modified  in-situ  process  will  generate among  other      •
products  the  following:    Mined  rock - 56,685  tons  per  calender
day; Wastewater -  1,458 gpm [EPA-6'00/7-79-075, 1979].                   B



                                                                        I
                              138
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3.5.3  Characteristics of Solid Wastes                !

Compositions  of  solid  and  liquid  waste  streams  are  shown  in
Table 3.5-2.   Available  data   on  spent  shale  are  presented  in
Tables 3.5-3 and 3.5-4.  Analytical data on core samples  are given
in  Tables 3.5-5 and  3.5-6.   Data  on  steam  boiler blowdown  and
wastewaters are shown  in Tables 3.5-7  to  3.5-9.  Finally,  various
leachate data are presented in Tables 3.5-10 to 3.5-12.
                            139
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  TABLE 3.5-3.   COMPOSITION OF OCCIDENTAL MIS PROCESSED SHALE
     Component
    Weight
    percent
Mass flow,
103 Ib/hr
                              Flow,
                         103  Ib-moles/hr
  Processed shale
    (in-place)       100.00

  Carbon (organic)     2.40

  Sulfur (total)       0.62
                 11,421

                    274

                     71
                   23

                    2.2
  Source:  EPA-600/8-83-004, 1983.  69,000 BPSD Plant Size

TABLE 3.5-4.  BORON AND FLUORIDE IN OXY RETORT 3E SPENT SHALE
         Sample
         number
      Depth,  ft.
        ±10%
                              |jg/g
                             _±io%
            i
            3
            4
           14
           15
           17
           18
  442 - 445
  457 - 460
  460 - 463
  483 - 485
483.5 - 485.5
  500 - 506
  506 - 515
                         470
                         530
                         680
                       1,200
                       1,100
                       2,600
                       2,300
                   210
                   140
                   110
                   275
                   210
                   470
                   550
          aF - gas diffusion-colorimetric

          DB - colorimetric  (Azomethine-H).

          Source:  DOE/EV-0078, May 1980
   TABLE 3.5-5.
MINERALOGICAL ANALYSES FOR SELECTED SAMPLES
OF OXY REPORT 3E SPENT SHALE CORE
                           No. 5
                               No. 16
  Mean depth  (ft)

  Major mineral  (s)

  Minor mineral  (s)
  Trace mineral  (s)
        464.5

        Calcite

        Diopside
        a-quartz
        Aragonite
        Kalsilite

        Akermanite
          493

          Akermanite

          Diopside
          Kalsilite
          2  Unidentified phases
   Source:  DOE/EV-0078,  May 1980
                             142
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        TABLE 3.5-6.  ANALYSIS OF CORE SAMPLES FROM OXY
                      RETORT 3E PRELIMINARY DATAa    ;
    Average
 cpncentrati on
                                 Element
                                                   Average
                                                concentration
  Al
  As
   °
  Ba*
 Cu
Fe
    d
    b
    d
 K
  b'd
 4.7 ± 2%
  26 ± 2 ppm
    256 ppm
 593 ± 60 ppm
  19 ± 1.4%
 5.0 ± 0.5 ppm
  44 ± 4.4 ppm
2.43 ± 0.07 ppm
  41 ± 6.2 ppb
 3.0 ± 0.3%
                                   Mg"
                                   Mn
                                   Mod
                                   Nab
                                   Nid
                                   Pbd
                                   ~d
                                    sid
                                    sr
  5.8 j± 0.6%
  520 :± 52 ppm
  10 ;± 1 ppm
1.26 ± 0.03%
  29 ifc 3 ppm
  26 ± 3 ppm
0.45 ± 0.07%
  19 ± 2%
     i
1100 ± 110 ppm
0.26 ± 3%
 Neutron activation analysis.
£*
 DC Plasma Emission Spectroscopy.
 X-ray fluorescence.
6
 Flameless atomic absorption.
Source:  DOE/EV-0078,  May 1980
                           143
 image: 










TABLE 3.5-7. OXY RETORT
Collected
except as


Aluminum
Arsenic
Antimony
Bromine
Calcium
Chlorine
Chromium
Cobalt
Iron
Magnesium
Manganese
Molybdenum
Nickel
Nitrogen
Selenium
Sodium
Sulfur (%)
Uranium
Vanadium
Zinc



6 STEAM BOILER BLOWDOWN
- March 6, 1979 (in ppm
noted )

NAA
<4.01
2.8 ± 0.2
; 0.09 ± 0.01
6.8 ± 0.2
<80
2,220 ± 25
! <o.l
<0.01
<5
120 ± 20
<0.2
7.3 ± 0.6
<1
216 ± 10
0.15 ± 0.02
14,100 ± 100
0.50 ± 0.08
0.22 ± 0.03
<0.01
±0.3

Source: DOE/EV-0078, May 1980


144
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TABLE 3.5-8.  COMPOUNDS IDENTIFIED IN OCCIDENTAL
              OIL SHALE RETORT WASTEWATERS    i
          m <- -.       -              2,300
          Total  organic carbon	ppm

         Toluene                     x
         Phenol                       xa
         o-Cresol                    x
         m-Cresol                    x
         p-Cresol                    x
         C2-Phenol                    x
         Cs-Phenol
         2,6-Dimethylphenol
         3,5-Dimethylphenol           x
         Methoxyphenol
         Naphthalene
         2-Methylnaphthalene
         C2-Naphthalene
         2-Methylpyridine
         4-MethyIpyridine
         2,3-DimethyIpyridine
         2,4-Dimethylpyridine
         2,5-DimethyIpyridine
         2,6-DimethyIpyridine
         2-Ethylpyridine
         C2-Pyridines
         2,4,6-TrimethyIpyridine     x
         C3-Pyridines
         4-(n-propylJpyridine
         C4-Pyridines
        4-(3-pentyl)pyridine
        C5-Pyridines
        Aniline                     x
        3-Methylaniline
        N-methylaniline
        N,N-dimethylaniline
        N-ethylaniline
        2,4-Diethylaniline
        N,N-diethylaniline          x
        Quinoline                   x
        Isoguinoline                x
                                              (continued)
                    145
 image: 











TABLE 3.5-8 (continued)

2,300
Total organic carbon ppm
2-Methylquinoline x
3-Methylquinoline x
7-Methylquinoline x
2 , 4-Dimethylquinoline x
2 , 6-Dimethylquino;iine
2 , 7-Dimethylquinoline
Trimethylquinoline
Acridine

Compounds marked with "X" were
identified in each sample.
Those not marked are not
necessarily absent.
Source: ESI, June 1983




i

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     TABLE 3.5-9.  OXY RETORT 6 PRODUCT WATER ANALYSIS ^RESULTS
                                      (ppm)            j
 Aluminum
 !Antimony
 Arsejnic
 Boron
 Bromine
 Calcium
 Chlorine
 Chromium
 Cobalt
 Copper
 Fluoride
 Gallium
 Iron
 Lead
 Lithium
 Magnesium
 Manganese
 Mercury
 Molybdenum
 Nickel
 Nitrogen
 Potassium
 Selenium
 Silicon
 Sodium
 Strontium
 Sulfide
 Sulfur
 Titanium
 Uranium
 Vanadium
 Zinc
                  NAA
                    XRF
                                                    Other
0.018 ± 0.008
 1.32 ± 0.06

 0.34 ± 0.06

  232 ±9
     <0.8
     <0.2
       <4
     <120


      <30
  0.3 ±  0.1
    <0.3
0.04 ± 0.01

2810 ± 20


3100 ± 870

   <0.06
   <0.04
    <0.2
 0.87  ± 0.01

 0.28  ± 0.04
 0.72  ± 0.43
  183  ± 8
    <0.07
    <0.02
 0.03  ± 0.01

    <0.01
 0.19  ± 0.02
    <0.04
   <0.04


   <0.02

  36 ± 2

    <160

0.57 ± 0.08

2720 ± 150
0.53 ± 0.07

   <0.12
12.6 ± 0.5a 113.1 ± 0.03]
      34.8 ±! 1.0°
            [



      1.80 ±; 0.05e



         <0.02d
         0.257a

      1500 ±1100
      112 ±;15
 DC plasma emission spectroscopy.

 Colorimetric.

 Selective ion electrode.

 Cold vapor atomic absorption.
Q
 Conventional atomic absorption.

Source:  DOE/EV-0078,  May 1980
                             147
 image: 








       TABLE 3.5-10.
       CONCENTRATIONS OF DISSOLVED SPECIES
       IN THE LEACHATE FROM OCCIDENTAL MIS
       PROCESSED SHALE
Ore
sample
number
1
2
3
4




Constituent
F
1.2
2.0
6.0
11.0
B
3.5
2.1
2.6
7.6
Mo
2.4
0.9
8.8
5.6
As
0.01
0.09
0.16
0.03




concentration

0
0
0
0
Se
.02
.02
.10
.15
S203
0
0
260
210


2
5
6



, mg/L
S04
990
,970
,340
,530
Ca
16
250
180
920
TDS
2,370
4,700
8,250
10,300
I
1
I
1
1

   Source:  EPA-600/8-83-004, 1983
TABLE 3.5-11.
CONCENTRATION RANGE OF MACRO IONS FOUND
IN THE FIRST FRACTION OF LEACHATES FROM
OCCIDENTAL MIS RETORTED SHALE
Core/samples
Quantity of shale in column (g)
Column volume collected (v/v )
PH °
Conductivity (pmhos/cm)
Organic C (ng/mL)
Inorganic C (as c03)(Mg/mL)
Boron (pg/mL)
Calcium (pg/mL)
Magnesium (pg/mL
Potassium (jjg/mL)
Sodium ((jjg/mL)
Lithium (pg/mL)
Strontium (pg/mL)
Silicon (pg/mL)
Zinc (jjg/mL)
. 4.0
0.28
7.75
1300
152
30
1.9
11
0.5
70
370
0.2
0.7
5.4
<0.01
- 7.7
- 1.11
- 10.6
- 15,000
- 2455
- 280
- 46
- 513
- 265
- 3360
- 14,400
- 87
- 10.8
- 122
- 0.48
       Source:  DOE/EV-0078, May 1980
                              148
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 3.6  T3 OIL SHALE RETORTING                           |

 3.6.. 1  Retorting Operating                            !

 The process (NTU/T3)  incorporates  the  salient features of the NTU
 batch retorting  process  developed in  the  U.S.  in  the 1920«s and
 improved by the  Bureau of Mines and Department of  Energy through
 extensive experiments with 10-ton  and  150-ton batch retorts FBLM
 February 1983].                                        ,       L'   '

 The name T3 was  derived  from  the three major Moroccan oil shale
 deposits at  Timahdit,  Tarfaya,  and  Tangiers  [Bouch'ta et  al.,
 1981J.    The  process  includes  significant  improvements based  on
 recent  technology   development  including  the  vertical  modified
 in-situ oil shale process.                            '

 The T3 process basically consists of  two  retorts;  retorting  and
 cooling sections  as  shown in Figure 3.6-1.   The air;enters  into
 the Bottom  of the retort  charged with  hot  spent shale,   The water
 is  injected into  the  air  stream by fog nozzles or atomizers.   The
 air mixed  with  water  passes  through holes  in  the  retort  bottom
 discharge cones.   The water in  the air   is 'evaporated when  it
 contacts  the hot spent  shale.   The bottom  layer of :spent shale
 is  cooled  and  most of the  sensible heat  contained in the spent
 shale  is recovered  in the form of  steam.   The mixture of air  and
 steam  flows through the  hot  spent  shale bed.  Since the residual
 carbon  produced  from  kerogen thermal  decomposition is  not  com-
 pletely  consumed  during retorting,  the  additional  heatienergy will
 be  recovered by  burning  the  residual  carbon in  the spent  shale.

 The  cooled  spent shale  near  the retort bottom  is discharged  and
 an  equal  volume of  raw shale is loaded at  the top of i the retort
 The  process is repeated  until the retort is recharged with the
 raw  shale.   The mixture of air and steam will heat  the raw shale
 entering  into the retort  from the top.   The water  in the raw shale
 is  also  evaporated  to  produce  additional  steam.  The; mixture of
 air  and  steam  exiting the retort  being operated in  Ithe cooling
 mode, is  introduced  into  the  retort being operated in the retort-
 ing  mode.  The  supplemental steam from the topping; turbine is
 mixed  with  the  steam  from  the retort in  the  cooling  mode   if
 necessary, to obtain the required steam  concentration of the inlet
 gas  into  the retort  in retorting mode.   However,  the supplemental
 steam is not expected to be required.

The  product  gas  leaving  the  retort in  the  retorting mode passes
tnrough knock-out pots and a gas cooler located before the blower.
Because of high water concentration in the product gas,  the blower
is  located  after  the  gas cooler to  reduce the actual  volume of
off-gass to  be handled by the blower.   The liquid and gas products
are  collected and separated in a  space below the retort bottom.
The  liquid  products  flow into the  oil  and  water  separator during
retorting.  The  water  is subsequently used during the  cooling
                             151
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 of  spent  shale.    The  liquid  products  are  separated  in  the
 collector into the  oil  and water phases.  The oil is  pumped into
 the heater  treater  to remove  the  water.   The  purging line  is
 provided to remove the  combustible  gases from the space below' the
 %£?*  •  ? Hu When  th\ ret°rting is  complete.   The isteam  intro-
 ~S5     °  -^  ueto2?  bottom wil1 also generate  the hydrogen and
 carbon monoxide  by the  reaction  of  steam with the residual  carbon
 in the  spent  shale.   This gas  may be used  as  a start-up  fuel.
                                                      f
 Since  the major mechanism  for transferring the  heat! energy  from
 hot spent  shale  to  the gas  stream is  the  evaporation of  water
 ?^™J:S^n     air(. ^ ^s necess*ry to carry the water droplets
 through  the spent shale bed.   The spent shale absorbs  the  water,
 Slnw  ?nno-30% nS,f  ^  Spe^ ?hale Wei9ht, ^ the temperature  is
 below  200°F.   Therefore, it is necessary to  discharge the  spent
 shale  incrementally  from the retort bottom to avoid the water ab-
 Sh?™101% Y the- Sfe.nt  S^ale'   In addition, the  incremental  dis-
 ?^5 2S ?  spent shale will also  allow the incremental  loading  of
 K^h  ?i!Uf   £hS retort-   Because of  a  large retort height,  the
 batch  loading of raw shale may cause  a  serious  damage to the  re-
 tort wall and may also  cause  degradation of  shale particles.   In
 order  to obtain  radially even movement  of shale,  it may be neces-
 sary to  use multiple vibrating retort  bottoms such  as bin acti-
 vators.  The charging and discharging cycle is dependent mainly  on
 the air velocity and water  injection rate.            i

 In  the T3  process  the spent shale is  cooled before discharge and
 the  significant  amount  of  sensible  heat contained in  the  spent
 shale  is recovered in  the  form of  steam.  A  mixture! of  air and
 steam instead of air and recycle gas mixture is used for retorting
 ?ii01?a.le  ln  lhe T3 process.   In addition to  controlling maximuS
retort temperature, the use of steam has the following!advantages:

 1.  The   steam  increases the  combustion rate of  residual  carbon
     in spent shale through the water gas shift reactions.
                                                      i
 2.  The  steam increases the hydrogen production  per ton to  oil
     shale by reacting with the carbon monoxide.   The  steam
     increases  the  reaction rate  of residual  carbon Jwith  carbon
     dioxide by  increasing the porosity of spent shale.!   The
     residual  carbon  in the  spent  shale  reacts  with; the  carbon
     dioxide to  produce  carbon  monoxide  which  reacts with  the
     steam to produce hydrogen.

 3.   The  steam reduces   the  oil loss  due  to  thermal cracking in
     the  retorting zone  by  increasing C02 production rate in  the
     combustion  zone.  The  steam  minimizes the oil loss when it
     is released  from the raw shale surface.           '

 4.   The  steam  increases the  retorting rate  compared with  the
     recycle gas.             .'   ,                      '
                             153
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                                                                       I
3.6.2  Solid Wastes

According  to  the  Magic  Circle proposed  alternative process  for     •
their  operation in Utah for  35,000  bbl/day plant,  about 49,000     H
tons per stream  day  of spent shale  would require  disposal.   It
would  be carried to the disposal area from  the processing plant
on  a covered belt conveyor.  Because  of the continuous  flow of
spent shale from the processing plant, the conveyor and associated
equipment  are  scheduled to  operate  continuously.   There  is  no
other  information available for  solid  waste  streams composition.     II

3.6.3  Characteristics of Solid Wastes

	
the Magic Circle proposal utilizing T? technology.

                                                                       I
                              154
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 3.7  HYTORT OIL  SHALE RETORTING                       j

 3.7,. 1  Retorting Operation                            :

 Controlled heating  of oil shale in hydrogen  at  elevated pressures
 can be used  to produce synthetic natural gas (SNG) of  a synthetic
 crude oil  [DRI,  SAI & KSC;  68-03-2795].   The relative amSunts of
 rne£:e products can  be varied by proper selection of tlhe operating
 r^M x0nS*  P11. shale research at the Institute of Gas Technology
 UL.I; Degan  in the 1950s, sponsored  by  the American Gas Associa-
 S°?i,Snd   i    by the fas Research Institute,  and this: program led
 to the development of the HYTORT process.   It has been tested in a
 Sf??JSS devlelopmei\t unit (p.DU> whicn is a one-tonne per hour adia-
 batic reactor and  is claimed to  increase  shale  organic  carbon
 conversions relative to other processes.               '      t-arcon
                                                       I
 The  design of  the PDU  is  shown  in Figure 3.7-1.   oil  shale
 S™ed t0 °'5 ln<rhes. average size,  with the  fines rempved,  is fed
 through screw mechanisms to  two  adiabatic reactors, the first for

  rSssu^eS u"sedghnatl°n and the second fo? shale gasifibation.  The

 from  1200 - 1475°F.   For  Colorado shales the oil-to-gas  ratio^in
 peJatur       cha^  from 4:1 to about 0.5:1 as the  average tern-

 shale and tSeS?I?e  of^emperaLre" rise°aisoTinfluencfthf ratiS of
 proaucts.   HYTORT shale oils  from both eastern and western  shales
 nave  relatively  low  viscosities and  pour points.   They can  be
 5S?!d ""irough pipelines  in  the raw  state,  in contrast to  most
 ^*KS%»£™^^^2^  processes.   HYTORT shale  oil
C°lor md  «»       30 prcent
 les  sultaha!  f                                    prcent
 less  sulfur than oils from  conventional  retorting,  because of the
                        treatment.   However, like* all  shale oils
The conceptual design  of  a  zoned  reactor  for  the  HYTORT process  i<?
shown in Figure 3.7-2.  Crushed shale  (fines  removed)  iSPf2d?o  the
high pressure reactor  through  liquid sealed lockhoppers.   The  shale
moves downward countercurrent  to  the hydrogen-rich  gas flow  through
neL ??f SfAi- A Jmali  a^n? °f °Xygen is in3ected  intp the  reactor
near its center for heat  balance  purposes.  Processed  shale  is re-
moved from the reactor through liquid  sealed  lockhoppers.  Product
gas is scrubbed to recover water  and shale oil.   A  bleed stream  of
™L  ^ ga! ^ !ent to  the steam reformer where hydrocarbons are
converted into hydrogen.  All  the make  up hydrogen  requirements  of
hydroretorting and  catalytic  hydrotreating are to  be produced  in
this fashion and  it is expected that  no  hydrogen will i need to  be
purchased   !n  some trials by the HYTORT precise,  2,5(>0t2 4? 000
?Sf °5 ^^en is  chemically consumed per ton of Devonian  shale.
The shale oil is catalytically hydrotreated to produce a low sulfur
low nitrogen refinery  feedstock product  and  a plant utility fuel
s "c.trs 9,111 *
                             155
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3.7.2  Solid Wastes                                   !
                                                      i

There  is  no information on  the subject of  solid  wastes or waste
streams of the HYTORT process.                        l


3 - 7., 3  Characteristics of Solid Wastes                '


Leaching characteristics and  hydraulic  properties  of retorted oil
shales have been investigated by McWhorter [EPA-600/D-84-228  19841
The data are presented in Tables 3.7-1'to 3.7-3.
                            157
 image: 








RUN-OF-MINE
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Figure 3.

ro,HALE F1NE5TODI5PQ-A1 RAW SHALE OIL
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f BYPRODUCTS
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L T.™-r-T—~.— SEPARATION 	 ~ 	

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'•'•'•••'•'--" -'••.. -M^VJITT RECYCLE HZ- RICH GAS r HZ

/ — UA?PIID MANUFACTURE
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Source: DRI, SAI & KSC; 68-03-2795
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  TABLE 3.7-1.  WATER HOLDING CAPACITY OF HYTORT PROCESSED
                SHALES AT VARIOUS PRESSURES AND BULK DENSITIES51

Sample
Packed to a
BD=1.30 g/cc
BD=1.45 g/cc
BD=1 . 60 g/cc

14.7 psi
(1 bar)

35.2
31.0
30.5

44.1 psi
(3 bar)

33.7
27.6
30.3
Pressure
73.5 psi
(5 bar)

32.6
25.3
28.9
	 P
147 psi ;
(10 bar) >
L
31.8
23.8 '.
25.4

200 psi
(13.6 bar)

31.0
23.2
24.6
BD = Bulk density

 Table entries are moisture contents (w) expressed on a weight 7
 basis (weight of water per unit weight of dry solids):.        °
 Source:   EPA-600/D-84-228, 1984                      \
                               159
 image: 








TABLE 3.7-2
CONCENTRATIONS IN ASTM WATER SHAKE AND
RCRA TESTS EXTRACTS - HYTORT SPENT SHALES

Parameter
pH
EC
ALK
H2CO3
HC03
C03
TDS
F
Cl
P04
N03
S04
Zn
Fe
Co
Li
V
NH3
B
Cd
Be
Mg
P
Si
Mo
Mn
Ni
Na
Cu
Al
Ca
Ba
K
Cr
Sr
Pb
Ag
TL
Se
As
Hg
Units
— ,
|jmhos/cm @ 25°
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
ASTM
9.76
1160
205
0.08
166
41.1
1060
3.4
12.4
0.59
5.2
178
0.212
0.033
<0.005
0.005
<0.002
16.4
1.110
<0.001
<0.0005
0.23
0.33
21
1.92
0.015
<0.005
26
0.013
0.86
250
0.120
60
0.030
0.85
<0.01
<0.001
<0.005
<0.020
0.037
<0.001
RCRA

4.94
1540
430
13278
525
0.002
1740
8.95
<0.1
2.3
97
0.477
0.078
0.120
0.019
<0.002
1.66
0.340
0.013
<0.0005
85
0.4
3.7
<0.05
8.98
0.971
11
0.023
0.44
319
0.210
22
<0.005
1.0
<0.01
0.003
<0.005
<0.02
0.010
<0.001

  Source:  EPA-600/D-84-228, 1984
                                                                   I
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                         160
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TABLE 3.7-3.
LEACHABLE MASS FROM HYTORT SHALE AS
INDICATED BY THE ASTM PROPOSED WATER
SHAKE TEST AND RCRA EXTRACTION
TEST - mg/g
Parameter
Na
Ca
Mg
S04
Cl
F
E
Mo
Al
TDS
ASTM
0.104
1.00
0.001
0.712
0.050
0.014
0.004
0.008
0.003
4.24
RCRA
0.220
6.380
1.700
1.940
0.179
— •
0.007
0.006
0.044
34.80
         Source:  EPA-600/D-84-228,  1984
                    161
 image: 








3.8  GEOKINETICS HORIZONTAL IN SITU OIL SHALE RETORTING

3.8.1  Retorting Operation

In the Geokinetics, Inc (GKI) horizontal in situ retorting process,
known  as LOFRECO  (low front  end  cost)(U.S.  Patent  4037657),  a
specific pattern of blast holes is drilled from the cleared surface
through any overburden and into the oil shale bed.  The schematics
of the process is shown in Figure 3.8-1.  Explosives are placed in
these holes and  detonated by use of a carefully timed and planned
blast  system.   The blast  yields  a well-fragmented mass  of shale
with  high  permeability,   and  also  produces  a  slightly  sloping
(approximately 4°) bottom surface that allows the produced oil to
drain into a sump for collection.  The fragmented zone constitutes
the  in situ retort.   The void space in  the  fragmented zone comes
from lifting the overburden, produces small uplift of the surface.
Submerged-type  oil  well pumps are used  to lift the recovered oil
to surface storage tanks.

Burning  charcoal is  introduced   into  drilled holes  at  the upper
end  of the  rubblized zone to ignite the retort.  Air inlet piping
is  also installed  at this  end   of  the retort.   The burn front,
consisting  of a vertical wall approximately  30-ft high,  travels
toward  the  deep or  low end of  the retort.   The  objective  is to
retort  the  shale from one end to the other in a plug-flow fashion
by maintaining a burn front that  occupies the entire  cross section
of  the bed.  Typically the front travels at a speed of one foot
per  day.

3.8.2   Solid Wastes

Since  this  is an  in situ process  very little above ground solid
waste  is expected to  be  generated.  The  largest volume of solid
waste  is the retorted shale which is left below ground.

3.8.3   Characteristics  of Solid Wastes

The  chemical composition  of leachates is summarized in Table 3.8-1
 [Fox,  1983].  Recent data are presented  in Tables  3.8-2 and 3.8-3;
and  in Figure 3.8-2  [DOE/FE/60177-1590,  April 1984].
1
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           163
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TABLE 3.8-1.


As
B
Ca
Cl
EC, |Jmhos/cm
F
HC03
K
Mg
Mo
Na
Se
S04
pH
Type of study
Particle diameter
Solid- to-liquid ratio,
Contact time
Other

Source: Fox, July 1983
INORGANIC COMPOSITION OF LEACHATES FROM
GEOKINETICS SPENT SHALE (mg/L)

Cleave et al., Krause et al., Krause, et al.,
1979 1980 1980
0.01 - 0.2 0.03 •- 0.3
0.5 - 6.7 0.6 - 2.6
747
29
321 - 16,200 741 - 8,430
0.32 - 10.1 2.3 - 13
797
34.4
0.2
0.4 - 17.1 0.7 - 6.4
542
<0.001 - 1.3 0.006 •- 0.16
2,298 170 - 16,435 790 •- 5,595
8.8 - 11.6 9.2 - 11.6
shaker Column Ball mill/batch
-1 in. -10 mesh
g/mL 0.5 - 0.4
48 hr 1 hr 2 wk
3 x 50 cm glass
column

164
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TABLE 3.8-3. CONCENTRATION (mg/L) OF TRACE ELEMENTS
FOR SELECTED PORE VOLUMES OF LEACHATE
(GEOKINETICS SPENT SHALE)


0.021

P 0.4
Al 0.6
Fe 0 . 04
Mn 0.03
Cu 0.18
Zn 0.03
Ni 0.03
Mo 33.1
Cd 0.01
Cr 0.07
Sr 2.3
B 11.9
Ba 0.19
Pb 0.1
As <0.1
Se 2.4
vt
L
0.090

0.3
0.4
0.02
0.01
0.15
0.02
0.01
17.4
0.01
0.03
13.4
7.7
0.21
<0.1
<0 . 1
1.1
Source: DOE/FE/60177-1590,


K
vt
L






Key
= 4.6 x 10~


0.510 1.977

0.2 0.1
0.5 0.3
0.01 <0.01
0.01 <0.01
0.14 <0.01
0.06 <0.01
0.01 <0.01
6.0 0.7
0.01 <0.01
0.01 <0.01
15.4 13.5
6.1 2.6
0.14 0.09
<0 . 1 <0 . 1
<0.1 <0.1
0.4 <0.1
April 1984


cm/s
= pore volume




166





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                                                                       I
3.9  SUPERIOR CIRCULAR GRATE OIL SHALE RETORTING                        "

3.9.1  Retorting Operation                                              H

A commercial-sized Superior retort incorporates a circular travel-
ing grate  retort  about 200 ft in diameter,  covered  by a hood and      ffl
made gas-tight  by water  seals  at the sides (Figure 3.9-1).  The      H
doughnut-shaped retort is  divided  into  five  separately enclosed
sections:   a loading  zone,  a  retorting zone, a  residual carbon      m
recovery  zone,  a  cooling  zone,  and  finally  an  unloading  zone.      •

The raw  shale is  fed  to the traveling  grate  retort  so  that the
finest material  is at the  bottom and coarsest on top.   The. pre-      A
pared bed  of shale passes first into  the retorting  zone where it      »
contacts a stream of  hot gases,  and  retorting occurs as the hot
gases pass down through the bed of shale.  The oil and gas mixture      m
passes to a separator/condenser system where shale oil is recover-      ||
ed, and  the cooled recycle  gases then  pass through the retorted
shale bed  in the  cooling zone of the retort to cool the processed      M
shale before dumping,  and heat the recycle gas.                         m

The retorted shale travels from the retorting zone  to the carbon
recovery zone where evolution  of  shale   oil vapors  is completed,      •
and residual carbon is  burned in  a  mixture  of  recycle  gas and      Ms
preheated combustion air.  From the combustion zone,  the processed
shale  travels to  the  shale cooling  zone  where  recycle gas  is      M
heated by  the hot shale.  The shale is  cooled further by ambient      B
air.  See Figure 3.9-2 for schematics of  directly heated operation
of  the  Superior  retort.   Processed shale  is discharged through
mechanical  seals  or a water seal which wets  the shale  for dust      m
control.    The traveling grate  is sealed between  stationary hoods      •»
on  top of the bed and the windboxes  underneath by  water troughs
on  both  sides,  which allows for expansion and contraction of the      •
retort structural members.                                              •
                                                                        ^*"

Preheated  recycle  gas  from the shale  cooling  zone is heated fur-      «.
ther by  mixing  with hot combustion gases  and  the  mixture is sent      9
to the shale heating zone to complete the cycle.                        *

Retort product gas is taken as a side stream from the recycle gas.      ffl
A  high  Btu  (400-600  Btu/scf)  gas  is produced  in  the  indirect-      ra
heated mode.  Gas from the direct-heated mode is  low-Btu (80-130
Btu/scf).                                                               ip

3.9.2  Solid Wastes

Figure 3.9-3  presents  the process operations  and  projected waste      W
streams  for  the Superior Circular Grate Process.  Dust fines are      •
generated  in the  raw  shale mining  and  crushing phase  and are
disposed of  in  the solid waste pile.  Retorted shale is moistened      JH
prior to the discharge from the circular grate.                         Hi
                             168
I

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3.9.3  Characteristics of Solid Wastes                i


N°x,da^ are aXailable on the characteristics of the retorted shale
and other  solid  wastes.   The soluble materials extracted by water

Ma  19^m10r Spent  shale  has  been reported  as  142  {Lb/ton (TRW,

                                                      i

Table  3.9-1 presents  process water  quality  parameters.   Tables
f> It  an<J  ^9-3  show results of leachate tests.   It  is not known
                                             .              nown
 the  shale used in these tests  had  undergone moisturization or
?   ^o ?r a^umjna and  soda  ash  removal.   The  information in
      '4  and  3.9-5  summarizes Superior  leachate!  data  using
       water and process water on process shale.    ;
                         169
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                                                COOL  RECYCLE GAS
               HOT RECYCLE GAS
            SHALE
            FEED
                                              PREHEATED COMBUSTION AIR
                                 DIRECT |
                                 HEATING
                                 BURNERS
                           AIR IN
HEATING |
COOLING BY iCOOLING
  RECYCLE  | BY AIR
    GAS
                                      V
                                     CARBON
                                    RECOVERY
                                       PROC-
                                       ESSED
                                       S'HALE
                                                                 LIQUID
                                                                 SEAL
                                                    GAS BLOWER
                                                                         -»»*
                                                          EDO]    :
                                                            GAS COMPRESSOR
                                              OIL 8 WATER
                                                            SURPLUS RETORT
                                       iGAS
          NOTE:
          THE CIRCULAR  PATH OF THE
          SOLIDS BED IS PICTURED  AS A
          STRAIGHT PATH  FOR CLARITY
c
G
C
C
                 Figure 3.9-2.   Superior direct-heated process^
                 Source:  DRI,  SAI & KSC; 68-03-2795
            171
 image: 








                                                                   I
TABLE 3.9-2.
INORGANIC COMPOSITION OF SUPERIOR LEACHATE
PRODUCED BY THE ASTM TEST METHOD D3987
                                                                   I
               Element
                Concentration0
                	mg/L	
Ag
As
B
Ba
Cd
Cl
Cr
EC (Mmho/cm)
Li
Mn
Mo
NH3
Ni
Pb
Se
SO
Sr
Th
TOG
pH
                               0.6 - 0.22
                                   <5

                               2400 - 3250
                               0.51 - 0.80

                               0.39 - 0.46
                                  0-2
                               0.14 - 0.20
                                896 - 1908
                               0.33 - 0.58
                               0.43 - 0.56
                                   <20
                                   9.4
     Samples were prewetted to 20 wt % with distilled
     water, compacted, equilibrated for 0 to 4 weeks,
     fractured, and leached by ASTM D3987.  In this
     test, 350 g of solid are leached in 1.4 liters
     of distilled water and the leachate diluted to
     2 liters prior to analysis.  Chemical analysis
     was by inductively coupled argon plasma spec-
     trometry and other methods.

