600 / &--QV-llS
LOGAN WASH FIELD TREATABILITY STUDIES OF
WASTEWATERS FROM OIL SHALE RETORTING PROCESSES
by
B. O. Desai, D. R. Day, and T. E. Ctvrtnicek
Monsanto Research Corporation
Dayton, Ohio 45407
Contract No. 68-03-2801
May 1983
Project Officer
Walter W. Liberick, Jr.
Oil Shale and Energy Mining Branch
Energy Pollution Control Division
Cincinnati, Ohio 45268
Industrial Environmental Research Laboratory
. Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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DISCLAIMER
This document is a preliminary draft. It has not been formally
released by the U.S. Environmental Protection Agency and should
not be construed to represent Agency policy. It is being
circulated for comments on its technical merit and policy
implications.
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FOREWORD
When energy and material resources are extracted, processed, con-
verted, and used, the related pollutional impacts on our environ-
ment and even on our health often require that new and increas-
ingly more efficient pollution control methods be used. The
Industrial Environmental Research Laboratory-Cincinnati (lERL-Ci)
assists in developing and demonstrating new and improved method-
ologies that will meet these needs both efficiently and
economically.
New synthetic fuel processes under development must be character-
ized prior to commercialization so that pollution control needs
are identified and control methods can be integrated with process
designs. Shale oil recovery processes are expected to have some
unique air, water, and solid waste control requirements. This
document describes pilot-scale treatability tests on wastewaters
from retort operations at the site of a major oil shale developer.
Further information on the environmental aspects of shale oil
processing can be obtained from the lERL-Ci.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
111
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ABSTRACT
Treatability studies were conducted on retort water and gas con-
densate wastewater from modified in-situ oil shale retorts to
evaluate the effectiveness of selected treatment technologies for
removing organic and inorganic contaminants.
At retorts operated by Occidental Oil Shale, Inc., at Logan Wash,
Colorado, treatability studies were conducted on retort water using
filter coalescing, flocculation/clarification, and steam stripping.
Studies also were conducted on gas condensate wastewater using
filter coalescing, steam stripping, activated sludge treatment
(both with and without powdered activated carbon addition), sand
filtration, and granular activated carbon adsorption.
Retort water had high concentrations of ammonia-nitrogen, total
Kjeldahl nitrogen, alkalinity, dissolved organics, phenols, sulfide,
total dissolved solids, boron, potassium and sodium. Filter
coalescing was not effective in further reducing the low concen-
tration of oil and grease in the retort water subjected first to
oil/water separation by Occidental. Flocculation/clarification
using lime as the chemical conditioning agent was not effective
in further reducing the low initial concentration of total
suspended solids, or the chlorides, fluorides, and metals at
dosages used. Steam stripping removed ammonia-nitrogen,
alkalinity, and sulfide from retort water and organics removal -
was low.
IV
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Gas condensate wastewater had high concentrations of ammonia-
nitrogen, total Kjeldahl nitrogen, dissolved organics, alkalinity,
phenols, sulfide, and pyridine compounds. Filter coalescing was
not effective in further reducing the low concentration of oil
and grease initially present. Steam stripping successfully
removed ammonia-nitrogen, alkalinity, sulfide, phenols, dissolved
organic carbon, total Kjeldahl nitrogen and chemical oxygen
demand, and it generated wastewater for downstream activated
sludge treatment. Organics removal in the stripper was high and
varied with the quality of the raw wastewater. Steam was used to
try and clean the steam stripper and overhead vapor condensate
lines of occasional clogging with partial and short-term success.
Conventional activated sludge treatment reduced chemical oxygen
demand, soluble biochemical oxygen demand, dissolved organic
carbon, and phenols. Despite a long sludge age, nitrification
did not occur. Alum was added to enhance settling of the aeration
basin overflow sludge. Biological cell growth was very slow.
Adding the powdered activated carbon into the aeration basin
increased removal of the chemical oxygen demand, dissolved organic
carbon, soluble biochemical oxygen demand, and phenols. Sand
filtration removed suspended solids from the secondary clarifier
effluent and prevented clogging of the downstream adsorption
columns. Granular activated carbon adsorption removed organics
from conventional activated sludge system effluent. The overall
scheme for the gas condensate treatment removed ammonia-nitrogen,
total Kjeldahl nitrogen, alkalinity, sulfide, biochemical oxygen
demand, dissolved organic carbon, chemical oxygen demand, and
phenols.
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CONTENTS
Foreword 11;L
Abstract iv
Figures viii
Tables xiv
Abbreviations xviii
Acknowledgement xix
1. Introduction 1
2. Conclusions 5
2.1 Retort water testing 5
2.2 Gas condensate testing 6
3. The Logan Wash Test Program 9
3.1 Test location 9
3.2 Occidental's MIS retorting technology. ... 9
3.3 MIS Retorts 7 and 8 12
3.4 Wastewaters generated from Retorts 7 and 8 . 13
3.4.1 Retort water 13
3.4.2 Gas condensate 17
3.5 Wastewater treatment schemes . 20
3.5.1 Retort water treatment 20
3.5.2 Gas condensate treatment 20
3.6 Field trial equipment and setup 23
3.6.1 Filter coalescer 28
3.6.2 Flocculator 30
3.6.3 Primary clarifiers. 30
3.6.4 Secondary clarifier 33
3.6.5 Aeration basin 34
0220-0220-2
VI
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CONTENTS (continued)
3.6.6 Sand filters 36
3.6.7 Carbon adsorption columns 36
3.6.8 Backwash module 38
3.6.9 Boiler module 38
3.6.10 Steam stripper 41
3.6.11 Pilot equipment trailers . 43
3.6.12 Mobile laboratory trailer 45
4. Program Implementation and Results 48
4.1 Program Sampling and Analysis Schedule ... 48
4.2 Retort water test results 53
4.2.1 Raw wastewater characterization. . . 53
4.2.2 Oil/water separation 56
4.2.3 Flocculation/clarification 60
4.2.4 Steam stripping. 62
4.3 Gas condensate test results 69
4.3.1 Raw wastewater characterization. . . 69
4.3.2 Oil/water separation 69
4.3.3 Steam stripping 71
4.3.4 Conventional activated sludge
treatment 104
4.3.5 PAC-activated sludge treatment.. . . 130
4.3.6 Sand filtration 138
4.3.7 GAC adsorption 142
4.3.8 Overall treatment 155
5. QA/QC Data Summary • 159
References 164
VI1
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FIGURES
Number
Pacre
1 Creating an MIS retort by (a) mining the voids,
(b) drilling the blast holes, and (c) frag-
menting with explosives 10
2 The four zones of an operating MIS retort ... 12
3 Occidental Oil Shale, Inc. Retorts 7 and 8. . . 14
4 Retort water supply point 15
5 Retorts 7 and 8 retort water production rate. . 16
6 Gas condensate supply point 18
7 Retorts 7 and 8 gas condensate production rate. 19
8 Retort water treatment scheme 21
9 Gas condensate treatment scheme 22
10 General equipment layout at the trial location. 26
11 Access road, Occidental's trailer park, and
pilot equipment position 27
vixi
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FIGURES (continued)
Number Page
12 Field setup of wastewater treatment facilities
at Logan Wash - general view 27
13 Field setup of wastewater treatment facilities
at Logan Wash - closeup 28
14 Filter coalescer 29
15 Flocculator 31
16 Primary clarifier 32
17 Aeration basin 35
18 Sand filters 37
19 Backwash module 39
20 Boiler skid 40
21 Steam stripper skid 42
22 Pilot equipment trailer 44
23 Mobile laboratory trailer 46
24 Percent removals of ammonia and alkalinity in
steam stripper at various G/L ratios 67
IX
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FIGURES (continued)
Number Page
25 Raw gas condensate wastewater ammonia concen-
tration variations (grab and composite
sample results) 75
26 Raw gas condensate wastewater alkalinity con-
centration variations (as CaCO3 to pH 4.5)
(grab and composite sample results) 76
27 Raw gas condensate wastewater soluble COD con-
centration variations (grab and composite
sample results) 77
28 Percent ammonia removal at various G/L ratios
for gas condensate 79
29 Percent alkalinity removal at various G/L
ratios for gas condensate 79
30 Percent DOC removal at various G/L ratios
for gas condensate 80
31 Percent soluble COD removal at various G/L
ratios for gas condensate 80
32 Long-term steam stripper performance - ammonia
removals between June 1 - August 26, 1982 . . 84
33 Long-term steam stripper performance -
alkalinity removals between June 1 -
August 26, 1982 . 87
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FICURES (continued)
Number Paqe
34 Long-term steam stripper performance - soluble
COD removals between June 1 - August 26, 1982 90
35 Long-term steam stripper performance - DOC
removals between June 1 - August 26, 1982 . . 93
36 Long-term steam stripper performance - phenols
removals between June 1 - August 26, 1982 . . 96
37 TSS and VSS concentration in secondary clari-
fier effluent during biological reactor
acclimation period 110
38 MLSS and MLVSS concentrations in biological
reactor during acclimation period Ill
39 Dissolved oxygen (DO) concentration and DO-
uptake rate in biological reactor during
acclimation period 112
40 Soluble COD concentration and removal in bio-
logical reactor during acclimation period . . 113
41 DOC concentration and removal in biological
reactor during acclimation period 114
42 Soluble BOD5 concentration and removal in bio-
logical reactor during acclimation period . . 116
XI
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FIGURES (continued)
Number
Paqe
43 Phenols concentration and removal in biological
reactor during acclimation period ...... 117
44 pH in biological reactor during acclimation
period ........ - ...........