     Source:  Fox, July 1983
                                                     I
                                                     I
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                                                     I;
                                                     r
                                                     r
                                                     r
                         174
 image: 








  TABLE 3.9-3.  THE EFFECT OF COPRODUCTED RETORT WATERS ON THE
                QUALITY OF SUPERIOR LEACHATES FROM SPENT SHALES'
,

As
B
Ba
Cl
Cr
EC, (j mhos/cm
Li
Mn
Mo
Ni
Se
S04
Sr
TOC
pH
Moisturization
water
composition
Retort water
0.25
1.83
<0 . 1
350
<0 . 1
>8,500
0.18
1.23
<0 . 1
<0.1
<0 . 1
3,000
0.21
5,000
7.0
Leachate composition
Spent shale
Distilled water
<0.1
0.16
<0 . 1
>5
<0. 1
3,250
0.51
<0 .1
0.39
<0 .1
0.14
896
0.33
>20
9.4
moisturized
Retort water
1 0.14
! 0.29
<0 .1
18
<0 . 1
3,900
i 0.63
<0.1
0.38
<0 .1
! 0.15 ,
! 1,073
0.39
53
i 9.2

 All values in ppm except EC which is in pmho/cm.      '•.

 Samples produced by leaching fractured cores cured for 4 weeks
 using ASTM D3987 (350 g of spent shale are batch leached in
 1,400 mL distilled water; the final leachate was diluted to
 2,000 mL prior to analysis).  Spent shale cores were produced
 by moisturizing each sample (12.5% water (w/w)) and compacting
 it according to ASTM D698-78.

Source:  Fox, July 1983
                             175
 image: 








TABLE  3.9-4.   EFFECT OF DISTILLED WATER,  AND TIME ON THE LEACHATE
               QUALITY OF MOISTENED, COMPACTED SUPERIOR SPENT SHALES
Shale
core aqe
0 Week
4 Week


PH
9.4
9.4

Conductivity
|jmhos/cm
2400
3250
Water quality parameters

Cl , mcr/L S04~, mg/L NH2-N, mq/L TOC, mq/L
>5 1908 0 >20
>5 896 2 >20
Source:  Jackson & Jackson, 1982
                             176
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 3.10   UNION OIL A OIL SHALE RETORTING                !
                                                       I
 3.. 10.1  Retorting Operation

 All three of  the processes developed by Union Oil  are  variations
 of an upflow vertical kiln retort using a rock-pump shale feeding
 mechanism [EPA-600/2-80-205a,  1980].   The retorts  are known  as
 Retort A,  Retort B, and  SGR-3.   In  all  three processes, the  oil
 shale is pushed  upward  through the  retort while the gas flow is
 downward.  In Retort A,  the heat for  pyrolysis is generated  by  the
 internal combustion of  residual  carbon on  the  spent  shale.   In
 Retort B and the  SGR  retort, the  heat is supplied  indirectly by
 externally heated hot  gases.                           !

 The Retort A  process  was  developed  through  2-,  50-,:  and  1,000-
 ton/day pilot plants  that  were operated  before  I960.!  A view of
 the Retort A process is shown in  Figure  3.10-1,   The retort is an
 inverted cone  fitted with a rock-pump shale feeder that  pushes  the
 oil shale upward through the vessel.   Air is injected  at the  top
 of  the retort to support combustion  of the residual  carbon  on  the
 retorted shale fragments in the  upper portion  of  the  retort.  This
 combustion provides the  heat necessary to  retort the upward-flow-
 ing shale.

 The crushed  shale feed is  removed  from the hopper and transferred
 to  the  bottom  of  the  retort by  a  shale  feeder.   As  the   shale
 enters  the retort,  it is contacted by a countercurrent flow  of  hot
 product gases leaving the  combustion  and  retorting zones  above.
 In  this  lower zone,  the gas-cooling zone, heat is  transferred from
 the hot gases  to the cool  incoming shale.  The feed  is  preheated,
 and the  oil vapors  are condensed while  the gases  are cooled.
 Passing  up   through the  retort, the  preheated  shale ! enters  the
 retorting or pyrolysis zone.  The  gases  passing  downward in this
 area,,  having just  left  the combustion zone,  heat the; shale to a
 temperature  such  that organic  material  is  pyrolyzed:,  producing
 shale  oil vapor,  product gas, and  residual carbon on the surface
 of  the shale.   As  the gaseous products of pyrolysis are evolved,
 they are swept downward by  the flow of  combustion  gases.

 The  retorted shale  fragments then enter the combustion  zone where
 they  encounter preheated combustion  air  passing  down 'through the
 retort.  This  air  sustains the  combustion  of the residual carbon
 that  remains  on  the  surface  of  the  shale  after  retorting.
 Temperatures    in   this  zone   may  reach  2000°F,   high  enough
 to  fuse a portion  of the shale.   In  earlier  versions of the
 retort,  retorting spiral plows  were  used to break  clinkers and
remove  retorted  shale.   In  later  versions,  these plows were not
used.                                                  :
                             177
 image: 








TABLE 3.9-5.
CONCENTRATION OF METALS IN LEACHATES
FROM SUPERIOR RETORTED SHALES:

Element
shale
Arsenic
Barium
Boron
Cadmium
Chromium
Lead
Lithium
Manganese
Molybdenum
Nickel
Selenium
Silver
Strontium
Thorium

Oa
<0 . 1
<0 . 1
0.22
Less
<0 .1
0.1
0.80
<0 . 1
0.46
<0 . 1
0.20
Less
0.58
0.56
ASTM
• 4a
<0 .1
<0 . 1
0.16
than 0.1
<0 . 1
<0 . 1
0.51
<0 . 1
0.39
<0. 1
0.14
than 0.1
0.33
0.43

oa
0.13
0.84
0.96
mg/1 for
0.10
0.16
0.36
3.3
0.25
0.19
0.45
mg/L for
10.5
1.4
RCRA
4a
0.1
0.63
0.71
all cases
<0 .1
0.32
0.49
3.8
0.22
0.18
0.48
all cases
10.0
1.4

  Shale age in weeks after moistening with
  distilled water.

  Source:  Jackson and Jackson, 1982
                         178
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3.10.2  Solid Wastes                                  j
                            -r        ?  '--               '
There is  not much information  available  on the  amounts  of solid
wastes or solid waste streams of the Union Oil A process.


3.10.3  Characteristics of Solid Wastes
                                                      !

Pertinent data are presented in Tables 3.10-1 to 3.10-4.
                             179
 image: 








    TABLE 3.10-1.  PHYSICAL PROPERTIES OF UNION A SPENT SHALE

                                        Shale ash 16 years "old"
                                       Composite sample in-place
t
I
1
Particle size                                                          •
  Percent cobble (1" - 6")                      8-28                 m
          gravel (4.76 mm - 1")                43 - 57
          sand (0.074 - 4.76 mm)               15-23                 •
          silt (0.005 - 0.074 mm)            ,   8-13
  Texture clay (-°-005 n™)           Graded gravel to silty gravel     #
  Color                                      Light brown               w
  Solids density, g/cc                          2.36                   »
  Dry bulk density, pcf                      60.3 - 90.5
Field, moisture, wt. %                        12.1-45.0               •
Source:  TRW/DRI, May 1977.

  TABLE 3.10-2.  CHEMICAL PROPERTIES OF UNION A RETORTED SHALE

Components a,
Si02
CaO
MgO
A1203
Fe20
Na2O
K20
S03
P205
Mineral C02
Organic C
Ignition loss @ 950°C
Free silica (quartz)
pH of slurry


Retort A
shale ash,
wt. % •
35.3
27.2
9.0
8.5
7.3
5.5
2.8
0.1
2.2
1.6
0.5
2.1
<2.0
12.5 - 13 (est. )

I

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1
             Analyses determined by heating sample to
             950°C except for pH measurement.   Analyses
             by Union Research Department.

            Source:  Wildung and Zachara,  1980
                             180
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TABLE 3.10-3.
ANALYSIS OF LEACHATE OBTAINED IN LABORATORY
TESTS OF UNION A RAW AND RETORTED SHALE
                               Quantity extracted per
                                unit weight of shale
                                     (kg/tonne)    :
                                             Retorted
                               Raw shale
                               Shale,
Inorganics
K+
Na+
Ca++
Mg++
HC03~
Cl"
S04
Total
kg/tonne
Ibs/ton

0.24
0.48
0.1
0.01
0.75
0.22
0.79

2.59
5.18
>
6.25
21.0-
3.27
0.91
0.28
0.33
62.3 i
1
94.3 '
188 :
       Source:   TRW/DRI, May 1977.

     TABLE  3.10-4.
     INORGANIC  COMPOSITION OF  LEACHATES
     FROM UNION A SPENT  SHALE,       '
Components
Ca
Cl
C03
F
HC03
K
Mg
Na
S04
TDS
EC, (jmhos/cm
PH
Particle diameter
Solid- to-liquid ratio, g/mL
Contact time, min
mg/L
327
33
21
3.4
28
625
91
2,100
6,230
10,011
11,050
9.94
-40 mesh
0.1
5
        Source:  Fox, 1983
                         181
 image: 








3.11  UNION OIL B OIL SHALE RETORTING                                  ~

3.11.1  Retorting Operation                                            9[

In the Retort B process, shown in Figure 3.11-1, crushed oil shale
in the  1/8 to 2  in.  size range flows through  two  feed chutes to     m
the  solids pump.   The  solids pump  consists  of  two  piston  and     ]|
cylinder  assemblies  which alternately  feed shale to  the retort.
As shale is moved upward through the retort by the upstroke of the
piston, it is met by a stream of 950 to  1,000°F recycle gas from     •
the recycle gas heater flowing downward.  The rising oil shale bed     w
is heated  to retorting temperature  by countercurrent contact with
the hot recycle gas, resulting in the evolution of shale oil vapor     tt
and make  gas.   This mixture  of shale oil  vapor and make  gas is     J|
forced downward by the recycle gas,  and cooled by contact with the
cold  incoming shale  in the lower section of  the retort cone.   In     g»
the  disengaging  section  surrounding  the lower cone,  the  liquid     M
level  is  controlled  by withdrawing  the  oil  product,  and  the     **
recycle and make  gas are removed from the  space above the liquid
level.                                                                 •

The make  gas is  first sent to a venturi  scrubber  for cooling and
heavy ends removal by oil scrubbing.  A portion of the 800 Btu/SCF     H
make  gas  is then processed  by  compression and oil  scrubbing to     Q
remove  additional heavy ends,  followed  by  a  Stretford unit to
remove hydrogen sulfide.   The sweetened make gas is used as plant     ^
fuel.  The remaining gas, taken off after the venturi scrubber, is     B
recycled  to  the retort through the recycle gas heater to provide     *
the heat for oil retorting.

The  rundown  oil   from  the   retort  is  treated sequentially  for     A
solids,  arsenic,  and  lightends  removal.   The  solids  removal is
accomplished by two  stages of water washing.  The shale fines are     M
collected  in the  water phase which is recycled to the water seal.     g
The water  seal  is a Union Oil concept, in  which a water level is
maintained in the conveyor for retorted shale removal to seal the     ^
retort   pressure   from   atmosphere.    For   arsenic   removal,  a     V
proprietary Union Oil process  employing  an adsorbent is utilized     •
to reduce  the  arsenic content of the raw shale oil from 50 ppm to
2 ppm.   The dearsenated  shale oil is  sent to  a stripping column     •
for stabilization and stripping prior to shipment.  This partially     (|
upgraded shale oil can now be marketed as a low  sulfur burner  fuel
in various locations  in the United States, and  is also a suitable     »
feedstock   for  refineries   that  have   adequate  hydrotreating     •
capacity.   The crude  shale  oil from the  Retort B process has a     *•
specific  gravity  of 0.918 (22.7°API), a pour point of  60°F, and a
kinematic  viscosity of  20 centistokes  (98.2  SUS) at 100°F.   It     H
typically  contains 1.74  weight percent nitrogen  and 0.81 weight     m
percent sulfur.
                                 182
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                                                                       1
3.11.2  Solid Wastes

Figure  3.11-2  presents the  process operations and-waste streams     JB
for  the Union  B prototype  plant.   The  solid waste  streams  are     m
highlighted in the figure.  Dusts and fines are generated from the
primary crushing, screening, and storage of raw shale prior to the
retorting phase.  Retorted  shale  is cooled and moistened for dis-
posal.

Table 3.11-1  lists  an inventory  of the  solid waste streams,  the     ffl
percent each  stream represents of  the total  mass  requiring dis-     J»
posal, and the components of each waste stream.

3.11.3  Characteristics of Solid Wastes                                fjf

Tables 3.11-2 through 3.11-3 provide chemical and physical proper-
ties of retorted shale.  Table 3.11-4 shows results of analysis of
the  process  water  to  be  used to moisturize  the spent  shale.
Table 3.11-5  list leachate  data.   Table 3.11-6 shows  results of
RCRA testing conducted on Union B shale.                               It
                                                                        a
                                                                        i
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TABLE 3.11-2.  PHYSICAL PROPERTIES OF UNION B SPENT I SHALE

                                  ;.After

                                                   •  compaction
                                                      at 12.375
                                      Initial        ft. Ibs/cf
Particle size
Percent cobble (1" - 6")
gravel (4.76 mm - 1")
sand (0.074 - 4.76 mm)
silt (0.005 - 0.074 mm)
clay (-0.005 mm)
Texture
Color
Solids density, g/cc
Dry bulk density, g/cc
Field moisture, wt. %

—
74
16
9
1


2.59
0.98
16
!
: _.
37
39
: 17
7
Silty gravel
Black

! 1.45
'• 21-23
a, , , , i
Source:  TRW, May 1977.


            TABLE 3.11-3.
                         CHEMICAL PROPERTIES OF
                         UNION B RETORTED SHALE

Components a,
SiO2
CaO
MgO
A12O3
Fe2O3
Na20
K20
S03
P/"\
o \J c
Mineral C02
Organic C
Nitrogen, Kjeldahl
Ignition loss @ 950°C
Free silica (quartz)
pH of slurry
wt %
31.5
19.6
5.7
6.9
2.8
2.2
1.6
1.9
0.4
22.9
4.3
0.2
26.9
8.0
8.7

               Analyses  determined by heating
               sample to 950°C except for pH
               measurement.   Analyses by
               Union Research Department.

               Source:   Battelle  PNL 3830
                          187
 image: 














TABLE 3.11-4. ESTIMATED3 COMPOSITION OF UNION B PROCESS WATER
IN THE ACTIVE BASIN AND THE REUSE WATER SUMP


Parameter
Alkalinity (as CaC03
Carbonate ( as C03 )
Bicarbonate ( as HC03 )
Chemical Oxygen Demand
Total Organic Carbon
Total Dissolved Solids
Total Solids
Hardness (as CaC03 )
Ammonia
Sulfides (as H2S)
Phenols
Cyanide ( CN )
Oil & Grease
Sulfate
Sodium
Arsenic
Chromium
pH units


aThese values are maximum

Active
Basin
(mg/1 )
5,800
2,500
1,000
200
50
4,500
4,500
1,100
2
0
10
-
50
3,000
1,500
0
5
8-10


design case
based on preliminary bench-scale
engineering calculations.

Reuse
Water Sump
(mg/1)
2,000
400
1,700
5,500
1,350
2,600
3,100
900
35
100
125
20
1,300
500
1,500
6.5
0.5
8-10


estimates
tests and
Source: Union. Oil, January 1984



188








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        TABLE 3.11-5.
INORGANIC COMPOSITION OF LEACHAT.ES
FROM UNION B SPENT SHALE, mg/L  •


Ag
Al
As
B
Ba
Be
Ca
Cd
Cl
CN
Co
cos
Cr
Cu
EC, |jmhos/cm
F
Fe
HC03
Hg
K
Li
Mg
Mn
Mo
Na
Ni
N, Kjeldahl
NH3-N
NOS
N02
Oil and grease
Pb
Phenols
PQ4
s
Se
S04
Sr
TDS
TOC
V
Zn
pH
Particle diameter
Solid- to-liquid ratio, g/mL
Contact time, min
Union, 1979c
<0.02
0.2
0.004
0.68
0.07
<0.01
95
<0.01
<2
<0.01
<0 . 1
0
<0.005
0.02
750
6.1
<0.05
25
0.0005
2.5
0.09
24
0.02
0.4
130
<0.04
0.6
<1. 0
<10
<5
6
<0.05
<1
<10
<0.01
<0.005
570
1.2
800
<1
<0.03
0.02
7.7
_
0.1
5
Cleave et al. , 197'
<0.0009
'' -
OJ001
0.97
O.;078
1 —
;243
0.016
7.0
; —
—
i —
<o.;on
<o.:on
i
H
<OJ025
172
-
;7.4
! —
i 58
<o.:oo7
! -
109
: —
i
'•
' —
| -
-
0.009
f
\
-
<0.|001
878
: —
1,518
11.3
': —
0.025
8.33
1 _
0.1
i 30

Source:   Fox, 1983.
                             189
 image: 










TABLE 3.11-6



Igniti ability

Causes fire through
friction
Oxidation
Corrosivity

a) pH
b) steel corrosion
(in./yr)
Reactivity
Yield gases, vapors
or flames when ex-
posed to water

Yields H2S or HCN
when exposed to pH
2 buffer
Reacts Explosively
(a) when subjected
to burner flame


. RCRA TESTING OF SIMULATED UNION B
OIL SHALE PLANT WASTES
Moistened
UNISULF Retorted shale Maximum Minimum
sulfur plus fines allowed allowed



No No - -
0°F 0°F


12.5 2.0
0.25




No No



No No

No No
(b) when under heated
confinement

EP Toxicity, mg/1
Arsenic
Barium
Cadmium
Lead
Mercury
Selenium
Silver

No No


<0.01 0.07 5.0
0.2 <2.7 100.0
<0.01 <0.01 1.0
<0.05 <0.05 5.0
0.002 <0.0005 0.2
<0.0005 <0.0005 1.0
<0.02 <0.02 5.0

woistened with simulated process water.
Source: Union Oil,


January 1984

190
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3.12  UNION OIL  SGR OIL SHALE RETORTING                ',

3.12.1  Retorting Operation                            !

In early 1977, Union Oil announced a process, that, when
retrofitted to a Retort B prototype unit, would further! improve
the economics of the process by utilizing the residual barbon left
on the spent shale.  This process, known as Steam-Gas Recircula-
tion  (SGR-3), [DRI, SAI & KSC; 68-03-2795; EPA-600/2-80-205a,
1980], provides  for the combustion of the residual carbon in a
separate vessel, thus producing enough hot flue gas to supply all
of the retort heat requirements.  This two-vessel SGR-3 process
produces a high  BTU (980-BTU/scf) product gas from the retort
vessel while maintaining a high thermal efficiency (83 percent) by
using the residual carbon on the spent shale in the combustor
vessel.  Following the removal of C^ plus hydrocarbons and acid
gases from the gas stream, the heating value is reduced; to approx-
imately 800 BTU/scf.  This value can be increased to more than
1,000 BTU/scf by methanation.  A flow diagram for the process is
shown in Figure  3.12-1.                                !

Because of the design of the rock pump feed mechanism, all of the
proposed Union Oil processes utilize fairly large shale: fragments
of 2 to 1/8 inches.  As in the other vertical kiln typeiprocesses,
very little attrition occurs during the retorting process, and
thus the spent shale fragments leave the retort essentially the
same size as they entered.  The spent shale from the direct-heated
Union retorts would be gray in color, having had some of the
residual carbon burned off.  The indirect-heated retorts, on the
other hand, would discharge shale still containing the residual
carbon.  The SGR-3 process employs a separate spent shale combus-
tor unit.  The spent shale from these processes, therefore, would
be light-colored, containing very little residual carbon.

The composition of the product gas from the retort largely depends
on the mode of heating.  Indirectly heated retorts like'• the SGR
will produce a high-BTU gas product whereas the product;from
direct-heated retorts will have a low BTU content because of
nitrogen dilution.                                     ;

3.12.2  Solid Wastes                                   [
                                                       i •
Nothing is available on this subject.                  ,

3.12.3  Characteristics of Solid Wastes                '-.
          ---      - ••	  -  	•""    • '      ——                [

Pertinent data are presented in Tables 3.12-1 to 3.12-10.
                               191
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        TABLE 3.12-1.
    PHYSICAL  PROPERTIES OF UNION
    SGR SPENT SHALE
                                   Decarbonized Shale
                                	Fresh	;
                                               After
                                             Compaction
                                              at 12j375
                                Initial         ft.lbs/cf
Particle Size:
% Cobble (I11 -
% Gravel (4.76
% Sand (0.074
% Silt (0.005
% Clay (-0.005
6")
mm - 1")
- 4.76 mm)
- 0.074 mm)
mm)
75
16
5
4
1
53
14;
33 ;
  Texture

  Color

  Solids Density, g/cc

  Dry Bulk Density, pcf
          Silty Gravel

             Buff

            2.69
                           68.5
   Analyses by Woodward-Clyde Consultants
   Source:  TRW, May 1977.
    TABLE 3.12-2.
PARTICLE SIZE, pH, AND ELECTRICAL
CONDUCTIVITY OF SPENT OIL SHALES
PRODUCED BY UNION SGR RETORTING I
PROCESS                         :
Process
Union decarbonized
Particles
Size
>2mm <2mm pHa
87 13 11.4
Electrical
Conductivity
(|j mhos/cm)
3
i
1
Electrical conductivity and pH were determined on ai
saturated paste extract prepared from spent shale
particles less than 2mm in size.

Source:  Schuman et al., 1976.
                         193
 image: 








TABLE 3.12-3.
CHEMICAL PROPERTIES OF UNION
SGR RETORTED SHALE
           Components
      SiO2                      39.2
      CaO                       27.3
      MgO                        8.2
      A12O3                      8.9
      Fe203                      3.8
      Na20                       3.7
      K2O                        2.7
      S03                        1.4
      P205                       0.5
      Mineral C02                3.1
      Organic C                  0.3
      Nitrogen, Kjeldahl
      Ignition loss @ 950°C      3.4
      Free Silica, quartz        2.5
      pH of slurry              12.5
       Analyses determined by heating
       sample to 950°C except for pH
       measurement.  Analyses by Union
       Research Department.  All num-
       bers except that for pH are in
       weight percent.
       Source:  Wildung & Zachara, 1980
I
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TABLE 3.12-5. WATER


QUALITY OF
SGR DECARBONIZED

1975

1976
Irrigation Spring
Total Percolate, cm 0.6
Electrical Conductivity,
jjmhos/cm 7 , 352
Salinity Hazard Very
High

Sodium Adsorption Ratio 72.5
Sodium Hazard High
pH 9.1

3.7+

9,400
Very
High

99.5
High
12.1





PERCOLATE FROM
SHALE

1976
Summer
0.1

7,770
Very
High

74.1
High
9.5



UNION



LYSIMETERS

1977
Spring
0.1

3,573
Very
High

58.5
High
9.5


1977
Summer
0.1

3,700
Very
High

60.2
High
10.6


1978
Spring
7.3

10,000
Very
High

115.6
High
11.8

1
1
1
1



1

e




i
n
Source:   Herron et  al., 1980                                                         •
                                                                                    I
                                   196
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 TABLE 3.12-6.  ANALYSIS OF SPRING SNOWMELT RUNOFF AND !PERCOLATE
                FROM UNION SGR DECARBONIZED SHALE LYSIMETER STUDY.
                APRIL 21,1976
Lysimeter number
Total runoff on percolate
(liters/plot)
EC pmhos/cm
@ 25°C
PH
Suspended solids, ppm
Dissolved solids, ppm
Settleable solids, ml/L
Na , ppm
Ca, ppm
Mg, ppm
K , ppm
Cl , ppm
S04 , ppm
CO3 , ppm
HC03 , ppm
P04, ppm
NO3, ppm
As , ppm
SAR
Runoff
4
143.8
260
7.7
8.0
152.0
0.1
10.0
13.7
15.7
3.6
17.5
44.0
0
77.6
0.7
0.5
0.005
0.43
samples
5
132.5
320
7.9
2.6
174.0
0.1
11.0
16.3
19.5
4.2
7.5
61.0
0
77.4
0.8
7.9
0.005
0.43
Percolate
4
280.1+
8,000
12.0
14.7
3,382
0.1;
1,050
19.3
2.7
170.0
37.5
271.0;
1,154.0;
236.0!
1.6:
2.5!
0.35:
i
60.4
samples
5
382.3+
10,800
12.2
11.3
3 , 922
0.1
1,480
8.6
0.0
210.0
65.0
625.0
1,065.0
487.0
0.6
11 ..4
0.31
138. .6
Source:  Herron,  et al,  1980
                             197
 image: 








                                                                  I
TABLE 3.12-7.  ANALYSIS OF RUNOFF AND PERCOLATE SAMPLES
               COLLECTED AUGUST 5, 1976 FROM UNION SGR
               DECARBONIZED SHALE LYSIMETER STUDY
1



Runoff samples
Lysimeter number
Total runoff on percolate
(liters/plot)
EC p mhos/cm
@ 25°C
pH
Suspended solids, ppm

Dissolved solids, ppm
Settleable solids, ml/L
Na , ppm
Ca , ppm
Mg, ppm
K, ppm
Cl , ppm
SO4, ppm
C03/ ppm
HC03 , ppm
N03/ ppm
P04/ ppm
As , ppm
SAR

aNo runoff.
No percolate.
Source: Herron, et al,


4
3.5

260

7.2
1,452.0

216.0
13.0
0.21
1.79
0.87
3.3
7.5
25.6
0
109.0
3.2
1.2
0.001
0.18



1980

198
5
0



_a
_a


_a
_a
_a
_a
_a
_a
_a
-a
_a
—
_a
_a
_a







Percolate
4
0

7,700

_b
_b


_b
_b
_b
_b
_b
_b
-b
_b
Jo
b

_b
-b
_b







samples
5
8.0

460

9.5
190.0

6,628.0
5.5
85.2
2.64
0
470.0
5.0
835.0
782.0
3,489.0
7.2
1.9
0.49
74.1









I



1
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1


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I

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1
1

1
1
1
 image: 








TABLE 3.12-8.  ANALYSIS OF SPRING SNOWMELT RUNOFF; AND
               PERCOLATE FROM UNION SGR DECARBONIZED
               SHALE LYSIMETER STUDY.  MARCH 30, 1977
1
^B
1




1

1



1

1



1

1
1"


1




1



Lysimeter number
Total runoff on percolate
(liters/plot)
EC p mhos/cm
@ 25°C

pH
Suspended solids, ppm
Dissolved solids, ppm
Settleable solids, ml/L
Na , ppm

Ca, ppm
Mg, ppm
K, ppm
Cl, ppm
SO4 , ppm

C03, ppm
HC03 , ppm
PO4, ppm
N03, ppm
As , ppm

SAR

aThis reading is felt to
verses dissolved solids,
678 |j mhos/cm.

Source: Herron, et al,





Runoff samples
4 5
132.5

530


6.75
2.25
346
<0.1
19.4

29.12
28.52
17.6
10.0
190

0.0
81.2
0.54
8.62
<0.001

0.62

be in error
143.8

3,500a


6.9
4.75
496
<0.1
11.8

48.25
66
10.1
10
294

0.0
91.03
0.34
17.51
<0.001

0.26

Using
this reading should


1980

199








Percolate
4 '
6.1:
|
3,150:


9.05i
67.33
2,454!
1.61
'910!

19.13
3.0
i
258
5.0J
6631

90.6
1,690
1.78
!
22.18i
0 . 16

50.9

a regress ion

samples
5
17.8

4,000


10.0
40.88
2,792
0.4
875

8.3
3.0
274
24
1,080

266
1,329
1.0
10.41
0.14

66.1

Of EC
be approximately












 image: 














1
1
TABLE 3.12-9. ANALYSIS OF RUNOFF AND PERCOLATE SAMPLES
COLLECTED AUGUST 30, 1977 FROM UNION
DECARBONIZED SHALE LYSIMETER STUDY

Lysimeter number
Total runoff on percolate
(liters/plot)
EC pmhos/cm
@ 25°C
pH
Suspended solids, ppm
Dissolved solids, ppm
Settleable solids, ml/L
Na , ppm
Ca, ppm
Mg, ppm
K, ppm

Cl , ppm
304 , ppm
C03 , ppm
HC03 , ppm
P04, ppm
N03, ppm
As , ppm
SAR

Source: Herron, et al, 1980




Runoff samples Percolate
45 4
4.5 0 0
215

7.0
2,080
158
6.3
4.8
16.41
6.21
6.0

5.0
10.9
0.0
98.45
6.56
1 . 32
< 0.001
0.87




200
SGR

samples
5
11.3
3,700

10.6
50.8
5,878
0.2
1,870
3.12
45.52
590

17.5
1,090
1,006
4,329
1.99
37.84
0.122
60.2





1
1
I



1
I
•
1

1



1

1


1

•
1
1
1
 image: 








    TABLE 3.12-10.  ANALYSIS OF SPRING SNOWMELT, RUNOFF;, AND
                    PERCOLATE FROM UNION SGR DECARBONIZED
                    SHALE LYSIMETER STUDY.  MAY 3, 1978'
1
Lysimeter number
Total runoff 'on percolate
(liters/plot)
EC |j mhos/cm
@ 25°C
pH
Suspended solids, ppm
Dissolved solids, ppm
Settleable solids, ml/L
Na , ppm
Ca, ppm
Mg, ppm
K, ppm
Cl , ppm
SO4 , ppm
CO3, ppm
HCOs , ppm
P04, ppm
N03 , ppm
As , ppm
SAR
Runoff
4
46.0
230
7.4
9.4
124
0.1
4.95
15.3
15.3
33.8
33.6
47.8
0.0
84.27
0.21
0.14
0.0
0.21
samples
5
155.2
230
8.5
3.10
140
<0.1
7.9
23.37
14.62
3.9
2.8
90.5
5.97
62.6
0.20
1.37
0.0
0.32
Percolate
4 ;
10.0 ;
7,100 ;
11.5 '
4,798 '•
l
754.9 ;
<0.1 :
1,200 i
25.5 ;
8.1 ;
380 ;
8.8 1
1,870 !
212 :
1,083 i
0.81 '
3.72 |
0.40 :
53.0
samples
5
3.6
12,900
12.5
5 , 032
549.2
<0.1
1,430
3.4
0.90
510
29.4
1,662
985
1,083
0.84
4.10
1.28
178.1

Source:  Herron, et al, 1980
                             201
 image: 








                                                                       I



 3.13   CHEVRON STB OIL SHALE RETORTING                                 •

 3.13.1  Retorting Operation                                           •

 Details  of Chevron's retorting technology have not been revealed,
 but a recent  U.S.  Patent  to  Chevron,  No.  4,199,432  entitled     •
 "Staged  Turbulent  Bed Retorting Process"  may give  some insight     •
 into the process  [DRI,  SAI  and  KSC,  68-03-2795].

 The  Staged  Turbulent  Bed  (STB)   Retort   is  a  small-particle     I
 retorting  process in which retorted  shale is burned in a separate     •
 combustor  and recycled  to  the  retort to  supply  the process heat
 requirement.   The  flow  scheme for  the core  of the  process  is     •
 shown  schematically  in  Figure 3.13-1  [Tamm et  al.,  May 1981].     |

 The environment in the  retort  section can best be described as a     n
 staged,  moving bed of particles, in  which a  portion of the parti-     •
 cles  are  "fluidized."   Solids  move  downward through  the  retort
 with  an average  velocity  of  2-5 ft/min.   Proprietary internals
 within the retort  restrict mixing  in the vertical  dimension and     •
 thereby  produce  "staging"  of  the   solids  flow.   The  "staging"     •
 gives  an   approach  to   plug   flow  for  the  solids  and  thereby
 improves the stripping  action  of the countercurrent  gas  flow and     H
 minimizes  the residence  time required  to assure  complete retort-     I
 ing.   Locally,  conditions within the bed have all the appearances
 of  fluidized state,  although the superficial gas  velocity  is far     „
 below  the  minimum fluidization  velocity of many of the particles.     I
 Rapid  local  mixing  and a high  rate of  heat transfer  keep the     *
 temperature profile in the  retort very nearly isothermal.

 The  retort can be operated  with a  stripping gas consisting  of     I
 either recycled product gas, steam,  or  an inert  gas.   The  super-
 ficial gas velocity at the  bottom of  the retort is within the range    m
 of 1-5 ft/sec.  The volumetric  flow of gas in the retort increases     I
 significantly  in  going from the bottom  to the  top because  of the
vapor  traffic added by the  pyrolysis products.

The combination of  thermal  shock experienced by the fresh shale on     •
entering the  retort,  removal of the binding kerogen,  and the tur-
bulent conditions within  the  retort causes  some breakup of the     •
shale.   The finest particles (<200 mesh)  are swept  overhead from     U
the retort with the product vapors.   Most of the elutriated parti-
cles are recovered from  the  vapor  stream before  condensation  of     «
the  oil.   The  recovered  particles, collected  by  primary  and     I
secondary  devices,  contain carbonaceous residue;  and they  are,      *
therefore,   sent to the combustor section  for recovery  of  their
fuel value.                                                            •

In the product  recovery section,  the product vapors  are condensed
in_ stages  producing  several  oil fractions  and foul water.   The     •
initial  condensation  stage has  to  be  capable of handling  some     H



                                                                       I
                             202
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                                                                        I



 solids,  as the  fines removal equipment  is never 100%  efficient.
 The noncondensable gases are either produced directly or a portion      m
 is recycled to  the retort for stripping.  With very  lean shales,      •
 some or all of  the product gas  can be used as  a  supplemental  fuel      *
 in the combustor.