45 MLSS and MLVSS concentration in biological
reactor during July . . ........... 122
46 Soluble COD concentration and removal in bio-
logical reactor during July ......... 123
47 Soluble BOD5 concentration and removal in bio-
logical reactor during July ......... 124
48 DOC concentration and removal in biological
reactor during July ............. 125
49 DO concentration and DO-uptake rate in bio-
logical reactor during July ......... 127
50 Phenols concentration and removal in biological
reactor during July ............. 128
51 MLSS and MLVSS concentration in PAC bioreactor,
August 11 through August 22 ......... 133
52 Soluble COD concentration and removal in PAC ;
bioreactor, August 11 through August 22 ... 134
Xll
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FIGURES (continued)
Number Page
53 DOC concentration and removal in PAC
bioreactor, August 11 through August 22 ... 135
54 DO concentration and DO-uptake rate in PAC
bioreactor, August 11 through August 22 ... 136
55 PAC bioreactor removal performance with
increasing PAC dosage 140
56 Schematic diagram of carbon column system and
sample points used for GAC adsorption tests . 143
57 Soluble COD breakthrough curves for GAC
columns 1 and 2 using stripped gas
condensate as influent 147
58 Soluble COD breakthrough curves for GAC
columns 1 and 2 using biologically
treated effluent, Test 1 153
59 Soluble COD breakthrough curves for GAC
columns 1 and 2 using biologically
treated effluent, Test 2 154
Xlll
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TABLES
Number 3L§c[_e
1 Program Major Events 49
2 Analytical Schedule - Retort Water 51
3 Analytical Schedule - Gas Condensate 52
4 Monitored Equipment Operating Parameters During
Retort Water Testing 54
5 Raw Retort Water Characterization - Conventional
Pollutants and Other Parameters 55
6 Raw Retort Water Characterization - Metals... 56
7 Raw Retort Water Characterization - Purgeable
and Extractable Organics 57
8 Raw Retort Water Characterization - DOC
Fractions 58
9 Filter Coalescer Performance Data Summary ... 59
10 Flocculator/Clarifier Performance Data
Summary
61
xiv
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TABLES (continued)
Number Page
11 Steam Stripper Performance Data Summary -
Conventional Pollutants and Other
Parameters 63
12 Steam Stripper Performance Data - Organics... 64
13 Steam Stripper Performance Data - Metals.... 65
14 Steam Stripper Performance Data - DOC Fractions 66
15 Monitored Equipment Operating Parameters During
Gas Condensate Testing 70
16 Raw Gas Condensate Characterization for Conven-
tional Pollutants and Other Parameters. ... 72
17 Raw Gas Condensate Characterization for Purge-
able and Extractable Organic 73
18 Raw Gas Condensate Characterization for Metals. 74
19 Raw Gas Condensate Characterization for DOC
Fractions . 74
20 Filter Coalescer Performance Data Summary -
Gas Condensate 78
21 Steam Stripper Performance Data Summary for
Conventional Pollutants and Other Para-
meters - Gas Condensate 78
xv
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TABLES (continued)
Number
22 Summary of Steam Stripper Performance from
May 26 to June 10, 1982 82
23 Summary of Steam Stripper Performance from
June 11 to August 26, 1982 83
24 Steam Stripper Performance Data for Purgeable
and Extractable Organics 101
25 Steam Stripper Performance Data for Metals. . . 102
26 Steam Stripper Performance Data for DOC
Fractions 103
27 Steam Stripper Performance Data for Ammonia
Grab Samples 103
28 Seeding Schedule for Biosystem ; 108
29 Bioreactor Steady-State Performance Data
Summary for Conventional Pollutants and Other
Parameters 119
30 Bioreactor Performance Data for Purgeable and
Extractable Organics 120
31 Bioreactor Performance Data for Metals 121
32 PAC Bioreactor Performance Data Summary .... 132
xvi
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TABLES (continued)
Number Page
33 PAC Bioreactor Performance Data Summary -
Increasing PAC Dosage Operation 139
34 Sand Filter Performance Data Summary 141
35 Performance Data For Carbon Column Testing
of Gas Condensate Steam Stripper Effluent,
June 22 to July 2, 1982 145
36 Operating Conditions for GAC Column Tests with
Biologically Treated Effluent . 148
37 Performance Data for Carbon Column Tests with
Biologically Treated Gas Condensate Effluent
Test No. 1: July 13 to July 27, 1982 .... 149
38 Performance Data for Carbon Column Testing of
Biologically Treated Gas Condensate Effluent
Test No. 2: July 29 to August 9, 1982. ... 151
39 Carbon Column Performance Data for Metals . . . 156
40 Carbon Column Performance Data for Purgeable
and Extractable Organics 157
41 Overall Treatment Scheme Performance Data
Summary for Conventional Pollutants and
Other Parameters 158
42 QA/QC Data Summary for All Analyses ...... 160
xvxi
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ABBREVIATIONS
BOD5 — biochemical oxygen demand (5 days)
COD — chemical oxygen demand
DO — dissolved oxygen
DOC -- dissolved organic carbon
GAG — granular activated carbon
GC/MS — gas chromatography/mass spectrometry
G/L — gas-to-liquid
HRT — hydraulic retention time
ICP — inductively coupled plasma optical emission spectroscopy
MIS — modified in-situ
MLSS — mixed liquor suspended solids
MLVSS — mixed liquor volatile suspended solids
NH3-N — ammonia nitrogen
NOg-N — nitrate nitrogen
PAC — powdered activated carbon
QA/QC — quality assurance/quality control
SD — standard deviation
SRT — solids retention time
TDS — total dissolved solids
TKN — total Kjeldahl nitrogen
TSS — total suspended solids
VSS — volatile suspended solids
xvi 11
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ACKNOWLEDGEMENTS
Monsanto Research Corporation (MRC) acknowledges the excellent co-
operation and support received from personnel of the Occidental
Oil Shale, Inc., Logan Wash Operations during the planning and im-
plementation of the field treatability studies described in this
report. The technical direction provided by Walter Liberick, Jr.,
EPA Project Officer, is greatly appreciated.
xix
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SECTION 1
INTRODUCTION
Oil shale has been recognized as a substantial energy resource
for more than 100 years. Recently, the increasing dependence of
the United States on foreign oil supplies, accompanied by rapidly
escalating oil prices, has provided incentives for shale oil re-
covery from deposits in the western United States. Several domes-
tic corporations have begun preliminary process research and
development and have acquired the necessary know-how for commercial-
scale shale oil production [1].
Despite the benefits of oil shale as an energy resource, waste-
waters generated from oil shale processing contain high concentra-
tions of organic and inorganic contaminants. If discharged un-
treated, these wastewaters could have an adverse impact on the
environment. Treatment methods capable of controlling these
potentially harmful discharges need to be demonstrated so that
adequate controls can be incorporated into full-scale plant designs
to assure industry compliance with future standards.
To assess the characteristics and treatability of wastewaters gen-
erated from the processing of oil shale, the U.S. Environmental
Protection Agency (EPA) contracted with Monsanto Research Corpora-
tion (MRC) to conduct a five-phase program having the following -
objectives:
• Summarize available information concerning oil shale retort
wastewater sources and characteristics;
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• Identify control technologies that are potentially applicable
to treatment of the identified wastewater streams;
• Design pilot-scale units capable of evaluating the applicable
technologies at oil shale processing sites;
• Construct the pilot-scale units; and
• Operate the pilot-scale units to develop information on treat-
ment technology performance.
The results of Phases I and II, which were completed in February
1980 and reported earlier [1], comprised:
• A survey of pertinent oil shale retorting processes and water
effluents;
• A survey of completed and ongoing research activities in oil
shale retort wastewater treatability; and :
• Identification of research needs, and development of a research
program to meet those needs.
The results of Phases I and II showed that little information ex-
isted on the basis of which to evaluate and select potentially
applicable technologies for testing, and that additional bench-
scale testing and wastewater characterization were warranted.
Wastewater characterization and bench-scale treatability studies
were thus conducted using samples of the wastewaters available at
the time. These studies specifically included:
• Steam stripping, hyperfiltration, and ultrafiltration of
Occidental Oil Shale Retort 6 retort water and gas condensate;
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• Carbon adsorption batch isotherm and respirometry testing of
steam-stripped Occidental Oil Shale Retort 6 retort water and
gas condensate;
• Carbon adsorption column testing and activated sludge treat-
ment of steam-stripped Occidental Oil Shale Retort 6 gas
condensate;
• Steam stripping of venturi scrubber water collected at the
Laramie Energy Technology Center (LETC); and
• Characterization of three gas condensate (Occidental Oil
Shale, Inc., Rio Blanco Oil Shale Company, and Development
Engineering, Inc.) and four retort water (Occidental Oil
Shale, Inc., Rio Blanco Oil Shale Company, Laramie Energy
Technology Center, and Geokinetics, Inc.) samples.
The results of these studies, and the information previously
collected were used to select the treatment schemes for implement-
ation under Phases III through V. The schemes were presented to
EPA in a Work Plan on July 24, 1981 [2] and, after some modifica-
tion, were approved for implementation. Pilot testing of the
schemes commenced on May 5, 1982 at the site operated by the
Occidental Oil Shale, Inc. in Logan Wash, Colorado. The tests
were completed on August 27, 1982.
This report presents the Logan Wash test program and discusses the
test results accomplished. Section 2 summarizes the conclusions
derived from the test results. Section 3 describes the Occidental
retorting facility, the test equipment, and the Logan Wash test
program that was implemented by MRC from May 5 through August 27,
1982. The test results are discussed and summarized in Section 4.
Analytical quality assurance/quality control (QA/QC) data are
summarized in Section 5.
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This report was submitted in partial fulfillment of Contract No.
68-03-2801 by Monsanto Research Corporation under the sponsorship
of the U.S. Environmental Protection Agency. This report covers
the period March 1980 to April 1983. Work was completed
May, 1983.
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SECTION 2
CONCLUSIONS
2.1 RETORT WATER TESTING
• Retort water has high concentrations of ammonia nitrogen
(NH3-N), total Kjeldahl nitrogen (TKN), alkalinity, dis-
solved organics, phenols, sulfide, total dissolved solids
(TDS), boron, potassium, and sodium. The retort water tested
had an average of 2,200 mg/L ammonia nitrogen; 2,100 mg/L
TKN; 14,000 mg/L alkalinity (as CaCO3 to pH 4.5); 1,700 mg/L
dissolved organic carbon (DOC); 4,100 mg/L soluble chemical
oxygen demand (COD); 2,000 mg/L soluble biochemical oxygen
demand (5-day) (BOD5); 56 mg/L phenols; 90 mg/L sulfide;
14,000 mg/L TDS; 37 mg/L boron; 170 mg/L potassium; 2,900
mg/L sodium; and a pH of 8.8.
• Filter coalescing was not effective in removing the low res-
idual oil and grease content from the retort water. On the
average only 6% removal was achieved, primarily owing to its
prior removal by Occidental and the resulting level (113 mg/L
average) in the retort water.
• Flocculation/clarification treatment of retort water was
conducted using lime as the chemical conditioning agent.
Testing was conducted at 90, 180, and 270 mg/L lime dosages.
This treatment was not effective in removing total suspended
solids (TSS), chlorides, fluorides, and metals from the retort
water at these dosages. This was primarily because of the low
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TSS content of the retort water (59 mg/L average), and
because the lime concentrations and pH were not high
enough to precipitate metals.
• Steam stripping tests were conducted at gas(steam)-to-liquid
(G/L) ratios of 70, 130, 180, 230, and 300 kg/m3 (0.6, 1.1,
1.5, 1.9, and 2.5 Ib/gal). Ammonia, alkalinity, and sulfide
could be successfully stripped from the retort water. Greater
than 97% of the ammonia nitrogen and 47% of the alkalinity
were removed at G/L ratios of 180 kg/m3 or above (1.5 Ib/gal
or above). Over 99% of the sulfide was stripped at G/L ratios
as low as 70 kg/m3 (0.6 Ib/gal). TKN and phenols removals
varied from 71% to 95%, and 27% to 54%, respectively, depend-
ing on G/L ratio. The stripper effluent had a pH about one
unit higher than that of the feedwater. Organics removal was
insignificant.
2.2 GAS CONDENSATE TESTING
• The retort gas condensate had high concentrations of ammonia
nitrogen, TKN, alkalinity, dissolved organics, phenols, sul-
fide, and pyridine compounds. The gas condensate tested had
an average of 9,000 mg/L ammonia nitrogen; 6,800 mg/L TKN;
31,000 mg/L alkalinity (as CaCO3 to pH 4.5); 890 mg/L DOC;
2,700 mg/L soluble COD; 800 mg/L soluble BOD5; 120 mg/L
phenols; 72 mg/L sulfide, 100 mg/L pyridine compounds, and
a pH of 8.5.
• Filter coalescing was ineffective in removing the low residu-
al oil and grease content of the gas condensate (19 mg/L
average). On the average, 28% removal was achieved, adding
little to the overall treatment.
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Steam stripping of condensate was conducted at G/L ratios
of 60, 120, 150, and 180 kg/m3 (0.5, 1.0, 1.25, and 1.5
Ib/gal). Ammonia nitrogen, alkalinity, sulfide, phenols,
COD, DOC, and TKN were successfully stripped from the
gas condensate: 99% of ammonia nitrogen and alkalinity
were removed at G/L ratios of 120 kg/m3 (one Ib/gal)
and above; 99% of the sulfide, 50% of the phenols, and
greater than 60% of the organics and TKN were removed
at G/L ratios of 60 kg/m3 (0.5 Ib/gal) and above. The
stripper effluent had a higher pH than the feed by about
one unit at all G/L ratios tested from 60 to 180 kg/m3
(0.5 to 1.5 Ib/gal).
The steam stripper performed consistently well during
the 14 weeks of operation in generating wastewater for
downstream activated sludge treatment. At an average
G/L ratio of 140 kg/m3 (1.2 Ib/gal), the ammonia nitro-
gen, TKN, alkalinity, and sulfide removal rates averaged
99%, 96%, 99%, and 97%, respectively. High organics
removal (COD >70%, DOC >80%) were obtained during the
early period of operation, but gradually these removal
rates decreased to 30-40%. This is believed to be due
to a change in the quality of the raw wastewater and/or
partial clogging of stripper packing; the organics con-
tent almost doubled during the later period of operation.
The stripper packing clogged up periodically (every 7-10
days) and was partially cleaned by blowing steam through
the column. Overhead vapor condensate lines also clogged
periodically with ammonium carbonate every 30-45 days
and required cleaning with steam.
The conventional activated sludge system removed an
average of 57% of the COD, 91% of the soluble BOD5, 52%
of the DOC, and 95% of the phenols. Despite an extended
sludge age of 32 days, nitrification did not occur. Due
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to financial and schedule limitations, and an expected
lengthly acclimation period, operation of the activated
sludge system for an entire sludge age and under steady-
state was not achieved. Data was collected at conditions
which represent consistent organics removals and DO uptake
rates. Alum addition was required to help settle the
sludge in the aeration basin overflow.