 The combustion  section receives  coarse  retorted shale  withdrawn      I
 from the  bottom of  the retort and  retorted shale fines  removed
 from the product vapors.   Air injected at the bottom of  the  com-      n
 bustor both transports the shale  pneumatically  and combusts the      I
 carbonaceous  residue.  The  temperature of the solids rises rapid
 ly.  At the outlet of the  combustor,  a solids separator  splits the      _
 stream once again into  fine  and coarse  fractions.   Most of the      I
 hot,  coarse fraction is  recycled to  the retort to  provide the      •
 necessary  process  heat.  The excess  coarse shale  is  sent on to the
 heat recovery  section, from which it  eventually  discharges as net      •
 coarse spent shale.   The  fine fraction  exits  the separator  with      |
 the flue gas.   This stream  is also  sent  to the heat recovery  sec-
 tion where it  is cooled and then  separated into  a net  fine spent      m
 shale  stream  and a flue gas stream.   The SO  content of  the  flue      I
 gas  is claimed to be unusually low (<20 ppm)Because of  the scrub-
 bing action of the  shale itself.

 Nominal  operating  conditions  for the process are  summarized in      •
 Table  3.13-1.    The  fresh shale  throughput for  this  process is
 5-10  times that of most  other  retorting  processes.   The use of      •
 small  shale particles, the  excellent heat transfer conditions in      I
 the  retort,  and  the "staging" effect  in  the  retort  make the resi-
 dence  time  required   for  complete   retorting  quite   low.   The      m
 extremely  low residence time required  in  the  combustor is  a conse-      I
 quence of  the high  reactivity of the carbonaceous  residue.              •

 The  STB Retorting  Process has been  tested by Chevron Research in      •
 several  pilot  units  including  a  one-ton/day  integrated pilot      I
 plant.   In 1984 Chevron commenced testing at a 350 ton/day semi-
 works  plant in Salt Lake City in Utah.  Figure 3.12-2 is a  simpli-      «
 fied  block flow  diagram  for  the  semiworks  facility  adjacent to      •
 Chevron's  Salt  Lake refinery.   The  oil  shale  feed  for the semi-
 works  unit is obtained from  the Chevron property in Piceance basin      _.
 in Colorado.                                                            •

 3.13.2  Solid Wastes

 In  the retorting process,  the  spent  shale  produced is  a hot dry      |
 powder.  Treated process water will be used to moisten the spent
 shale.  The moistened spent shale leaving the pugmill  will  have      •
between 10 and 25%  water on  a dry basis.                                •

According  to Chevron's Final Environmental Impact Statement [BLM,
 September 1983],  wastewater generated  from  the process  plant and      9
 ancillary  facilities would  include  effluent from the  oil separ-      "
 ation  unit,  cooling tower  and boiler  blowdown,  clarifier sludge,

                                                                        I
                             204
I
 image: 








   TABLE 3.13-1.  NOMINAL PROCESS OPERATING CONDITIONS

                  FOR THE CHEVRON STB RETORT
Fresh Shale Throughput          2000-5000 Lb/hr/ft2: Retort



Retort Temperature              890-950°F
                                                   1


Retort Residence Time           2-8 Min.           •
                                                   i


Stripping Gas Velocity          1-5 Ft/Sec.



Combustor Residence Time        1-5 Sec.           !



Combustor Outlet Temperature    1100-1500°F        ;



Recycle Shale Ratio             2:1 to 5:1






Source:  Tamm et al., May 1981
                         205
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filtration backwash,  demineralizer  waste,  wash waters' from boiler
feedwater treatment,  sour  water from retort and upgrading facili-
ties, and sanitary wastewater.  All collected waters would be sent
through  the  water  treatment system  before being used  for spent
shale conditioning.                                   i

3.13.3  Characteristics of Solid Wastes               ,

The chemical and  physical  properties of the spent shale [Chevron,
May  1981]  are  presented  in Table  3.13-2.   The  information  was
generated during  process development tests  using  Anvil  Point Oil
Shale.   It  is  anticipated  that  the spent shale produced  using
shale  from  the  Chevron property will  have  similar i properties.
Calcite  and  feldspars  comprise  approximately  one-half  of  the
shale, depending  on the feed source.  The  physical  properties of
the  spent shale,   important in  the  disposal,  are primarily  a
function  of  moisture  content  though  degree of  compaction  and
curing  are   factors.    Permeability,  dry  density  and;  unconfined
compressive  strength  data  are also presented  in  the  foregoing
Table.  The  chemical and  physical  data shown are characteristic
of the material  to be disposed.  The results  of leachate  testing
conducted on spent shale samples from  the Clear  Creek  Shale  Oil
Project are presented in Table 3.13.3.                '.
                             207
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TABLE 3.13-3. CHEVRON STB SPE

,
Sulfur Species
H?S (Hydrogen Sulfide)
Thiol
Sulfate
Thiosulfate
CN (Cyanide)
Nitrogen
NH3 (Nitrate)
Metals
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Copper
Iron
Lead
. tfercury
Nickel
Potassium
Sodium
Seilenium
Silver
Thallium
Zinc
General Water Quality
BOD (Biochemical Oxygen demand)
COD (Chemical Oxygen demand)
TDS (Total dissolved solids)
TSS (Total suspended solids)
O and G (oil and grasses)
Chloride
Calcium/as CaC03
Magnesium/as MgC03
Hardness
CO2 (Carbon dioxide)
pH
Organics
TOG (Total organic carbon)
Phenol

aA=E'irst 1280 ml collected (1 pore
bB=Third 1280 ml
°ND-Not detected, below detection
Source: BLM, September 1983
%
NT SHALE LEACH TEST

Run 45 Aa

3.5
30
3,250
140
1

415

0.03
0.03
0.2
0.01
3.2
0.03
0.02
0.05
0.1
0.12
1 ppb
0.08
NA
1,700
0.03
0.02
0.1
0.14

500
1,100
10,900
14
12
17
85/212
0.06/0.24
212
26
10.9

660
18

volume )

limits

RESULTS

Run 45 Bb
:
1.1
4.2
1,133
21
4.5

37

0.03
0.01
0.3
0.01
1.9
0.03
0.02
0.03
0.1
0.05
1 ppb
0.04
NA
84
0.02
0.01
0.1
0.01

80
120
4,120
15
12
5.5
180/450
0 . 12/048
450
6
10.8

230






209
 image: 








3.14  ALLIS-CHALMERS OIL SHALE RETORTING

3.14.1  Roller Grate Retorting Operation
I
I
I
The Allis-Chalmers  approach [Faulkner et al, 1983] to the retort-
ing of oil shale is shown  in Figure  3.14-1.   This is only one of      H
many  possible flowsheets that may be used  depending on the shale      I
grade  and type.  Raw  shale with a  size distribution of 1-3/4" x
1/4"  enters the Preheat  Zone  after  a  minimum amount of crushing
and  screening.  Minus 1/4"  material  generated in  the crushing      •
circuit  is agglomerated  and  fed on  top  of the crushed material.      •
The  shale  is conveyed  by  a  series  of closely  spaced,  slotted
rollers  rotating in  the same direction.   Beds up  to  three feet      •
deep are used.                                                          H

In  the Preheating  Zone  the shale is heated by the off-gas from      «
the  adjacent  first  retorting zone.   In addition  to heating the      •
shale,  the  energy  in the gas  is  recovered  and  the  light oils      B
contained  in  the gas stream are condensed.

After  preheating,  the  shale is  conveyed to  the  first retorting      B
zone where  recycled noncondensible retort gases with  a temperature
in  the range  of 900-1000°F are  induced down through the  bed of      a
shale  and through the slotted  rollers.  In  this  zone  and in the      |
Preheat  Zone,  the oils  driven  off and  condensed  will  be lighter
and more heavily hydrogenated  than  the oils  driven off  in the      _
following zone.                                                         u

Upon  exiting  Retorting   I,  the   partially  retorted  shale  enters
the second retorting zone  where  a 1200°F on-gas of recycled non-      H
condensible  retort  gases is used to complete  the  retorting.   In      H
this  zone,  the  heavier  and less  highly  hydrogenated oils  are
evolved.  At  the exit of the zone, the gases are directed to Heat      a
Exchanger  I where the heat is  recovered and the  oils  condensed.      H

When retorting is complete, the  shale is conveyed through a seal-
ing  zone  to  the  Combustion Zone.   In  the sealing zone,  solid      •
rollers are used to help the underbed windboxes to prevent mixing      •
of the two  atmospheres.  The most difficult area to seal is at the
top of the bed.   This is accomplished by using hinged drag plates      •
at the entrance and  exit of the Sealing Zone and by maintaining      |
equal  overbed pressures.   In  the combustion zone,  the residual
carbon  and hydrogen   are  combusted  with ambient  air to  recover      g
energy for driving  the retorting process.   Contrary to  the pro-      •
ceeding three zones,   air  flows  up through  the  rollers  and exits      *
from the  top  of the bed.   By doing  this, the mechanical elements
are not  exposed to the  hot off-gas  and a  low temperature  fan is      fl
used to blow ambient air through the bed.                               I

After  removal of the  thermal energy in the  Combustion Zone,  the      n
shale proceeds to the Cooling I  Zone where the shale is cooled and      g
its sensible  heat is  recovered  by an  ambient  air stream.   Final
                             210
I

I
 image: 








 cooling  of  the  shale  to  an  acceptable discharge  temperature is
 performed in the Cooling II Zone also with ambient air.

 The hot  off-gas streams from  the  Combustion and  Codling I Zones
 are  combined and  sent  to Heat Exchanger  II where  the heat is
 transferred  to  the recycled  retort gases  used in the  retorting
 zones.  Depending on the grade of shale and its carbonate content;
 a portion of the retort gases generated may need  to [be  combusted
 to achieve adequate heat transfer in the second heat exchanger.  A
 portion of the reheated retort gases coming from HeatiExchanger II
 are sent directly to Retorting II.   The remainder is'blended with
 the reheated  retort  gases  from  Heat Exchanger I and1  are used as
 the on-gas for Retorting I.                          I

 Commercial Roller Grate  Retort modules have been designed  with a
 raw shale  capacity of  20,000 TPD  which results  in; the need of
 only three such  modules  in parallel to produce 43,000 BPD  of oil
 from a 30 GPT shale.   Such a  device would  have  an active width of
 15 teet and  a working length of 500  feet.

 The size  of  the  raw feed shale is a  trade-off between !the benefits
 of a  small  shale  size and costs associated  with obtaining  that
 size and disposing of the  fine  shale.   The Allis-Chalmers process
 uses the largest size  that can be efficiently processed.   Under-
 size material  that results  from the  crushing  operation can  be
 agglomerated into flakes and fed directly to the  top ;of  the shale
 bed.   Tests  have confirmed that  these  agglomerates maintain their
 integrity throughout the entire retorting and combustion process.

 The  rollers  used to  convey  the bed  of  shale  give  it  relative
 motion along  with  causing a  natural  size  segregatidn to  occur
 The  relative motion keeps exposing fresh shale surface and  allows
 tne  theoretical  heat  transfer potential  to be  achieved.  Fines
 carried in with the feed quickly migrate to the bottoh of the  bed
 and  fall  into  the  underbed windbox.   This prevents  pockets  of
 fines  from forming and causing gas channeling.  Natural size segra-
 tion puts the  larger particles on top and the smaller on  the bottom
 o±  the bed.   Thus .the  downdraft  retorting  gases  give the largest
 thermal  driving  force  to  the  particles that  need ifc the  most.

 For  any  process to  reach  its  maximum efficiency, the   residual
 carbon  and hydrogen in the retorted  shale  must be utilized.  The
 energy  contained  in  these  components  amounts  to 10-15% of the
 energy  in the raw  shale.   In  the Allis-Chalmers  process ambJent
 air  alone is  used to  combust the  residual carbon  and hydrogen.
The  excess  air to the  Combustion zone  along  with the moderating
effect  of the calcination  reaction  prevent unacceptable  tempera-
tures  from being reached.   In  the case of a very high! grade shale
with a higher level of residual  carbon and  hydrogen, ^a tempering
gas  such  as  recycled heat exchanger  II  off-gas can be  used.  The
retorting gases used in the Roller Grate Retorting Process are the
recycled  gases generated from  the  decomposition of the  kerogen.
                             211
 image: 








Tests have shown that the fully combusted and cooled shale exiting
the Allis-Chalmers  Process  still maintains  its  integrity.   Fines
generated in  processing represent a  small  fraction of  the  total
feed.   Residual  carbon  in  the combusted shale  is less  than  1%.

A Roller  Grate Process  Development  Unit was designed  and  built.
This unit is  capable of processing charge weights up to 1500  Ibs
with bed  depth up  to  21 inches.  It is designed  to  simulate  the
process  from  raw  shale  to  fully  combusted  spent  shale.    A
schematic of the entire system is shown in Figure 3.14-2.

Table 3.14-1  depicts  results  for a typical test starting with raw
shale continuing through retorting  and combustion and ending with
fully processed  and cooled spent shale.  During a test less than
0.2% of the raw shale  was  carried out of the retort as dust.   A
relatively  small  1.1%  of the  shale reported to  the  windbox  as
fines.  Size  analysis comparison between the raw and  fully com-
busted  shale  showed that there  was very little  size  degradation
during  processing.   Agglomerated  fines  also  maintained  their
integrity after retorting and combustion.

It  should,  however, be  emphasized  that studies  by Allis-Chalmers
have been limited  to process  development unit  (PDU)  bench scale,
batch equipment only.   The  system has not been tested in any con-
tinuous retorts;  the 500 TPD  and 60,000 TPD units  have not been
built and operated.  Also no  demonstration  units  have  been built
or operated.

3.14.2  Solid Wastes

There is no information  on this subject.

3.14.3  Characteristics  of Solid Wastes

There is no information  on this subject.
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         TABLE 3.14-1.
                Basis:
ALLIS-CHALMERS WESTERN SHALE TESTS
100 kg dry raw shale          i
                                 Total
                   Carbon
       Sulfur
IN
  Dry raw shale
            100.0
11.7
1.33
OUT
Residual solids
Windbox fines
Cyclone fines
Dry gas produced
Water produced
Oil produced
Co2 calcined in retorting
C02 calcined in combustion
Carbon combusted
Sulfur combusted
TOTAL

74.2
1.1
0.2
2.1
1.5
9.9
1.2
8.0
1.8
0.01
100.0

0.5
_
-
1.1
-
8.3
-
-
1.8
—
11.7

0.90
—
-
0.35
-
0.10
-
-
-
0.01
1.33

 Oil produced:   100% of Fischer assay.
""organic removal:   97% of initial kerogen
 Source:  Faulkner et al.,  1983
                             215
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 3.15  DRAVO OIL SHALE RETORTING

 3.15.1  Retorting Operation

 In  the _ Dravo  Retorting Process  [Forbes  & Kinsey,  1981]  the raw
 shale is retorted  on  a traveling  grate  (Figure  3.15-1).   The
 retorting section is divided into three parts:  an initial heat-up
 zone; the burning of residual carbon; and  initial cooling of re-
 torted shale.   The  shale is then  cooled  for disposal.  Off-gases
 from the retorting  and cooling sections,  after  cooling  and oil
 recovery, are  reused in the  process  as heat carriers.  Excess, or
 by-product gas, is bled from the system as necessary.
                       Dravo Traveling Grate Oil Shale Retorting Process
              Figure  3.15-1.   Dravo  Retorting Process
                              Source:   Forbes & Kinsey,  1981


During  retorting there  is  no relative movement between  particles
where  abrasion could degrade the particles  and  disrupt the  pro-
cess .  _ Free  water can be removed from the  shale concurrently  with
retorting  or in  a  separate zone ahead of the retorting zone,  if
necessary.

The  heating  value and  quantity of byproduct gas  are  principally
determined by the  amount and  purity of oxygen  added, the effi-
ciency  of  processing,  and the  amount of kerogen  in the shale.  A
heating value of 100-110 BTU/SCF is  indicated in this  process for
28  GPT  Western  oil shale.    The  ultimate  use  of  air  or  oxy-
gen would depend  on  an economic evaluation.

The weight of spent  shale for a 28 GPT Colorado shale would be 83%
of the shale  charged to  the grate.  Less than 10% of the carbonate
is  calcined   and  about   half  the  carbon is  burned  out.  Disposal
problems are  not  unique.
                             216
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 The  technical feasibility  of agglomerating  oil shale  fines and
 recycling  solids  separated  from the  oil was  verified  by Dravo
 ^em Iatte5   Processing   would  eliminate  a  difficult  disposal
 pioblem.  One would expect agglomeration to be used, however, only
 if economically viable for a given property.

 Dravo's Shale  Oil  Pilot Plant is located  in  Cleveland,  Ohio.  It
 was originally constructed in 1974,  and operated for several runs
 snrt  i? i   n- ,revamPed to conform with  the  latest Dravo techno] ogy
 SSiiar^JfJ?11,reclove1ry methods.   It is a circular grate havincf 88
 square feet of actual grate area.  It can process 300 tons-per-day
 °!  L11  S£?Ie^  -The  pllot Plant flowsheet (Figure  3Jl5-2)  illu-
 strates the  basic  flow  scheme  of  this  facility.   Raw  shale  is
 crushed and screened.   Belt conveyors  move  the crushed  shale  to
 the traveling  grate  over a  weigh belt scale  for  material  weiaht

 hoodrdl^g-' H The +-Shale ,bed travels under the  first  retorting zone
 k°°d'  .   c   contains hot,  oxygen-free, process  gas.! The  first
 retorting zone covers several of the machine's 12 windBoxes.

 Th! <ffCOnd arld  ??ird retorting zones  cover additional windboxes.
 The second  retorting  zone is  fed by  oxygen-enriched,  recycled pro^
 cess  gas.   The third retorting zone is fed with oxygen-free  pro-
 £™lgaS'   he a\r  th.at ls in:iected  into the second retorting zone
 hoods  causes  combustion  of shale carbon  to  provide the  heat for
 further  retorting.   At the discharge end of the retort zone  160%
 °£ ^e °x^ ha^  bten  extracted  from the shale, approximately 50%
 Sh.t   vcarbon  has been burned,  and a significant percentage of the
 shale  has_ been  cooled.    The cooling  zone consists o;f  the  last
 several  windboxes  which  has  been fed with cool, oxygen-free  pro-
 ?S  T???'*.      Sha^S  1S  then conveved  ^ the  discharge area where
 the  pallets are  tipped  and  the shale  falls  into  a water-sealed
 discharge hopper   A  belt conveys the  shale to a refuse pile  for
 aiS^i^J^SpOSa1---,  ThS  ret°rt gases  are  collected in windboxes
 and ducted to  an oil  recovery system.

 3.15.2  Solid Wastes                                    '

There is no information on the subject.                 !

3.15.3  Characteristics of Solid Wastes                 i

There is no information on the subject.                 |
                             217
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OIL SHALE
FEED CHUTE BLEED
 TO INCINERATOR
     SHALE OIL
   STORAGE TANK
  TO INCINERATOR
(INERT GAS GENERATOR)
                                    ELECTROSTATIC
                                    PHECIPlTATORS
      Figure  3.15-2.   Dravo Pilot Plant Flowsheet Schematic
              Source:   Forbes  & Kinsey,  1981
                               218
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                              SECTION 4                ;

                 ENVIRONMENTAL CONTROL TECHNOLOGIES


 4.1  ENVIRONMENTAL IMPACTS

 4.1.1  Introduction                                   i

 An oil shale operation will  result in significant land'disturbance
 on and  near the  development site  [DRI,  SAI  & KSC;  68-03-27951.
 Land  will be required  for access  to the site  for mining,  process-
 ing facilities, and  for  waste disposal, all of which will  perma-
 nently modify the surrounding terrain  and influence the ecosystem
 by causing changes  in the vegetation and habitat.   Local aesthe-
 tics  will also  be  affected.                            ;

 The most prominent impacts will probably  result  from the  disposal
 of the shale wastes.   Unlike potential  impacts  on  air and water
 systems,  the  solid waste  impacts will  linger long  after a mine has
 been  depleted and the  shale processing  facility  is closed down
 For this  reason,  the measures taken  for mitigating  the impacts of
 solid waste  disposal must withstand a  minimum test  of.time, with-
 out the possibility  of  a  breakdown.                    I

 One factor of paramount  importance in  the  disposal o;f the solid
 wastes is  the surface and groundwater regime of the  site.  While a
 waste  landfill should blend in cosmetically with the  surroundings,
 so_t]?a'!:  lts  existence can go  practically  undetected, it should be
 sufficiently  isolated  from  the  surrounding  strata s|o  that  the
 hydro-logic  environment is protected.    Other  factors ;influencing
 the waste disposal and land disturbance impacts are  the scale and
 duration  of  the  oil  shale operation, and  the mining  and retorting
 technologies used.                                     '
                                                       |

 The surface  and subsurface impacts will vary depending  upon  the
 waste disposal approach used.  Available disposal methqds are can-
 yon or valley fill,  surface  landfill,   open pit  backfill,  under-
 ground mine  backfill  and least likely, a commercial i market  for
waste utilization.  Selection of any of these approaches,  or their
 combination,  is  largely dependent  on  the site-specific features
mining method used,  and  the  properties  of  the  processed  shale
 (retorting method used).                               '
                             219
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                                                                       I


                                                                       1
4.1.2  Raw Shale Mining and Handling

A substantial amount  of raw shale would need to be mined and pro-     •
cessed to  produce oil.  This  is primarily because  the oil shale     H
can be considered as  a low-grade ore.  A Mahogany Zone oil shale
averaging 26 gal/ton  contains  approximately 17 percent kerpgen by     «
weight,  of which  about 75 percent can  be  converted to  oil (-13     ||
percent  of  the  raw shale  weight).   An oil  shale plant producing
66,700 bbl/day  of crude shale oil from the  26 gal/ton shale will
need to  process  70,000 ton/day of raw shale  as  a minimum (at 100     •
percent  of  Fischer assay yield).  This is a large quantity by the     m
existing standards of the mining  industry.
                                                                       I
The  shale  handling will  include blasting,  conveying, stockpiling     Hi
and  several stages of crushing  to prepare  the  feed  for the re-
torts.   The particulate control operations  will produce raw shale     „
fines which cannot be retorted by many of the retorting processes     •
therefore, they must be disposed.  The preheat system of the TOSCO
II  process  produces   a  raw  shale  sludge  which  also  must  be
discarded.  As much as  10 percent of the mined out shale  (or 7,000     ffi
ton/day  for 66,700 bbl/day production) may  be disposed of in the     «
case of  Paraho, while  the raw  shale waste for  the TOSCO II process
may  range  from  1.5 to  2 percent  of the  run-off-mine shale (or     ffi
1,000  to 1,400  ton/day).  When compared with the  amount  of the     ||
processed  shale  (e.g.,  80 percent  of the  raw  shale  weight,  or
56,000 ton/day),  the  raw shale  quantities seem insignificant, but      „
they will increase the carbon  content of the waste piles.  For the      •
Paraho  direct-heated,  processed shale,  the  carbon  content will      ™
change from an  initial 2 percent to approximately 3 percent, or  a
50 percent increase in the amount of carbon.  The impact on TOSCO      fU
II  processed shale  is  less  significant, because  of its already      &
high   carbon  content.    This  increase  in  the  carbon   value,
nonetheless,  increases a potential for volatiles  release from the      m
waste  pile,  in  the event that self-heating  (autooxidation)  occurs      g
within the pile.  The physico-chemical impact  of mixing the raw
and processed shales  is unknown.  There  could be  problems with the
waste  pile stability or  increased  permeability, hence  leaching.      •

Several  conceptual measures  are available  for mitigating the im-
pact of  raw shale disposal.   The raw  shale  can be disposed of sep-      •
arately  from other wastes.   This approach  can  have its own pro-      H
blems  as additinal maintenance and monitoring may be required, but
they should be easily manageable due  to the much smaller size of      ..
the  raw shale disposal pile.   It would also allow future recovery      ||
of the resource.   The resource recovery simultaneous with the pro-
cessing, however,  may be a preferred approach, because it will not      •
require  the additional handling  of the  raw shale.   Several  alter-      «
natives  can be pursued  and developed  regarding  the  utilization of      m
the  shale fines.  The  fines  can be  briquetted into  larger  pieces,
then processed by the same retorting technology.   Another  option      •
is to have a  small  fines handling retort  on the  site.   Current      §
thinking by some  oil shale  developers  is  to burn the fines in  a

                                                                        1


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 fluidized bed or lift pipe and utilize the energy to provide pro-
 cess  heat and steam.  The process  fuels saved by this Approach can
 be  put to better use  or  sold  commercially.

 4.1.3  Processed Shale Handling and Disposal          ;

 The processed shale will be the major waste produced by oil shale
 processing;  therefore,   its  disposal  will be of  primary concern.
 The vast quantities  of  the processed  shale  produced may make its
 safe  handling and disposal the greatest environmental issue of oil
 shale processing.    The  environmental  repercussions can  be  long
 lasting;  therefore,  utmost  care should be taken before implement-
 ing any long-term plans.   To the extent  possible,  the processed
 shale disposal  should  occur in  such a  manner as  to  return the
 disturbed land to its original  state of  landscape,  use and bio-
 logical productivity.  This would  require proper handling and dis-
 posal practices, protection of air and water  quality and surface
 reclamation.                                         ' \

 The physical  and chemical properties  of  the processed shale  will
 be  the determining factors in the selection of disposal and rec-
 lamation  approaches.  Every  retorting method produces a processed
 shale that is unique in quality,  and every development site has
 features  not  found  elsewhere;  therefore,  their combination should
 be  analyzed  on  an  individual basis.   The physical  and chemical
 characteristics  of  the  processed shale  are  determined by  the
 source  of the  raw  shale,   its  particle  size  after  crushing  and
 retorting,  the  retorting  parameters, and most importantly,  the
 temperature of retorting.

 There are primarily two types of processed shale—carbonaceous and
 burned  (decarbonized).  Carbonaceous processed shales are produced
 by  indirect  retorting  in  which   residual  coke on  the  retorted
 material  is  not incinerated.  Examples of this type of retorting
 are the TOSCO II and Union B processes.   Burned  shales originate
 either  from  direct-heated  processes,  such as Paraho and Modified
 In  Situ (MIS),   in which the air  is  introduced in the  retort  to
 cause combustion of'the  residual  carbon,  or from combination-mode
processes, such  as,  Lurgi  Superior and Union C, in  which  the  re-
 torting primarily  occurs in  the  indirect-mode, but  the  resid.ual
 coke  on the  processed shale  is  incinerated in a  separate stage.

The carbonaceous processed  shales have usually been subjected  to
low enough temperatures  (980°F)  so that  significant 'calcination
and other mineral transformations do not  occur.   These  type  of
shales  normally yield  less  water soluble  material than  burned
shales but have poor cementation  properties which result in  in-
creased water permeability,  hence leaching.   The buirned  shales
 (1290-1830°F),   indicate  considerable  calcination   and  mineral
transformation.  As   a   result,  they  behave more  like  Portland
cement and thus form an impermeable mass upon wetting and setting.
                             221
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                                                                       I
                                                                       1
Once penetrated, however,  usually more water soluble material may     **
be  leached out  than can  be  leached  from  carbonaceous  processed
shales .                                                                I

The particle size, or the texture of the processed shale, also has
significant impact  on the physical properties.   The  TOSCO II and     «
Lurgi processes  use finely crushed raw shale  as  the  retort feed.     |f
In  the  former process,  the shale is  further  divided due  to the
ball-milling  action in  the retort.    Some  disintegration  of the
Lurgi processed shale occurs in the lift pipe and recycle loop. As     •
a  result,  both  of  these  processes  produce an even  finer,  silty     w
processed  shale.   Although better  compaction,   cementation,  and
lower  permeability  are  obtained with  the   fine  material,  the     •
potential  for  erosion due to wind and run-off is increased.  The     f|
Union B,  Superior,  and  Paraho  processes  use  rather  coarse shale
for retorting.  Accordingly, the processed shale also has a coarse     »
texture. While resistant to erosion,  the  coarse material does not     •
have good cementation properties and water permeability is higher.     m
The characteristics for some of  these processed  shales  have been
discussed in Section 3 .                                                •

4.2  DISPOSAL ALTERNATIVES

The mining and  processing of  oil  shale actually  results  in an     f
increase in the  volume  of the shale.  In-place density of the raw
shale is approximately  2.16 g/cm3,  but the processed shale can be     _
compacted to only about 1.6 g/cm3 by practical means.  Even after     •
losing  about  20 percent  of  the  original  weight,   which  is  a     ™
reasonable assumption, the shale after retorting will occupy about
10 to 15 percent more volume than it originally occupied.  This is     tf
an important factor when considering different approaches for the     fli
processed shale disposal.

Processed  shale  moisturizing will be an essential  ingredient in     •
disposing  of  the processed shale.   It will serve  numerous func-
tions.  The processed shale will emerge  from most  retorts at an
elevated temperature;  therefore,  it will  require  cooling and/or     ffi
moisturizing prior  to  handling and  disposal.   Transportation of     •
the processed  shale to  the disposal  area  will  involve  extensive
materials  handling  and  transfers which are potential sources of     ffi
airborne   particulates .    The   particulate   emissions    can  be     p
minimized,  by  moisturizing and using covered  transport.  Perhaps
the most  significant  advantage of  moisturizing  is  in  obtaining     «
proper  compaction,  and  cementing  reaction,  which in turn will al-     •
low disposal  of  a  maximum  quantity  of  the  material in  a given     **
space  and will  provide  greater  stability  to a waste  landfill.

Several alternatives  are available for the disposal  of  the shale     •
processing wastes.   The  mining and  retorting methods used, geo-
graphy of the disposal site, and the surface and subsurface hydro-     •
logy  of  the   area  will  dictate the selection  of  the disposal     |j
approach (es) .
                             222
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 Surface landfill—Disposal  in  a valley  or canyon near  the  plant
 site may  be  the preferred approach by many  oil  shale developers.
 This selection  is influenced  by the  rugged terrain i of the  oil
 shale areas  in  Colorado and Utah.  Usually,  large  valleys  and/or
 canyons are  available  on the development  sites  to  accomodate  the
 wastes  generated throughout the  operational  life of the projects.

 With proper reclamation the landfill  can be blended into the sur-
 rounding terrain so that it can go unnoticed.  The landfill  can be
 built as deep as the valley or canyon so that the bulk of the  ma-
 terial  is  protected from  the  weather.   Additionally,1 this  would
 reduce  the surface  area that would need to be reclaimed or revege-
 tated.   Water contamination due to run-on and run-off,land mechan-
 ical _ failure  due  to  mass  movement  and slippage  are  some adverse
 possibilities in this type of landfill.

 To avoid  or  reduce the mechanical instability,  the  face of  the
 pile should be built at an angle well  below the  internal angle of
 friction.   The laboratory data for most  processed shale  would  in-
 dicate  that a waste pile with  a  2:1 slope (2 units  horizontal  for
 every unit vertically,  or  approximately  a 27° angle)  would be  me-
 chanically stable,  but  potential operational safety, lerosion  and
 revegetation  problems  suggest that the slope should be no steeper
 than 3:1  and  possibly 4:1.                             ;

 If the  disposal  area is flat,  then  the landfill  would' need to  be
 built above the surface.   This type of waste pile will not blend
 into  the surrounding environment and  will be visible from a dis-
 tance.   The run-on and run-off problems  would be  limited and per-
 haps, easily manageable.   The  pile-up operations may be  somewhat
 difficult  when  compared with  the valley fill operations.  Also,
 exposure to wind and water  may  result in  excessive erosion.

 Solid  waste  management employs  several  integrated  controls  and
 practices.   Techniques   for controlling  erosion  due  t!o  wind  and
 water, controlling  natural water contamination due to xun-off  and
 leachate,  controlling permeability through the waste pile, run-on
 and  run-off diversion,  leachate collection, monitoring', revegeta-
 tion, etc., are employed  to mitigate  the  adverse impacts of  the
 solid waste disposal.                                  \

 The processed  shale and other processing wastes, when disposed  of
 in  a surface landfill,   will  be  exposed  to rain,  snow;,  and wind.
 These natural  forces will  disturb or erode the waste particles  on
 the surface.   Upon  disturbance,  these  particles may either become
 airborne  or may  be carried with  the run-off.   While a direct  im-
pingement of  the wind  and  water  on the waste pile is unavoidable,
 the  erosion can be minimized  by proper  sloping  and Compaction,
 surface stabilization and  vegetation.   Surface stabilization con-
 sists of the  application of water or chemical spray, oir the addi-
tion of emulsified asphalt or limestone.  These techniques help in
binding particles  together and in hardening  the  surface, thereby
minimizing erosion.                                     ;
                             223
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                                                                       I
Depending upon  the surface permeability,  the  impinged water will     •*
run off the pile, infiltrate the pile, or both.  The water can in-
filtrate the waste pile by permeation through the surface and/or by    •
channeling through cracks  and other artifacts.  In such an event,     H
the potential of leaching the water soluble material from the waste
is greatly increased.   In  the case of more permeable,  coarse pro-     «
cessed shales,  some  fines can  be added to  fill  the void spaces,     ||
thereby reducing the water permeability.   Creating an impervious
cover on  the surface of  the  waste pile using a processed shale/     ^
soil-cement  mixture  can  also  reduce  the  water  permeability.     H
Several feet of plant growth medium. would then  have to be placed     *
on top of the cover in order to vegetate the pile.  Low precipita-
tion  and  high evaporation rates  in the semi-arid  oil shale area     Bj
help to minimize the potential of leaching.                            I

Water flow  diversion and  collection  structures  would  greatly re-     »
duce the erosion and leaching potential.  The waste piles would be     M
built in benches, perhaps 50 ft. high.  Each bench can then be back-   m
sloped into  a drainage system at the base of each bench.  The run-
off from a section of the bench would be collected by the drainage     •
system rather than letting the run-off  flow onto the  next bench.     W

Similar collection and diversion systems  can  be built around the     as
waste pile at the junction of the pile and the surrounding strata,     J|
to divert any run-on,  thus preventing its contact with the waste.

Catchment basins at the bottom and perhaps above the landfill, are      fl
practically  essential for any  surface landfill.   While  the pile      •
impermeability is preferred in order to reduce the leachate poten-
tial, it will increase the run-off potential.   The uncontaminated      m
run-on can be collected in the catchment pond above the pile, re-      H
ducing the quantity  of water to run off the pile.  This uncontam-
inated  water  can be  diverted around  the  landfill into natural      n
drainage.                                                               f§

The catchment pond at the base of  the  pile  will collect the con-      &
taminated run-off.   The  area of this basin  should be  large enough      •
so that  the  average  evaporation  rate is  higher than  the average      •
in-flow rate and be  designed with a  capacity for containing the
run-off from major (100 year)  storms.   The  basin should be lined      •
with  impervious  material to prevent infiltration.                       9

In the  event of excess  water collection  in the catchment basin,      »
some  mitigating  measures  can  be  taken.    During  the processing      •
operations,   the necessary   amount  of  collected  water  can  be      ^
treated to  meet the  discharge or underground injection standards
and  disposed of accordingly.   Since  most of  the contaminants in      H
the  collected water  would have  originated from  the  waste pile,      •
the excess water can be reused  for moisturizing the process wastes
and for dust suppression at the disposal site.  These  reuse options     m
may reduce the  overall water  consumption by  the plant.                  f|



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 Monitoring  the  changes  in the  geologic  conditions of  the area
 groundwater quality, waste properties, etc., should be an integral
 part  of  the overall  solid  waste  management.   Any! significant
 change in these indicators may dictate a change in disposal strat-
 egy,  or  replacement/repair  in  the  built-in  structures,  etc
 Thermocouples can be installed in the pile to monitor self-heating
 processes.  Volatile components  can  also  be monitored for any in-
 dications of  self-heating in the  pile.   A sudden  degradation  of
 groundwater quality  may  indicate breakthrough of the ileachate  or
 run-off.  A preventive cure  may not be  possible  for all  of  the
 causes.   However,  retrofit measures  can be taken in some  case  to
 reduce further degradation or hazard.                 •
                                                       i
 Open pit backfill—This method of disposal may be viewed as a type
 of surface landfill.  As  a prerequisite,  the mining  operation must
 have been performed by open pit mining to allow  this  type  of dis-
 posal.   This mining allows  more  resource  recovery than the under-
 ground methods,  but additional handling of the overburden and sub-
 ore is also  necessary.                                 '

 The logistics of simultaneous  mining and backfilling  operations
 require  that the  mine  be  developed  for  20-30 years at  a  commer-
 cial scale  rate  (100,000  ton/day)  before backfilling can com-
 mence.   The  overburden,  subbre,  and processing  wastes  generated
 during these years must be  temporarily stored or permanently dis-
 posed  somewhere  else so  that  the full resource can be  developed
 Even after  all  the backfilling  has been done, some off-site dis-
 posal may be necessary because the  volume  of the  backfill material
 W1Z *>e  greater  than  the volume being created  by  the mining.  With-
 out additional off-site disposal, the backfilling operations will
 catch up  with and  inhibit  the  mining  operations.       ',
                                                       I
 After the project shutdown some waste from  the off-tract' disposal
 can be  returned to  the mine,  but  approximately  20-30' percent of
 the total mined  out volume would need to be stored or 'disposed of
 permanently  outside_the pit.   By  complete backfilling, 'the  land can
 be  brought back  to its original contour.   If the pit is; backfilled
 to  a level surface,  a depression may  later develop due to  compac-
 tion and settling, allowing water  collection and possible infil-
 tration.    Hence  it may be desirable  to pile  the wast^ above the
 existing  terrain.   However,  the surface  reclamation  and  aesthe-
 tics,  in this case,  may  be of  inferior quality compared  to the
 leveled backfill.                                      i

 It  is likely that not all of the controls necessary fojr a surface
 landfill  may be  required  for  the open pit backfill.   The erosion
potential will be  greatly reduced,  because a bulk of the material
will be unexposed  to  the  weather elements.  Certainly,: the catch-
ment ponds will  not be required.  Use of  extensive  diversion and
collection systems  may  be  discontinued if original  drainage pat-
terns can be restored.                                 !
                             225
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                                                                       I



One potential  problem of the  open pit backfill  could be ground-     *
water contamination.   If  the  pit intersects any existing aquifer,
the waste will be placed in the course of the aquifer.  After mix-     •
ing when  the aquifer  dewatering  is discontinued, the  water will     V
penetrate the waste mass and eventually saturate it.

Underground mine backfill—Return  of the processed  shale  to  the     |
underground  mine  is an attractive disposal approach.   Several of
the problems associated with  the exposed (surface) landfills will
be nonexistent in the underground  disposal.   Since the waste would     •
be  protected from  the weather,  erosion potential  is diminished.     m
Surface reclamation and vegetation would be reduced.  Most impor-
tantly, the  danger of mine  subsidence would be  greatly reduced.     •

However, the logistics of simultaneous mining and backfilling oper-
ations  could be  complex  and may  require  substantial aboveground     —
disposal  capacity.   Furthermore,  due to volume  expansion  on re-     •
torting, not all  of the processed  shale can be accomodated under-
ground  using practical compaction machinery.   Total accomodation
of  the  waste may be achieved if it is compacted in excess of 1.84     •
g/cm3.   While  this magnitude of  compactive  effort  is attainable     V
aboveground  with very large,  heavy  equipment, operation of such
equipment would be  very difficult  in the underground mine.             if

Several underground backfilling methods are available, but none of
these  have been tested on a  large scale.   Slurry backfilling via
pipelines  is practical for fine  processed  shale  disposal but not      •
suitable  for  the  coarse materials.   This  method would have the      •»
disadvantages  of  adding water enhancing groundwater contamination,
and would require excess water collection  systems.  Other methods     • V
involve transportation, either by  conveyors or by trucks, followed      ffl
by  compaction using standard machinery.   Pneumatic transport is
also  a  possibility.  A  combination  of these  methods, perhaps,      »
would  yield  the best  results, but realistically, not more  than 60      |y
percent of the processed shale  can be returned to the mine.  Re-
lease  of  volatiles may  create  a  worker safety  and fire  hazard.

In  situ retort abandonment—Even though the in situ  retorting pro-      P
cesses  do not involve disposal of the processed  shale  per  se, the
retorted  mass  underground represents  the shale waste  that  must be      H
attended.   Perhaps one can  consider  the spent  retorts  as  equiv-      f|
alent  to  the  backfilled underground mine.   Some  differences do
exist,  however.   The groundwater seepage  in an underground  mine is      -
detectable and manageable before backfilling.   In the case of an      H
in  situ retort,  the problem, if  existent, must be taken  care of      •*
after  the retort is spent.  The  size and placement of the material
in  backfilling  is  controllable,  while  the  same is not possible      •
with the  in  situ retorts.                                              •

Of  greatest concern in the abandonment  of  the in situ retorts may      n
be  the  groundwater infiltration,  heat retained  in the  retorted      ||



                                                                        1
226
                                                                         I
 image: 








 mass,  and air leakage in  the  retort causing a potential  for  com-
 fai  tv\?aha^?°??e Average- temperature in  a  spent retort may Se
 fare £nig  <532 *)•  .Some retorting and/or  softening of  the  pil-
 lars, will occur  reducing  their structural strength.   Due to  the
 ?u?ldh^LPreSSUre mai?tained in the  retorts,  air  inflow may occur?
 Furthermore, some partially retorted shale pieces may lexis t in the

 bus?ion in           ™ °f
 The  spent retorts  can be  grouted by injecting  cement slurry at
 high pressure  in  the retort.  While this approach may not prevent
 the  groundwater  from entering the retort,  it will  slow the water
      atl- V? ^r°Ugh the rubble and Caching the shale   Filling the
      poWtentiaT.r°Ve     structural strength and reduce the subsl?
 4.3  CONTROL TECHNOLOGIES
be rlon
be done  on
               ooTUSfq°£iiS draWn Princi.Pally from EPA! publication
          •    t   '   1983]   and   summarizes   the  major   control
 technologies to  prevent contamination of  surface and^ groundwater
 supplies by  runoff or  leachate,  prevent generation  of wSdblSSn
 dusts   and  prevent  mass  failure  of  a  surface landfill    The
        0n and aPPllcat%lon of appropriate control technologies must
             a site and  plant specific basis wherein  the  controls
     no        -1^°-f sPecific disposal  design.  A  few  specific
 examples  of  individual   control  technology   costs :  have   been
                                   idea °f Boosts involved.  The
                                   and compacting  the  solid wastes
    a,     estimated costs  since  these activities must
    accomplished  for  process  rather than environmental purposes?

 4 • 3 . 1  Surface Hydrology Control Technologies          ;

            ,man,a?ement practices in the  area of surface hydrology
            handling of  surface waters  on and around the  disposal
            Specifically,  surface  streams  and  precipitation  a?e

 wa    s  rrnn?1  f™^? fntO  the Waste  Pile'  and  contaminated
 watSrs. (runoff'  leachate)  are  kept  from mixing with the  natural
  su3facenHfi                     th°Se that are Applicable to
  suiface  landfill,  and they are summarized in Figure !4.3-l   The
key  features  of the  technologies  are highlighted  in  Table "4.3-1
and a more detailed description with cost data is presented in the
T^GX^. *
Runon Diversion System                                 i

A runon diversion system will generally be needed with any surface
landfill to prevent  surface  water from flowing onto the waste ma-
terial and  becoming  contaminated or  causing erosion.   The system
                             227
 image: 








      SURFACE
      HYDROLOGY
      CONTROL
      TECHNOLOGIES
                           RUNON
                         DIVERSION
                           SYSTEM
  RUNOFF
COLLECTION
  SYSTEM
                          RUNOFF/LEACHATE
                          COLLECTION PONDS
                  —  WITH RETENTION

                  -  NO RETENTION
Figure 4.3-1.   Surface Hydrology Control Technologies
Source:  EPA-600/8-83-003,  1983
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may  include  ditches,  lined  channels,  conduits,  and  embankments
arranged to direct the flow of surface water  around  or away from
the waste material,  and energy dissipators to moderate the impact
of the flow.

The complexity  and extent of the system will vary widely based on
the  amount  of  water to  be diverted  and the  arrangement  of the
site.  For  a fill on a relatively level site, runon diversion may
be only a system of channels and small embankments to deflect sur-
face flow away  from the landfill.  In the case of a head-of-valley
fill or  a cross-valley fill, runon diversion might include an em-
bankment dam  to retain peak  flows from the design storm until they
can be passed through a conduit beneath or around the fill.  Alter
natively, the  system  may consist of  a conduit or  channel large
enough to pass  the design flow without an embankment (without re-
tention) .

The  costs  for  three runon  diversion systems  were  estimated and
they  are plotted in Figure  4.3-2.  Examples  1 and 2 consisted of
runon  retention in  combination  with  continuous release.  Example
3 was  designed for no retention, which necessitated a  large chan-
nel  and extensive use  of reinforced concrete energy dissipators;
the  higher  cost  associated  with such a  system is illustrated in
the  figure.

Examples 1  and  2  also  consisted  of an  earth embankment  for the re-
tention  of  runon  and  an embedded conduit for controlled release.
Channeling  of the controlled release flow around the _waste pile in
Example  1  was  accomplished  with a lined canal,  while Example  2
utilized an  extension  of the embedded conduit  for the  controlled
release.

The  cost of  a  runon diversion system will be influenced by:  the
size of the  drainage  area  and  topography which affect the  runon
rates,  retentions,  and  embankment  material .quantities; the  size,
length,  and complexity of controlled  release  structures and chan-
neling systems; and the  need  for and  extent of energy  dissipators
and/or drop  structures.   For example,  the runon from  a site with
a large drainage  area  in a gently  sloping topography could *>e di-
verted quite efficiently by an unlined canal  or  channel;  another
site with  small  runoff  rates, but  high erodible steep  topography,
may necessitate cost-intensive lined channels, flumes or conduits,
as  well as  drop structures or energy dissipators.   In summary, the
cost of this sytem is  highly site-specific.

Runoff Collection System

A runoff collection system usually consists  of a system  of chan-
nels,  ditches, and  conduits arranged  to prevent the surface water
 that has contacted the waste material from leaving the site.
I
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                                 230
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                    250
                              500        750


                        RUNOFF RATE, cfs
1000
NOTES :
     i*1 f 2  incjude  retention with embankments and contin-
     uous controlled release through an embedded conduit.
                                                        i

     retention was desi9ned  to handle the  maximum flow without



     Example 2 is specific to the TOSCO II  case  studies, except the
     embankment dam  is smaller than  the one proposed by .Colony.

     Mid 1980 $                                         '


Source:  EPA-600/8-83-003, 1983                         ;
              Figure 4.3-2.  Runon Diversion Costs
                             231
 image: 








Another purpose of  this  system is to drain the surface water from
the wastes to  limit the  erosion and infiltration potential.  Col-
lected water may also be used to meet process needs.

The basic  elements  of this  system are backsloped  benches  on the
face of the  landfill and a means of collecting the water from the
fill surface.  Generally,  half-round pipes,  impervious membranes,
or highly  compacted soil or wastes are used to line ditches which
collect the  runoff  from  the bench and the segment of the landfill
slope above it.  The ditches then must be drained to a containment/
evaporation pond  at the  toe of the landfill, or the water must be
impounded  on the  benches or top of  the  landfill.   A problem with
using embankments  on the  waste  pile is  that  the  water ponded on
the landfill will have  a greater tendency to infiltrate the waste
material.   This  increased  infiltration  could have a detrimental
effect on  the stability  of the slope and  will  somewhat increase
the amount of  water which must be handled by the leachate collec-
tion system  (discussed under subsurface hydrology).

The costs  for a variety  of runoff collection  system designs were
estimated  and  these are plotted in  Figure  4.3-3.   Example 1 used
shaped benches with  unlined ditches  for lateral  conveyance and
concrete  weir collectors  and corrugated metal  pipe  with energy
dissipators  for vertical  conveyance.  It  also  incorporated some
temporary  retention of runoff on the waste pile surface, which re-
duced the  necessary capacity  and  cost of the vertical conveyance
portion of the system.  Example 2 used split corrugated metal pipe
to  line  the collection  ditches  to facilitate lateral conveyance,
and concrete weir collectors and corrugated metal pipe with energy
dissipators  for vertical  conveyance.  Example  3   used  the  lined
ditches  for   lateral  conveyance,   with   a  concrete  flume  and   a
stilling basin for  vertical conveyance.

The cost data, as can be  seen  in the  plot, are highly dependent on
the particular design, an no single  cost  curve relationship can be
drawn  through the  data  points.   Example 1, which assumes a more
modest  design, defines  the lower boundary of the cost envelope,
and Example  3  defines the high end of the cost envelope.

Runoff/Leachate Collection Ponds

At  the  outlet of  the  collection  system  for surface  runoff,   a
structure  is  needed to contain  the collected water  for reuse,
treatment  and discharge, or for evaporation.  The  structure  would
consist  of an embankment  across a  former stream channel to form  a
pond,  and the pond may  be lined or unlined  depending upon  the na-
ture of the impounded material.   If a liner  is needed,  it would be
protected  from wave  action,  as necessary,  using  rip-rap,  a  sand
layer,  soil cement or similar materials.   Since the pond would be
located  at the base of the landfill,  it  might  also  be used to col-
lect the  leachate from the fill.
1
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                      RUNOFF QUANTITY, ACRE-FT
       4OD
NOTES:                                                 :
                                                       |
                                                       j
     Example 1 utilizes shaped benches  as  unlined ditches for
     lateral runoff conveyance.                        |

     Examples 2 & 3 utilize buried  corrugated metal  pipe to line
     ditches for lateral runoff conveyance.

     Examples 1 & 2 utilize buried  corrugated metal  pipe and energy
     dissipators for vertical runoff conveyance.       ;

     Example 3 utilizes a concrete  flume with stilling basin for
     vertical runoff conveyance.                       ;

     Mid 1980 $                                        :

     The costs indicated are cumulative for the project  life.

Source:  EPA-600/8-83-003, 1983

             Figure 4.3-3.  Runoff  Collection Costs    i
                             233
 image: 








Cost  data   for  four  examples   of  runoff/leachate  collection     ™
ponds  are presented  in  Figures  4.3-4  and  4.3-5.   Figure  4.3-4
presents  the  total  cost  of  the  embankment  and  liner  as  a     fl
function  of the  construction  material quantities  used  in  each     QJ
case,  while Figure  4.3-5  isolates  the cost  of  the liner  as  a
function of the liner material quantity only.                          n

Examples  1,   2 and  3  utilized compacted  processed  shale   as  a
liner,  while  Example  4  used  Mancos   Shale  as  the  liner.   The     «
relatively high  cost of  using  an  off-tract material  (Example 4)     •
is  evident  in  the  figures.  The  cost  increase  is  incurred due     m
to  the  source  development,  processing and  hauling of  Mancos
Shale.                                                                 •
Slight cost  differences may be  observed  between similar systems,
and  these  can  be  attributed  to site-specific  features,  such as
the  arrangement and  configuration  of  the  embankment  and ponds.
4.3.2  Subsurface Hydrology Control Technologies                        gj


The technologies and practices in the area of subsurface hydrology      •
involve the  handling of groundwater  seepage under a  landfill . to      pi
prevent infiltration of the pile and the control of water from the
pile to prevent contamination of the groundwater.                       «


The  technologies,  as summarized  in Figure  4.3-6,  are applicable
to  a surface  landfill,  and their  key features are presented  in      at
Table  4.3-2.  Detailed  descriptions  of  the technologies,  along      J|
with cost information, are presented below.
                               234
                                                                        I
Liners and Covers

A  liner is  essentially  a material with low water  permeability      •
that  is installed  at  the bottom  of  a landfill  or pond.   Its      m
purpose  is to  prevent  the  contaminated waters  from the  wastes
from  mixing  with the  groundwater.   It  also  prevents groundwater      •
from infiltrating the bottom of the landfill.                           H


A cover  is also made up of a  low-permeability material  and it is      I
used  as  a surface  sealer  for the  landfill.    It  prevents  the      •
runoff  from  infiltrating the  pile, thereby  reducing  the quantity
of the leachate and minimizing stability problems.                      ffi
1

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                   °-l         0.2        0.3        0.4

               CONSTRUCTION MATERIAL VOLUME,  I06 yd3
          0.5
     All Examples  include cost of embankments and pond liners.

     Examples  1,2  &  3  include pond liners constructed of processed
     snale.

     Example 4 includes  a liner constructed of Mancos Shale (off-
     tract material);  cost is increased due to processing and
     transport.                                         •

     Mid 1980  $                                         |
Source:  EPA-600/8-83-003, 1983
            Figure 4.3-4.  Runoff/Leachate Pond  Costs
                             235
 image: 








                                                                         I
       1000
       800
     10
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     _- 600
     cn
     o
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     g 400

     Q
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NOTES:
                             O,
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                              100                  200

                     LINER MATERIAL QUANTITY, I03 yd3
     Examples 1,  2  &  3  include liners constructed of processed
     shale.

     Example 4  includes a liner constructed of Mancos Shale  (off-
     tract material); cost is increased due to processing and
     transport.

     Mid 1980 $
     Source:  EPA-600/8-83-003,  1983

         Figure 4.3-5.   Runoff/Leachate Pond Liner Costs
                              236
8
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        SUBSURFACE
        HYDROLOGY
        CONTROL
        TECHNOLOGIES
                              LINERS
                               AND
                              COVERS
 LEACHATE
COLLECTION
  SYSTEM
                            GROUNDWATER
                            COLLECTION
                            SYSTEM
                  r- SYNTHETIC !

                     OFF-SITE  i
                     NATURAL MATERIAL

                  i— COMPACTED i
                     PROCESSED i
                     SHALE
       Source:   EPA-600/8-83-003,  1983
Figure 4.3-6.   Subsurface  Hydrology Control Technologies
                            237
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There  are  several  materials  which  can  be  considered  for the
liners  and covers.   Probably the least expensive material would
be  compacted  processed shale.   It  has  the  advantage  of being
readily  available  at the site.  A similar lining  could be made, of
processed  shale  or  clay  from  off   site  if  the  quality  of the
processed  shale   from  the  site  is  unsuitable;  however,  these
options  would be  relatively  expensive due to  the extra handling
and  hauling  costs.  There  is  also  a variety  of synthetic liners
which could be considered.  High-density polyethylene, for example,
would range  upward from a price similar to  that for the off-site
materials, depending upon  the thickness used.  This would make it
very  expensive for  use  in a processed shale  landfill and it may
have questionable  long-term durability.

Linings  made  of natural or synthetic materials  may  dry and crack
if  they  are  left exposed to the  weathering elements  for  long
periods.  The catchment and evaporation ponds presumably will need
only  one liner or no liner since they will  not contain hazardous
materials.  If a  combination  of two  liners is used,  the synthetic
liner may be placed  above the natural material  linerj to prevent
its  drying and  cracking.   In  cases where  a  synthetic  liner  is
used,, it should be covered by a layer of sand or gravel to protect
it  from  traffic  and wave action.  Also, because of  the weight of
the  fill and  because the fill may be placed above an iunderground
mine,, the  liner  must accommodate  a   certain amount  of subsidence
and stretching and still function properly.            !

The cost of  liners and  covers depend on the quantity and type of
material used.  Figure 4.3-7 presents the costs for three separate
liner and cover  systems.   Examples  1 and  2  assumed the  use  of
highly compacted  processed shale for construction of ithe liners,
while Example 3  assumed the  use of  Mancos  Shale.  The compacted
processed shale represents the lowest material cost option, while
Mancos Shales is   a  more expensive  natural material  since it has
associated source  development,  processing  and  hauling costs.   The
cost curve in the  figure may be used to obtain an  "orde;r-of-magni-
tude" estimate of  liner cost  utilizing highly compacted processed
shale as the  construction  material.   The  estimated cost for other
liner materials would fall above this curve to  a  degrbe  which is
dependent on the source development,  processing, and hauling costs
associated with  delivering these materials  to  the disposal site.

Leachate Collection System     -                        j

The purpose  of a  leachate collection system is to  collect water
which infiltrates  a  landfill  and drain it efficiently ;in order to
prevent  the  saturation of   the landfill  and  contamination  of
grouridwater beneath  the  waste  pile, as  well  as to; facilitate
handling of the leachate.

Leachate  collection  systems  typically  consist of  blankets,  or
zones, of highly pervious  sand and  gravel.  In some  cases this is
                             239
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                        MATERIAL QUANTITY,  I06 yd3
16
NOTES:
1

1

1
     Examples 1 & 2 utilize  3  feet  of highly compacted processed
     shale for liner material.
     Example 3 utilizes 3  feet of compacted  Mancos  Shale  (off-
     tract material) for liner material;  cost of processing and
     hauling this material makes this  option more expensive than
     the others.
     Mid 1980 $
Source:  EPA-600/8-83-003, 1983
                   Figure 4.3-7.  Liner Costs
                             240
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augmented with  embedded  perforated pipe to increase the capacity,
and it may also include collector ditches where the system emerges
onto  a  broad level  area.   The sand or  gravel  layer  would be lo-
cated just above  the bottom liner and it may be wrapped in filter
fabric  or  surrounded by carefully graded  sand  filters to prevent
infiltration  by the  processed shale particles.   In  either case,
collection system  should be designed so that movement jand settle-
ment do  not  result in discontinuity of the gravel layer or impede
drainage to the collection or evaporation ponds.       j

The costs for four distinct leachate collection systems were esti-
mated and these are  presented in Figure 4.3-8.   In Examples 1 and
2, due  to  the  valley shape of the  disposal  site,  onliy the drain
material was necessary for the collection system.  The!leachate in
these two cases was drained in the runoff/leachate collection pond
located  downstream from the landfill.   In Example  3,  ia toe ditch
was necessary to  collect the leachate due to the  presence of the
broad valley  area  at the toe of the landfill.  The ditch was then
drained  into  the  common  runoff/leachate collection pond.  Example
4 also required a toe ditch which was drained into a leachate col-
lection pond, while the runoff was impounded separately in evapor-
ation ponds on  the waste pile surface.  Examples 3 and 4 required
the same drainage  material  quantity.  The cost difference between
the two  examples  is  due  to the inclusion of a separate collection
pond in Example 4.  Data point 5 on the figure represents the cost
of drainage material  only  for Examples 3 and 4.   The  cost of the
toe ditch  may  be  obtained  by subtracting data point  5  from 4.

The costs for similar systems should be proportional to the volume
of drainage  material used, but  slight deviations may! be encoun-
tered due to the site-specific conditions.

Groundwater Collection System                          j

The purpose of a groundwater collection system is to relieve pres-
sure from  the seeps and springs beneath a  landfill.   !This situa-
tion is most likely in the cases of cross-valley or head-of valley
landfills.   The system will be essentially identical to the leach-
ate collection  system except  it would be below the  bottom liner
rather than above it.                                  i
                                                       f

Groundwater collection  systems typically  consist of  blankets or
zones of pervious  sand  and gravel  drained beyond the perimeter of
the landfill.  This may be augmented with embedded perforated pipe
to increase capacity and with collector ditches.  The sand or gra-
vel layer would be lined as necessary with filter  fabric or sur-
rounded  by  properly  graded  sand  filters to  prevent  infiltration
of smaller  particles from  adjacent materials.   The  system  must
also be  designed  to  maintain its  continuity despite possible sub-
sidence or settlement of the landfill.                 ,
                             241
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                     VOLUME OF DRAIN MATERIAL, yd3
NOTES:
     Examples 1 & 2 require only  drain material  due  to the valley
     shape; leachate containment  is performed by the contaminated
     runoff catchment pond of which the  leachate is  a negligible
     component.

     Example 3 includes cost of toe ditch  for collection due  to
     broad valley at waste pile toe;  containment is  also by the
     contaminated runoff catchment pond.

     Example 4 includes toe ditch collection  and separate contain-
     ment pond because, in this case, contaminated runoff is  con-
     tained in evaporation ponds  on the  waste pile surface.

     Example 5 includes only the  drain material  cost of Examples
     3 & 4.

     Mid 1980 $

     The costs indicated are cumulative  for the  project like.

Source:  EPA-600/8-83-003, 1983

            Figure 4.3-8.  Leachate Collection Costs
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                             242
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 The  costs  of two  groundwater  collection  systems were estimated  and
 these  are  plotted in  Figure 4.3-9.  Both systems used gravel blan-
 kets under the pile to collect  the groundwater seepage.   In Exam-
 ple  2  the  gravel blankets  were  used  only  above the  seeps  and
 springs,  while in Example 1  an  extensive network of the  blankets
 was  considered,  resulting in a higher cost.  The  cost;of  the col-
 lection  system  should be  proportional  to the  quantity  of  the
 drainage material used.                               :

 4.3.3  Surface Stabilization  Technologies             ;
                                                      i
 The  activities  and technologies  in the  area of surface stabiliza-
 tion involve the  treatment of the  disturbed  land surface and  the
 problems associated with  the  disposal and reclamation of the waste
 material.   These  technologies are  outlined in Figure;  4.3-10  and
 their  key  features are presented in Table 4.3-3.

 Dust Control

 The  purpose of dust  suppression is to  limit  pollution from air-
 borne  dust,  particularly  during  the placement of the yaste mater-
 ial  in a fill.   Dust  suppression can  be accomplished 'by  spraying
 the  haul  roads  and  fill  surface with  water or a combination of
 water  and  a chemical  binder.   Haul roads could, alternatively, be
 paved.                                                ;

 Use  of water  along for dust suppression would necessitate  repeated
 applications, often more  than one per day, to be effective.  Water
 with a chemical  binder should necessitate only a few applications
 to a given surface to stabilize it for a  year or more  unless it
 receives heavy traffic.   Finally, vegetation would provide perhaps
 the  most  permanent means of  dust control, but this  would not be
 practical  except  on surfaces which  would not be  disturbed for a
 number of years.                                      i
                                                      E
 The  dust  suppression  technology assumed  in  developing the  cost
 data for  two examples consisted of routine spraying pf  the pro-
 cessed shale  pile with water and additives to minimize  the dust
 generated  due to  the wind and  the waste  hauling and  placement
 activities.   Depending on  the  processed  shale  characteristics,
 this operation could  either  be  continuous or  intermittent.   The
 cost curve  in Figure  4.3-11 is based on the  assumption  that both
 the  manpower  and  equipment  operation requirements  are !continuous.
 Theoretically, these  requirements could differ depending on the
 rate of waste production and the surface  area of the;  particular
 waste  pile;  however,  both cases estimated  were  assumed to  be
 equivalent in this respect.                            j

 Erosion Control                                       \
                                                      I
The  purpose of erosion control  is  to keep the waste material  in
place  so  that the surface drains remain free  flowing, |  the slopes
                             243
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                        VOLUME OF DRAIN MATERIAL, I06 yd3
     Examples  1 & 2 consist of gravel blankets for collection of
     groundwater from springs and seeps;  extent of blankets dic-
     tated by  the existence and extent  of such conditions.

     Mid 1980  $

     The costs indicated are cumulative for the project life.


Source:  EPA-600/8-83-003, 1983
           Figure  4.3-9.   Groundwater Collection Costs
                              244
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     SURFACE  .
     STABILIZATION
     CONTROL
     TECHNOLOGIES
                          DUST
                          CONTROL
EROSION
CONTROL
                        STABLE SLOPE
                           DESIGN
                    WATER AND
                    BINDERS
                    PAVE HAUL
                    ROADS
                                          "— REVEGETATION
                 i— MULCH
                  — REVEGETATION
   Source:   EPA-600/8-83-003, 1983                ;


Figure 4.3-10.  Surface Stabilization Technologies
                         245
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      en
      8  30

      o
      z
      ft.
      UJ

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         10
                               I
                               I
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                          _L
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                          10              20

                          PROJECT LIFE, YEARS
                                                        30
NOTES:
                     •
     Example 1  assumes  a 30-year project life, while Example 2
     assumes a  20-year  life.

     Mid 1980 $

     The costs  indicated are  cumulative for the project life.

Source:  EPA-600/8-83-003,  1983




                Figure 4.3-11.  Dust Control Costs
                              248
1


1


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 remain stable, eroded  material does not pollute  surface  streams,
 and reclamation  and  revegetation efforts are not hampered.   Some
 means of  limiting  erosion include  contouring  the surface  with
 short and gentle slopes,  providing for drainage  of the slopes  at
 frequent intervals,  using mulch or filter fabric to dampen the im-
 pact  of  water  flow,  and  revegetating the  completed! faces.   Of
 these measures,  grading and drainage  are  essential,  take  effect
 immediately,  and  last  as long  as  they are maintained.   Mulch  or
 filter fabric also provide a quick control,  but  they are of a tem-
 porary nature.  Revegetation provides  a permanent control,  but  it
 is  generally  slower  to  take effect.                    !

 A major consideration in planning erosion control measures  is the
 severity of rainfall  in the area.  A  large proportion  of the water
 from a high-intensity rainfall  would  run  off the surface,  thus in-
 creasing the  erosion.
                                                       1
 Reclamation and revegetation consist  of placing  a  subsoil  and top-
 soil strata  of sufficient  thickness to support  vegetation, and
 then seeding  the  disposal area with  native  or introduced  species.
 The  greatest  contributor to the magnitude of cost  for this control
 technology is the thickness  of  the soil strata and the'costs  asso-
 ciated with the delivered soil  material, i.e., the source  develop-
 ment,  processing  and  hauling   costs.   Soil   and subsoil   stripped
 from the disposal site may not  be available  in sufficient  quantity
 to meet  the  reclamation needs.   The  cost curves presented in Fig-
 ure  4.3-12  illustrate five examples.   Examples  1  and 5 included 2
 feet of subsoil  (sand-gravel material)  and  30  inches  iof topsoil,
 both of which were brought  in  from off-site sources and thus had
 additional costs  involved.  Examples  2 and 3 also used the  same
 thicknesses,  but  the  soils were available on the  site.  Example 4
 used no  subsoil and only  6  inches  of topsoil which wa|s available
 on  the site;  therefore,  additional  material costs were  not in-
 volved.  All  examples included  the  cost of  revegetation.   It is
 evident  from  the  figure that the cost  of erosion  control can vary
 significantly depending  on the  factors considered; however, in any
 category,  the  costs  are proportional  to the area reclaimed and
 revegetated.                                           \

 Besides improving the appearance of the landscape, the vegetation
 of the waste  landfill will serve other purposes that ate important
 from  the pollution control point of view.  The physical effect of
wind and water will be greatly influenced by the presence of vege-
 tation on the surface.  Dense vegetation and root systems will re-
 duce  the weathering  impacts, thereby  reducing the erosion by wind
 and precipitation run-off.  The vegetation will aid in levapotrans-
piration  of  the   surface-absorbed  water  thereby  reducing  water
 infiltration  and  leaching.  Vegetation will  also  provide  a suit-
able  environment  for other biological  activity  which  will aid in
restoring the local ecosystem.                          ;
                             249
 image: 








             60


          O
          •*•  50
          CO

          8  40

          O
          <  30
          tr
          UJ
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                        500        I.OOO       1,500

                          RECLAIMED AREA, ACRES
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                   2,000
I
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NOTES:

     Examples 1 &  5  include 2  feet of subsoil and 30 inches of
     topsoil, both obtained off site.