The powdered activated carbon (PAC) activated sludge
system, at a PAC dosage of 400 mg/L, removed 70% of the
COD, 59% of the DOC, 96% of the soluble BOD5, and 99%
of the phenols. At a PAC dosage of 1,900 mg/L, 86% of
the COD, 84% of the DOC, 95% of the soluble BOD5 and
100% of the phenols were removed.
Sand filtration was effective in removing suspended
solids from the secondary clarifier and prevented
clogging of downstream granular activated carbon (GAC)
adsorption columns.
The GAC adsorption treatment was effective in removing
organics from conventional filtered activated sludge
system effluent. With an empty bed contact time of 22
minutes, the GAC adsorption produced an effluent with a
COD <90 mg/L, DOC <26 mg/L, BOD5 <10 mg/L, and phenols
<0.015 for 225 hours.
GAC adsorption of the stripper effluent with an empty
bed contact time of 22 minutes resulted in a COD <50
mg/L, DOC <35 mg/L, BOD5 <50 mg/L, and phenols <0.005
mg/L for 72 hours.
The overall gas condensate treatment scheme was effective
in removing ammonia nitrogen, TKN, alkalinity, sulfide,
BOD5, DOC, COD, and phenols.
8
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SECTION 3
THE LOGAN WASH TEST PROGRAM
3.1 TEST LOCATION
The test program was implemented at Occidental's Logan Wash test
site. Occidental Oil Shale, Inc. (Occidental), a major oil shale
developer, purchased this 16 km2 (4,000 acre) site in 1972 to
pursue their interest in shale oil extraction technology develop-
ment. The site is located on the western slopes of the Rocky
Mountains about 16 km (10 mi) northeast of DeBeque, Colorado, and
is estimated to contain 0.12 km3 (750 million barrels) of shale
oil in medium-grade deposits. The deposits are 80 m (250 ft)
_s
thick and average about 71 x 10 m3 (17 gallons) of oil per tonne
(ton) of shale [3].
3.2 OCCIDENTAL'S MIS RETORTING TECHNOLOGY
Occidental Oil Shale, Inc., is involved in the development of
modified in-situ (MIS) retorting of oil shale. Starting in 1968,
Garrett Research and Development Company, the forerunner of Occi-
dental Research Corporation, started developing this technology
through laboratory studies in LaVerne, California, and field tests
at Logan Wash near DeBeque, Colorado.
An MIS retort is a fixed-bed chemical reactor constructed within
"unbroken" shale rock, (see Figure 1). In the Occidental process
rooms or voids are first mined out of the shale strata to define
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the retort boundaries. Using explosives placed strategically in
holes drilled in the shale between the mined-out voids, the re-
maining shale is fractured (or rubblized) and expanded into a
column of shale with the desired size and void distribution. The
mined void defines the ultimate average rubble void and provides
for effective flow of process gases and products through the
retort. The quantity, placement, and delay pattern of the
explosive provide the desired rubble size and void distribution.
After rubblizing, the retort is fitted with means for introducing
the retorting gases (air and steam) and withdrawing the liquids
and gases produced. The rubble bed is then ready for ignition
and processing. Ignition, is accomplished by heating the rubble
surface as uniformly as possible to the auto-ignition temperature.
At that temperature, residual char and organics in the surface
shale react with oxygen in the retorting gases and generate the
energy needed to establish and sustain the retorting front.
During retorting, the rubble bed comprises four distinct zones as
shown in Figure 2:
(1) A preheating zone in which sensible heat in the spent shale
is transferred to the incoming retorting gases;
(2) A combustion zone in which oxygen in the preheated retorting
gases reacts with residual char in the retorted shale and
generates heat for retorting;
(3) A retorting zone in which the hot gas leaving the combustion
zone heats the downstream shale sufficiently to break down
the kerogen (carbonaceous portion of shale) into oil, gas,
and residual char; and
11
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AIR
STEAM
GAS
PREHEAT
ZONE
COMBUSTION ZONE
RETORTING ZONE
RAW SHALE
PREHEAT ZONE
e
RETORT OFFGAS
RAW SHALE OIL
RETORT WATER
Figure 2. The four zones of an operating MIS retort.
(4) A raw shale preheat zone in which product vapors and liquids
are cooled and condensed and the unretorted shale is preheated
in preparation for retorting. Simultaneously, condensed
liquids, collected in sumps at the bottom of the retort, and
the retort off-gas are brought to the surface for further
processing.
The Logan Wash test program was implemented during Occidental's
burn of Retorts 7 and 8. Prior to Retorts 7 and 8, Occidental
has completed six MIS retorts, three of which were of commercial
size.
3.3 MIS RETORTS 7 AND 8
Commercial-size Retorts 7 and 8 were prepared for ignition in late
1981 and early 1982 to demonstrate the capability of MIS technology
for recovery of 60% of the oil from the shale. Thus, with an
12
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_3
average shale grade of 71 x 10 m3 per tonne (17 gallons per
ton), these two retorts, each 50 m (165 ft) square by 74 m (245
ft) tall, contained approximately 45,000 m3 (283,000 barrels) of
oil. Some 27,000 m3 (170,000 barrels) of this oil were expected
to be recovered: 2,200 m3 (14,000 barrels) as light oil for use
as fuel in the site steam plant and the remainder to be brought
to normal shipping standards in a heater treater before shipment
off site for testing and further upgrading.
The relative positions of Occidental's Retorts 7 and 8 are shown
in Figure 3. Also shown in this figure is retort 8X which was
not burned, but rather was designed to evaluate "communication"
(through undisturbed shale) between the two adjacent retorts.
Retort 7 was ignited on February 1, 1982 and reached a steady
burn condition about March 1, 1982. Retort 8 was ignited on
December 27, 1981 and also reached a steady burn on March 1,
1982. Thus, by the time the Logan Wash test program began on
May 5, both retorts were operating in a steady mode.
3.4 WASTEWATERS GENERATED FROM RETORTS 7 AND 8
Four types of wastewaters were generated from the operation of
Retorts 7 and 8: retort water, gas condensate, steam plant blow-
down, and mine wastewater. The two wastewater streams, retort
water and gas condensate, are generic to oil shale retorting and
were the only streams tested in this study.
3.4.1. Retort Water
Retort water is generated during MIS retorting when a portion of
the water vapor in the retort off-gas condenses in cooler sections
of the retort. This water typically mixes with crude shale oil in
the retort and percolates down through the unburned, rubblized
13
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Figure 3. Occidental Oil Shale, Inc. Retorts 7 and 8.
shale. The retort water/oil mixture accumulates in the product
collection sump at the retort bottom and is subsequently pumped
out and treated to recover the bulk of the shale oil.
Retort waters are heavily contaminated, containing significant
concentrations of organics, ammonia, and acid gases (hydrogen sul-
fide and carbon dioxide). In addition, the intimate contact between
this water and the rubblized shale results in leaching of inorganic
salts, yielding a substantial concentration of dissolved inorganic
solids. Although the volume of retort water produced can vary
widely depending upon the amount of injected steam and the -extent
to which groundwater infiltration into the retort occurs, MIS
retorts using steam as diluent gas are reported to produce retort
water at a rate of approximately 0.4 m3 (0.4 barrel) of water per
cubic meter (barrel) of product oil [4].
14
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At the Logan Wash site, the oil/water separation equipment for
Retorts 7 and 8 was located on a bench on the side of the
mountain adjacent to the product collection sump. The oil/ water
mixture was pumped out of the retort sumps to the measuring tank
(Tank 6) where the crude shale oil and the retort water were
separated by passing through several oil/water separation steps.
Figure 4 is a schematic diagram of this arrangement. The retort
water used in this study was supplied from the measuring tank
(Tank 6) at point A in Figure 4. Retorts 7 and 8 retort water
production rate over the test period ranged from 670 cm3/s to 740
cm3/s (360 barrels per day to 400 barrels per day) as illustrated
in Figure 5.
AIR/STEAM
FROM SURFACE
AIR/STEAM
FROM SURFACE
I
cc
1
RETORT
v \
r \
'RODUC
)LLECTIC
SUMPS
7
F
GAS
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i — i
Lj
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)N
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\
URFACE
1 i
— -
RETORT 8
.1.
1
MEASURING TANK-
_—— ^^
OIL
RETORT WATER
(TANK6)
Figure 4. Retort water supply point.
15
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16
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3.4.2 Gas Condensate
Retorting of oil shale generates gases from shale pyrolysis, com-
bustion of carbonaceous residues, and decomposition of inorganic
carbonates such as dolomite and calcite. Typically, water vapor,
ammonia, hydrogen sulfide, carbon dioxide, and organics are
present. The off-gases exit the retort bottom and are brought to
the surface and condensed to a liquid. This condensate is con-
taminated with light oils, dissolved organic compounds, ammonia,
and minor concentrations of metallic elements. In addition, a
high concentration of alkalinity (dissolved carbon dioxide)
resulting in a pH of approximately 9.0 and a very high buffering
capacity, is present. MIS processes may produce approximately
0.8 m3 (0.8 barrel) of gas condensate water per cubic meter
(barrel) of crude shale oil [4].
At the Logan Wash site, the off-gases from Retorts 7 and 8 were
brought to the surface at the top of the mountain and, after
passing through a series of contact coolers, were discharged to
the atmosphere. The condensate formed upon cooling the off-gases
flowed into holding tanks which facilitated oil/water separation
and oil removal. A portion of the oil-free gas condensate stream
was cooled in the fin coolers and subsequently used to contact
the retort off-gases in the contact coolers to form new condensate,
The unused portion of the condensate was expected to require some
treatment before discharge or disposal. A general schematic
diagram of gas condensate formation at Retorts 7 and 8 is provided
in Figure 6. The gas condensate used in the treatability tests
was supplied from the surface level at point B indicated in
Figure 6. Retorts 7 and 8 gas condensate production rate over
the test period ranged from 3,400 cms/s to 3,800 cms/s (1,840
barrels per day to 2,050 barrels per day) as illustrated in
Figure 7.
17
-------
GAS TO STACK •
RETORT
OFF-GASES
AIR/STEAM
SUPPLY
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3.5 WASTEWATER TREATMENT SCHEMES
After extensive review of proposed approaches to treatment of the
retort water and gas condensate [1] and through a series of
laboratory treatability and wastewater characterization studies,
two treatment schemes to remove contaminants typically found in
the retort water and gas condensate were identified and proposed
for testing at Occidental's Logan Wash test site [2]. The retort
water testing scheme was subsequently reduced in scope for
financial reasons and because of site test time availability
constraints. The finalized treatment schemes are described
below.
3.5.1 Retort Water Treatment
The treatment scheme proposed for retort water is shown in
Figure 8. It comprised filter coalescing, flocculation/clarifi-
cation, and steam stripping. These steps were intended to remove
residual oil, suspended solids, and dissolved gases from the retort
water. The filter coalescer was to enhance gravity removal of
free oils, even though the retort water available for testing at
Logan Wash had undergone primary oil/water separation prior to its
use. Effluent from the filter coalescer, expected to contain
colloidal and possibly emulsified oils and fine suspended solids,
passed through a flocculator/clarifier to remove these suspended
materials and reduce the potential for fouling the steam stripping
unit. Finally, steam stripping provided an effective means for
removing ammonia and alkalinity from retort water.
3.5.2 Gas Condensate Treatment
The treatment scheme proposed for gas condensate treatability test-
ing is illustrated in Figure 9.
20
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Two oil/water separation steps were provided for oil/water separa-
tion. The filter coalescer was to remove free oil and minor con-
centrations of suspended solids from raw gas condensate. The
gravity separator installed after, the steam stripper, was to
assure that oil separated due to breaking any oil/water emulsion
upon heating the wastewater in the steam stripper will be removed
and not foul or otherwise interfere with operation of downstream
units. Steam stripping was included to reduce the high levels
of ammonia and alkalinity in the gas condensate. It also was ex-
pected to remove a considerable fraction of the volatile organic
compounds as well, thereby altering the organic loadings on down-
stream treatment units. Following the gravity separator, an acti-
vated sludge system (aeration basin/clarifier) and/or activated
carbon adsorption were proposed for further removal of organic
materials from the steam-stripped and oil-free gas condensate. To
prevent fouling of the activated carbon adsorbers, the effluent
from the secondary clarifier, which was expected to contain
residual suspended solids of largely bacterial origin, was passed
through sand filters. Granular activated carbon adsorbers were
used to remove residual dissolved organic compounds from the acti-
vated sludge effluent or the steam stripper effluent (following
gravity separation) to complete the proposed gas condensate
treatment scheme.