     Examples 2 &  3  include 2  feet of subsoil and 30 inches of
     topsoil obtained  on site.

     Example 4"includes  no  subsoil and only 6 inches of topsoil
     obtained on site.

     Mid 1980 $

     The costs indicated are cumulative for the project life.


Source:  EPA-600/8-83-003,  1983
       Figure 4.3-12.   Reclamation and Revegetation Costs
                              250
                                      1


                                      I


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 image: 








 The  use  of the processed  shale  itself  as  a plant  growth medium may
 be  questionable.   The  texture,  salinity, alkalinity,!color, etc,
 of  the processed  shales  play an  important  role  in the growth of
 vegetation.   Some  type  of  modification  in the processed  shale
 properties and/or application of  a  natural  soil  cover may be ne-
 cessary  to induce and  sustain  vegetation on the processed shale.

 If  the top layers of the processed shales are thoroughly leached
 so  that the salinity is  within acceptable range, the;planting or
 seed germination  may be  possible  in  the  processed shale itself.
 Otherwise  topsoil  may  need to be  placed  on  the shale '• waste,  or a
 nu_xture  of rock,  topsoil and subsoil  can be mixed  into  the top
 layers.  Topsoil  in  the oil shale area is usually  insufficient to
 provide  a  good cover;  therefore,  mixing with  rocks  and subsoils
 may  be necessary to give  proper depth.   Also,  a proper selection
 of the plant  species that would survive the climate of the region
 and  high salt concentration of the processed shale  should be made.
 Soil  fertilization should  be carried out to make  up for the nutri-
 ent  deficiency,   and sufficient  water should  be  made  available
 while  establishing the vegetation.                     ;
                                                       I
 Stable Slope Design                                    ;

 The  purpose of designing  the slopes to be stable under prevailing
 conditions  is  to  minimize the maintenance of the landfill  and to
 avoid  hampering of the  reclamation and revegetation efforts.   The
 techniques  used  in designing stable  slopes  are  a  wel'l  developed
 part  of soils engineering.   To arrive  at the most  advantageous
 slope  design, other  factors  besides basic stability,  such as ero-
 sion,  ease of placement,  reclamation  and revegetation,  must  be
 considered.  However,  the physical  characteristics ot the  waste
 material  will dictate  a limiting  slope  angle.  The  costs  of
 achieving  a  stable slope  design  are incidental  to the  placement
 and revegetation of the fill material;  hence, additional costs are
 not involved.                                           j

4.3.4  Summary of Control Technologies                 i

Table 4.3-4 presents a summary of the control technologies and es-
timated costs (1980 dollars)  for disposal  of retorted shale  from a
small  (47,000  bbl/day)  oil shale plant.  Not  included are  the
costs for offsite disposal of hazardous wastes.   Also  excluded are
the considerable costs  for transporting the  retorted  Shale  to the
disposal site and compacting it in lifts which  would! have to  be
done for process  reasons rather than environmental control.
                             251
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DOE/EV-0078,  May  1980.   Environmental  Research on ia  Modified
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DOE/EV-86,  June 1980.  Paraho Environmental Data.  Part I:  Process
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R. D.  Giaugue and D.  B.  McWhorter.  Work  performed under Inter-
agency   Agreement  AD-89-F-0-026-0   and   Cooperative!  Agreement
DE-FC21-83FE60177 for U.S. Department of Energy by Western Research
Institute,  Laramie,  Wyoming.                           :
                                                       i
Donnell,  J. R.   Tertiary Geology  and Oil  Shale  Resources  of the
Piceance  Creek  Basin, NW  Colorado.   USGS  Bulletin  10£2-L,  1961.
                                                       i
Donnell,  J. R.  Mercury in Oil Shale From the Mahogany Zone of the
Green River Formation.  USGS,  Journal  of Research,  Vol. 5,  No.  2,
March-April 1977.                                      i

Dravo Corporation.  Materials Handling Techniques for Backfilling
Proposed Oil Shale Mines.  1975.
                                                       i
Duncan,   D.  C. and V.  E.  Swanson.  Organic Rich Shales of the U.S.
and World Land  Areas.   U.S.  Circular 523,  U.S.  Geological Survey,
Denver,  Colorado,  1965.                                 :
                                                       i
Engineering-Science,  Inc.,  Denver,  Colorado   80212.   Draft Summary
Report:    Hazard Assessment  of Pollutant Emissions from Shale  Oil
Production  Facilities.  Prepared for USEPA Region VIII,1 June 1983.
                              257
 image: 








                                                                       I



EPA-600/7-79-075, March 1979.   Technological  Overview Reports for     B
Eight  Shale  Oil  Recovery Processes.  C.  C.  Shin, J.  E.  Cotter,
C.  H.  Prien  and T.  D.  Nevens,  U.S.  Environmental  Protection     m
Agency, Cincinnati, Ohio  45268.                                       ™

EPA 600/7-80-181,  1980.   Reconnaissance  Study of Leachate Quality     «
From  Raw-Mined  Oil  Shale-Laboratory  Columns.   D. B.  McWhorter,     H
Colorado State University.   U.S.  Environmental  Protection Agency,
Cincinnati, Ohio  45268.                                               «

EPA-600/2-80-205a, 1980.  Environmental Perspective on the Emerging    ™
Oil Shale Industry.  EPA Oil Shale Research Group.  E. R. Bates and
T. L. Thoem,  U.S. Environmental Protection Agency, Cincinnati, Ohio    •
45268.                                                                 V

EPA-600/8-83-003, April 1983.  Pollution Control Technical Manual:     «
TOSCO  II Oil  Shale  Retorting with Underground  Mining.   Denver     •
Research   Institute.    U.S.   Environmental  Protection  Agency,
Cincinnati, Ohio  45268.                                               _

EPA-600/8-83-004, April 1983.  Pollution Control Technical Manual:     •
Modified In  Situ Oil  Shale Retorting.  Denver Research Institute.
U.S.  Environmental Protection Agency,  Cincinnati,   Ohio   45268.     m

EPA-600/8-83-005, April 1983.  Pollution Control Technical Manual:
Lurgi  Oil  Shale Retorting with Open Pit Mining.  Denver Research     »
Institute.  U.S. Environmental Protection Agency, Cincinnati, Ohio     •
45268.                                                                 m

EPA-600/2-84-153, 1984.  Auto-oxidation Potential of Raw and Retor-    •
ted Oil Shale.  A. D.  Green,  Research  Triangle Institute.   U.S.     •
Environmental Protection Agency, Cincinnati, Ohio  45268.

EPA-600/D-84-036,  March 1984.   Environmental Research  Brief, Oil     £
Shale  Potential  Environmental  Impacts   and  Control  Technology.
E. R.  Bates, W. W. Liberick,  J.  Burckle,  U.S.  Environmental Pro-     _.
tection Agency,  Cincinnati, Ohio  45268.                               I

EPA-600/D-84-228,  1984.   Leaching   Characteristics and Hydraulic
Properties  of  Retorted Oil  Shales.  D.  B. McWhorter,  Colorado     fii
State  University.   U.S.  Environmental Protection Agency,  Cinci-     0
nnati, Ohio  45268.

EPA  600/D-84-143,  August  1984.    Environmental Research  Brief.     ||
Quality and Quantity of Leachate from Raw Mined  Colorado Oil Shale.
D.  B.  McWhorter,  Colorado State University.   U.S.  Environmental
Protection Agency, Cincinnati, Ohio  45268.                            n

Fahey,  J. J.   Saline  Minerals of the Green River Formation.  USGS
Professional Paper 405, 1962.                                          •
                                258
1

I
 image: 








Faulkner, B. P., M.  H.  Weinecke and R. F.  Cnare.   Results  of the
Processing  of  a Western  Oil  on  the Allis-Chalmers  Roller Grate
Retort System.  Sixteenth Oil  Shale Symposium,  April 13-15, 1983;
Proceedings published by Colorado  School  of Mines Press, (Editor:
J. H. Gary), August 1983.

Forbes,  F.  and F.  W,  Kinsey.   The Dravo  Traveling Grate Process
for  Oil  Shale  Retorting.    Proceedings,   1981  Eastern  Oil Shale
Symposium,  November  15-17,  1981,  Lexington,  KY.   Proceedings pub-
lished by  Institute  for Mining &  Mineral  Research,  Lexington,  KY
40512.
                                                      i
Fox, J. P.   Leaching of Oil Shale Solid Wastes:   A Critical Review.
July  1983.   Prepared for  the  Center for  Environmental  Sciences,
University of Colorado at Denver,  Denver,  CO 80202.  Work supported
by  U.S.  Department  of  Energy  under Contract NumbersiDE-AC02-79-
EV10298 and DE-AC03-76SF00098.                         ,

Guney, M.,  and D.  J.  Hodges.   Adiabatic Studies  of'Spontaneous
Heating  of Coal,  Part I.  Coll.    Guard.,  V.  217,  No.   2,  1969,
pp. 105-109.                                          :
                                                      I
Heistand, R. N.,  8185 E. Geddes Ave.,  Englewood,  CO 80112.  Private
Communication,  September 1984.                         i

Kite,  R.  J.,   and  J. W. Dyni.   Potential Resources  of  Dawsoriite
and Nahcolite in the Piceance Creek Basin, NW Colorado.   Quarterly
of the Colorado School of Mines, Vol.  62,  No. 3,  1967,'pp. 591-604.

Herron, J.   T., W.  A. Berg  and H.  P. Harbert III.   Vegetation and
Lysimeter  Studies  on  Decarbonized Oil   Shale.   Colorado  State
University  Experiment  Station,  Fort  Collins,   Colorado  80523,
Technical Bulletin 136, January 1980.

Holtz, W.  G.   Woodward-Clyde  Consultants.  Disposal :of Retorted
Oil  Shale   from  the Paraho  Oil  Shale  Project.   USBM Contract
J0255004.  December 1976.                              ;

Jackson,  L.  P. and  K. F.  Jackson.  The  Co-disposal of Retorted
Shale  and  Process  Waters:   Effect on  Shale Leachate Composition.
Fifteenth Oil Shale Symposium,  April 28-30, 1982, Golden, Colorado.
Proceedings (J. H.  Gary,  Editor)  published  by Colorado  School  of
Mines Press, August 1982.                              i

Kim, A.  G.  Laboratory  studies on spontaneous  heating; of coal:   A
summary  of Information in  the Literature.   U.S.  Dept.   of  the
Interior, Bureau of Mines,  IC8756, 1977.              ;

Lowry, H. H.   Chemistry of Coal Utilization, Vol. 1, John Wiley &
Sons, 1954.                                           .i
                             259
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                                                                        I



Margheim,  G. A.   Water Pollution  from Spent Oil  Shale.   Ph. D.      •
Dissertation,  Colorado  State University,  Fort Collins,  CO,  May
1975.                                                                   B,

Matzick,  A., and others.  Development  of the USBM Gas Combustion
Oil Shale Retorting Process.  USBM Bulletin 635, 1966.                  m

Monsanto  Company,  1515 Nicholas  Road,  Dayton,  Ohio 45418.  Duane
Day, Personal Communication,  February 1984.

Monsanto  Company,  1515 Nicholas  Road,  Dayton,  Ohio 45418.  A. K.      •
Agarwal, August 1984.  Based  on TRW, March 1977.

Murray, D. K., and J. D. Haun.  Introduction to the Geology of the      p
Piceance  Creek  Basin and  Vicinity,  Northwestern Colorado.  Rocky
Mountain Association of Geologists, Guidebook, 1974.                    «

Paraho  Development Corporation,  June  1982.   Paraho-Ute  Project      ""
Technical Report.  Requested  by the Bureau of Land Management EIS
Services, Denver, CO.           -                                        B

Poulson,  R.  E.,  and others.   Minor Elements  in  Oil Shale and Oil
Shale  Products.   Presented  at the  NBS/EPA Workshop  on Standard      m
Reference   Materials   for   Oil  Shale   Environmental  Concerns,      I
Gaithersburg, Maryland, November  1975.

Roehler, H. W.  Depositional  Environments of Rocks in the Piceance      8
Creek  Basin,  Colorado,  Rocky Mountain  Association of Geologists.      *•
Guidebook  to the  Energy Resources  of  the Piceance  Creek Basin,
Colorado, 1974.                                                         •

Roehler,  H.  W.   Mineral Resources  in the Washakie Basin,  Wyoming
and  Sand Wash  Basin,  Colorado.   Wyoming  Geological  Association      •
Guidebook, Greater Green River Basin Symposium, 1973.                   I

Schemling, W. A.  et  al.   Spontaneous Combustion Liability of Sub-
bituminous  Coals:   Development of  a Simplified Test Method  for      •
Field  Lab/Mine  Application.   Analytic  Chemistry  of  Liquid  Fuel      ™
Sources, P. C. Uden et al., eds, ACS 1978.

Schuman,  G.  E.,  W. A.  Berg   and  J. F.  Power.  Management of Mine      |
Wastes  in the Western United States,  Land Applications  of Waste
Materials.   Published in  1976 by Soil  Conservation Society of      m
America, Ankeny,  Iowa.                                                  •

Sellers,  J.  B.   Rock  Mechanics  Research  in Oil Shale  Mining.
100th National Meeting of AIME, New York, N.Y., 1971.                   f

Smith,   J.  W.  Specific  Gravity - Oil  Yield Relationships  of  Two
Colorado  Oil Shale Cores,  Industrial  and  Engineering Chemistry,
Vol. 48, No. 3,  1956,  pp. 441-44.
                             260
I

I

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 image: 








 Smith, J.  w.   Ultimate Composition  of Organic Material  in Green
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 Smith, J.  W.   Stratigraphic Change  in  Organic  Composition Demon-
 strated by  Oil  Specific Gravity-Depth  Correlation  in1 Green River
 Oil Shale.  AAPG Bulletin,  Vol. 47,  No.  5,  May 1963.  :

 Smith, J.  W.,  and  N.  B.  Young.   Specific  Gravity to  Oil  Yield
 Relationships for Black  Shales of Kentucky's New Albany Formula-
 tion.   USBM Report of Investigations No. 6531,  1964.  i

 Smith, J. W., and N. B.  Young.  Organic Composition of Kentucky's
 New Albany  Shale;  Determination and Uses.   Elsevier  Publishina
 Company,  Amsterdam,  1967.                              i

 Smith, J. W.  Simultaneous DTA-TG-MSA Apparatus  for Thermal  Study
 of Natural  Fuels,  International  Conference  on Thermal  Analysis
 1968.                                                  !
                                                       i

 Smith, J.  w.   Theoretical  Relationship Between Density and  Oil
 Yield  for Oil Shales.   USBM Report of  Investigations ; 7248,  1969.

 Smith, J.  W.,  W.  A.  Robb,  and  N.  B.   Young.   High i Temperature
 Reactions of Oil  Shale Minerals  and Their  Benefit to Oil  Shale
 Processing in Place.   Presented at  the  llth Oil Shale  Symposium,
 Colorado  School of Mines, Golden,  Colorado, 1978.      \

 Stanfield,  K. E.  Properties of Colorado Oil Shale.  USBM Report
 of Investigations 4825, 1951.                          :

 Stollenwerk,  K.   G.   and  D.  D. Runnells.   Env.  Sc.  & Technol
 November  1981, pp. 1340-1346.                          ;

 Taback,  H.  J.,  G.  C.  Quartucy and  R.   J.  Goldstick.  ; KVB,  Inc.,
 Engineering  and  Research Division,  Irvine,  CA 92714.   Test  of a
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 Shale  In  Sztu Retort at  Geokinetics, Inc.,  Uintah  County, Utah.
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                                                       t
 Tamm,  P.  W.,  C.  A. .Bertelsen,  G. M. Handel, B. G. Spars and P. H.
 Wallman.   Chevron Research Company, Richmond,  CA.    The Chevron
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 1981,,  Chicago, Illinois.  American Petroleum Institute/ Washington,
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 Tarman, P. B., H.  L.  Feldkircher,  and S. A. Weil.  Hydroretorting
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                                261
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                                                                        I


Tisot, P.  R.   Physical Structure of Green River  Oil  Shale.   USBM      •
Report of Investigations 6184, 1963.

Tisot, P.  R.,  and H.  W.  Sohns.  Structural  Deformation of  Green      •
River Oil  Shale  as it Relates to In. Situ  Retorting.   USBM Report      •
of Investigations 7576, 1971.

TOSCO Development Corporation, Denver,  Colorado.  Project Descrip-      |
tion Technical Report, Sand Wash Shale Oil Project.  Uintah County,
Utah.  May 1982.                                                        .

TRW.  Denver  Research Institute.   An  Engineering Analysis Report      •
on the  Union Retort B Process.  Prepared  for Industrial Environ-
mental  Research  Laboratory,  U.S.E.P.A.,  Cincinnati,   Ohio 45268,      •
under Contract No. 68-02-1881, March 1977.                               •

TRW.   Denver  Research  Institute.    Management  of  Solid  Waste      n
Residuals from Oil  shale  Recovery  Processes.   Prepared for Indus-      |
trial Environmental  Research Laboratory,  U.S.E.P.A.,  Cincinnati,
Ohio 45268, under Contract No. 68-02-1881,  May 1977.

TRW.  Denver  Research Institute.   Trace Elements Associated with      •
Oil  Shale  and its  Processing.   Prepared  for Industrial Environ-
mental  Research  Laboratory,  U.S.E.P.A.,  Cincinnati,   Ohio 45268,      •
under Contract No. 68-02-1881, May  1977.                       .         i

Union Oil Company of California, Energy Mining Division.  Environ-      „
mental Monitoring Plan Outline.  Parachute Creek Shale Oil Program,      •
Phase II, January 23, 1984.  U.S. Patent 4037657.                       •

Vanderborgh, N. E.  Characterization of Oil Shales by Laser Induced     •
Pyrolysis.  FACSS, Atlantic City, N.J., Nov.  19, 1984.                  •

Wildung, R.  E.,  and J.  M.  Zachara.   Geochemistry of  Oil  Shale      m
Solid  Waste Disposal.   Proceedings  of International  Symposium,      g
August 11-14, 1980.  K. K. Peterson, Editor.  Sponsored by the Oil
Shale Task  Force and U.S. Department  of  Energy.   Colorado School
of Mines Press, Golden, Colorado, 1981.                                 •
                                                                        1
                                                                        1
                                262
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                           APPENDIX A                 .:

AUTO-OXIDATION POTENTIAL  OF  RAW AND SPENT SHALE AND THE SUGGESTED
      DESIGN OF PILES TO AVOID THE AUTO-IGNITION OF SHALES
                                                      i

A.I.  Auto-oxidation Potential of raw and Spent Shales;

At the present  time,  considerable effort is being devoted to com-
mercialization of processes to produce liquid fuels from oil shale
deposits in the western United States.  The retorting of oil shale
produces large quantities  of solid waste.  This material, mineral
matter from which  kerogen has been thermally removed to a varying
extent, is referred to as retorted or spent oil shale.;  This spent
oil shale contains a considerable amount of carbonaceous material.
The amount  of spent  shale  to be disposed  of after retorting the
raw shale  is  dependent upon  the  retorting  technology;  and retort
efficiency.   For  example,  a  50,000  tons  per  day re'tort,  using
25  gallons per ton  raw  shale  has  been  estimated to  produce
42,500 tons  per day  of spent  shale  for disposal  [Brpwn  et al.,
September  1977].   Retorted  shales  from internal  combustion  gas
retorts have  carbon  compositions of  2% 'to  3%  and  are  soft  and
friable.    Retorted shales  from  indirect heated  retdrts  (Paraho
indirect mode,  TOSCO II,  Union  B)  have a higher  carbon content
which  may  be reduced to  less  than 1%  if  the retorted  shale  is
subsequently combusted.                                i

Most  developers  are  currently  planning  on disposing of  the  the
spent  shale,  overburden  and rejected raw  shale  fines  in nearby
canyons.   Disposing of  this  material  in landfills several hundred
feet  thick  and  covering  several square miles each  is  a likely
prospect.    The   phenomena of  auto-oxidation,  self-heating,  and
spontaneous combustion have  long  been  observed in large masses of
carbonaceous materials  such  as coal  storage  piles,  coal mining
refuse piles,  and dump  sites.   Where spontaneous  combustion  has
occurred,  extinguishing measures have been difficult or impossible.
Hence  the potential  of spontaneous combustion in  spent  oil  shale
disposal areas is a matter of serious environmental concern.

Most of the work in  the area of auto-oxidation potential has been
done on coals.   Several  factors have been found to have a signifi-
cant effect on the rate  of spontaneous heating of coal>[Kim,  1977]
as described below:
                               A-l
 image: 








                                                                        I
Air Flow Rate                                                           K

The air  flow rate  is  a complex  factor  because  air both provides
oxygen for oxidation of the coal and dissipates the heat generated      •
by  oxidation.   A  very high  flow rate  provides  almost unlimited     • •
oxygen, but dissipates heat efficiently.  A low flow rate restricts
the amount of oxygen available, but allows heat generated to remain     m
in  the coal.   A critical  flow rate  would be one  that provides      g
sufficient oxygen  for  widespread oxidation but does not dissipate
the heat generated.                                                     «

Particle size

Particle size has  an inverse relationship to spontaneous heating.      B
The smaller  the particle size, the greater is the exposed surface      m
area  and  the greater  is  the  tendency toward spontaneous heating.

Rank                                                                    |

It  is generally agreed  that  spontaneous  combustion is  a  rank-
related phenomenon.  As the rank of coal decreases, the hazard of      •
spontaneous  heating increases.  Lignites  and subbituminous  coals      P
are most susceptible to spontaneous heating.

Changes in Moisture Content                                             •

The  moisture content  of the  coal,  or  more exactly,  changes in      _
moisture  content,  affect  the  tendency of  coal  to spontaneous      ••
heating.   Drying,  lost  of  moisture,  is  an endo thermic process      m
and  lowers  the temperature  of  the   coal;  it also  exposes more
oxidative  sites.   Wetting,  gain  of  moisture,   is  an exothermic      •
process,  and the  heat liberated  may be sufficient  in itself to      •
cause  spontaneouts  heating.    For  a  given  coal  at temperatures
below  212 °F,  the  heat of wetting  is  greater  than the  heat of      •
oxidation.                                                              |

Temperature                                                          •   «

The rate of  coal oxidation  is  a direct function of temperature; the     ™
higher the temperature,  the  faster the rate at which coal  reacts
with  oxygen.  This  is particularly  important in  areas where  heat      H
generated  by oxidation accumulates,  further  accelerating  the  rate      H
of  oxidation.

Pyrite Content                                                          H

The  presence  of  the   sulfur  minerals  pyrite  and  marcasite  may
accelerate spontaneous  heating.  Under certain  conditions,  the      •
pyrite may  swell  and cause  the coal  to  disintegrate,  exposing      •
more  oxidative  sites.   If the  pyrite  is finely divided  and  can be
rapidly converted to ferrous  sulfate,  the coal is more  susceptible      m
to  spontaneous  heating.  Generally,  the pyrite concentration  must      H
exceed 2 pet. before it has a significant effect.
                                A-2
1
1
 image: 








The  various  methods  used  to study  spontaneous heating  are de-
scribed  in  detail in  the literature  (Guney and  Hodges,  1969],
most  are variations  of the  four basic methods  described  in the
following paragraphs  [Kim, 1977].

Adiabatic Calorimetry

The coal sample is placed in  an  insulated container or bath, and
the whole system is heated to  a preselected temperature.  When air
or oxygen is  added, the temperature of the coal rises;,the material
surrounding  the coal is heated so that its temperature coincides
with the measured  temperature  of the coal.  Since there is no heat
loss to the surroundings, changes  in coal temperature  are measured
accurately.   The change  in the temperature of the coal in a given
time,   the  time needed to reach a preselected temperature,  or the
amount of heat generated per unit of time is used to  Evaluate the
spontaneous heating potential  of the coal.             ;

Isothermal Calorimetry                                 !

In this  method, a coal  sample is placed in  a  large b'ath held at
a  constant  temperature.   Heat generated  in  the coal, sample,  by
oxidation or  wetting,  is measured by thermocouples and dissipated
in the relatively large heat  sink.   The  measured rate of  heat
generation  is  correlated  with  the combustibility  of  the  coal.

Oxygen Sorption

In the oxygen-sorption method, a coal sample is  placed  in  a con-
tainer and  air or oxygen  is  added.  In  a closed system, gaseous
reaction products  are  periodically removed,  and the amount of air
or O2  that  must be added to maintain the system at constant pres-
sure is used  to estimate the amount of oxygen absorbed.  In a flow
system, the flow rate and analysis of the effluent gas j are used, to
estimate the  amount  of oxygen adsorbed by the coal.  The tempera-
ture  increase per unit  of  oxygen consumed  indicates the  coal's
potential for spontaneous heating.                     '

Temperature Differential                               :

The coal sample is placed in a bath and heated at a constant rate;
the  temperature  difference   between  the  coal  and  the bath  is
measured.  Initially, the  temperature  of  the  coal lags behind the
bath temperature.  When the coal begins to self-heat, the tempera-
ture of  the  coal will coincide with,  then exceed, the I temperature
of the bath.  Usually, some variant of a temperature differential-
time relationship indicates the combustibility of the coal.
                                                       i
Most  experimental  studies  use   one  of  the  four  basic  methods
described,  but  other factors vary for each experiment.   The  coal
samples  vary,  particularly  in origin,  amount,   preparation,  and
particle size.   The  atmostphere is usually air  or  O2  ^although N2
                               A-3
 image: 








                                                                        I
or other inert gas may be used for baseline evaluation or to bring      •
the coal  to the starting temperature.   The  oxidizing medium used
may be moist  or  dry,  flowing or static.  The initial temperature,
final temperature, and  heating rate also vary.  In some case, the      ja
effluent gas is analyzed for CO, CO2 , O2 , CH4 , and other hydrocar-      •
bons to  provide  a more of its relatively simple  adaption to the
detection of spontaneous heating.                                        •

A  readily determined,  universally applicable index  of combusti-
bility would  be  the  preferred method of evaluating  liability to      ».
spontaneous heating.  Although several  indices  of combustibility      m
are proposed  in  the  literature for coals, none is in general use.      *
The most  common  indices are described in the following paragraphs
[Kim,  1977].                                                            •

Heating Rate

The temperature  increase under controlled conditions, measured in      ||
degrees Centigrade per  hour per  gram (°C/hr/g).   Another variant
involves  the  measurement  of  the  quantity  of  heat  released,      _.
measured  in  calories per hour per gram  (cal/hr/g).   The greater      •
the heating  rate,  the  greater  is  the  tendency to  spontaneous      •
heating.  Two variations of this method are:

     Relative Heating Rate  The heating rate relative to the            I
     heating rate of some standard sample.

        amic Heating Rate  Rate at which the temperature of             I
         coal increases with respect to its surroundings                 -
     within a given temperature range.

Crossing-Point Temperature                                              •

The temperature  at which the temperature of the coal and a heated      •
bath coincide, also called relative ignition temperature.               ||

Ignition Temperature                                                    «
                                                                        I
The temperature  at which the coal ignites.  The ignition tempera-      m
ture  at  which  the  coal ignites.   The  ignition temperature  is ,
determined by observation;  that  is,  the temperature  at which an      fl
observer  sees  the coal  fire.   It cannot be  exactly defined and,      H
therefore, can only  be used to determine relative spontaneity of
the coals tested.                                                       n
The ratio  of CO  formation  to oxygen  adsorption,  also called the      •
"CO  index."  The increase  in  the  concentration  of CO  and the      •»
decrease  in  the  concentration  of  oxygen  are  related  to  the
temperature  of  the  coal.   Monitoring  air for CO  and  oxygen is      A
the basis for a method of detecting spontaneous heating.                p
                               A-4
1

I
 image: 








Combinations of the preceding  indices  also are used in an attempt
to achieve greater accuracy.  All of the indices are determined by
a laboratory procedure and require  standard  conditions  to obtain
reproducible results.   In some studies, the  index  of;interest is
compared to  some  internal  standard; oxygen content  of  the  coal,
for instance, without mathematical correlation.  In other studies,
a simple  ranking  system is used to  evaluate  the coal^s  combusti-
bility. .  Indices  determined  in  the   laboratory  have  not  been
compared  to  the actual  incidence  of spontaneous heating.   Owing
to the lack of an objective criterion and the diversity of experi-
mental conditions under which the indices were developed, comparing
various indices would be  inaccurate and possibly misleading.   No
particular index has been shown to be significantly more accurate,
and none is  in  general use.  At present, the CO index; is probably
receiving  the  most interest  in the United States.  This is  not
because of demonstrated superiority as an index of combustibility,
but because  of  its relatively simple adaptation to the  detection
of  spontaneous  heating.   In  many  instances,  evaluation of  the
hazards from  spontaneous heating  is based on previous  experience
with a given coal.                                    >

Recently  Green  of Research  Triangle  Institute (RTIJ)  conducted
experimental work on measuring auto-oxidation potential of  raw
and retorted oil  shale for the U.S. EPA [EPA-600/2-84-153, 1984].
This study was  conducted to assess the potential spontaneous com-
bustion hazard  of solid waste streams  produced in  the  processing
of  oil  shale.   In additon,  the  utility and  precision  of various
test methods  to assess  this  hazard were  assessed.   This_work_is
the  most  comprehensive  work  done  to  measure the  autoignition
potential of raw and spent shales and is summarized below:

A.1.1.  RTI Study On Auto-oxidation Potential of Raw and
        Retorted Oil Shale

Factors which  influence the tendency  of a storage  pile to  self-
heat and eventually ignite can be grouped into two main categories.
The first category includes those properties which are peculiar to
the solid itself:  reactivity toward oxygen, and heat release as a
function  of  temperature.  The second  group of  factors  are  those
relating  to  the pile and its construction:   overall dimensions,
particle size, degree of compaction, homogeneity, ambient tempera-
ture, temperature  of  placed materials,  precipitation, «wind speed,
etc.   It  is  quickly  seen that pile characteristics  are going to
be  more  difficult to  measure  and  most  likely subject  to  more
variation than the properties of the solid itself.     i

In  this  study,  an investigation of laboratory  methods  of deter-
mining  spontaneous combustion tendencies  was  conducted.   These
methods were  then applied  to  raw and  retorted oil shale samples
to  determine the  relative hazards presented  by these  materials.
                               A-5
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                                                                         I
In  addition,  several coal samples were tested by the same methods       •
so  that the hazards  of the oil shale materials could be related to       ™
the better known phenomenon of self heating in coal storage piles.

Retorted  shale samples  from  the Lurgi, TOSCO  II,  Paraho direct-       ffl
mode, Hytort  and Union B processes were tested.  A raw shale from
Federal  lease tract C-a in  Colorado,  two  raw  shale samples from       «
Federal  lease tract Ua/Ub in  Utah,  Wyoming  subbituminous  coal,       •
Western  Kentucky #9 bituminous  coal  and Pocahontas #3 (Virginia)
bituminous  coal  were  also   tested.   Sulfur  and  organic  carbon
contents  and  heating  values  of these  materials  are  given  in       ja
Table  A-l.    Heat capacities  of  these materials,  as  determined       *
by  differential scanning calorimetry are given in Table A-2.

RTI  tested  shale samples  for auto-oxidation potential by various       §|
methods  such  as:  nonadiabatic  oxygen  absorption test, adiabatic
oxygen  absorption test,  differential  scanning  calorimetry  test,       «,
isothermal  pressure  differential  scanning   calorimetry  test,       •
peroxide  test  and  thermal  graviometric  analysis testing.   The       ™
best  method  found   involved  a  differential  scanning calorimeter
test  and a nonadiabatic oxygen absorption test.  In  the former       •
case, endothermic  activity was  monitored;  in  the latter, changes       m
in  gas composition (outlet vs inlet) were monitored.

A.1.1.1  Differential Scanning Calorimetry                               I

Differential  scanning  calorimetry (DSC) involves  the measurement       _.
of  the heat evolved  or absorbed  by a sample at a given temperature       •
relative  to  a known reference  material at the  same  temperature.       ™
When the temperature is  increased or decreased, heat effects arise
from  differences in specific heats, phase changes  and  chemical       flj
reactions.  Low  temperature  oxidation  is  an exothermic reaction.       |{
When  spontaneous  heating  occurs,  the  heat  produced  by  this
reaction  (and other  exothermic reactions  including  the  heat  of       m
wetting)  is  greater  than the  heat  which  is  rejected to  the       •
surroundings  and  the  material which  is  oxidizing  increase  in
temperature.   As  the   temperature  of  the  material  increases,
the  rate  of   oxidation  increases  and,  in some  cases,  a  rapid       H
temperature increase then occurs.                       .                 H

DSC  data,  obtained  while  the  temperature  of the  sample  and       tt
reference  are increased at  a  slow constant  rate,  indicate  the       j|J
difference in heat flow between  sample and reference as a function
of temperature.  When the reference is an empty sample pan of equal      «
mass and specific heat to the pan in which the sample is held,  the       •
net heat effect is that produced by the sample.   When the tempera-      .
ture  of  the apparatus is restricted to eliminate the possibility
of phase changes in the  sample,  endothermic effects are associated       H
with  the  heat capacity of the  sample,  and with  some  materials,       •
such effects as drying,  desorption of gases, and devolatilization.
Exothermic effects in excess of  the sample heat capacity are asso-
ciated with exothermic chemical  reactions.
I
                               A-6
                                                                        I
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          TABLE  A-l.   DESCRIPTION OF SAMPLES TESTED  BY RTI
        Materal (-325 mesh)
                   Total sulfur
                      wt. %
                    dry basis
 Organic
carbon %
dry basis
 Higher
 heating
  value
 Btu/lb
dry basis
Western Kentucky #9 Bituminous Coal
Pocahontas #3 Bituminous  Coal
Wyoming Subbituminous Coal
Utah Raw Shale (66 GPT)
Utah Raw Shale (28 GPT)
C-a Raw Shale
TOSCO II Retorted Shale
Hytort Retorted Shale
Paraho Retorted Shale
Union Shale Mixture
Lurgi Retorted Shale
                       3.73
                       0.65
                       0.63
                       1.85
                       0.75
                       0.98
                       0.58
                       2.40
                       0.57
                       0.68
                       0.86
  61
  69
  64
  28
  11
   5.2
   3.5
   3.8
   3.1
   4.1
   0.13
 13,050
 12,120
 11,560
  6,240
  2,090
    878
    433
    420
    188
    209
     44
Source:  EPA-600/2-84-153, 1984
     TABLE A-2.
MEAN HEAT  CAPACITY OF  COAL AND SHALE MATERIALS
BASED ON INITIAL SAMPLE WEIGHT (J/G,  -325  MESH)
              Materal
                     25 - 200
                                               Temperature range, °C
25 - 400
25 - 600
C-a Raw Shale
Utah Raw Shale (66  GPT)
Utah Raw Shale (28  GPT)
Hytort Retorted Shale
Pocahontas #3 Bituminous Coal
Western Kentuck #9  Bituminous Coal
Wyoming Subbituminous Coal
Lurgi Retorted Shale
TOSCO II Retorted Shale
Paraho Retorted Shale
Union Shale Mixture
                       0.76
                       2.18
                       1.17
                       1.08
                       1.19
                       0.69
                       1.28
                       0.82
                       0.39
                       0.73
                       2.57
  0.72
  2.13
  1.15
  1.03
  1.28
  0.47
  0.67
  0.87
  0.89
  0.71
  1.75
  0.73
  2.56
  1.23
  1.17
  1.40
  0.44
  0.63
  0.92
  0.86
  0.66
  1.60
Source:   EPA-600/2-84-153, 1984
                                    A-7
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                                                                        I


Samples were tested in a DuPont Instruments Model 951 differential      |f
scanning calorimeter  equipped with a  standard low pressure cell.
The calorimeter  was coupled  to  a DuPont  Instruments  Model 1090/      _
1092 thermal analyzer which permitted temperature programming and      fl
data acquisition/playback using magnetic disk storage.  Samples of      •*
between 17 and 54 mg were used.  Variations in sample mass for the
different  materials tested  were  primrily  due to  differences  in      •
bulk density.   Samples  were  loaded  into open  aluminum  pans;  the      f|
pans were  completely filled  to  the  top edge  and excess material
was removed so that the sample surface was level.  An empty pan of      «
comparable mass  (and heat capacity) was used as a reference in all      ||
tests.

With air flowing through the cell, a preweighed sample in a tared      tt
aluminum pan was  placed on  the  sample thermocouple  disk  and an      9
empty  sample  pan was placed on the  reference thermocouple disk..  .

The test  was conducted by programming  the heater to increase the      f|
temperature  of  the Constantan disk to  which sample and reference    ;
thermocouples were  attached.   A precisely controlled heating ramp      ..
of 2°C per minute was followed from slightly above ambient temper-      •
atures  (25°-30°C).  Different samples  were heated  to  different      **
final  temperatures  (380°-550°C)  but  in  all  cases the  test was
continued  to  the end of  the exotherm.   Exothermic reactions were      0
sensed by  a  slight lead in temperature of the sample thermocouple      •
over  the  reference  thermocouple.   The  instrument was calibrated
to convert this  lead into an  actual heat effect.                        n

The most  important  measurement relating DSC  data to spontaneous
heating  behavior   is  the  onset  temperature  of  the  exothermic
oxidation  reaction.   When an exotherm  is  observed while a sample      fl
is being  heated, this  temperature is characterized by extrapola-      •
ting the  slope  of the leading edge of  the exothermic peak to the
baseline.   It is assumed that  the lower this temperature is, the      M
greater the  tendency of the material to spontaneously heat.  This      H
provided  a  means  for  empirically  ranking materials  of unknown
self-heating potential by comparison to materials  of known heating      am
potential.   The  results of this test are  summarized in Tables A-3      •
and A-4.   The  Wyoming subbituminous  and Western Kentucky bitu-      m
minous coals  exhibited  the earliest exothermic onset temperatures
followed by  the  66 gallon/ton raw Utah  shale.  The low volatility      •
bituminous  Pocahontas  #3 coal  was less reactive  than any of the      •
raw western shales which  were tested.  The carbonaceous retorted
shale  samples   exhibited  considerably  higher   exothermic  onset      m
temperatures  than the raw shale indicating  that  they present less      |
of  a  spontaneous heating hazard than  the  raw shale and much less
than the coal.   Decarbonized shale from  the  Lurgi  process was also      «
tested but  absolutely  no  exothermic  reaction  was  observed at      •
temperatures up  to  550°C.  The Hytort  retorted shale was extremely      «
unreactive,  exhibiting  an exothermic  onset temperature higher than
that  of any  of the retorted shale  samples  except for  the Lurgi      •
T<a4-nT-t-e»H cVial (* .                    -                                    B
retorted shale.
                                A-8
                                                                        i
                                                                        i
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  TABLE A-3.
EXOTHERMIC ONSET TEMPERATURE OBSERVED IN1OXIDATION
OF COAL, OIL SHALE AND RETORTED OIL SHALE
(2°c/minute heating ramp, -325 mesh)
              Materal
                          Atmosphere
Temperature
    °C
Wyoming Subbituminous Coal
Wyoming Subbituminous Coal
Western Kentucky #9 Bituminous Coal
Western Kentucky #9 Bituminous Coal
Utah Raw Shale (66 GPT)
C-a Raw Shale
C-a Raw Shale
Utah Raw Shale (28 GPT)
Pocahontas #3 Bituminous Coal
TOSCO Retorted Shale
Paraho Retorted Shale
Paraho Retorted Shale
Paraho Retorted Shale
  (-48 + 100 mesh)
Paraho Retorted Shale
  (-48 + 100 mesh)
TOSCO II Retorted Shale
Union Shale Mixture
Hytort Retorted Shale
Lurgi Retorted Shale
Lurgi Retorted Shale
                          Humid air
                          Dry air
                          Humid air
                          Dry air
                          Dry air
                          Humid air
                          Dry air
                          Dry air
                          Dry air
                          Humid air
                          Dry air
                          Humid air

                          Humid air

                          Dry air
                          Dry air
                          Dry air
                          Dry air
                          Dry air
                          Humid air
    190
    190
    190
    193
    211
    225
    226
    227
    230
    296
    300
    300

    300

    302
    306
    331
    357
 No exoterm observed up to 550°C.

 Source:  EPA-600/2-84-153,  1984
                               A-9
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TABLE A-4.
MAGNITUDE OF  EXOTHERMIC REACTION OF  COAL,  OIL SHALE AND
RETORTED OIL  SHALE (2°C/minute heating ramp,  -325 irresh)

Materal
Bituminous Coal (Pocahontas #3)
Bituminous Coal (W. Kentucky #9)
Bituminous Coal (W. Kentucky #9)
Sub-Bituminous Coal (Wyoming)
Sub-Bituminous Coal (Wyoming)
Utah (66 GPT) Raw Shale
Utah (28 GPT) Raw Shale
Hytort Retorted Shale
Raw Shale (C-a)
Raw Shale (C-a)
TOSCO II Retorted Shale
Union Shale Mixture
TOSCO II Retorted Shale
Paraho Retorted Shale
Paraho Retorted Shale
Paraho Retorted Shale
(-48 +100 mesh)
Paraho Retorted Shale
(-48 +100 mesh)
Lurgi Retorted Shale
Lurgi Retorted Shale
Atmosphere
Dry air
Dry air
Humid air
Humid air
Dry air
Dry air
Dry air
Dry air
Humid air
Dry air
Humid air
Dry air
Dry air
Humid air
Dry air

Humid air

Dry air
Dry air
Humid air
Exo therm
J/g
15,700
13,800
13,800
11,200
10,900
8,320
2,990
1,340
1,050
920
880
860
560
490
480

470

430
0
0
Temperature
range, °C
150-575
90-550
120-550
50-440
50-550
125-420
125-575
175-575
125-550
160-480
125-550
200-575
160-410
175-410
150-550

175-550

175-550
30-550
30-550

Source:  EPA-600/2-84-153,  1984
                                                                           1
                                                                           1
                                                                           1
                                                                           I
                                                                           I
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                                                                           1
                                A-10
                                                               1
                                                               I
                                                               I
                                                               1
                                                               I
                                                               1
                                                               I
                                                               1
                                                               I
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A . 1 . 1 . 2  Nonadiabatic Oxygen Absorption Test           !

The materials described  above were  also subjected to  a nonadiabatic
oxygen  absorption test  [Schmeling et  al., 1978].   In this test
100 g samples of material were placed in  a  glass cell, i Humidified
air  at  60 cc/min was passed through  the  cell  and the temperature
of  the  cell and  contents  were increased at  a rate of 25°C/hour.
The  exhaust gas  from the cell was analyzed chromatographically;
the  depletion of  oxygen and  increased  levels  of  carbon dioxide
were used as an indicator of reactivity.               ;

Based  on the  gas  analysis,   a  spontaneous  combustion liability
index  (the  S index)  was calculated.   The  formula  for this index
was  devised  by  Schmeling and  is based  on  the   conversion  of
oxygen in the inlet gas  to CO2 .
where S  = the spontaneous combustion index.           i
      hi =21 - oxygen concentration at 125 °C.         ,
      h2 =21 - oxygen concentration at 150 °C.
      hs = 21 - oxygen concentration at 175 °C.         \
      x± = carbon dioxide concentration at 150 °C - carbon dioxide
           concentration at 125 °C.                     .
      x2 = carbon dioxide concentration at 175°C - carbon dioxide
           concentration at 150°C.                     i

All concentrations are expressed in volume percent.    \

The results  of this test  are summarized in  Table A-5.   The test
indicated that the Wyoming subbituminous  coal was by far the most
reactive material with  an  S index of 108 in  the -48+100 particle
size test and  an  S  index of 165 when tested  in the -3,25 particle
size.   This is consistent with the generally observed phenomena of
spontaneous heating in  low rank coals.   The criterion,! adopted by
Schmeling;  that materials  with  S indices  greater than |30 (for the
-48+100 mesh  size)  are dangerous, also puts  the Western Kentucky
No. 9  bituminous  coal  (S  = 37.5) in this category.  As would be
expected from  historical  observations of spontaneous  combustion,
the bituminous coals  are much less dangerous than the: subbitumi-
nous coal .                                              i

The tests  indicated,  as  expected, that  the retorted j shales  are
less likely to spontaneously  combust  than any of the coals or raw
shales.  The  three coals  rank  in the  order  expected  from  past
experience   and larger  scale  testing.    The raw shales  exhibit
oxygen absorption behavior which ranks  with their energy content.
(The richer Utah shale  has a  higher S index than  the  leaner Utah
shale   and  the three  western shales  follow the  same brder in  S
index  as in higher heating  value ) .
                               A-ll
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                                                                                 I
TABLE A-5.
SPONTANEOUS  COMBUSTION INDEX  AND CALCULATION  PARAMETERS
OF MATERIALS SUBJECTED TO NONADIABATIC TEST  (TESTED DRY)

Material
(-325 mesh unless stated)
Wyoming Subbituminous Coal
Wyoming Subbituminous Coal
(-48 + 100 mesh)
Raw Utah Shale (66 GPT)
W. Kentucky #9 Bituminous Coal
Raw Utah Shale (28 GPT)
Pocahontas #3 Bituminous Coal
W. Kentucky #9 Bituminous Coal
(-48 + 100 mesh)
Raw Shale, C-a
(-48 + 100 mesh)
Raw Shale, C-a
Union Shale Mixture
Hytort Retorted Shale
TOSCO II Retorted Shale
(-48 + 100 mesh)
TOSCO II Retorted Shale
Paraho Retorted Shale
Paraho Retorted Shale
(-48 + 100 mesh)
Lurgi Retorted Shale
Lurgi Retorted Shale
(-200 + 325 mesh)

S
165
108
86
60
44
42
37.5
6.89
5.59
4.6
3.8
3.60

1.38
0.27
0.21

0.00
0.00

hi
9.44
3.55
7.41
2.97
1.55
3.43
4.85
0.45
1.12
0.41
0.90
1.10

0.57
0.10
0.68

0.38
0.32

h2
17.42
17.60
19.7
12.59
8.49
11.2
12.34
2.60
2.50
3.00
3.14
1.44

1.28
0.47
0.84

-0.04
0.14

hs
20.97
20.88
20.8
20.87
18.2
21.0
20.35
6.55
6.09
6.37
5.26
2.79

2.02
0.78
1.04

0.00
0.15

Xi
4.48
2.80
3.56
1.16
1.10
1.03
1.13
0.23
0.17
0.61
0.43
0.22

0.08
0.01
0.02

0.00
0.00

X2
5.48
4.10
1.86
3.05
2.88
2.13
1.70
1.43
1.23
0.76
0.68
1.57

0.79
0.42
0.21

0.00
0.01

Source: EPA-600/2-84-153, 1984


KEY










               S  = the spontaneous combustion index.
               hj = 21 - oxygen concentration at 125°C.
               h2 = 21 - oxygen concentration at 150°C.
               ha = 21 - oxygen concentration at 175°C.
               KI = carbon dioxide concentration 150°C -
                      carbon dioxide concentration at  125°C.
               X2 = carbon dioxide concentration at 175°C -
                     carbon dioxide concentration at 150°C.
                                   A-12
1
I
1
I
1
I
t
1
I
1
I
I
I
1
1
1
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 ™          -        raw ^ales  rank as high  as the subbituminous
   fH*  V1!?1161-,*6* ?PT) Utah  shale ranks intermediate between it
 and  the high volatility  Western Kentucky #9  bituminous  coal and
 SSi-     Sr J2?  GILT)  Utah Shale  ranks intermediate  Between the
 Western  Kentucky  #9  coal  and the  low volatility  Pdcahontas #3
 Bituminous coal.  On the basis  of this test, the rSw sales present
 a  hazard  of spontaneous  combustion on  the  order  of bituminous
 coals, and the greater the energy content of the shale > the great-
 t *  v, i   tendency for spontaneous combustion.  All of the retor-
 ted shales tested rank well below the bituminous coals: in spontan-
 eous combustion risk based on Schmeling's index.

 A. 1.1. 3  Conclusions From RTI Stud
          be, noted that  the results reported  are based on  a very
         number of samples  of raw and retorted shale.  : Substantial
 variations in composition  of raw shales occur with geographic and
 nnSaSaP51C  locatlon'  ^he retorted  shale  samples!9 came  from
 pilot plant operations  which may not be completely representitive
 of commercial  operation.   Hence  it. is strongly  recommended that
 a£ ^L//1^16/  °f .waste   materials  proposed  for  field  disposal
 be tested to  determine their actual spontaneous combustion hazard.

 Retorted shales investigated  in  the  study are unlikely to present
 a  spontaneous   combustion  hazard  if  properly  handled.   These
 include retorted shales from  the  Paraho  direct,  TOSCO 'II   Hytort
 an?njf^,g*  Pf°CeS|es  |nd  a mixture of  retorted shale, raw  shale
 nSSJn'-H  £  sulfur  from  the Union  B process.  These materials
 £??V®r to be ?ar Jre?:s .reactive than Pocahontas  #3  loW-volatility
 bituminous  coal which is generally regarded  at the  low1 end of the
 spectrum of coals susceptible to spontaneous heating.! This  con-
         was  bas^d  on . the basis  of  both the  exothermic  onset
         ure' ,, ^ determined  by differential scanning  calorimetry,
         nonadiabatic  oxygen absorption test,  and supported by TGA
 androniHOS%d£ta*   Tte Lurgi retorted  shale is nSS-bombustible
 and could not burn even  if  an attempt was  made to ignite it.

 The _raw  western shales,  while  not  as  liable  to  ignite as  the
 Wyoming  Smith-Roland  subbituminous   coal  (which  i s : generally
 placed  at the higher end of  the  spectrum of coals  susceptible "to
 spontaneous  heating)  present  a potential hazard.   Thd richer of
 SL^n h4 halJr  samPles (f.6 GP.T)  is particularly  reactive, falling
 between  the Wyoming  subbituminous and the Western  Kentucky hiah
 volatility bituminous  coal  (of intermedial reactivity with regard
 to coal)  in the nonadiabatic  oxygen  absorption test,   jln the DSC
 rest,   it falls  below  the  Western Kentucky  coal but  above the
 S a L^S iy unreactive  Pocahontas  #3 coal.  In the TGA weight loss
 test  (based  on  mass  remaining after heating  to  300°C) a greater
weight  loss  is  observed with  this  sample than  with  the  Western
Kentucky bituminous coal.                               !
                               A-13
 image: 








                                                                        I


                                                                        I
The leaner Utah shale (28 GPT) is intermediate in tendency to auto-     w
ignite  between the  Western  Kentucky  coal  and the  Pocahontas  #3
coal in both the nonadiabatic oxygen  absorption  test  and the DSC      •
test  (ranked  by exothermic  onset  temperature).  This  material      ffi
falls below the coal  samples in the  TGA weight loss  tests.   By
Schmeling's  criteria (S  index  > 30),  this  is  also  a potential      «
hazard.    The  C-a  shale  has  about  the same   exothermic  onset      W
temperature  as the  leaner Utah  shale  (i.e.,  intermediate between      w
the  Western Kentucky and Pocahontas bituminous  coals,  but ranks
considerably  lower  than  the  Pocahontas coal in  the nonadiabatic      if
oxygen  absorption test  with an S  index of about  6).   This  is      9
probably the least reactive of the three western raw shales tested
but should still be regarded as posing potential problems.              m

The  results  of the  study suggest that carbonaceous  retorted oil
shale poses  less  hazard  of spontaneous combustion than bituminous      _
coal and  it is logical that the more severe the retorting process      fl
and the more complete  the removal of the organic matter, the less      "
reactive the resulting waste product will be.  This does not imply
that the  risk of spontaneous combustion can be ignored but rather      |f
that  the risk should  be low  if proper disposal  practices  are      0
followed.   Good  practice  would likely  include cooling  before
disposal, compaction in  lifts,  and excluding  air  flow into the      •»
pile.                                                           ,        H

Decarbonized shales, such as the Lurgi decarbonized retroted shale,
are essentially inert since substantially all of  the energy content     H
has  been removed.  Such  shales  should present  no hazard of spon-      •»
taneous combustion.

On  the  basis  of DSC  testing,  codisposal of byproduct elemental      H
sulfur  with retorted  oil shale  will  not increase  the hazard of
spontaneous  combustion of the  mixture.   The mixing  of raw shale      «
fines with  retorted oil  shale  for disposal  should  be  approached      j|
very  cautiously and preferably be  avoided.   The addition of as
little  as   5  percent  raw  shale  fines,  appears   to  lower  the
exothermic   onset  temperature  of  the mixture   to  approximately      If
that  of the fines  themselves.   Although the energy available in      9
the  mixture is much less than that of the raw  shale fines, the
potential   for  spontaneous   combustion  may   be   significantly      •
increased as compared  to the retorted  shale alone and  may  in fact      |
be as great  as that  of the raw shale fines alone.  For  example the
addition  of as little  as 5 percent  raw shale fines  (Utah 28 GPT)      —
lowered the exothermic onset temperature of Paraho retorted shale      •
to  that  of  the raw  shale  fines  alone.   However  it  must  be      •
emphasized  that the data on  this point are somewhat  conflicting.
The  Union B shale mixture which  contained 5.47 weight  percent raw      V
shale   fines  behaved in  a manner  similar to  other  carbonaceous      H
retorted  oil shales which did not include  a mixture of raw shale
fines.   Hence it is recommened that anyone proposing  disposal of      »
retorted  and  raw shale  mixtures should evaluate their  particular      j|
mixture to  define its  properties.   It is  considered likely that
                               A-14
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for  each specific  retorted raw  shale  mixture there  is  a unique
value of raw to retorted shale ratio which if exceeded will cause
the mixture to  assume the properties of the raw shale.

The  raw western shales present a  potential  hazard,  but if stored
and disposed of under conditions suitable for long term storage of
reactive  coals, then they  sjiould  pose no greater  risk than such
coals.   Ideally, however, raw shales should be processed for ener-
gy  recovery to the greatest extent possible.   Material  produced
during  crushing operations that is too  small  for retorting would
be  preferably  subject  to  combustion  for  productionj of  process
heat, or if feasible,  agglomerated with a binder to aj size where
it could be retorted for maximum energy recovery.      i

Of the  test methods used in the RTI study,  the differential scan-
ning calorimetry test  and the nonadiabatic  oxygen absorption test
appear  to be the most meaningful.  These tests  were reproducible
and, when the  tests  were  applied to  coal  samples,  the  results
conformed to generally observed rankings of spontaneous combustion
potential.   Of  the other tests considered,  the  peroxide  test was
technically  unsound;  pressure  differential scanning icalorimetry
and  adiabatic  oxygen  absorption  tests did  not produce  useful,
reproducible  results  in  the course  of this particular  study.
These methods  may,  however,  after further  development be  made
useful.    The thermogravimetric analysis  weight  loss  |test,  while
potentially useful  in characterizing  samples was found unsuitable
as results  for  coal samples -did not conform to generally accepted
spontaneous  combustion rankings  and  the  retorted  shale  samples
produced an insufficient reponse to evaluate.          ,
                                                       i
A  summary  of  results  obtained  in  the  differential  scanning
calorimetry  and nonadiabatic oxygen  absorption  testing is  given
in  Table A-6.  As  no reference  standards  are available  for the
test parameters which were determined,  the accuracy of ithese tests
cannot  be  determined.   However,  the ranking of  the  materials can
be used as an indicator of relative spontaneous combustion hazard.

In summary,  the carbonaceous  retorted  oil  shale samples appear to
present  less  hazard of  spontaneous  combustion than  bituminous
coal.   None  of the raw  shales  were found to  present ' as  great a
hazard  as  Wyoming  subbituminous coal.  However,  the tyo raw Utah
shale samples tested were found to present hazards exceeding those
of - less reactive bituminous  coals.   These  materials  represent a
potential hazard,  but  if stored and disposed  of under conditions
suitable  for  long-term   storage   of  reactive coals,  !should  not
spontaneously combust.  The  co-disposal  of raw and retorted shale
should  be  approached  cautiously  and  preferably be ; avoided  if
possible as the presence of raw shale increases the energy contents
of the mixture  and in some cases decreased the temperature  at which
exothermic activity was observed.   Co-disposal of byproduct sulfur
with retorted shale appears  to  cause  no increase in risk of spon-
taneous  combustion (but may lead to leaching  problems).;
                               A-15
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         TABLE A-6.   SUMMARY OF RESULTS FROM DIFFERENTIAL
                      SCANNING CALORIMETRY AND NONADIABATIC
                      OXYGEN ABSORPTION TESTING

Materal
Wyoming Subbituminous Coal
Western Kentucky #9 Bituminous Coal
Utah Raw Shale (66 GPT)
C-a Raw Shale
Utah Raw Shale (28 GPT)
Pocahontas #3 Bituminous Coal
Paraho Retorted Shale
TOSCO II Retorted Shale
Union Shale Mixture
Hytort Retorted Shale
Lurgi Retorted Shale

Onset,
°C
190
193
211
226
227
230
300
306
321
357

DSCa
Exo therm,
J/g
10,900
13,800
8,320
920
2,990
15,700
480
560
860
1,340
'V-O
Nonadiabatic test
S index
165
60
86
5.6
44
42
0.27
1.4
4.6
3.8
0.00

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 Tested in dry air, particle size:  -325 mesh.
b                                                                             H
 No extherm observed to 550°C.                                                   •

 Source:  EPA-600/2-84-153, 1984
                                 A-16
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A,2  Raw and Spent Shale Storage Design To Avoid Auto-Ignition

As described earlier,  the  carbonaceous retorted oil shale samples
appear  to  present  less  hazard  of  spontaneous  combustion than
bituminous  coal.  None of  the raw shales were found to present as
great  a hazard  as  Wyoming  subbituminous coal.   These materials
represent a potential hazard, but if stored, and disposed of under
conditions  suitable  for  long-term  storage  of   reactive  coals,
should  not spontaneously  combust.   The co-disposal i of  raw and
retorted shale  should be  approached  cautiously and preferably be
avoided if possible.

There has been  no work in the area of practices of storage of raw
and  spent  shales.   The work  has  been  done in the airea  of coal
storage practices based on experience from the coal storage piles
auto-ignition  behavior.   As  raw  and  spent  shale present  less
hazard of auto-ignition than coal,  the use of coal storage designs
should  prevent  auto-ignition  phenomena  in  raw and  spent shales.

A.2.1  Coal Storage Pile Design to Avoid Auto-ignition.Phenomena

Since  spontaneous combustion  is  a serious  hazard in \stockpiling
low-rank coals, it would be well  to outline the mechanism of such
combustion.   Given   a  low-rank coal  and  a  high-rank;  coal,  the
greater moisture  content  and reactivity of the  lowejr-rank  coal
make it the more  susceptible to spontaneous combustion and there-
fore more difficult  to  stockpile  safely.   Low-rank coals have  a
greater tendency  than  high rank coals to slack and absorb oxygen.
Although loss  of moisture  is ultimately beneficial iin that  it
actually results  in  an increase in heating  value,  the  absorption
of oxygen is  detrimental.   The slight weight increase;  represents
a loss in B.t.u.  per pound,  and the reaction  is  accompanied  by  a
heat release,  which  can cause an  increased rate of oxygen absorp-
tion,.  This oxygen absorption is further aggravated by :the smaller
particle size and associated  large  increase  in total surface area
resulting  from  the   slacking.   Unless  checked,  the!  exothermic
reaction may eventually result in  actual combustion.  :
                                                      f
In a surface  storage  pile the rate  of  oxygen absorption can be
retarded only be  restricting the  movement of air  into!  and out of
the pile.   These air movements are caused by:         ;

 1.   Convection currents within the pile  -  the  "chimney  effect"
     of drawing fresh air in at the sides and expelling  pile
     gases  at  the top.                                 i

 2.   Barometric pressure changes.                      j
                                                      |
 3.   Changes in ambient air temperature.               ;

 4.   Differential wind  pressures  on various portions of  the  pile
     surface.                                          \
                               A-17
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Convection currents may always be considered  to  exist in any pile.
Their  rate  of movement,  however,  will vary  greatly depending  on
the  degree  of compaction of the coal  and the presence  or  absence
of air channels  within the coal mass.  Convection currents may  be
minimized  by  avoiding  segregation and  by  thorough  compaction,
which  is most  effective when  applied to  thin  increments  as the
pile is  formed.   The effects of compaction are  shown in Table A-7
[Allen and Parry, 1954].
     TABLE A-7.
EFFECT OF COMPACTION IN REDUCING THE VOLUME
OF AIR ENTERING OR LEAVING A COAL MASS  IN
RESPONSE TO BAROMETRIC PRESSURE CHANGE


Bulk
density,
Ib/ft*
40
45
50
55
60
65
70
75
80


Total volume,
coal and air,
cu ft
5,000,000
4,445,000
4,400,000
3,636,000
3,333,000
3,078,000
2,860,000
2,666,000
2,500,000


Volume of
coal.
cu ft
2,500,000
2,500,000
2,500,000
2,500,000
2,500,000
2,500,000
2,500,000
2,500,000
2,500,000


Volume of
air,
cu ft
2,500,000
1,945,000
1,500,000
1,136,000
833,000
578,000
360,000
166,000
0


Volume of air
entering coal
mass, cu ft
125,000
96,700
74,800
55,660
41,650
28,900
18,000
8,280
0
Heat released
by complete
combustion
of coal with
entering air.
Btu
12,500,000
9,670,000
7,480,000
5,566,000
4,165,000
2,890,000
1,800,000
828,000
0
aAssuming 100,000 tons of coal in storage and 5 percent increase in barometric
 pressure.

 Source:  Allen and Parry, 1954

Although barametric  pressure  changes  cannot be controlled,  the
resultant  movement of  air  into  and  out  of  the  pile  can  be
minimized  by  thoroughly compacting the  coal mass,  thus  reducing
the volume of air  within the pile.

Ambient air   temperature  changes  cannot  be  controlled  but  the
resultant  air movement into  and  out of the pile, although slight,
can be minimized by reducing the  air volume of the pile.

Air currents  set up in the pile by differential wind pressures are
best  suppressed by avoiding  segregation,  adequate compaction, and
smoothing  the pile surface.
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When  the  movement of air into and  out of a pile is restricted as
outlined  above,  the absorption of  oxygen from the airi within the
pile  renders the pile  gases inert thus  effectively checking the
dangerous  cycle  of oxygen  absorption, heat release and increased
rate  of oxygen absorption.                             i

In  reviewing  the various  methods of restricting  air movements
within  the  pile  it  is  evident  that  compaction  and avoidance
of  segregation are the most important factors in combating every
cause  of  air circulation.   Both  must be  accomplished! to achieve
trouble-free  storage.   Omission of either  one or the lather could
result in eventual heating  and  combustion, since the ;success of
the  storage  effort  will  be no  better  than the poorest piling
technique employed.                                    j

Numerous  methods  of sealing  storage  piles  of low-rank, coals have
been  attempted  [Allen and Parry 1954].   Since the mos£ desirable
seal  is one which permits the gradual  infiltration of air over the
entire pile surface, asphalt seals are considered to be undesirable
because they effectively seal most of the  pile  surface but leave
some  _small  openings,  which  act as  orifices  for  relatively high
velocity  air movements  into and out of the  pile.   Packed earth
seals  are subject to  the same  criticism,  plus  the problems  of
maintenance  of of the seal  and  recovery of clean coal.   Ash and
cinder  coverings  are  considered  to  be  ineffective  ;and  merely
contaminate  the  coal.   The cheapest  and most  effective  seal
appears to  be the well  slacked  coal   on  the surface  of the pile.
This  seal, which  represents  no  contamination problem,  will absorb
oxygen from  the  entering  air so  that air  reaching  the  interior
of the pile will  be virtually inert.                   ;

There  are  some   other  considerations  which  can be  taken  into
account when designing a coal pile storage [Lowry, 19541] and these
are summarized below:                                  ;

 1.   Storage area  should  be level, firm,  well drained, and free
     of fences, piers,  etc.                             '

 2.   Build up the piles in  increments not exceeding  1 to  2 ft.  in
     depth.                                             ,

 3.   Thoroughly compact each increment before placing ! additional
     coal  on  the  pile.   This compaction should be applied  to  the
     entire pile  top,  sides  and  edges.                 I

 4.   Maintain the side  slope  at  14°  or less to prevent segregation
     and  to  facilitate the  compaction.   Though one study  [Davis
     and Boegly,  January 1978] has  recently suggested a\ side slope
     up to 30° or less.
                               A-19
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                                                                        I


                                                                        I
 5.   Decreased height of storage piles  results  in decreased              U
     probability of spontaneous  combustion since  (a)  the  effective
     resistance to heat flow is  lower  which results  in the  faster       B
     heat of  oxidation  dissipation with less rise in  temperature       H
     (b)  lower piles tend to decrease the amount  of segregation  of
     sizes when coal  is piled  carelessly and (c) it is  easier  to       «
     remove "hot spots"  when they occur.                                 W

 6.   Segregation of sizes  should be avoided since many  fires occur
     near the  boundaries  of zones of coarse coal that apparently       B
     act as chimneys for conducting air into the  pile.                   H

 7.   Preferably coal 'should not be piled in hot weather since many
     fires apparently are due to this cause.

 8.   A shipment of coal  that is wet should not  be piled with other       _
     coal.                                                              H

 9.   Coals from different sources should not be stored  in a  common
     pile.                                                              I

10.   Care should  be taken to keep out  extranenous material which
     may cause fires.                                                   •

11.   After storage  the  temperature of  a pile should  be determined
     regularly  by means  of thermometers in previously  installed
     pipes.   The  extremely local nature  of "hot spots"   makes  it       •
     necessary  to test at  points on 10  to 20  feet centers.   If       •
     temperatures  of  140  to 150 °F are found,  the temperature  of
     the coal near these points should be taken on 5  foot centers.       H

Although these techniques deal with the storage of low rank highly
reactive  coals,  it is obvious  that  any stockpiling  technique re-       _
suiting in trouble-free storage of these fuels would  be even safer       B
for storing less reactive raw and spent shales.