The gas condensate treatment scheme was tested during the fourteen
weeks from May 22 through August 27, 1982, and information was
developed on both conventional and powdered activated carbon (PAC)
addition biological treatments.
3.6 FIELD TRIAL EQUIPMENT AND SETUP
Except for the steam stripper and filter coalescer, equipment for
the field trials was procured by EPA and made available to this
study. The steam stripper and filter coalescer were procured
under this contract.
23
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The equipment procured by EPA comprised eleven skid-mounted treat-
ment units housed in two 13.7-m (45-ft) long, fully enclosed trail-
ers and a field analytical laboratory built into a 7.6-m (25-ft)
house trailer. The skid mounted units were furnished fully instru-
mented and piped, and they were arranged inside the trailers in
accordance with the flow of the two treatment schemes described
earlier. The eleven treatment units, including a flocculator,
four clarifiers, a compartmented aeration basin, two sand filter
columns, two granular activated carbon columns, a backwash module,
a trickling filter (not used in field testing), and an anaerobic
filter (not used in field testing; it was delivered after the
field tests were completed) provided the bulk of treatment
capability needed for testing the proposed treatment schemes
in the field.
The equipment was freighted to the site, requiring an area of
18-m x 24-m (60-ft x 80-ft). The area levelled by Occidental
on the slopes of the oil product level was at an elevation .
of 2,300 m (7,700 ft). The arrangement of the pilot plant ,
equipment at this location is shown in Figures 10 through 13.
Several auxiliary systems had to be installed to facilitate the
field tests (refer to Figure 10). These included the electrical
switchgear, five storage tanks, and freshwater supply and :
distribution system.
A 15-m3 (4,000-gal) water tank was used to supply municipal water.
The tank was filled twice a week with municipal water. The water
from this tank was distributed to all locations, including the
boiler, laboratory trailer, safety shower, and several all-purpose
water hoses. Another 15-m3 (4,000-gal) tank, filled with No. 2
fuel oil on an as-needed basis, was used to supply fuel to the
steam boiler.
24
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A 23-m3 (6,000-gal) tank on the terrace (see Figures 11 and 12)
built on the mountain slope 18 m (60 ft) above the pilot plant
location provided for an uninterrupted supply of wastewater. The
was filled twice a day with the wastewater being tested. The
retort water was pumped into the tank from the measuring tank
(Tank 6), which was on the same product level. The gas condensate
was supplied by gravity through 370 m (1,200 ft) of high-pressure
hose connecting the contact condenser at the mountain top with the
wastewater supply tank (the black tank installed on a bench above
product level as shown in Figures 11 and 12). Flow of either
retort water or gas condensate wastewater from the wastewater
supply tank to the pilot treatment units was by gravity.
Two additional tanks were installed to contain the treated effluent
and the wastes generated by the field analytical laboratory.
A 1.1-m3 (300-gal) effluent sump tank, installed one meter
(3 ft) below the product level and fed by gravity, was used as a
holding tank for all treated effluent. This is the white, half-
buried tank in Figure 13. When actuated by a level sensor inside
the tank, a sump pump at the tank bottom emptied the tank auto-
matically, returning the contents to the Occidental mine sump. A
2-m3 (500-gal) tank buried underground was used to receive all
laboratory wastes except COD analysis wastes and was emptied per-
iodically by a local contractor who hauled the wastes to a municipal
sewage treatment plant for disposal. COD analysis waste was col-
lected separately and treated (by precipitating the mercury and
silver with sodium chloride and sulfide addition) before disposal
in the laboratory waste tank.
The following subsections provide brief descriptions of equipment
used during the Logan Wash study.
25
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SUPPLY TANK
25 m3
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Figure 11. Access road, Occidential's trailer park, and pilot
equipment position.
Figure 12.
Field setup of wastewater treatment facilities
at Logan Wash - general view.
27
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l|ii=:gp^
''ifV^'-SF,4'"*?*- iffcsfc15 '*; "-i£*"SfcL. -. .•• '»*IL . "•?•-. •-"•- -. "l:,': .-JT, '; .- •-- .„:•,?i "".',- ---?>^Sy,," • ™ ..; ^'-^v ^
"iF^ls*11'11^Si MS$i$^»'i.s^a!^***'**'* ijA>.-h.= .•.,-= •• - -..-''••> '• "•- -. ;'•;;:";: *-"'*,-••'• --.-:'"^.-s; •:*.-•„--•; r*^||
flSSira?! rr^BK^SMsWiB^
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Figure 13. Field setup of wastewater treatment
facilities at Logan Wash - closeup.
3.6.1 Filter Coalescer
The filter coalescer is illustrated in Figure 14. This
made of fiberglass with PVC inlet and outlet'connecting flanges,.
was used to separate and remove residual oil from ,the' raw waste-
waters. It is rated to handle a,wate?r flow of up J:o 0.3 m3/s
(5 gal/min). ; _
The coalescer employs a battery of perforated polypropylene tubes.
The oleophilic (oil-attracting) properties of these vertically
arranged tubes attract particles of oil from the water. As larger
oil globules develop, they either wick up the tubes or, if suf-
ficiently large, they break free and float to the surface! '_ Oil
from the surface drains by gravity over- an adjustable weir to the
slop tank section, and the cleaned water, after passing under the
retention baffle, is discharged.
28
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3.6.2 Flocculator
The flocculator, shown in Figure 15, is a 163-cm long x 76-cm
wide x 181-cm high (5 ft 4-in. long x 2 f t 6-in. wide x 5 ft
11.5-in. high) rectangular module. The flocculator holding
vessel is constructed of 304 stainless steel with PVC connecting
pipes and fittings. It is designed for up to 20 minutes of
hydraulic detention time at flows of up to 0.158 ms/s (2.5
gal/min). The flocculator has four sections separated by walls.
A 1.9-cm (0.75-in.) hole in each wall permits the water to flow
from one section to the next. The first three floe formation
sections are equipped with a low-energy flocculator paddle. The
three paddles, driven by a common variable-speed drive, rotate at
speeds of 0 to 200 rev/s. The three sections are interconnected
by PVC piping through a single opening in the bottom of each
section to permit flushing and removal of settled floe. The
desired detention time can be obtained by varying the influent
flow rate. Flocculating (chemical conditioning) agents are added
through one or more of the three ports (identified by the letter
A in Figure 15) by means of variable-speed chemical metering pumps.
The ports are interconnected with sections of static mixers, which
assure initial mixing of flocculating agents with the influent.
The treated water from the third section, after passing through
an effluent collection section, is discharged through an outlet
port. The effluent collection section has a baffle and a port to
handle overflow from this section.
3.6.3 Primary Clarifiers
The primary clarifiers, shown in Figure 16, are rectangular tanks '
constructed of 304 stainless steel. They are 107 cm long x 107 cm
wide x 177 cm high (3 ft 6 in. long x 3 ft 6 in. wide x 5 ft 10 in.
high) and have conical bottoms. The section above the cones
contains a 45-cm (1 ft 6-in.) tall bundle of inclined plastic
settling tubes and and an inlet flow deflection plate which,
30
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OVERFLOW COLLECTION SECTION
FLASH MIXER —
DRAIN OVERFLOW WEIR
OVERFLOW TO DRAIN 4- i
OUTLET
METERING 1PUMP
MOUNTING PLATE
DEFLECTION
PLATE
BUN OLE OF
INCLINED TUBES
£4 INLET
53cm (Itt9in.)_
V-NOTCH OVERFLOW WEIR
-40cm (in 3-3/4in.)
10cm
(3-3Win.)
ORIFICE WEIR
(OPTIONAL; MOUNTS ON THE
OVERFLOW WEIR PLATE)
Figure 16. Primary clarifier.
32
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minimizes turbulence in the clarifier. Each clarifier handles
overflow rates up to 3.8 x 10~4 m3/m2•s (800 gpd/ft2) at
corresponding throughput rates up to 132 cm3/s (2.1 gal/min).
The influent enters the clarifier at the center of the tank 6.4
cm (2.5 in.) above the cones through a nozzle that is pointed down
toward the deflection plate. As the water slowly rises in the
clarifier, solids settle into the cones by gravity. The treated
water overflows into the effluent collection section through an
orifice or V-notch weir (the orifice weir provides for oil/water
separation prior to discharge). The effluent collection section
is equipped with chemical metering pumps, a flash mixer or a
turbidity meter. The settled solids from the cones are removed
by opening the four (one for each cone) motor-operated ball valves,
which are automatically controlled by a programmer. The programmer
can operate the valves in any desired sequence, at any desired
frequency, and for any desired duration.
3.6.4 Secondary Clarifier
The secondary clarifier is quite similar to the primary clarifiers,
so only the features different from those of the primary clarifier
are described below.
The secondary clarifier module is a 137-cm (4 ft 6-in.) long,
107-cm (3 ft 6-in.) wide, and 161-cm (5 ft 4-in.) high rectangular
tank, and it is designed for overflow rates up to 2.8 x 10~4 m3/
m2-s (600 gpd/ft2) at influent flow rates up to 132 cm2/s (2.1
gal/min). It has dissolved oxygen and turbidity meters for
effluent monitoring. The settled sludge from the four cones
flows to a common sludge line from which it is either returned
to the aeration basin or disposed of as waste.
33
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3.6.5 Aeration Basin
The aeration basin, shown in Figure 17, is a 335-cm (11-ft) long,
145-cm (4 ft 10-in.) wide, 213-cm (7-ft) high unit comprising a
3.8-m3 (1,000-gal) compartmentalized rectangular tank made of
304 stainless steel. The unit, used for biological treatment of
wastewater, is capable of accomodating the following operating
conditions:
Hydraulic detention time: 3.6-28.8 ks (1-8 h)
Sludge recycle ratio: 0-1.5
Food-to-microorganism ratio: 0.2-1.5 :
Organic loading: 0.6-59.8 x 10~6 kg BOD5/s/m3
(37.4-3,740 Ib BOD5/day/1,000 ft3)
The hydraulic detention time can be varied by the use of specific
sections and/or by varying influent flow rate.
The aeration basin has four sections with respective volumes of
0.950 m3 (250 gal), 0.475 m3 (125 gal), 0.475 m3 (125 gal), and
1.90 m3 (500 gal). The four sections are connected by a 1.9-cm
(0.75-in.) diameter hole through each of the section walls and can
be operated individually or in parellel. Each section has its own
variable-speed agitator and an air diffuser to provide both mixing
and the air required to keep the biological mass suspended and
aerobic. The air, supplied to the four air diffusers by a common
blower, is measured for each section by an air rotameter. Each
section is monitored for dissolved oxygen by its own dissolved
oxygen meter.
The influent enters the aeration basin through an influent
manifold that distributes it into desired sections at controlled
rates through use of flow-splitting orifices and plugs. The over-
flow from each section is collected by a common overflow line from
which it is gravity fed to the secondary clarifier.
34
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DRAIN
* INLET t
DRAIN
/MANIFOLD DISTRIBUTION
I I
^=q^ I!
' SECTION 4
SLUDGE RETURN LINES
ROTAMETER
AIR DIFFUSERS
Figure 17. Aeration basin.
35
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A separate line for each section is provided for the return of
activated sludge from the secondary clarifier. Each line has a
rotameter and a diaphragm valve to monitor and control the rate
of return of activated sludge.
3.6.6 Sand Filters
The sand filtration module, shown in Figure 18, is a 117-cm
(3 ft 9 in.) long, 112-cm (3 ft 8 in.) wide, 267-cm (8 ft 9 in.)
high unit comprised of two 7.6-cm (3-in.) diameter, 236-cm (7 ft
9-in.) long clear PVC columns. The bottom flange of the columns
has a filter media-retaining screen and silk cloth with quick
connects to facilitate air scouring and backwashing. The columns,
used for filtration of suspended solids from the wastewater, have
a design capacity of 1.4-14 x 10~3 m3/m2-s (2-20 gpm/ft2), and can
be operated in parallel or series. During testing, the columns
were filled with 12 x 40 mesh sand, approximately 1.7 m (5.5 ft)
in depth and operated in parallel. :
Influent wastewater is pumped into the top of the column by a
variable-speed pump and flows down the column through the filter
medium. The filtered effluent enters a standpipe and is discharged.
The standpipe maintains a constant liquid level in the filter
columns. A rotameter monitors the flow through the columns, and
turbidity meters are provided to monitor the turbidity of each
column effluent. The pressure drop across each column is measured
by pressure differential measurement cells.
3.6.7 Carbon Adsorption Columns
The carbon adsorption column module is identical to the filtration
module described in Section 3.6.6 except that the columns are
15.2 cm (6 in.) diameter instead of 7.6 cm (3 in.). The columns
were packed with virgin activated carbon having the following
characteristics:
36
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INLET
ROTAMETER
STANDPIPES
VARIABLE -
SPEED PUMP
OUTLET
?7.6cm(3in.)
PVC COLUMNS
F
112cm Oft 8in.)
Figure 18. Sand filters.
37
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Surface area: 1,525 m2/g
Apparent density: 340 kg/m3
Larger than No. 12 mesh: 3% (maximum) :
Smaller than No. 40 mesh: 3% (maximum)
Iodine No.: 1,265 mg/g (minimum)
Abrasion No.: 65 (minimum)
3.6.8 Backwash Module
The backwash module is 86 cm (2 ft 9 in.) long, 81 cm (2 ft 7 in.)
wide, and 102 cm (3 ft 4 in.) high. As shown in Figure 19, it is
comprised of a water pump and an air compressor. The air and water
flowrates are controlled using separate rotameter and diaphragm
valve systems, respectively. The unit is used for air scouring
and backwashing of filtration and carbon adsorption columns.
3.6.9 Boiler Module ;
The boiler module, shown in Figure 20, is 457 cm (15 ft) long,
244 cm (8 ft) wide, and 140 cm (4 ft 7 in.) high. It is com-
prised of a boiler, a boiler feedwater tank, a water softener,
and an air compressor. The module is used to deliver steam to the
steam-stripping column. It is designed to deliver up to 110 g/s
(860 Ib/h) of steam at 103 kPa (15 psig) gauge pressure.
The boiler feedwater is pumped through the water softener, which
has an automatic resin regeneration capability using common salt
pellets, into the boiler feedwater tank. The water is pumped from
the feedwater tank into the boiler by a pump that is actuated by
the water level in the boiler. The boiler, which is fired with
No. 2 fuel oil, shuts off automatically when a preset steam pres-
sure is achieved. The air compressor provides air to the pneu-
matically controlled instruments on the steam-stripper skid.
38
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3.6.10 Steam Stripper
The steam stripper module, shown in Figure 21, is 610 cm (20 ft)
long, 244 cm (8 ft) wide, and 344 cm (11 ft 4 in.) high. It is
comprised of a packed column, an air cooler, a chiller, and an
overhead vapor condensate storage tank. Instrumentation and
automatic controls are provided to monitor and control the opera-
tion of equipment on the stripper skid with minimal operator
attention. The unit, used for removal of dissolved gases from
wastewaters, is designed for liquid throughputs of up to 378 cm3/s
(6 gal/min) and steam rates up to 91 g/s (720 Ib/h).
The stripping column, made of 316 stainless steel, is 40 cm (1 ft
3 3/4 in.) in diameter and 244 cm (8 ft) high. It is packed with
®
170 cm (5 ft 6 in.) of Goodloe packing, a high-efficiency stain-
less steel wire mesh with 95% void space. The air cooler is a
forced-air-cooled, finned-tube heat exchanger designed to cool up
to 378 cm3/s (6 gal/min) of water from temperatures near boiling
to 49°C (120°F) at air temperatures below 38°C (100°F). Five
fans, each having 5.6 ms/s (11,800 ft3/min) capacity, are used to
force the air around the finned tubes and remove heat from the
water passing through the tubes. The air cooler is 138 cm
(4 ft 6 in.) long, 104 cm (4 ft 5 in.) wide, and 200 cm (6 ft
7 in.) high. The chiller is a packaged, fully automated unit
designed to deliver 35 kW (10 tons) of refrigeration energy.
Glycol, refrigerated inside the chiller and circulated at a con-
stant rate through an external shell-and-tube heat exchanger, is
used as a cooling and heat transfer medium. The chiller is 137 cm
(4 ft 6 in.) long, 130 cm (4 ft Sin.) wide, and 183 cm (6 ft) high.
The 91-cm (3-ft) diameter, 142-cm (4 ft 8 in.) high overhead vapor
condensate storage tank is made of stainless steel and has a
holding capacity of 0.870 m3 (230 gal).
41
-------
WW OUT
STEAM COOLING
IN WATER
j W'A' IN'
CONDENSERS
»1 *2 »3 PREHEATER
SIDE ELEVATION
Figure 21. Steam stripper skid.
42
-------
Feedwater, after passing through a 50-micron filament cartridge
* it
filter and two heat exchangers (No. 2 and No. 3), is fed to the
top of the column where, by means of a distribution plate, it is
dispersed over the packing and trickles down through the column
by gravity. The filter is used to remove any suspended solids
and prevent clogging of the column packing. Two filter cartridges
connected in parallel are employed and used interchangeably to
permit uninterrupted column operation. The two heat exchangers,
connected in series, are used to preheat the feedwater to near
boiling temperature. Heat exchanger No. 2 uses column overhead
vapors, and No. 3 uses steam as the heating media.
Steam is introduced at the bottom of the column and exits at the
top. As it passes through, the steam heats and strips the feed-
water of the volatile components.
The column overhead vapors are either vented to the atmosphere or
condensed by two heat exchangers (No. 1 and No. 2). Heat exchanger
No. 1 uses cooling water and No. 2 uses column feedwater as cooling
media. A storage tank is provided for overhead vapor condensate
storage.
3.6.11 Pilot Equipment Trailers
Two semitrailers, Figure 22, each 13.7 m (45 ft) long, 2.4 m
(8 ft) wide, and 2.6 m (8 ft 6 in.) high were used to house
the pilot treatability equipment modules. Each trailer has a
side and back door, a feedwater pump and flow monitoring
instruments, Unistrut rails for fastening equipment, a sink, an
emergency eyewash and shower, an exhaust fan, a space heater,
electrical outlets, and an effluent discharge line.
43
-------
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-------
Primarily the side door was used for personnel access and the back
door for equipment installation and removal. Quick-disconnect
male couplers are provided outside the trailer for feedwater and
monitoring loop effluent hookups. Two pressure gauges, a basket
strainer, and a rotameter are located in the influent line to mea-
sure pressure, to remove large-size coarse solids, and to measure
flow rate, respectively. During operation, a variable-speed in-
fluent pump transfers the wastewater to be treated from its supply
point to the first treatment unit. A small fraction of the influent
stream passes through a loop for measurement of dissolved oxygen,
temperature, turbidity, and pH, and then proceeds to the drain.
Four Unistrut rails were provided to securely fasten the skid-
mounted treatment modules in the trailer. An acid-resistant sink,
an emergency eyewash, and an emergency shower were provided with
municipal and drain hookups underneath the trailer. An exhaust
fan circulates air through the trailer to prevent buildup of vapors
from the treatment operations. A series of electrical outlets
(110/220/440 V) were provided along the trailer wall to supply power
to pilot equipment. A 10.2-cm (4-in.) diameter PVC pipe with mul-
tiple inlets is located on the floor for discharge of effluent
from the treatment units in the trailer.
3.6.12 Mobile Laboratory Trailer
A mobile laboratory trailer, 7.6m (25 ft) long, 2.4 m (8 ft) wide,
and 2.4 m (8 ft) high, shown in Figure 23, was used to conduct
field laboratory analyses. The trailer is equipped with basic
laboratory glassware, reagents, other support supplies, an analyt-
ical balance, a triple-beam balance, a microscope, a gas chroma-
tograph, a muffle furnace, an oven, a vacuum pump, a spectrophoto-
meter, a COD analyzer, a specific-ion meter with pH, dissolved
oxygen and ammonia probes, a calculator with printer, 4m2 (45 ft2)
of bench space, a fume hood, cabinets and drawers, a kitchen hood,
45
-------
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a refrigerator, a dishwasher, a sink, a desk, a space heater, an
air conditioner, a water demineralizer, LPG racks, and brackets
for compressed gas cylinder storage.
47
-------
SECTION 4
PROGRAM IMPLEMENTATION AND RESULTS
After considerable preparation and planning, the tests began on
May 5, 1982. Initial testing was performed with retort water for
sixteen consecutive days. Two days were needed to perform equip-
ment and minor plumbing changes and to set up for gas condensate
testing, which began on May 22. The gas condensate testing lasted
14 weeks and was terminated on August 27. After two days of equip-
ment decommissioning and site restoration activities, the equipment
was removed from the site on September 2 and returned to MRC's
Dayton Laboratory for further servicing and maintenance.
A chronological listing of the more important events are given in
Table 1. It provides an overview of the Logan Wash test program
and permits relating the most important events to the program
results and vice versa.
4.1 PROGRAM SAMPLING AND ANALYSIS SCHEDULE
To identify components in the streams before and after treatment
and to evaluate the performance of each treatment step as well as
of the entire treatment scheme, a significant number of analyses
were performed on samples collected at predetermined locations in
the treatment schemes (refer to Figures 8 and 9). Unless dictated
otherwise by upsets or selective equipment performance evaluations
(e.g., determinations of steam stripping efficiency as a function
of steam-to-water ratio, or evaluation of flocculator removal with
48
-------
TABLE 1. PROGRAM MAJOR EVENTS
Dates
1981
12/27
1982
2/1
3/1
4/3
4/26
5/4
5/5
5/5 - 5/16
5/16 - 5/18 -
5/19 - 5/20 -
5/20
5/20 - 5/21
5/22
5/22 - 5/23
Retort 8 ignition
Retort 7 ignition
Retorts 7 and 8 reach steady state
Test equipment arrives at the trial location
Field laboratory arrives at the trial location
All systems installed and in working condition
Start retort water tests
Test filter coalescer, flocculator/clarifier with
fixed lime dosage, and steam stripper with varying
G/L ratio and constant liquid throughput of 190
cms/s (3 gal/min)
Test filter coalescer, flocculator/clarifier with
variation in lime dosage, and steam stripper with
fixed G/L ratio of 160 kg of steam per cubic meter
of liquid throughput (1.5 Ib of steam per gallon)
and constant liquid feed of 190 cms/s (3 gal/min)
Test steam stripper at 380 cm3/s (6 gal/min) liquid
throughput (unsuccessful)
End retort water tests
Equipment changeover in preparation for gas
condensate tests
Start gas condensate tests
Test steam stripper with varying G/L ratio at a
constant liquid throughput of 190 cms/s (3 gal/min)
(continued)
49
-------
TABLE 1 (continued)
Dates
1982
5/25
5/25
7/31
7/31
8/10
8/10
8/23
8/24
8/25
8/26
8/27
9/2
11/9
11/19
Test filter coalescer, steam stripper, aeration
basin (all four sections full; hydraulic detention
time of 24 hours), and secondary clarifier
Seed aeration basin (bioreactor)
Increase PAC dosage to 2,000 mg/L in Section 1
PAC-activated sludge treatment
Inadvertent addition of PAC (1,000 mg/L) to conven-
tional activated sludge system, Section 4 in;
aeration basin
End PAC-activated sludge system in Section 1 of
the aeration basin
Conventional activated sludge system in Section 4
of the aeration basin converted to PAC-activated
sludge system at 400 mg/L PAC dosage
Increase PAC dosage to 475 mg/L in Section 4; PAC-
activated sludge system
Increase PAC dosage to 950 mg/L in Section 4 PAC-
activated sludge system
Increase PAC dosage to 1,425 mg/L in Section 4 PAC-
activated sludge system
Increase PAC dosage to 1,900 mg/L in Section 4 PAC-
activated sludge system
End gas condensate tests
Transport test equipment to MRC's Dayton Laboratory
Retort 8 shutdown
Retort 7 shutdown
50
-------
varying flocculant additions), the types and frequency of sampling
and analyses performed during the retort water and gas condensate
trials are indicated respectively in Tables 2 and 3.