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                               A-20
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                  APPENDIX B
USE OF SPENT OIL SHALE AS A LINER MATERIAL AT
          SPENT SHALE DISPOSAL SITES
                 Prepared by:

          William J. Culbertson, Jr.
             Charles H. Habenicht
           Denver Research Institute
   Chemical and Materials Sciences Division
             University of Denver
            Denver, Colorado  80208
                     For:

               Monsanto Company
               Dayton Laboratory
              1515 Nicholas Road
              Dayton, Ohio  45407
          Contract No. EPA 68-01-6487
                          B-i
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                                CONTENTS
I
I
I.  INTRODUCTION AND SCOPE	    1                        I
     A.  Object	    1                        •
     B.  Approach	    2
     C.  Experimental Plan and Independent Variables
         Used	   3
I
II.  DISCUSSION OF RESULTS	   7                        „
     A. Permeability	   7                        •
     B. Peak Angle of Internal Friction 0  Related                                  «•
        to Self Healing and Its Trade OffpWith
        Permeability 	  17                        B
     C. Residual Shear Strength and Critical                                        •
        Void Ratio Related to Slope Stability	19
     D. Brittleness Index Related to Cementation and                                p
        Permeability 	  19                        B
     E. Relation of Peak Friction Angle Op and
        Brittleness Index BI with Initial Torsional
        Stiffness and Shear Modulus G	 -20                        il
     F. Relation of Peak Friction Angle with Twist                                  •
        at Peak Strength	24
     G. Relation of Peak Friction Angle and                                         •
        Squashiness Index with Cured Void Ratio	24                        H
     H. Hydrate Species Determined by EGA	28
     I. Secondary Compression Index C                                               «
        Related to Cementation and Mellowing 	  31                        •
     J. Indirect Tensile Strength  (Brazilian)  Test  ...  33                        H
     K. Compression Index	36

III. CONCLUSIONS AND RECOMMENDATIONS 	  41                        B

IV.  REFERENCES	43
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I
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                                         LIST OF TABLES
            Table B-                                                       !       Page
                   Void Ratios e and Compression Indices C	: ...  37
                                                          c                >
•          II    Experimental  Design - TOSCO II.   Lurgi,  and Mixtures
                   of Mellowed TOSCO and Mellowed Lurgi  with Burned  and
                   Unburned TOSCO and Unmellowed Lurgi  Spent Shale.  .  .
•          II 1.   Pneumatic Arm Oedometer Results  from Fresh Specimens:
                   Void Ratios e and Compression Indice
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Figures
II 1.


II 2.
II 3.


II 4.

II 5.

II 6.

II 7.


II 8.
II 9.
II 10.
II 11.
II 12.
II 13.
II 14.

II 15.

II 16.
II 17.

II 18.


II 19.





LIST OF FIGURES
B-
Permeability of Mixtures of Burned TOSCO and Unburned
TOSCO Spent Shale after Approximately Four Weeks
Curing in Spring Oedometers 	
Permeability of 100% TOSCO II Spent Shale (TOSCO 100) . .
Permeability of 90% TOSCO II - 10% Burned TOSCO
Spent Shale (TOSCO 90) 	

Permeability of 80% TOSCO II - 20% Burned TOSCO
Spent Shale (TOSCO 80) 	
Permeability of 70% TOSCO II - 30% Burned TOSCO
Spent Shale (TOSCO 70). .. 	
Permeability of Lurgi Spent Shale 	

Permeability of Mellowed Lurgi (M14) mixed into Lurgi and
Mellowed Burned TOSCO (M-15) Mixed into TOSCO II and into
Burned TOSCO Spent Shale 	
Mineral Grain Density vs Time for TOSCO 100 Spent Shale .
Mineral Grain Density vs time for TOSCO 90 Spent Shale. .
Mineral Grain Density vs Time for TOSCO 80 Spent Shale. .
Mineral Grain Density vs Time for TOSCO 70 Spent Shale. .
Mineral Grain Density vs time for Lurgi Spent Shale . . .
Permeability of Spent Shales Correlated with Void Ratio .
Permeability Of TOSCO Spent Shale Mixtures Correlated
with Peak Friction Angle 	
Permeability of Lurgi Spent Shale Correlated with
Peak Friction Angle 	
Brittleness Index Correlated with Peak Friction Angle . .
Permeability Compared with Brittleness Index 	

Peak Friction Angle Compared with Initial Shear
Modulus G 	

Brittleness Index Compared with Initial Shear


B-iv



Page


8
. 9

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11
. 12
. 12
. 13
. 13
. 14
. 16

18

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. 21
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 II 20.     Extent  of  Twist  at  Peak  Strength  Correlated  with Peak
           Friction Angle.  .......  ;  .	!. .  .  .  20

 II 21.     Peak  Friction Angle of TOSCO  100  vs  Void  Ratio.  ......  27

 II 22.     Peak  Friction Angle of TOSCO  90 vs Void Ratio  ...:....  27

 II 23.     Peak  Friction Angle of TOSCO  80 vs Void Ratio  .......  27

 II 24.     Peak  Friction Angle of TOSCO  70 vs Void Ratio  ...;....  27

 II 25.     EGA Hydrate Water Peak of Tobermorite and  Ettringitel
           vs Time for TOSCO 100, 90, and 70 Specimens  ........  29
                                                               i
 II 26.     Peak  Friction Angle vs Time for TOSCO 100, 90, and 70
           Specimens	.  ...  29
                                                               i
 II 27.     Initial Torsional Stiffness vs 115 to 135°C  EGA      \
           Peak  Height	;.  ...  30

 II 28.     Twist at Peak Strength vs 115 to 135°C EGA Peak  Height.  .  .  30

 II 29.     Final C  at 45°  Peak Friction Angle  for Oedometer    I
           Specimens of Various Spent Shale Mixtures  	  ....  32

 II 30.     Final C  vs Peak Friction Angle for  TOSCO 100 Specimens  .  .  32

 II 31.     Final C  vs Peak Friction Angle for  TOSCO 90 Specimens.  .  .  32

 II 32.     Final C  vs Peak Friction Angle for  TOSCO 80 Specimens.  .  .  32

 II 33.     Final C  vs Peak Friction Angle for  TOSCO 70 Specimens.  .  .  32
                                                               i
 II 34.     Final C  vs Peak Friction Angle for  Lurgi  Specimens  ....  32

II 35.    Torsion Test Twist at Peak Strength  vs Brazil        \
          Tensile Strength	i  ...  34

II 36.    Brazil Tensile Strain At Failure vs  Torsion Test Twist
          at Peak Strength	;  ...  34

II 37.    Brazil Tensile Strength vs Initial Water Content. .....  35

II 38.    Compression Index of Fresh Specimens  for Loading Increment
          155 to 310  PSI	'.....'... 35
                                     B-v
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SYMBOLS AND ABBREVIATIONS
     The following symbols have been used in this Appendix.
TA
TOS100
TOSCO 100
100% TOSCO II
TOS90
TOSCO 90
TOS 80
TOSCO 80
TOS 70
TOSCO 70
MEL
 A
51

24%

PS I
Gm
cc
Lb
EGA
e
C<x
Fluidized bed burned TOSCO II spent shale from TOSCO
Rocky Flats site (from drum number TA).   Unburned
scalped retorted spent shale from a pilot size TOSCO
II retort at the TOSCO Rock Flats site.
A mixture of 90% unburned TOSCO II spent shale with
10% of burned spent shale from a pilot size
fluidized bed burner fed TOSCO II spent  shale at the
TOSCO Rocky Flats site.
A mixture of 80% unburned TOSCO II spent shale with
20% of the burned spent shale.
A mixture of 70% unburned TOSCO II spent shale with
30% of the burned spent shale.
Autoclave mellowed material.
Triangle data points on graphs are usually for standard
proctor specimens.
Square data points on graphs are usually for modified
proctor specimens.
Number by data point on graph signifies oedometer
loading number of specimen tested.
Percentage figure by data point on graph signifies
percent water dry basis added to spent shale mix before
loading oedometer.
Pounds per square inch
Grams mass
Cubic centimeters
Pounds
Evolved gas analysis
Void ratio
Secondary compression index =de
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                                                  d log t
                    = slope of void ratio vs logarathim of time plot of
                    secondary compression.
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 o                  Normal stress = stress normal to shear plane1

oy                  Vertical stress.                            \

ay '                Effective vertical stress = vertical   stress less any
                    pore water pressure.  Important to the mechanics of the
                    soil skeleton.                              I

T                   Shear stress                                !
                                       - -.-                        i
TP                  Peak or failure shear stress.
T                                                               :
 R   .               Residual shear stress                       i

tip, dp'             Angle of internal friction (or friction angle)
                    at peak shear strength - particularly useful for
                    noncohesive or silty soil. 0p = arctan T/a. '

0n> fin'             Same as above but for residual strength.    >

BI                  Brittleness index = TP - TR
                                          Tp                    !

PL                  Plastic limit, % water dry basis            :
                                                                l
LL                  Liquid limit, % water dry basis             ;

PI                  Plasticity index = LL - PL                  i

CSH I               One type of tobermorite, CaO Si02 nH^O using
                    cement chemists terminology                 ',
                                     B-vii
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                                                                                I
                        Acknowledgments
The following people have contributed particularly to this work:
     Russell Nye, Senior Research Technician
     Michael Shaffron for Consolidation Data Reduction                          •
     Lindsay Patten, Student Chemist                                            •
     Penny Hudson, Mineralogist
     Dr. Paul Predecki, X-ray Diffraction                                       •
     Ed Bates,  EPA Cincinnati                                                   •
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I.   INTRODUCTION AND SCOPE
                                                                I
     A.   Object                                                 !

     This Appendix presents a summary of work conducted  under Contract
68-01-6487 and Cooperative Agreement CR809233.   A more complete report
including detailed descriptions of materials used, testing procedures,  and
results  will  be published upon completion of Cooperative Agreement CR809233.
This work was undertaken to survey the possibility of use of spent oil  shale
itself in constructing a deeply buried liner below embankments of spent oil
shale.  Some possible modification of these spent oil shales were to be
tried including the admixing of autoclave mellowed burned spent oil  shale
with the hope of reducing the cementation tendencies of  otherwise rather
fine grained material, sometimes of low emplaced permeability, ahd^of
reducing the permeability due to hydrothermal generation of clay like
species.  In general a material was sought which had much of the;frictional
characteristics and volume stability of silt but the impermeability of  clay
without a tendency for eventual cementation on the one hand or Teachability
and partial soil skeleton loss on the other.                    :

     One of the important needs of a spent oil shale based "clay" liner is
low permeability.  Perhaps the next most important is self healing ability
if it risks being cracked through subsidence below or geologic faulting.  A
disadvantage of high strength soil such as can be achieved by cementation,
dehydration or compaction is that, "once ruptured, the structure; does not
readily,  if at all, reform.  Weak bonds possess a certain capacity for  self
healing.  . ."  (Ingles 1968).  A third requirement is volume stabjility or
resistance to  swelling and shrinking.                           \

     The  present  study has mostly been concerned with 100% standard and 100%
modified  proctor  compacted specimens of spent oil shale althoughj static
compaction of  some TOSCO  II  and Lurgi material to some 280 psi was done
during  torsion  shear  strength apparatus  "shake down."  The specimens have
often seemed  too  brittle  for good self healing due to high compaction and/or
cementation.   Their volume stability to consolidation under  280 >psi pressure
 has  been good, however.                                         j

     Any detrimental  effect  of  drying on the  spent oil shale  liner materials
 is  presently speculation.  There  seems to  be  little  shrinkage,  in general,
 but  the effect on permeability  and  self  healing  capability when re-wetted is
 unknown.   The self healing capability while still dry is  perhaps  nil!  for
 some of the  more  cemented materials  but  lesser cemented materials sucn_as
 TOSCO II material  may show some ability  to flow  into tension  cra'cks while
 dry under say 300 psi  overburden  vertical  pressure.             !

      Fortunately the  underground  environment of  the  liner will  probably be
 moist on the country rock side of the  liner and  can  be made  moist on the
 spent  shale  embankment side.                                   :

      An important possible hazard to be  considered  is that  of increased
 pore water pressure in loosely compacted somewhat saturated  liner due  to
 shearing, chemical defloculation  due to  permeate composition, or earthquake
                                    B-l
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                                                                                    I
liquification.  In a too impermeable liner, an increase in pore water pres-          m
sure may not dissipate rapidly enough so that shear strength would drop due          gj
to reduced friction between soil skeleton particles as the effective normal
stress is lowered.  The liner might then become more like a grease than a
liner allowing a spent shale embankment to slide.                                   •

     Some specimens of the present study have been proctor hammer compacted
so well that they apparently begin on the dense side of the critical volume          Bj
line so they generally dilate at the beginning of shear.  This should reduce        g
pore pressure rather than increase it as shear occurs.  Standard proctor
TOSCO II spent shale cured for a short time shows no peak in the                    _
stress/strain curve and must begin above the critical volume line and               •
although probably self healing to some degree might, in spite of its silty          •
nature and high permeability, develop pore pressure during rapid shearing  or
other disturbance.  These considerations have not been directly addressed  in        H
this study.  Mainly plasticity and self healing problems in the face of             H
cementation have been addressed.

     Compressibility coefficients at various normal pressures in conven-            ||
tional oedometers have been determined on compacted specimens of zero age  in
looking for any collapse of the soil skeleton at  higher pressures than even
the 280 psi vertical pressure of the torsion tests.  Of course the vigorous          H
compaction used in preparing the specimens has reduced any tendency for             •
collapse and pore pressure increase but study of wetting or saturating is
also needed.  Wetting has been tried for spring oedometer specimens after            •
various aging times before determination of torsion shear strength and ^            Q
accompanied by specimen volume measurement before and after wetting during
permeability testing.                                                               n

     B.  Approach

     The routine testing approach has centered around study of rather highly        •
consolidated specimens of various mixtures of spent oil shale at two                H
moisture contents, one at optimum water content for maximum dry density, the
other at a somewhat wetter than optimum water content.  Often wetter than            n
optimum material is used for small dam cores and  around abutments for               ||
increased flexibility and lower brittleness and sometimes lower permeability
also results.  A vertical consolidation pressure  of around 280 psi was
produced  by spring  loaded  oedometers.                                               •

     To simulate a liner placement technique sometimes  proposed, the speci-
mens were compacted in spring oedometer sheaths to 100% of standard proctor         •
or  100% of modified proctor.  These compactions allowed a small further             g
consolidation in the oedometers.  The oedometer consolidation  is a  sort of
model  of  burial  under  an  embankment  of  moderate  height  and  allows  a standard        __
and somewhat  realistic environment for  subsequent aging/curing/and  or               H
cementation processes  in the specimen.  There  is  some unreality in  immediate        •
application of the  full 280  psi consolidation  pressure  just after compaction
however,  as some  time  is needed for  construction  of  full  embankment height.         •

     After permeability testing a specimen,  it was transferred from the
spring oedometer  to a  rubber membrane in  a triaxial  chamber for torsion             «
                                    B-2
I

I
 image: 








testing under a confining water pressure generally corresponding to an
assumed K  of 0.5 to 0.7.  A K  of 0.7 is higher than corresponds to a
two dimensionally normally consolidated silty,material but may tie about
right for certain specimens.  In this way the tendency for swelling in
diameter of a specimen as it in effect is extruded from the oedometer sheath
to the rubber membrane in the triaxial chamber is mitigated.  Such swelling
might break cementation of cemented specimens.  Without the confining
pressure even some stiff somewhat cemented specimens were crushed when only
moderate vertical pressures were applied prior to torquing.     !

     It is desirable to perform shear strength tests on undisturbed
specimens.  Specimens may be disturbed by swelling which softens them, by
over-consolidation which during extrusion hardens them or by breaking
cementation which softens them or fractures them prematurely.  After
obtaining the torsion stress/strain curve, the specimens were removed from
the triaxial container and their enclosing gum rubber membranes!cut away so
previously transferred longitudinal acrylic paint stripes on the specimens
could be examined and the specimen photographed.                i

     Some physical and chemical properties of the specimens were next
determined on dried fragments left from the torsion test.  These include EGA
analysis for hydrate water of species formed during curing.  Some of these
species are of a cementing or potentially Teachable nature.  X-ray
diffraction scans for confirmation or identification of these species were
also made.                                                      [

     The Atterberg limits of beginning materials and blends of spent shale
materials are a parameter important in soil mechanics correlations.  These
were obtained for some raw material spent shale and mellowed spent shale.
Atterberg limits on cemented specimens were not made.           ;

     Considerable time was needed to learn how to best operate the specially
built triaxial torsion machine.  Some specimens from preliminary series were
tested under various confining water pressures and with different variations
of specimen extrusion methods before the combination of conditions used for
most of the specimens prepared for the following experimental plan was
standardized.  At the beginning it was believed that cured specimens con-
taining much of the burned TOSCO spent shale would be too cemented to be
handled by the triaxial torsion apparatus and this material wasilimited to
30% in mixtures with less cementing TOSCO II material.  This fear was
validated as tests preceded.  Some of the 30% mixtures were strong enough to
cause slipping of the piston rod in the torque transmitting collet gripping
it.  Usually this could be remedied by further tightening of the collet.
Also sometimes a little bending over of the brass vanes in the pore stones
gripping a well cemented specimen occurred during twisting.

     It was also feared that there might be poor contact and gripping of the
top of the specimen by the piston pore stone when standard proctor and
particularly when modified proctor compaction was used, especially since a
3/32 inch cross section rubber o-ring was being used at the periphery of the
piston pore stone between the specimen and stone.  Preliminary experiments
using a pneumatic loaded oedometer with proctored material seemed to
                                   B-3
 image: 








                                                                                    1

partially support this fear and many of the main series of specimens were           «,
loaded in the spring oedometers using the o-rings but with some loose               |
material sprinkled on top of the compacted specimen within the o-ring before
insertion of the piston and application of spring pressure.  Previous static
compactions with the spring alone without proctor compaction had shown              •
attainment of rather high density although not as high as by some standard          •
proctorings and all modified proctorings   For this reason so"J Jope was
held that the thin loose layer would bond well enough to the piston pore            |
stone-vane structure.  When torsion tests^were made, however, it was found          f
that slippage often occurred between specimen top and the piston pore stone
without  involvement of the interior of the specimen to much extent.  More-
over disassembly of the specimen and porestones after torsion testing               |
revealed that the material at the top of the  specimen was much softer than
that at  the bottom and should not be expected to be as strong.

     Immediately a new procedure of torsion testing was  devised wherein  the         |
vertical pressure  on  the  specimen was brought up to that originally existing
 during consolidation  in  the  spring  oedometer  with  the hope that  this could          .
dig the  vanes  into the top of  the specimen  and  secure  a  f.0od/nnp0"Shpngrd1P-ina        I
 This was somewhat successful.   The  vertical  pressure  on  the specimen during
torsion  tlsti^n^  should  probably be  kept  at  that during consolidation anyway
 for  ess likelyhood  of  disturbance  of  the  specimen.   With fixed  upper and          |
 lower  specimenporestones about 1/2 of the  vertical  pressure  is  lost during        •
 extrusion  of the specimen in the triaxial  confining  chamber and  should be
 replaced before torsion.   As this  fraction  was  apparently unaffected by            |
 elimination of the loose layer and  piston  porestone  o-nngs in * ™"«J           I
 specimen loading procedure some other  reasons for the loss have  been sought.

      Loss of vertical pressure on the  soil  skeleton Curing unsheathing is          |
 oresentlv believed to be due to (1) some back lash in the pedestal pins and
 £a?1nfshea?n holes and (2) some specimen overconsolidation caused by excess
 piston  pressure on the specimen generated by friction drag bet«een the             |
 teflon  coated sheath and the specimen.  As the results of the effect are           •
 apparently of little consequence at the present rough stage of development
 ofPPtheenmetyhodf and useful correlations and comparisons between specimens were       .
 being made a further change in methodology was not instituted.  One change         |J
 might be to grease the inside of the oedometer sheath contacted by the
 specimen but this would make temporary adherence of the  acrylic paint marker
 stripes difficult.                                                                 H

       C. Experimental Plan  and  Independent Variables  Used

       Table  B-I  1  summarizes the experimental plan.   Each box  under columns        I
  test   These Brazil test specimens are denoted by "B"  in the boxes
  columns Cl and C2.

       The boxes under the C3 columns which have entries represent specimens
  prepared by standard pr0ctor compaction and tests by pneumatic arm oedometer
                                     B-4
I

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 image: 








                            TABLE  B-I   1.  Experimental  Design  - TOSCO  II,  Lurgi, and
                               Mixtures of mellowed TOSCO and Mellowed  Lurgi With
                                 Burned and Unburned TOSCO And Unmellowed Lurgi
                                                   Spent Shale
Material
Unburned TOSCO
10% Burned TOS
90% Unburned
TOSCO II
20% Burned Tos
80% Unburned
TOSCO II
30% Burned TOS
70% Unburned
TOSCO 11


II

:o,
Spring Oedometer and Triaxial Torsion Tests
Later
Satd.?
Yes*
No
Yes*
No
Ampl e +
Moisture
:o
Yes+
No
Ampl e +
Moisture
CO
Yes*
NO
Ample +
Moisture
Ample Moisture
75% Mellowed Burned
TOSCO, 25% Burned
50% Mellowed B
TOSCO, 50% TOS
_Am pie Moisture
• Lurgi
urned
CO II

Yes+
Yes+
Yes+
No
Ampl e +
Moisture
75% Mellowed Lurgi
25% Unmellowed
Ample Moisture
50% Mellowed Lurgi
50% Unmellowed
Yes+
Yes+
Cl = Modified Proc.
Tl
22%
54 B
22%
55**
23
56 B
23%
57**
28%
53 B
24%
75 B
24%
67
29%
66 B
25%
76 B
25%
77
34%
74
55%
92 B
40%
93 B
22%
51 B
22%
50
27%
52 B
25%
82 B
25%
84 B
T2
22%
34 B
22%
35
23%
39 B
23%
49
28%
62 B
24%
60 B
24%
63
29%
61 B
25%
58 B
25%
68
34%
59
55%
8& B
40%
87 B
22%
72 B
22%
73
27%
69 B
25%
83 B
25%
85 B
T3
22%
46 B
22%
47
23%
48 B i


36 B


25%
40 B




22%
43 B
22%
44
27%
45 B
C2 = Standard Proc.
Tl
25%
71 B
25%
91
27%
70 B
27%
90

24%
80 B
24%
81

28%
89 B
28%
88



30%
78 B
30%
79

T2
25%
32 B
25%
33
27%
31 B
27%
30

24%
37 B
24%
38

28%
41 B
28%
42


'
30%
64 B
30%
65




!






Pneumatic Arm Oedometer
C, = Standard Proc.
except with * which
is Modified Proc.
*
22% 25% 20% 30%
H20
!
1
* *
23% 28% • 22% 27% 33%
I
* *
24% 29% ' 24% 29% 34%
1
* *
25% 34% ! 28% 33% 39%
* '
55% !
40% 45 i
* * i
22% 27% ; 30% 35% 40%
i
* '.
25% 25 ! 30 35
* " ;
25% 25 ; 30 35
*  Modified Proctor                                                                        !

+ Permeability determined also                                                             !

**Permeability determined out of order resulting  in  "yes"  instead of "No" later saturation. ,-
                                                 B-5
 image: 








at five consolidation pressures up to 310 psi.  The water contents chosen
were those for optimum moisture for maximum dry density for standard and
modified proctor and several water contents including some wetter than              •
optimum for standard proctor, four or five water contents total, for each of        •
the nine spent shale raw material types or mixtures tests by the other
methods .  The loading number for the spring oedometer experiments is given         BJ
in the lower left corner of each applicable box in Table B-I 1.  This number        |
is followed by B if Brazil tests specimens were to also be prepared.  The
water to be added, percent dry basis, in preparing the specimens is entered         -.
in the upper area of each box.                                                      •

     Cl represents modified proctor compaction, C2 standard proctor com-
paction.  Tl, T2, and T3 represent curing times of nominally 2, 4, and 8            •
weeks respectively.  "Yes" represents that later "saturation" was to be             •
carried out by means of permeability measurement operations, "No" represents
that the spring oedometer specimen was to be torsion tested without                 m
saturation after consolidation and before torsion testing.                          |j



                                                                                    I


                                                                                    I


                                                                                    1


                                                                                    I


                                                                                    I


                                                                                    I


                                                                                    I


                                                                                    I


                                                                                    I


                                                                                    I


                                                                                    I



                                                                                    I


                                                                                    I
 image: 








II.   DISCUSSION OF RESULTS

     A. Permeability

     Permeability coefficients were more reproducible and self consistent
than expected.  Perhaps the high consolidation pressure (280 psi) contrib-
uted to minimum channeling along the wall of the oedometer sheath as well
as to minimizing flow between peds of soil fabric which may produce vari-
able permeabilities at lower vertical pressures.  Also bimodaV permeation
channel development may be minimized by the compaction at optimum water
content often used in producing these specimens.              '

     During mixing of material wetter than optimum, granulation occurred in
which  pellets of material formed which seemed to be wetter on Itheir surface
than inside.  This seeming tendency toward synergesis probably!disappears as
mineral hydrates form during curing but during compaction and initial
consolidation the wet surface of the granules may allow smearing of their
surfaces with development of parallel alignment of any clay-like mineral
platelets present during compaction by proctor hammer.  This may account for
some of the observed lower permeability at wetter than optimum'moisture
content compared to a dryer moisture content.

     Reduced permeability for compacted specimens of most spent shales at
wetter than optimum moisture content was observed.  Figure B-IJ 1 shows this
effect for both standard and modified proctored specimens madej from mixtures
of burned TOSCO and unburned TOSCO II spent shale.  However, the effect i-s
weak or nil for 100% unburned TOSCO II material, at four weeks, curing time.
Of course some other factor may be influential with these cementing mate-
rials  such as increased hydrate formation at higher water contents.

     Figures B-II 2, 3, 4, 5, 6, and 7 show a general but not universal mild
downward trend of permeability at  increasing curing times, especially beyond
30 days with the exception of the  more cementaceous 70% TOSCO 'II with 30%
burned TOSCO blend and the Lurgi spent shale which showed increased per-
meabilities beyond 30 days even though the latter had shown a decrease  up to
30 days.  The lower permeability at wetter than optimum water content is
evident again with the Lurgi material in  Figure B-II  6 when the  22% water
added  is compared with the 27% water added curves within the modified
proctor constraint  (square data points).

     It is  difficult to make  sense of the sketchy permeability; vs curing
time curves of Figures  B-II  2,  3,  4, 5  and  6.   This  is  perhaps caused by the
irregular course of mineral  hydrate  formation and disappearance  as  curing
time increases.  Reduction of the  mineral grain density  (determined by  the
Beckman air pycnometer)  of pulverized 48  C oven dried material from the
torsion test  is  assumed  to be an  indication  of  the extent of  h,ydrate  water
incorporated  in  cementaceous  and/or  bulk producing species  in ;the specimen.
Figures B-II  8,  9,  10,  11, and  12  plot  the remarkable course  qf  the extent
of  hydrate  water present  in  the specimens after torsion  testirig  as  indicated
by mineral  grain density.   If a lower mineral grain  density indicates more
mineral  hydrate  water  there  is  an  appreciable maximum in mineral  hydrate
                                 B-7
 image: 








              % NOTATIONS ARE WATER

                  INITIALLY ADDED TO MIX

              OPEN SYMBOLS - OPTIMUM MOISTURE

              SOLID SYMBOLS - WET OF OPTIMUM
   10
     -9
            100             9O             8O
                PERCENT TOSCOII WITH BURNED TOSCO

Figure B-II 1.  Permeability of Mixtures of  Burned  TOSCO  And  Unburned
                TOSCO Spent Shale After Approximately Four  Weeks  Curing
                in Spring Oedometers.
                               B-8
                                                                              1
                                                                              1
                                                                              I
                                                                              I
                                                                              I
                                                                              I
                                                                              I
                                                                              I
                                                                              I
                                                                              1
1
1
I
I
1
 image: 








   10
     -5
   10
     -6   _
Figure B-II 2.  Permeability of  100%  TOSCO  II  Spent  Shale (TOSCO 100)
   10
     - 5
   10
     - 6
                 J_
Figure B-II 3.
           Permeability of  90% TOSCO  II
           Shale  (TOSCO 90)
- 10% Burned TOSCO Spent
   lO
 o
 m
 < 10
 UJ
 X
 <r
 LU
 CL
   10
-7
     -8
                                  29%
                                  TRIANGLES STANDARD PROCTOR
                                       SQUARES MODIFED  PROCTOR
                                       SOLID SYMBOLS WET OF OPTIMUM
                                 I
                                           _L
           I
Figure B-II 4.
            10      20      30     4O      50      60   ;   7O

                          CURING TIME,DAYS           !

           Permeability of 80% TOSCO II  - 20%  Burned  TOS:CO Spent
           Shale (TOSCO 80)                             |

                        B-9                             !
                                                                       80
 image: 








I
1
io-7




io-8



to-9

1 1 i 1 1 i i
TOS 70
584I
vvfj 25%
28%

— —
34%
74
^"""---•^5976 25% TRIANGLES STAND. PROC.
• D SQUARES MODIFIED PROC.
! I I 1 1 1 1

I

1

I

1
•n
i
1
Figure B-II 5. Permeability of 70% TOSCO II - 30% Burned TOSCO Spent Shale
(TOSCO 70) •
1
io-5
o
LD
V)
\
O
"
H ID'6
_J
CO
<i
LU
2
CC
LJ
Q.
ID"7

	 1 	 , 	 1 	 1 i i |
| t 1 1 1 • '
|-| LURGI
22% A"s>1\>^ 72 ^ 	 ~~ ^43
78\ ^ 	 " 22%
30%\ 22%
52 N,

^^^\ 3 0 % ^-^"27%
^^J 27% ^^^-"^


SOLID SYMBOLS WET OF OPTIMUM
i 1 I 1 i I 1


1
1

1




mm
1
0 IO 20 30 4O 50 ' 60 70 80 "*
CURING TIME, DAYS m
Figure B-II 6. Permeability of Lurgi Spent Shale
I
B
i
B-10 : M
 image: 








     ,-4
    ID
      " 5
  o
  UJ
  to
    io
      -6
  o
 m
 UJ
 o.
    io
      -8
     o
      -9
           25%LURGI

           MELLOWED
                55%
             SQUARES-MODIFIED PROCTOR
0       10      20      30     40     50

                      CURING TIME, DAYS
                                                       60
70
80
F:igure B-II 7.  Permeability of Mellowed Lurgi (M14) Mixed into Lurgi and
                Mellowed Burned TOSCO (M-15) Mixed into TOSCO II and into
                Burned TOSCO Spent Shale                     ',
                             B-ll
 image: 








   2.74 ,
   2.72Q- UNM01STENED
        ,0%
   2.7 O
    2.68
    2.66
    2.64
                                        TOSCO  100
                              32
                              A 2 5%
22%
 47

 D

 D
 46
 22%  ~
                             35
                             Q22%

                          33   34

                          A   D
                          25%  22%
                           JL
                                 _L
Figure  B-II  8.  Mineral  Grain Density vs Time for  TOSCO
                 100 Spent Shale
    2.76
       >r-	1	

       O UNMOISTENED
          0%
    2.74
     2.60
               IO
                     20
                                               60
                                                      70
                                                            8O
                          30    40     50

                         CURING TIME, DAYS

Figure B-II  9.  Mineral  Grain Density  vs Time for  TOSCO 90
                 Spent  Shale
                           B-12
1
1
1
1
I
I
I
I
                                                                                  I
                                                                                  I
                                                                                  1
1
I
1
I
I
 image: 








2.78
2:76 -
2.74 -
          Fig. B-II 10.  Mineral  Grain Density vs Time"for
                         TOSCO  80 Spent Shale
           10     20    30    40     50     60  •  70    80
  2.6
Figure  B-il  11.   Mineral  Grain Density vs Time for TOSCO  70
                  Spent Shale
                   B-13
 image: 








  2.64
o
         UNMOISTENED

         O%     50
                 D 52
                22%D
  2.58
              1O      20      30     40      50

                            CURING TIME, DAYS
60
70
80
Figure B-II 12.  Mineral Grain Density vs Time for Lurgi Spent Shale
                         B-14
                         I
                         I
                         I
                         I
                         1
                         I
                         1
                         1
                                                                             I
                                                                             I
                                                                             1
1
                         I
                         1
                         1
                         I
 image: 








water at around 20-30 days as curing progresses with time for all unmellowed
TOSCO spent shale materials studied including unburned TOSCO II spent shale.