TABLE 2. ANALYTICAL SCHEDULE - RETORT WATER
a,b
Raw
Parameter wastewater
Total COD
Soluble COD
Total BOD5
Soluble BOD5
Dissolved organic carbon
Oil and grease
NH3-N
Total Kjeldahl nitrogen
N03-N
Alkalinity
Sulfide
Phosphorus
Cyanide
Phenols
Fluoride
Metals
TSS
VSS
TDS
Organic compounds
(by GC/MS)
pH
Temperature
Chlorides
DOC fractions
3
5
5
5
5
3
5
5
2
5
5
1
2
2
2
(1)
5
5
2
(1)
[1]
[1]
2
(1)
Filter
coalescer Clarifier
effluent effluent
3 3
-
2 5
5
5
3
-
'
-
-
_
-
-
-
-
-
5 5
5 5
-
-
[1]
-
-
- —
Steam
stripper
effluent
_
5
-
5
5
-
5
5
-
5
5
-
2
2
-
(1)
-
-
-
(1)
[1]
tl]
-
(1)
Single numerical values indicate number of analyses per week. Paren-
thesized values indicate number of analyses during the entire study
period. Bracketed values indicate number of analyses per day.
Unless reported otherwise, all analyses performed on 24-h composite sam-
ples except for oil and grease, phenols, cyanide, pH, and temperature.
51
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All analyses were performed in accordance with the Standard Methods
for the Examination of Water and Wastewater, 15th Edition, 1980,
except for nitrate nitrogen (ASTM D922), mercury, arsenic, and
selenium (EPA Interim Method 200.7), organic compounds (EPA Methods
624 and 625), and DOC fractions (DOC fractionation procedure).
The following sections present the results from the Logan Wash
treatability study of retort and gas condensate wastewaters.
4.2 RETORT WATER TEST RESULTS
Retort water testing was performed May 5, 1982 through May 18,
1982. In general, the treatment units were operated continuously
24 hours a day. For each treatment unit, the parameters listed
in Table 4 were monitored on a periodic basis by the operating
personnel and entered into the equipment operation log once every
two hours. Samples of the influent and effluent were collected in
accordance with the schedule presented in Table 2. Presentation
and discussion of the results follow.
4.2.1 Raw Wastewater Characterization
Raw wastewater was analyzed for conventional pollutants, metals,
and organics (by GC/MS and DOC fractionation). The results of
these analyses, from samples collected over 16 days of retort
water tests, are summarized in Tables 5 through 8. As expected,
the results show that the raw retort water contained high concen-
trations of TDS, ammonia, TKN, organics, sulfide, alkalinity,
phenols, chlorides, fluorides, boron, potassium, and sodium.
Sixty-eight percent of the organics were hydrophobic; the remainder
were hydrophilic.
53
-------
TABLE 4. MONITORED EQUIPMENT OPERATING PARAMETERS
DURING RETORT WATER TESTING
Filter coalescer
Influent pH
Influent temperature
Influent flow
Oil volume collected
Flocculator
Mixing energy (RPM)
Chemical (flocculant) added and its dosage
Primary clarifier ;
Overflow pH
Steam stripper
Column feed flow and temperature
Steam flow and pressure
Column bottoms flow, temperature and pHa
Overhead flow and temperature
Column temperature - top and bottom
Column pressure - top and bottom
Column level
Boiler
Steam pressure
Boiler water level
Boiler feedwater tank level
As shown in Table 5, the TKN value is less than the NH3-N value.
This is not possible since TKN equals the sum of organic and
ammonia nitrogen. This discrepency occurs throughout the retort
water, gas condensate, and treatment unit performance data. Data
will be presented and the reader should use his discretion.
Unfortunately, causes for the discrepency can at best be estimated
and may include the following:
54
-------
TABLE 5. RAW RETORT WATER CHARACTERIZATION - CONVENTIONAL
POLLUTANTS AND OTHER PARAMETERS
Parameter
Total COD
Soluble COD
Total BOD5
Soluble BOD5
DOC
Oil and grease
NH3-N
TKN (N)
N03-N
Alkalinity as CaC03 to pH 4.5
Sulfide
Phosphorus (P)
Cyanide
Phenols
Fluorides
Chlorides
TSS
VSS
TDS
PH
Temperature
Number of
analyses
performed
4
4
4
4
5 b
(5)b
6(5)
6(2)
5
6(4)
3
4
(4)
(5)
7
6
8
6
6(1)
(10)
(10)
Concentration
Range
3,400-6,000
3,100-5,400
2,200-4,000
1,900-2,200
1,400-2,300
(50-170)
1,600-3,900
(1,700-3,700)
1,700-3,000
(2,100-2,200)
3.0-4.8
12,000-17,000
(13,000-16,000)
50-130
0.8-2.1
(<0. 02-0. 08)
(47-70)
36-63
500-1,000
27-93
23-78
10,000-15,500
(15,000)
(8.6-9.4)
(21-46)
, mg/La
Average
4,700
4,100
3,200
2,000
1,700
(110)
2,200
(2,200)
2,100
(2,100)
4.3
14,000
(14,000)
90
1.5
(0.05)
(56)
45
800
59
54
14,000
(15,000)
(8.8)
(35)
Except for pH and temperature; pH is reported in standard pH units,
and temperature in °C.
Data reported in parentheses pertain to grab samples; the other data
pertain to 24-hr composite samples.
TKN QA/QC is continuously poor; analyses was performed by
an outside lab while NH3-N analyses was performed internally.
Interference by amines on the NH3-N titrimetric method may
cause false positive NH3-N results.
Available methods for TKN and/or NH3-N analyses on wastewaters
as complex as these oil shale waters may not be reliable.
55
-------
TABLE 6. RAW RETORT WATER CHARACTERIZATION - METALSa
Concentration,
Parameter mg/L
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
K
Mg
Mn
Mo
Na
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
<0.18
0.22
4.9
37
0.14
<0.01
4.3
0.01
<0.06
0.05
0.05
0.65
170
2.3
0.01
1.2
2,900
0.15
<0.42
<0.27
0.04
5.8
0.29
<0.08
0.07
0.09
aOne 24-hr composite sample
taken on May 18, 1982.
i
• No organic Nitrogen is present and the TKN and NH3-N values
are within the effeciency of the sampling and analyses' methods
and (in some cases) are equal.
4.2.2 Oil/Water Separation '.
A filter coalescer, the first step in the treatment scheme, was
used for oil/water separation. Its performance was evaluated at
220 cm3/s (3.5 gal/min) throughput flow.
56
-------
TABLE 7. RAW RETORT WATER CHARACTERIZATION - PURGEABLE
AND EXTRACTABLE ORGANICSa
Concentration,
Parameter mg/L
Base/Neutral Extraction Fraction
C2-Pyridine 3.3
C3-Pyridine 4.0
C4-Pyridine 4.2
Phenol and isomers of phenol 35
Methyl cyclopentenone 2.2
Benzenamine 1.55
C3-cyclohexen-l-one 1.45,
Aziridine, ethylmethyl (isomer) NpP
Pyrrolidinone, cyclohexylmethyl NP
Pyridinedicarbonitrile 4.6
C3-piperidinium bromide 0.6
Butenone, dimethylamino (isomer) 0.7
Methyl quinoline or
methyl isoquinoline 3.5
Cyclohexadienedione, tetramethyl 1.8
Pyrrole, methylphenyl 1.4
C2-quinoline (isomer) 1.3
Unknown 47
Acid Extraction Fraction
Unknown carboxylic acid 56
Unknown 34.4
Benzoic acid, methyl (isomer) 4.0
Benzene acetic acid 3.2
Benzene propanoic acid 0.5
Pyridinone, methyl (isomers) 0.1
Decanedioic acid 7.9 ,
Furanone, ethyldihydromethyl NP
One 24-hr composite sample taken on May 18, 1982.
NP - not presented; no chromatographic peak was
found for the sample.
Influent temperature ranged from 21°C to 46°C. Influent pH ranged
from 8.6 to 9.4. The performance of filter coalescer is
summarized in Table 9.
57
-------
TABLE 8. RAW RETORT WATER CHARACTERIZATION - DOC FRACTIONS9'b
Concentration,
Parameter mg/L
Total DOC 2,280
Hydrophobia fraction 1,550
Acid 690
Base 100
Neutral 690
Unrecovered 70
Hydrophilic fraction 730
Acid 410
Base 60
Neutral 110
Unrecovered 150
aThe DOC fractions represent the
following compound categories:
Hydrophobic
Acid (aliphatic carboxylic acids C5
to C9; 1- and 2-ring aromatic
carboxylic acids; 1- and 2-ring
phenols; fulvic acid)
Base (1- and 2-ring aromatic amines
except pyridine)
Neutral (hydrocarbons; aliphatic
alcohols, amides, esters,
ketones, and aldehydes >C5;
aliphatic carboxylic acids
and aliphatic amines >C9;
aromatic carboxylic acids
and aromatic amines of
> 3 rings)
Hydrophilic
Acid (aliphatic acids of
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59
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The filter coalescer on the average removed 6% of the residual
oil and grease, 21% of the TSS, and 20% of the VSS. Organic
removal associated with oil and grease removal was insignificant
as indicated by the removals of total BOD5 and COD, respectively.
The raw retort water tested had already been through an oil/water
separation step and insignificant BOD5 and COD removals indicate
the effectiveness of this initial treatment. In addition, the
filter coalescer received raw retort water from the 23-m3
(6,000-gal) supply tank (refer to Figure 10), which acted as a
gravity oil/water separator. This explains the low oil and
grease concentration in the raw wastewater and the resulting low
oil and grease removal by the filter coalescer. Visual observa-
tions of the 23-m3 (6,000-gal) supply tank confirmed oil floating
on the surface. Hence, an oil/water separation step would be
necessary in a retort water treatment scheme.
4.2.3 Flocculation/Clarification :
The flocculator/clarifier was operated at 220 cms/s (3.5 gal/min)
throuphput flow and at mixing energy (paddle rotation velocity)
of 0.4 to 0.5 s"1 (24 to 30 RPM). Lime was added as a slurry
through the flocculant addition port (refer to Figure 15) by a
chemical metering pump and flocculator influent and clarifier
effluent were analyzed using 8-hour composite samples. Flocculator
influent; and clarifier effluent pH ranged from 8.6 to 9.4.
Due to the presence of high alkalinity, low lime dosage (90 mg/L to
270 mg/L) resulted in insignificant contaminant removal as reported
in Table 10. Lime dosages as high as 9,000 mg/L to 13,000 mg/L may
be required to reduce high alkalinity levels and effect removals of
settleable and/or floatable solids, metals, and fluorides from the
oil/water separator effluent. Because of generally lower alkalin-
ity levels in the stripper effluent, lime treatment of this efflu-
ent offers an alternative which could result in comparable
treatment at lower lime dosage and consumption.
60
-------
TABLE 10. FLOCCULATOR/CLARIFIER PERFORMANCE DATA SUMMARY*
Lime dosaae , mg/L
90
Concentration, mg/L
Parameter
TSS
Flourides
Chlorides
c
PHC
Ag
Al
B
Ba
Be
Ca
Cd
Co
Crd
Cu
Fe
K
Mg
Mn
Mo
Na
Ni
Pb
Sb
Sn
Sr
Ti
V
Zn
Influent
22
44
950
8.7
0.20
0.28
45
0.16
<0.01
3.0
<0.01
<0.06
0.04
0.07
0.74
225
2.6
0.01
1.5
3,540
0.14
0.42
0.31
7.3
0.33
0.02
0.09,
b
Effluent
22
41
850
8.7
<0.18
0.22
42
0.13
<0.01
3.3
<0.01
<0.06
0.03
0.41
0.65
191
2.3
0.01
1.3
3,210
0.10
0.42
<0.27
5.8
0.30
0.01
0.03,
b
180
Concentration, mg/L
Influent
_b
41
900
8.7
<0.18,
_b
44
0.19
<0.01
3.5
<0.01
<0.06
0.04
<0.04,
b
223
2.9
0.01,
b
3,510,
_b
<0.42
<0.27,
b
0.31
0.02
0.04,
b
Effluent
_b
34
860
8.7
<0.18,
_b
43
0.17
<0.01
15.2
<0.01
<0.06
0.03
0.3,
b
214
2.9
0.01,
b
3,465,
_b
<0.42
<0.27,
b
0.29
0.02
0.03^
b
270
Concentration, mg/L
Influent
23
38
1,000
8.8,
b
0.25,
_b
0.12
<0.01
3.6
<0.01
<0.06
0.04
0.09
0.69,
b
b
0.01
1.38,
b
0.18
<0.42
0.30,
_b
0.26,
b
~b
0.05
Effluent
21
34
800
8.8,
_b
0.24,
_b
0.12
<0.01
13
<0.01
<0.06
0.04
0.45
0.68,
_b
~b
0.01
1.35,
_b
0.15
<0.42
<0.27,_
_b
0.26,
b
"b
0.04
All samples were 8-hr composite except for pH analysis samples.
Corresponding influent and effluent analyses gave inconclusive results.
pH is in standard pH units.
T'he increase in the effluent copper concentration is significant; cause
of this increase in unknown.
61
-------
4.2.4 Steam Stripping :
The effluent from flocculator/clarifier was fed without pH adjust-
ment into the steam stripper. Unavailability of cooling water at
the Logan Wash test site did not permit use of the stripper over-
head condenser. Hence, the stripper overhead stream was vented to
the atmosphere and no data on this stream are available.
Steam stripping was performed to evaluate the removal of ammonia
and alkalinity at various steam/liquid (G/L) ratios. During
testing, the steam stripper was operated at a constant liquid
feed rate of 190 cm3/s (3 gal/min), and steam feed rates were
varied to achieve the desired G/L ratios. The stripper was
operated a minimum of 24 hours at each condition.
Other relevant parameters were monitored to observe incidental
concentration changes of TKN, sulfide, DOC, soluble COD, soluble
BOD5, phenols, and cyanide. Samples of stripper liquid feed and
effluent (bottoms) were analyzed for these parameters to determine
their degree of removal. The stripper performance data, which
summarize stripper feed and bottom concentrations for conventional
pollutants, are presented in Table 11. Data on organics by GC/MS,
DOC fractions, and metals data for the stripper feed and bottoms
are presented in Tables 12 through 14, respectively, for a constant
G/L ratio of 180 kg of steam per cubic meter of feed water (1.5 Ib
steam per gallon feed water). Percent ammonia and alkalinity
removals as a function of G/L ratio are displayed in Figure 24.
Review of conventional pollutant data (Table 11) show that ammonia
and alkalinity are readily stripped from retort water. As the G/L
ratio increases, the degree of removals of these two pollutants
also increases as expected. Greater than 97% ammonia removal and
47% alkalinity removal were achieved with G/L ratios equal to or
greater than 180 kg of steam per cubic meter of feed water (1.5 Ib
steam per gallon feed water). TKN and ammonia removals increase
62
-------
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-------
TABLE 12. STEAM STRIPPER PERFORMANCE DATA - ORGANICS^
(May 12, 1983)
Organic compound
Base/Neutral Extraction Fraction
C2 -Pyridine
C3-Pyridine
C4 -Pyridine
Phenol and isomers of phenol
Methyl cyclopentenone
Benzenamine
Butenone, dime thy lamino (isomer)
C3 -cyclohexen-1-one
Aziridine ethylmethyl (isomer)
Pyrrolidinone, cyclohexylmethyl
Pyridinedicarbonitrile
C3 Piperidinium bromide
Butenone, dimethylamino (isomer)
Methyl guinoline or methyl isoguinoline
Cyclohexadiene-dione, tetramethyl
Pyrrole , methylphenyl
C2-Quinoline (isomer)
Unknown
Acid Extraction Fraction
Unknown carboxylic acid
Unknown
Benzoic acid, methyl (isomer)
Benzene acetic acid
Benzene propanoic acid
Pyridinone, methyl (isomers)
Decanedioic acid
Furanone, ethyldihydromethyl
Total organics
Concentration, mg/L
Feed
3.3
4.0
4.2
35
2.2
1.5
0.7
1.4
NP
NP
4.6
NP
0.7
3.5
1.8
1.4
1.3
46
56
34
4.0
3.2
0.5
0.1
7.9
NP
216
Bottoms
NPb
NP
NP
31
2.2
NP
2.6
1.0
2.4
. 1.0
1.3
2.0
NP
NP
1.5
NP
NP
39
32
86
3.3
4.5
NP
NP
NP
0.6
210
aG/L ratio of 180 kg of steam per cubic meter of feed water
(1.5 Ib steam per gallon feed water).
NP - not present; no chromatographic peak was found for the
sample.
64
-------
TABLE 13. STEAM STRIPPER PERFORMANCE DATA - METALS3
(May 12, 1983)
Metal
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
K
Mg
Mn
Mo
Na
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Concentration,
mg/L
Feed Bottoms
<0.18
0.22
4.9
37
0.14
<0.01
4.3
0.01
<0.06
0.05
0.05
0.65
170
2.3
0.01
1.2
2,900 3,
0.15
<0.42
<0.27
0.04
5.8
0.29
<0.08
0.07
0.09
0.34
0.19
4.9
39
0.13
<0.01
5.2
0.02
0.06
0.05
0.22
0.57
190
1.8
0.02
1.4
000
0.18
<0.42
0.27
0.04
8.1
0.26
<0.08
0.08
0.08
G/L ratio of 180 kg of steam
per cubic meter of feed water
(1.5 Ib steam per gallon feed
water).
as the G/L ratios increase. Virtually similar TKN and ammonia
values indicate TKN to be all ammonia. Sulfide is readily
removed (>99%) at G/L ratios as low as 60 kg steam per cubic meter
of feed water (0.6 Ib steam per gallon feed water). Significant
amounts of phenols, 27 to 54%, also were strippable, and the
removals appear to depend on both G/L ratio and feed phenols
concentration. Incidental removals of organics occurred.
65
-------
TABLE 14. STEAM STRIPPER PERFORMANCE DATA - DOC FRACTIONS'
(May 12, 1983)
Concentration ,
mg/L
Parameter/ fraction
Total DOC
Hydrophobic fraction
Base
Acid
Neutral
Unrecovered
Hydrophilic fraction
Base
Acid
Neutral
Unrecovered
Feed
2,280
1,550
100
690
690
70
730
60
410
110
150
Bottoms
1,930
1,250
65
640
540
5
680
110
510
35
25
°/
/o
Removal
15
19
35
7
22
3
x to
(83)"
(24)
68
Fraction
distribution,
°/ •
/o
Feed
68
7
45
45
3
32
8
56
15
21
Bottoms
65
5
: 51
: 43
, 1
35
i 16
75
5
4
aG/L ratio of 180 kg of steam per cubic meter of feed water (1.5
Ib steam per gallon feed water).
^Number in bracket indicate increase.
Removals ranged from 0 to 25% for DOC, 5 to 11% for soluble BOD5,
and 16% for COD at the G/L ratios tested. Organics in retort
water are relatively nonvolatile; therefore, high organics removals
by steam stripping were not expected. The pH of the stripper
bottoms was higher than that of the feed by 0.5 to 1.2 units. The
pH was affected by ammonia and alkalinity removals. Ammonia
removal decreased pH while alkalinity removal increased the pH.,
Organic compounds data (Table 12) show that about 63% of the
organic compounds in the feed water and 75% of the organic com-
pounds in the stripper bottoms were unidentifiable owing to the
complexity of the matrix in which they were present. Also, only
3% of the organics were removed by steam stripping. Phenols con-
stituted about 16% and 15% of the organics in the stripper;feed
and bottoms, respectively. GC/MS analysis showed about 10% phenols
66
-------
100
90
80
70
60
40
30
20
10-
AMMONIA
"ALKALINITY
60 120 180 240 300
(0.5) (1.0) (1.5) (2.0) (2.5)
G/L RATIO, kg steam/m3 feed water (Ib steam/gallon feed water)
Figure 24. Percent removals of ammonia and alkalinity
in steam stripper at various G/L ratios.
67
-------
removal compared to 32% removal reported in Table 13 at a G/L ratio
of 180 kg steam per cubic meter of feedwater (1.5 Ib steam per
gallon feed water).
Metals concentrations (Table 13) in the stripper feed and bottoms
did not change significantly, as expected, because metals are
nonvolatile.
Fractionation data (Table 14) show that 15% of the DOC was removed
by the steam stripper. Removal of hydrophobic compounds was 19%,
while hydrophilic compound removal was 7% (refer to Table 8 for a
list of compounds represented by each fraction). Although the
percentages of hydrophobic and hydrophilic compounds in the feed
and bottoms did not change significantly, the acid, base and
neutrals present in each catagory changed significantly, as can
be seen in the fraction distribution percentage columns in
Table 14. This suggests that perhaps the organics in the
retort water are reactive and undergo chemical changes when
exposed to the elevated temperatures and steam inside the ;
stripper.
Attempts were made to obtain performance data at various G/L
ratios and constant liquid feedrates of 190 cms/s (3 gal/min) and
380 cm3/s (6 gal/min) using raw retort water as feed. Because of
partial clogging of the overhead vapor lines with condensed ammo-
nium carbonate these attempts were unsuccessful. The clogging
increased the pressure across the stripper column and eventually
led to column flooding. Steam cleaning of the column improved the
column performance but did not increase the column throughput
capacity to the desired 380 cm3/s level. Unless condensate con-
tinually flushes out the ammonium carbonate and prevents build up
and clogging of the stripper overhead line, use of the steam
stripper for retort water treatment on a continuous basis may not
be practically feasible.
68
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4.3 GAS COMPENSATE TEST RESULTS
Gas condensate testing was performed May 22, 1982 through
August 26, 1982. In general, the treatment units were operated
continuously 24 hours a day. For each treatment unit, the para-
meters listed in Table 15 were monitored on a periodic basis by
the operating personnel and entered into the equipment operation
log book once every two hours. Samples of the influent and
effluent were collected in accordance with the schedule presented
in Table 3. Presentation and discussion of the results follow.
4.3.1 Raw Wastewater Characterization
Raw wastewater was analyzed for conventional pollutants, metals,
and organics (by GC/MS and DOC fractionation). The results of
these analyses on samples collected during 14 weeks of gas con-
densate tests are summarized in Tables 16 through 19. Ammonia,
alkalinity, and soluble COD results were also graphed, to show
their variation in these parameters with time (see Figures 25
through 27). As expected, the treated gas condensate contained
high concentrations of ammonia, TKN, organics, alkalinity, phenols,
and sulfide. Forty-five percent of the organics were hydrophobic;
the remainder were hydrophilic. The gas condensate also contained
high concentrations of pyridine and phenolic compounds as shown
in Table 17.
4.3.2 Oil/Water Separation
A filter coalescer was used for oil/water separation during the
entire gas condensate test period. Its performance in removing
oil was evaluated at influent flow rates ranging 220 to 250 cms/s
(3.5 to 4.0 gal/min), temperatures ranging 26°C to 45°C, and
influent pH ranging 8.3 to 8.7. The performance was determined
by monitoring the oil and grease levels in both the influent and
effluent, (see Table 20). Although removal was as high as 52%,
69
-------
TABLE 15. MONITORED EQUIPMENT OPERATING PARAMETERS
DURING GAS CONDENSATE TESTING
Filter coalescer
Influent pH
Influent temperature
Influent flow
Steam stripper
Column feed flow and temperature
Steam flow and pressure
Column bottoms flow and temperature
Overhead flow and temperature
Column temperature - top and bottom
Column pressure - top and bottom
Column level
Stripper bottoms - ammonia (field kit ) '
Boiler
Steam pressure
Boiler water level
Boiler feedwater tank level
Primary clarifier
Influent pH and dissolved oxygen i
Aeration basin
Influent flow
Aeration basin pH
Air flow
Aeration basin dissolved oxygen
Agitator RPM
Sludge wastage rate ]
Nutrient addition
Secondary clarifier ;
Overflow dissolved oxygen
(continued)
70
-------
TABLE 15 (continued)
Multimedia filters
Effluent flow
Carbon adsorption columns
Effluent flow
Backwash module
Air flow
Water flow
pH recorded in a lab notebook, not in the log.
Semiquantitative determination performed as needed to provide a
quick test to estimate ammonia levels in stripper bottoms.