     The Lurgi spent shale, however, showed not only less reduction in
mineral grain density after curing compared to the grain densityiof the
uncured_dry raw material  but no  clear  cut minimum and  some  scatter of the
data points.  Apparently  a different cementation mechanism  is involved with
the Lurgi material than with the TOSCO materials or else the Lurgi pilot
plant pre-hydrated the material to considerable extent during post pyrolysis
operations.                                                      ;

     The interpretation of the minimum in the mineral  grain density plots  of
the TOSCO spent shales (Figures B-II 8, 9, 10, and 11) as due to imineral
hydrate maxima is substantiated by Figure B-II 5, introduced late'r, which
shows maxima in a low temperature evolved gas analysis water peak (at
approximately 150 C) at curing times corresponding to the minima In
mineral grain density.  This peak appears to be due to a tobermorite-like
species, CSH I (CaO S^  nHgO) and ettringite.                   |

     Figure B-II 13, shows the permeabilities found for autoclave mellowed
Lurgi (autoclave run M 14) mixtures with Lurgi, an autoclaved burned TOSCO
(M15) mixture with unburned TOSCO II and an autoclaved burned TOSto (M15)
mixture with burned TOSCO spent  shale  plotted vs void  ratio e for certain  of
the spring oedometer specimens.  These were all modified proctor ispecimens
and the water added and curing times are noted by the data  points plotted.
The low permeability of the 75% autoclave mellowed burned TOSCO sjpent shale
mixed with 25% of burned  TOSCO spent shale is to be particularly noted in
view of its low cementation to the time curing was stopped.  Before con-
cluding that the mixtures containing burned TOSCO spent shale giviing the
lowest permeability are most desirable in a liner the brittleness! of the
liner must be considered  and also its ability to self heal  after fracture or
during tension movement.                                         •
                                                                        /
     The permeabilities were determined just before torsion testing, the
void ratios were based on mineral grain densities determined on 4J8 C oven
dried material  after torsion testing and bulk dry density of the specimens
just after loading in the spring oedometers.  The bulk dry density was
calculated based on water added to the wet mixture loaded into thfe
oedometer.                                                        i

     Figure B-II 13 shows that in general the greater the fractio'n of burned
TOSCO spent shale that is blended into the unburned TOSCO II spen|t shale the
less the permeability at a given void ratio.  Lower void ratios give lower
permeabilities also, however, as is the well known trend for ordijnary soils.
Fairly clearly the hydrate forming cementation reactions of burned TOSCO
containing spent shale reduce permeability beyond that to be expebted  by
simple reduction of void  ratio determined using mineral grain density.   This
may be due to deposition  of fine precipitate or gel within  the spient shale
particles interstitial  spaces or it may be due to deposition at spent  shale
particle contacts that grows to invade the interstitial spaces.   Growth  of
cementaceous hydrates within a given porous spent shale particle should  not
influence permeability of the specimen much.                     \
                                  B-15
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                                         ft
     B.  Peak Angle of Internal Friction  P Related to Self Healing and
         Its Trade off with Permeability

     Figure B-II 14 shows a dilemma in trying to compound a liner material
made from any mixture made from burned TOSCO and unburned TOSCO Ijl spent oil
shale.  Both low permeabilities and low peak friction angles are desirable
but they seem to be nearly mutually exclusive.  A low friction an;gle allows
easier or more extensive rapidly self healing.  A high peak friction angle
is shown by the more cemented specimens.

     The peak angle of internal friction plotted in Figure B-II 14 is more
easily reduced from the torsion data than a normalized peak shear! strength.
Also Op may be directly used in one model of the rapid self healing
process.                                                         ;

     For a silty material (as many of the specimens here studied are) the
torsion shear strength measurements give shear strengths proportibnal to the
normal pressure on the failure plane (which is practically the same as the
vertical pressure on the specimen).  This is because the specimens are small
enough so relief of pore pressure of a silty material is rapid and also
because cementation in these specimens is nil.  For such specimens in such a
test that is not too quickly performed the peak shear strength and residual
shear strength data obtained at known vertical pressure can be reduced to
0p and Q'p. respectively.

     Many of the peak friction angles of the more cemented specimens
measured are not as high as they should be because the looser, less
compacted, specimen material near the top pore stone tends to fail before
the more representative center of the specimen.  Thus the dilemma in trying
to attain low cementation as well as low permeability is probably more
serious than even indicated by Figure B-II 14.  Also probably few; if any of
the peak friction angles determined by the present torsion apparatus are as
high as they should be for the more cemented specimens due to eccentricity
of the rotating piston and top pore stone and vanes due to any noh trueness
or bowing of the piston rods which can cause development of much side thrust
without registering of much torque.  This would be an insignificant factor,
however, with a soft specimen which can deflect to accommodate a little side
thrust with no rupture.                                          ]

     The curve of Figure B-II 15, permeability vs peak friction apgle, for
the Lurgi spent shale seems to run counter to the curve of Figure! B-II 14
for TOSCO spent shales.  There appears to be a difference in the materials
causing for the Lurgi a reduced permeability with reduced angle biit for
TOSCO materials an increased permeability with reduced angle.  For TOSCO
spent shale of Figure B-II 14 less cementaceous species seem to be the cause
of low friction angles but for Lurgi spent shale of Figure B-II 15 greater
water content may be operative, at least at the short curing times involved.
With the fast setting TOSCO mixtures perhaps the water contents role in
softening a material is overshadowed by rapid cementation.  With (longer
curing times perhaps the slow setting Lurgi material would more resemble the
TOSCO mixtures in its permeability vs friction angle plot.
                                    3-17
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     C.  Residual Shear Strength and Critical Void Ratio Related j
         to Slope Stability
                                              - -   - -               I
     Data obtained as 0p and 0R can be used in a soil mechanics model
where drainage of pore pressure is rapid.  Drainage  of pore pressure in the
field is relatively rapid, even for a thick  liner layer, if rate^of shear  is
relatively slow.  However if pore pressure drainage  is not rapid la more
complicated and hazardous case must be considered.               '

     Before the liner shears and therefore before the soil  skeleton in the
shear zone might be compressed (if its void ratio is above the "critical
void ratio" for the material) the peak shear strength may be used to esti-
mate the maximum angle of inclination of a liner below a spent shale pile
before the pile will slide through shear failure in the liner parallel to
the weak liner.  But if the liner does begin to  shear at some place due to
the peak strength being locally exceeded and if the  liner material does
contract during shear (the "critical void ratio" of the shearing ;liner being
lower than the emplaced liner void ratio) and if pore water pressure can
build up in the plane or zone of failure trouble is  probable.   Pore pressure
will reduce the effective vertical pressure  a.1  and  reduce the effective
peak shear strength T '  of the section of liner  beginning to shear.  The
reduced strength of the initially shearing section and the strain occurring
shifts the stress toward the remaining intact section of liner and its
strength may also be exceeded.  Thus a "progressive  failure" occurs which
results in a slide.                                              ;

     The most conservative design strengthwise (and  possibly the linost
expensive) is (1) to design using the weak strength  developed after shearing
occurs with no drainage where the effective  normal stressaHs reduced and T'
is also reduced (since? =a" cos 0) or (2) to design  with the low'residual
shear strength T  which is developed as the thrust of the failure shear
plane increases vand any cementation or particle to  particle interlocking is
broken and any clayish mineral species platelets are aligned parallel  to the
plane thus producing a more slippery shear plane), whichever is lowest.  It
was beyond the scope of this present work to test the true residual shear
strength of the many materials and conditions of emplacement ring shear
apparatus.                                                       I

     The change in void ratio from emplaced void ratio to the critical void
ratio at failure has not been measured in the torsion apparatus used in this
study.  Probably it is best measured (for plastic specimens) in a
conventional "triaxial" soil testing apparatus in which the volume of the
specimen can be measured throughout a test.  Attempts to make this
measurement on cemented specimens will probably be futile, however.  It
should be done on good candidate (non cementing) liner materials.  The
change in void ratio at critical conditions  (where shearing, particularly
simple shearing, has caused the specimen to reach a  steady state) helps
determine the pore pressure during failure and its degree of influence on
the shear strength during failure.                               i
                                                                 i
     D.  Brittleness Index Related to Cementation and Permeability
                                  B-19
 image: 








                                                                E
     In calculating the brittleness index two shear strength values T   and
TR must be not only be normalized to the same vertical pressure but good,              n
0p and 0R data is needed as a working number is derived from the                      §|
difference between two large numbers.  This decreases the chances for  a good
brittleness  index, BI, result compared to those for a good  0p.  This  is              «.
believed to  be one reason correlations using 0p show less scatter than                •
those using  the  brittleness index.  On the other hand this is not a                   **'
substitute for BI which is retained in spite of its imprecision for certain
illuminating correlations.                                                            flj

     Figure  B-II 16 is a comparison of BI and 0p for Lurgi, TOSCO, and the
mixtures involving mellowed material.                                                 «

     Figure  B-II 17 is a plot of permeability vs brittleness index of
specimens made from TOSCO 70, TOSCO 80, TOSCO 90, TOSCO 100 mixtures con-
taining mellowed materials, and Lurgi spent shale raw materials.  Difficulty          JB
in selecting materials giving both low permeability and low brittleness               9
index from materials giving curves on the right of the plot is evident.
Some materials of the curve on the left of the plot are, on this basis,               ft
perhaps acceptable for a liner, however.  These materials give a negative             §|
brittleness  index calculated from the quick torsion shear strengths
0p and 0R.                                                                            «

     The cause of a negative brittleness index seems to lie in low perme-              ™
ability along with neglegible cementation.  Low permeability of a specimen
in the torsion test is believed to prevent rapid drainage at the beginning            ft
of torsion with  development of appreciable positive pore pressure as speci-           H
men distortion and contraction occurs which reduces the effective vertical
stress ° .   As  twist precedes the excess pore pressure drains and                    m
°  increases causing T to rise.  The result is an increasing torque vs                •
tYme plot on the x-y recorder of the torsion test machine.                            v

     For screening candidate liner materials the ability of the torsion test          •
to indicate  low  permeability, non-cemented, simple shearing materials  seems           H
useful.  Whether the added ability of the torsion tester to transfer con-
solidating curing specimens from oedometer to torsion tester without much              0|
sample disturbance is essential is perhaps debatable.  It seems, however,              p
that every opportunity should be given the specimen to demonstrate any small
extent of cementation it has achieved during aging.  Disturbance would tend           ™
to break the cementation before testing thus reducing the peak of the                 •
torsion stress strain curve.

     E.  Relation of Peak Friction Angle 0p and Brittleness Index                     ffl
         BI  with Initial Torsional Stiffness and Shear Modulus 6~                     H

     Figure  B-II 18 is a correlation of peak friction angle 0p with simple            m
shear modulus G  obtained from the initial torsional stiffness, derived from           ||
volts/degree twist on the stress strain plot.  There  seems to be a  higher
curve for  brittle material and a lower curve for soft material.                       ^
                                                                                      I
     In comparing these G's with others the increase of G with confining              •
stress (some 280 psi au usually existed here) must be remembered.  Some of

                                                                                      1
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           B-20
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                              O  MIXES WITH MELLOWED  MATERIALS,
                                      MODIFIED PROCTOR         '

                              A  TOSCOS  &  LURGI, STD. PROCTOR

                              D      "     "     "     MOD. PROCTOR
                      40              45              5O

                PEAK INTERNAL FRI CTI ON .ANGLE , 0  .DEGREES
                                                    55
 Figure B-II 16.   Brittleness Index Correlated with  Peak Friction Angle.
                                B-21
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io-4t-
          -0.1
 o             o.i
BRITTLENESS  INDEX
                                                         0.2
Figure B-II 17.  Permeability Compared with Brittleness Index
                             B-22
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                                                                                      1
the points plotted in Figure B-II 18 no doubt correspond to specimens with             g.
soft tops which too easily sheared and cause displacement of the points               •
downward.  Soft tops are caused by poor emplacement of the top pore stone             •
and vanes into the proctor compacted specimen during loading of the spring
oedometer.                                                                            H

     An apparent higher values of these slow shear moduli for more cemented
specimens, suggests that perhaps rapid shear moduli from resonant dynamic             «
tests might be used to nondestructively periodically assay a given curing             p
specimen for cementation.  The very small  sample needed for an EGA assay
suggest this might be periodically done on the specimen also without much
altering its integrity for the dynamic test.  Perhaps the specimen should be          A
kept under high vertical or high confining pressure to simulate burial  even           w
during dynamic G testing.  Perhaps it can be shown that proctor compaction
is adequate to simulate this and such pressures are unnecessary.  With                H
proctor compaction the persistant problem of weak specimen tops would occur.          p
Probably static compaction at the high vertical pressures of interest would
simulate a real liner adequately.                                                     H

     Figure B-II 19 plotting BI vs shear modulus G also suggests a dis-               ™
tinction between brittle and soft material.  Here also some points are no
doubt too low.                                                                        |l

     F.  Relation of Peak Friction Angle with Twist at Peak Strength

     Figure B-II 20 shows the peak friction angles of the TOSCO 100, 90, 80           g
and 70 series and the Lurgi material as a function of twist produced during
torsion testing at peak strength.  There seems to be a trend for greater
twist (or strain) before failure for the less compacted standard proctored            •
material than for the more compacted modified proctored material, especially          P
for material giving lower peak friction angles.  Greater strain before
failure  is advantageous  in a  liner.  This does not necessarily  correlate              ||
positively with tensile  strength, however, which has little relation to               ff
strain before  failure.   Tensile  strength  is more related to shear strength
where a rule of thumb says that  it is about 1/20 of the shear strength of a           «
cohesive clay soil.                                                                   H

     Also plotted in Figure B-II 20 are points for loadings 86 and 92 for a
75% mellowed burned TOSCO'- 25%  burned  TOSCO mix and the point  for loading            M
87 which is of a 50% mellowed burned TOSCO - 50% unburned TOSCO II mix.  A            H
large extent of strain before peak strength at low peak friction angles is
possible with these mixtures  involving mellowed material.  In fact this sort          A
of material with  low  (in  these cases negative) brittleness index tends  to             ||
exhibit simple shear or  zone  shear and  larger twists than those plotted may
be more appropriate for this  plot since for these materials peak strength
does not necessarily imply failure.                                                   I

     G.  Relation of Peak Friction Angle and Squashiness With
         Cured Void Ratio                                                             A

     Figures B-II 21, 22, 23  and 24 show a regularity in peak angle of
internal friction plotted vs  void ratio for cured TOSCO spent shales, TOSCO           _

                                                                                      I
                                  B-24
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    O.05
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               QA TOSCO  100

               g) A TOSCO  90

               •US A TOSCO  80
               .• A TOSCO  7O

                     LURGI
               SQUARES = MODIFIED  PROC.

               TRIANGLES=STANDARD PROC./ ^3
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         0,000                20,000                 30,000

                      TANGENT SHEAR MODULUS G, PSI
Figure  B-II  19.  Brittleness Index  Compared with  Initial Shear
                  Modulus G                                     !

                             B-25                                !
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                      WITH  MELLOWED
                                      TIP
                                 SYMBOLS SAME AS FOR FIG, B-V1  18
                                 P DENOTES PERMEATED SPECIMEN

                                      I	I	
                      "10              20             30

                    TWIST AT  PEAK  STRENGTH,'DEGREES
40
 Figure  B-II  20.   Extent of Twist at Peak Strength  Correlated with Peak
                   Friction Angle
                                  B-26
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                  TOSCO  100
Figure B-II  21.   Peak Friction Angle

of TOSCO  100 vs  Void Ratio
                                    Figure B-II 22..  Peak  Friction

                                    Angle of TOSCO 90 vs Void  Ratio
     O.6
   0.7     0.8    0.9

   CURED VOID RATIO
                                                O58
                                                   76
                                               t-  o
                                              0.6
0.7    0.8    0.9

CURED VOID RATIO
                                                                        1.0
Figure B-II 23.   Peak Friction Angle
of TOSCO 80 vs Void  Ratio
                                   Figure  B-II 24.  ,Peak Friction
                                   Angle of TOSCO 70 vs Void  Ratio
                                B-27
 image: 








         -o
115 to 135 C peak as for ettringite itself.  There is a sudden appearence
         -o
                                  B-28
                                                                                      1
100, 90, 80, and 70, as the fraction of cementaceous burned spent shale               tt
increases.  Greater void ratios (determined after curing) are associated              if
with lower peak internal friction angles for the TOSCO spent shales.  This
suggests that a liner made from spent shale should be as little compacted as          «•
possible so a lower friction angle and resulting greater squashiness is had           EH
which allows better self healing of the rapid type,'other factors such as             *
not too much shrinkage at a shear zone being acceptable.  The squashiness is
inversely proportional to the shear strength which for a silty draining               |8
material is °  tan 0p.                                                                m

     H.  Hydrate Species Determined by EGA                                            m
           	                                            I

     In the early stages of curing of the series of mixtures TOSCO 100, 90,
80 and 70 rise and fall of an EGA water peak at 115 to 135 C was found.
Since both tobernite and ettringite may manefest themselves in this peak              •
some ambiquity exists without x-ray diffraction or other means of distin-             *»
quishing between them.  Figure B-II 25 is a plot of this peak curing time
for crumbs of spring oedometer specimens after torsion testing.  Timing of            ft
this peak is similar to that in development of strength of 0D in Figure               if
B-II 26.                                                    p

     Another EGA water peak at around 225°C becomes prominent with TOSCO              •
70 material.  This is believed to be where the "carbonate ettringite"                 *
(ettringite with sulfate replaced by carbonate) manefests itself as an
additional part of its EGA curve.  The main part, however, still is at the
I
of the 225 C peak at a sharp threshold with a burned spent shale content
below 70%.  This suggests that the pH of the water remaining in the mix               «
and/or the carbonate ion concentration level left after some of the                   H
alkalinity and carbonate has attacked the unburned TOSCO II spent shale
component of the mixture may determine whether ordinary sulfate ettringite            _
or carbonate ettringite is formed.  The identification of this peak is                il
substantiated by its reduction in side experiment curings where some gypsum           »
as a source of sulfate is added, its accentuation when Na2C03 is added,
and its elimination when Bad, or Ba(NO-)0 as a sulfate scavenger is                  fl
added.                       232                                            ||

     Figure B-II 27 is a plot of the initial shear modulus G vs the 115 to            n
135 C EGA peak height for several of the spent shale mixes after curing.              •
Although there is some rise in stiffness at the highest quantities of
tobermorite and ettringite found, the effect is not very strong and moreover
for low peak heights which are in the low cementation region of most                  H
interest the effect is nil.  Thus study of cementation of this sort by                '•
dynamic G testing does not seem straight forward.  It must be recalled that
ettringite is not very cementaceous compared to tobermorite and we have not
yet analyzed the 115-135 C EGA peak for these.
I
     Figure B-II 28 shows strong inverse correlation of twist at peak                 ^
strength vs the 115 to 135 C EGA peak height.  Several  high data points.,,              •
are probably the result of slippage between specimen and upper pore stone.            *"
Any cementation produced by these hydrates seems to operate against
                                                                                      e
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           91 TOSCO  100
           D	
                      33Q
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          10    2O    30     4O    50
                      CURING  TIME, DAYS
                                         60
                                               7O
                                                      80
Figure  B-II  25.
EGA  Hydrate  Water Peak of Tobermorite and
Ettringite vs  Time for TOSCO 100, 90.J and
70 Specimens                         |
   30
           10
                 20
      3O     40    5O
      CURING TIME, DAYS
                                          60
                                                70
Figure B-II 26.
Peak Friction Angle  vs  Time  for TOSCO; 100, 90
and 70 Specimens                      '
                        B-29
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                         234

                    II5-I35°C  EGA PEAK HEIGHT
                                  D TOSCO 100

                                  O TOSCO 90

                                  A TOSCO 70

                                  V LURGI

                                  O MEL.TOS 75%.TA25%|
1
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 Figure  B-II 27.   Initial Torsional Stiffness vs 115  to  135°C
                    EGA Peak
      30
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                                 49
                                       SPECIMEN TOP
                                       TO TOP VANES
                                       SLIP •>
           SYMBOLS  AS FOR FIG. B-VI 27
                        234
                  II5-I35°-C EGA PEAK HEIGHT
I
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Figure  B-II 28.   Twist at Peak Strength  vs  115 to 135°C EGA
                   Peak Height
                                B-30
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 extensive deformation,  the action  of interest  in  self healing,  rather  than
 against small  deformation  involved in initial  stiffness.          ;

      The peak  strength  friction  angle is  quite dependent  on  the extent of
 formation of cementaceous  hydrates under  conditions  of the torsion  test.
 Peak strength  also  correlates  fairly well  with the void ratio within types
 of spent shale mixtures such as  TOSCO 100, 90, 80, 70 or  Lurgi.   A  better
 correlation  with  strength  than either of  the above should be obtained  by
 plotting the family of  void ratio  vs peak shear strength  curves with the
 amount  of tobermorite water present as a  parameter (ignoring any ettringite
 and hydromagnesite  cementing action).   The tobermorite might be determined
 assuming all gttringite is the kind with  also  a peak at 225°C as  well  as
 at 120  to 135  C (carbonate ettringite or  hydroxy  ettringite  but not
 sulfate ettringite).  The  early  peak at 120 to 135°C or so (depending  on
 its height)  results  from both  tobermorite and  ettringite  largely super-
 imposed.   The  tobermorite  peak area alone might be obtained  by  subtracting
 out a calculated  carbonate ettringite area for the 115 to 135 C  part of
 its water evolution  calculated from a ratio of the 225°C  part of its water
 evolution.                                                        j

      I.  Secondary Compression  Index Ca related to                 !
         Cementation and Mellowing"      :;
      Figure  B-II  29  summarizes Ca,  the secondary compression index of  the
 spring  oedometer  specimens  just  before the specimens  removal from:its  LVDT
 height  measurement  system  prior  to  permeability determination (if-made) and .
 torsion  testing.  In general some  specimens showed a  uniform height vs log
 time plot while others  showed  a  fairly sharp downbend  in  this plot at  around
 of 1 to  5 days  as though some  kind  of friction  of cementation were broken
 loose then in  response  to  a particular environmental  change.  The>nature of
 these possible clock reactions has  not been considered here  but  should be at
 some time for  whatever  type of material might  be considered  a further
 possible  candidate  liner.                                         I
                                                                  i
     Figure  B-II  29  shows  that at a  burned  TOSCO spent  shale content of
 about 10% in TOSCO  II spent shale shale a  minimum Ca occurred for^specimens
 showing  a given peak friction  angle.   Figure B-II 29 is a cross  plot of the
 data shown in  Figures B-II  30, 31,  32,  33,  34  and 35 for the last!Ca from
 the  LVDT measurements and  the  peak  friction angle later determined by  the
 torsion  tester.  The scatter of the  data  in these latter figures  is believed
 to  often  be due to premature slippage  of the specimen at its weaker top
 rather than  failing  in a more  representative portion in the middle; of  the
 specimen.  The  "best" curves have been drawn through reasonable hi'gher 0P
 values of presumed better  failed specimens.                       :

     It  should  be commented that none  of the Ca values  seen to datie seem too
 high for  use of a liner for a  period of 10,000 years.  There is sqme pos-
 sibility, however, that the same secondary compression vs log time1 curves
may turn downward even further were  specimens studied for longer periods.

     The secondary compression index Ca, that can be  calcualted fr|om
Townsend and Peterson (1979) data for their unscalped TOSCO II  spent shale
 for modified and standard proctor material at 10  minutes consolidation
                                  B-31
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Fig. B-II 29. Final Ca at 45° Peak B-II 32. Final Ca vs Peak Friction
Friction Angle for Oedometer Specimens Angle for TOSCO 80 Specimens fj
of Various Spent Shale ™




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PEAK FRICTION ANGLE $,, DEGREES PEAK FRICTION ANGLE /p .DEGREES ||
r
B-II 31. Final Ca vs Peak Friction B-II 34. Final Ca vs Peak Friction H
Angle for TOSCO 90 Specimens Angle for Lurgi Specimens
B-32 |
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 and  interpolated  to a  CT  of 280  psi are about two or three times the
 values we  have  found  (Figure B-II  30).  These higher Ca values would be
 explained  if much of  the larger  chunks of spent  shale  in  their unscalped
 sample soften when water soaked  so the bridging  between them is weakened at
 their point  to  point  contacts.   The & values reported by these authors for
 standard and modified  proctor are  roughly comparable with 0p measured with
 our  torsion  apparatus  although a number of variables are  important to the
 exact values which are found.                                    j

      3.  Indirect Tensile Strength (Brazilian) Tests             ;
                                                                 ;
      In  Figure  B-II 35 Brazil indirect tensile strengths  of specimens
 compacted  and cured with no confining pressure are compared with the twist
 at peak strength  from  the torsion  test of counterpart specimens cured in the
 spring oedometers at around 280  psi vertical pressure and tested near that
 pressure.                                                        |

     There is a trend  in Figure  B-II 35 for more cementaceous TOSCO 80
 material to  give  greater tensile strength than less cementaceous TOSCO 90
 material and  for  it to give greater tensile strength than the TOSCO 100
 material.  Lurgi spent shale gives relatively high tensile strengths while
 mixtures including mellowed material  as noted give low to medium tensile
 strengths.  The negative slope of the trend lines drawn for the different
 materials  suggests that the kind of tensile strength measured by the
 Brazilian  tests is a brittle cementaceous  type strength associated with
 rapid attainment  of peak cementaceous shear strength as strain progresses.
 This slope is opposite to that expected for a correlation of the shear test
 twist and  tensile strength for a cohesive  plastic material.       ;

     For the silty and sometimes cemented materials of most of the specimens
 studied here high tensile strength primarily indicates cementation.  A more
 clayish material might show both high twist before peak shear strength and
 relatively high tensile strength.  Tensile strength, as weak as it is, in a
material  at the overburden depths involved for the liner being considered
 does not seem to be an important consideration in the face of the |hi'gh
 vertical  stress involved at depth which greatly increases shear strength.

     Figure B-II 36 is a plot of the tensile strain at failure with the
 Brazil tests vs the twist at peak strength for the torsion tests, i  It is
 concluded that only a little cementation reduces the tensile strain at
 failure considerably.   The largest torsion twists (strains)  of cenjented
 specimens and less cemented specimens at peak torsion shear strength seen
 are about the same but the Brazil test tensile strains at tensile 'failure
are much greater for less cementaceous material.                  '

     Figure B-II 37 shows some classical  shaped  tensile strength  ys water
content curves for specimens made from mixtures  involving mellowed^
materials.   Even for the 75% mellowed TOSCO - 25% burned TOSCO specimens
which are undergoing some cementation, a peak tensile strength vs Water
content is observed.  The points corresponding to specimen water  additions
 used in the main series of oedometer - torsion tests are indicated  by the
oedometer loading number of this main series.   According to  data  for these
                                  B-33
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little aged specimens optimum tensile strength was not usually attained.
But as observed above, the properties of the liner is shear at higher                 H
vertical pressure which will far over-shadow the weak tensile strengths.              »

     K.  Compressibility Coefficients                                                 Oj

     Pneumatic arm oedometer tests were made on standard proctored or
modified proctored specimens one inch high and 2% inch diameter.  Table B-I       •    at
1 lists the types of mixes studied by arm oedometer.  Table B-II lisa              ft
summary of some results and some calculations.  In the first column t                 •
signified TOSCO, m modified proctor, s standard proctor, etc.

     Primary consolidation was finished after 80 minutes for the one inch             p
thick double pore stone specimens used.  For this time the total compression
of the specimen from the data collecting computer print out for each loading          «
increment was read and entered in a computer spread sheet program, Table              «
B-II 1 column D, as steady state Schaevitz units.  After converting these to          "
mm compression and correcting for arm oedometer apparatus deflection at the
particular load (column C) the net compression was calculated  (column F) for          H
that  loading  increment.   Load  increments producing  vertical  pressures on the          •
specimens  of  19.4,  38.8,  77.5,  155.0, and  310  psi were  used.   From the
initial water added, mineral grain density of  the initial dry  mixture before
wetting, specimen loaded?weight,' cell volume of 80.44 cm  and  specimen  top
surface area  of 31.67 cm  the dry densities and void ratio for each
loading were  calculated and for each change in load  the delta  void ratio and
compression index C  were calculated  (columns  K and  L).                               •

      From  the data  calculated  in  Table  B-II  1   a  variety  of  correlations may
be made.   Void ratio  e  plotted  against  consolidation stress  (load) gives              m
curves  typical of silt.   Figure B-II  38 shows  the compression  index  for the           p
last  loading  increment  (155 to  310  psi) for each  specimen, plotted against
the  initial water added to  the  specimen in mixing it.   There  is much                  «.
similarity in the position  of  the curves for  the  various  types of spent              ||
 shale.

                                                                                      1


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III.  CONCLUSIONS AND RECOMMENDATIONS                             .       .

     1.  A softer less brittle material after placement seems desirable for
most of the specimens tested.  Apparently the angularity and harshness of
silt and sand sized particles in most mixes is the cause of a relatively
high angle of internal friction for the peak shear strengths and residual
shear strengths found after yielding.  Such high strengths do not :seem
necessary nor desirable and should be traded off for lower angles of
friction through less compaction, some heap mellowing time which will allow
more particle surface roughening and floculation and looser compaction while
retaining some measure of swelling and shrinkage stability, and/or addition
or generation of some quantity of clayish material.  The latter can
apparently be made from certain spent oil  shales by autoclave mellbwing but
it may be more economical to add clay from other sources.  Trial of further
autoclave mellowed or other mellowed materials seems desirable.   j

     2.  Trial of addition of clay or other similar fines to reduc'e
permeability in the case of the TOSCO  II spent shale or the average Lurgi
spent shale is desirable.  This could be an added component or could be
generated from autoclaving an especially active burned spent shale such as
the burned TOSCO material.                                        |

     3.  Ring shear tests should be made to get 0R at large displacements
for several examples of candidate liner material.                 ;

     4.  The cementing characteristics of burned spent shale seem to be a
detriment to self healing as any shear movement needed for closure; of a
vertical tension crack by "caving in"  of liner material would produce shear
plane separated fragments.  The planes may be possible water channels.
Moreover the depth into the liner away from the tension crack for la source
of fill material will be less for high shear strength liner material.
Extrusion of a non brittle plastic liner material, into a tension'crack, on
the other hand, should not produce such distinct planes.  Autoclave
mellowing inhibi-ts cementation of materials.                      i     '

     5.  The high friction angles observed in most of the liner specimens
tested are useful in that there will be less tendency for a pile of  spent
oil shale founded on a liner to slip down a valley.  Silty sandy materials
producing high friction  angles are generally rather permeable and luncemented
specimens of the materials here tested are no exception.  To reduc'e perme-
ability clay sized material can be mixed in or a non strength producing fine
precipitate or colloid within the interstitial spaces of the siltjgrains
might conceivably be internally generated.  In this way a synthetic boulder
clay having both low permeability yet  a reasonably high  friction amgle might
be produced.                                                      :
                                                                  r
     6.  Quick clay inadvertently made in any of the above ways should be
avoided.  Even a material that has only a little above critical vo;id volume
should be suspect until  proven unlikely to soften  or liquify whenisubjected
to slip or earthquake produced shear.  Even though a liner material! in
unsaturated condition may not soften or liquify the same material ;when
                                 .B-41
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                                                                                      1
saturated may soften under shear strains.  This must be predictable and               a*
eventually probably must be studied for any candidate liner material.                  |j|

     7.  The "final" secondary compression rates or Ca for none of the                _.
materials, when measurements ceased just before torsion testing, was ex-              »
cessive.  Rates below 2% settlement at 10,000 years by extrapolation were             &
about as large as observed.  Much lower rates were more typical.  However
since the settlement vs log time curves plotted were often concave downward           j|j
specimens should be followed for longer periods and chemistry of the                  fl
apparent softening with age ascertained.

     8.  The effect of additives on spent shale should be further studied in          ffl
a more methodical experimental design.  Gradations of mixes between silty             m
spent shale and clayish material should be tested for the following:
          1.  Permeability                                                            m
          2.  Shear strength by a quick method  relative to the  permeability           m
              so any softening due to  reduction of soil skeleton volume
              during shear is observable.                                             ffl
          3.  Shear strength of both saturated and unsaturated material               ||
              should be studied..
Well mixed or pugged materials should  be used or fines should be generated
internally.                                                                           n

     9.  Possible methods for in situ  fines generation include  the
following:                                                                            II
          a.  Mix two slow precipitating liquid intereactants in with the             p
              spent shale.
          b.  Mix in one liquid reactant which  reacts with the  spent shale            «g
               itself.                                                                 •
          c.  Mix in a  solid reactant  which  reacts with the spent  shale.              ^

     The spent shale base for the mixture should not be burned  spent shale            ffl
to  avoid the cementation already demonstrated but one such as TOSCO II                t§
material.   Perhaps mildly autoclave mellowed burned spent shale would not
cement even though much ettringite may be initially formed.                           m

     10.  Periodic non  destructive resonant measurement of shear modulus G
may be valuable for following development of any cementation  in a  given               ^
specimen as curing or aging precedes.   EGA and  to a lessor degree  x-ray               II
diffraction may also be done on the same specimen without affecting G since           '*•
such small  samples are  required.

     11.  Experiments with  physical models of liner materials should be made          H
 in which a  tension  crack  is induced  in brittle  containment  strata  and  the
 ability of  liner  material  to  suppress  water  flow as  the crack opens is                «
measured.   It  is  desirable  to be able  to  perform meaningful experiments of            •
this sort without the need  for  continuous high  vertical pressures  during
 aging  of the  liner.   Strong forces  at  the time  of,  say,  flexing or
stretching  a model to generate  a tension  crack  would,  of  course be necessary          M
 however.  Proof is  desirable  that  proctor or other compacted  liner material           P
 in such  a model approximates  a  real  liner aged  with  considerable  overburden
 pressure.                                                                             ffl
                                                                                      1



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IV.  REFERENCES                                                  :
                                                                 i

Ingles, O.6., "Soil Chemistry Relevant to the Engineering Behavior of Soils"
in I.K. Lee, Editor, Soil Mechanics Selected Topics, American Elslevier
Publishing Co., Inc., New York 1968.                             i

Townsend, F.C. and R.W. Peterson, Geotechm'cal Properties of Oil Shale
Retorted by the Paraho and TOSCO Processes, Tech. Rept. 61-79-22,^
Geotechm'cal Laboratory, U.S. Army Engineer Waterways Experiment Station.
Vicksburg Miss.  For U.S. Dept.  of Interior, Bur. of Mines, Spokape Mining
Research Center, Spokane Wash. Under Contract No. H0262064.      !
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