CHEMetrics, Inc. Model AN-10 ammonia-nitrogen test kit was used
for this determination. The kit contains Nessler's reagent which
forms a colored complex with ammonia. The color intensity is
indicative of ammonia concentration which is estimated by compar-
ison of a sample with color standards of known concentrations.
the maximum removal obtained corresponded to 5.8 mg of oil removed
per liter of gas condensate. This removal is insignificant and
added essentially nothing to the overall treatment.
The raw gas condensate had an average 7 mg/liter of TSS and 5 mg/
liter of VSS during the test period. Because these concentrations
were insignificant, filter coalescer performance for these two
parameters was not evaluated.
4.3.3 Steam Stripping
Three types of steam stripping tests were performed: (1) at
various G/L ratios, (2) over an extended period to produce an
effluent suitable for biological treatment with ammonia levels
71
-------
TABLE 16. RAW GAS COMPENSATE CHARACTERIZATION FOR CONVENTIONAL
POLLUTANTS AND OTHER PARAMETERS
Parameter
Total COD
Soluble COD
Soluble BOD5
DOC
Oil and grease
NH3-N
TKN
NO3 -N
Alkalinity as CaCO3 to pH 4.5
Sulfide
Phosphorus
Cyanide
Phenols
Fluorides
TSS
VSS
TDS
PH
Temperature
Number of
analyses
performed
2
37 (13)b
8
33
(13)
40 (33)
21
16
27 (19)
17
6
(4)
(21)
9
8
8
6
(-V560)
(-v-560)
Concentration ,
Range
2,000-4,100
1,400-4,100
(2,000-4,200)
600-1,000
500-1,400
(1.8-76)
6,100-14,000
(4,800-11,000)
1,300-9,700
0.3-3.0
21,000-37,000
(22,000-40,000)
18-190,
<0.01-1.3
(<0. 02-0. 11)
(70-150)
0.07-1.05
<5-14
<5-6
48-140
(8.3-8.7)
(26-45)
mg/L,a
'Average
; 3,100
. 2,700
; (2,800)
800
890
; d8.6)
: 9,000
(8,200)
6,800
1.1
31,000
(31,000)
72
0.26
'• (0.04)
(120)
0.43
: 7
5
98
(8.5)
(34)
Except for pH and temperature; pH is reported in standard pH
units and temperature in °C.
Data reported in parentheses pertain to grab samples; the remain-
ing data pertain to 24 hr composite samples.
below 25 mg/liter, and (3) over an extended period to produce
an effluent suitable for biological treatment with ammonia :
levels of about 100 mg/liter.
72
-------
TABLE 17. RAW GAS CONDENSATE CHARACTERIZATION FOR
PURGEABLE AND EXTRACTABLE ORGANICS
Parameter Concentration, mg/L
Base/Neutral Extraction Fraction
Pyridine compounds and their isomers 100
Trichloromethane 3 •2
Benzene 5-4
Cyc1ohexene 9•2
Methylcyclopentenone 2.6
Phenolic compounds and their isomers 150
Trimethylcyclohexenone 3.9
Quinoline and/or isoquinoline 2.9
IH-Indole or benzeneacetonitrile 2.1
Methyl quinoline or methyl isoquinoline 3.4
Unknown 67 .•
Acid Extraction Fraction
Trichloromethane 1 • 9
Benzene 4 • 2
Cyclohexene 1°
Carboxylic acid 20
Phenols 1 • 1
Alkenes >C8 °-81
Unknown " 6-3
aOne 24 hr composite sample taken on August 4, 1982.
The capability of the steam stripper to remove ammonia and alkalin-
ity from filter coalescer effluent was evaluated first. The
evaluations were performed at various steam/liquid (G/L) ratios
with a constant liquid (filter coalescer effluent) feedrate of
190 cms/s (3 gal/min) and with no feed pH adjustment. . Average
bottoms rates were equal to feed rates of 190 cm3/s (3 gal/min).
Unavailability of cooling water at.the Logan Wash test site did
not permit use of the stripper overhead condenser. Hence, the
stripper overhead stream was partially condensed to preheat
stripper wastewater feed and the remainder vented to the
atmosphere. Thus, no data on the overhead stream are available.
73
-------
TABLE 18. RAW GAS CONDENSATE CHARACTERIZATION FOR METALS9
Parameter
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
K
Mg
Mn
Mo
Na
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Concentration, mg/L
<0.19
0.20
<0.01
0.40
<0.01
<0.01
1.91
<0.01
<0.04
<0.02
<0.03
0.16
<0.01
<2.6
0.18
<0.01
<0.05
10
<0.08
0.1
<0.01
<0.01
<0.5
<0.01
<0.02
0.03
0.19
aOne 24 hr composite sample taken
on August 4, 1982. I
TABLE 19. RAW GAS CONDENSATE CHARACTERIZATION FOR DOC FRACTIONS61
Parameter Concentration, mq/L :
Total DOC 482
Hydrophobic fraction 216
Acid 47
Base 96
Neutral 73
Hydrophilic fraction 266
Acid 17
Base 52
Neutral 197 '
One 24-hr composite sample taken on
August 4, 1982.
74 ;
-------
15,000
14,000
13,000
12,000
11.000
I
"10,000
i
9,000
6,000
7,000
6,000
5,000
4,000
MEAN: 8,500 ing/L
SD: l,800mg/L
20 25 30 5 10 15 20 25 30 5 10 15 20 25 30 5 10 15 20 25
MAY JUNE JULY AUGUST
1982
Figure 25. Raw gas condensate wastewater ammonia concentration
variations (grab and composite sample results).
Although ammonia and alkalinity were the parameters of primary
interest, other parameters such as soluble COD, DOC, sulfide,
phenols, TKN, and pH were also monitored to observe any incidental
removal or change. The results of these initial
75
-------
MEAN: 31.000mg/L
SD: 4.300 tng/L
20 000' ' ' ' —————
20 25 30 5 10 15 20 25 30 5 10 15 20 25 30 5 10 15 20 25
MAY JUNE JULY AUGUST
1982
Figure 26. Raw gas condensate wastewater alkalinity concentration
variations (as CaCO3 to pH 4.5) (grab and composite
sample results).
evaluations are summarized in Table 21. Ammonia, alkalinity,
soluble COD, and DOC removals observed during these evaluations
also are plotted as a function of varying G/L ratio in Figure 28
through 31.
76
-------
MEAN: 2,700/ng/L
SD: 730mg/L
20 25 30
MAY
10 15 20 25 30
JUNE
5 10
1982
15 20 25 30
JULY
10 15 20 25
AUGUST
Figure 27.
Raw gas condensate wastewater soluble COD concentration
variations (grab and composite sample results).
A review of the initial results revealed that ammonia, alkalinity,
sulfide, phenols, DOC, TKN, and COD could readily be stripped from
gas condensate and that the removal efficiencies increased, as
expected, with an increase in G/L ratio. Ninety-nine percent of
both alkalinity and ammonia were removed at G/L ratios of 120
kg/m3 (1 Ib/gal) or higher. Ninety-nine percent of the sulfide
77
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100
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.1
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Figure 28. Percent ammonia, removal at various
G/L ratios for gas condensate.
100
90
80
60
t
30
(0.25)
60
(0.5)
90
(0.75)
120
d.0)
150
(1.25)
183
(1.5)
Figure 29.
Percent alkalinity removal at various
G/L ratios for gas condensate.
79
-------
100
90
r
i
70
60
30 60 90 120 150 IK
(0.25) (0.5) (0.75) (1.0) (1.25) (1.5)
G/L RATIO, kg steam/m3 feed water (Ib steam/gallon feed water)
Figure 30.
Percent DOC removal at various
G/L ratios for gas condensate.
100
_r 90
K 80
o
o
o
a 70
60
T
30
(0.25)
60
(0.5)
90
(0.75)
120
150
(1.25)
180
(1.5)
Figure 31.
Percent soluble COD removal at various
G/L ratios for gas condensate.
80
-------
was removed at G/L ratios of 60 kg/m3 (0.5 Ib/gallon) or higher.
Phenols removals were about 50% and were relatively independent of
G/L ratio. More than 60% of the TKN, DOC, and soluble COD were
removed at G/L ratios of 60 kg/m3 (0.5 Ib/gallon) or higher. The
pH of the stripped effluent was always higher than that of the
gas condensate feed.
The second type of stripper test comprised operation of the strip-
per for extended periods to produce an effluent for biological
treatment. These tests were performed from May 26 to August 26,
1982. During that period, the biological treatability of pre-
treated gas condensate was being investigated. An effluent suit-
able for biological treatment was required to have an ammonia
concentration that would not lead to poor COD removals during
biological treatment as a result of inhibition by ammonia. Thus,
from May 26 to June 10, 1982, the stripper was operated within a
rather narrow range of operating conditions to produce an effluent
with ammonia levels ranging from 10 to 32 mg/liter (see Table 22).
However, at this level of ammonia the effluent contained only 210
to 510 mg/liter of soluble COD (down from 1,400 to 2,400 mg/liter
in the raw gas condensate owing to incidental removal of COD in
the stripper). This relatively low COD concentration in the ef-
fluent was increased to provide an increase in the amount of sub-
strate for the biomass in the biological treatment (see Section
4.2.5). Therefore, for the remaining period, from June 11 to
August 26, 1982, the stripper operation was adjusted to produce
an effluent with an ammonia level from 46 to 180 mg/liter as the
third type of stripper test . This led to a corresponding increase
in COD level, of 470 to 2,100 mg/liter (see Table 23). Data show-
ing variations in stripper operation (G/L ratio) and removals for
ammonia, alkalinity, soluble COD, DOC, and phenols over the test
period are plotted in Figures 32 through 36, respectively.
81
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83
-------
cn
E
170(1.4)
cT 120(1.0)
5/26 - 6/10/82
MEAN: 100%
SD: 0.1%
5/26 - 6AO/82
MEAN: 22mg/L
SD: 7mg/L
5/26 - 6/10/82
MEAN: 9,700mg/L
SD: 600 mg/L
o
Figure 32
5/26-6/10/82
MEAN: 200 kg/m (1.6 Ib/gal)
SD: 10 kg/m3 (0.1 Ib/gal)
6/11 - 8/27/82
MEAN: 99%
SD- 0.4%
6A1 - 8/27/82
MEAN: 100 mg/L
SDr 26 mg/L
STRIPPER EFFLUENT
6/11 - 8/27/82
MEAN: 8,300 mg/L
SD: 1,600 mg/L
STRIPPER FEED
6/11/82 - 8/27/82;
MEAN: 140 kg/m3 (1.16 Ib/gal)
SD: 2 kg/m3 (0.02 Ib/gal)
135 7 9
11 13 15
JUNE 1982
17 19 21 23 25 27 29
Long-term steam stripper performance - ammonia
removals between June 1 - August 26, 1982.
84
-------
r. loo
I 99
^
uj 98
97
200
160
120
80
40
0!
15,000
"J 14,000
S 13,000
§ 12,000
< 11,000
10,000
9,000
8,000
7,000
6,000
5,000
to
-CD
220(1.8)
, 170(1.4)
-120(1.0)
QC
6/11-8/27/82
MEAN: 99%
SD: 0.4%
6A1 - 8/27/82
MEAN: lOOmg/L
SD: 26 mg/L
6A1 - 8/27/82
MEAN: 8,300 mg/L
SD: 1,600 mg/L
STRIPPER EFFLUENT
STRIPPER FEED
6/11 - 8/27/82
MEAN:140kg/m3(l.l6lb/gal)
SD: 2kg./m3(0.02lb/gal)
1357
9 11 13 15 17 19 21 23 25 27 29 31
JULY 1982
Figure 32 (continued)
85
-------
TsP. 1UU
^ 99
1 98
g yo
02 97
7 1
*«
^v^rt
200
160
120
80
40
«*•
> 15,000"
g- 14,000
§ 13,000
i 12,000
11,000
10,000
9,000
8,000
7,000
6,000
~ 5.000
to
•S?
?T *i
"3= 220(1.8)
•^ 170(1.4)
HI i?nn ni
^«* XkU 11. \J)
O£.
6A1 - 8/27/82
_^r^ ^^^ ^^ i^ — ^ l^*^"^^^*^^.
---"* ^**^ MEAN: 99% >
SD:0.4% :
.
= 6/11 - 8/27/82
MEAN: lOOmg/L
SD: 26mg/L STRIPPER
_ ^-. ^^\ ^^ /EFFLUENT
^^
|
: o.ll - 8/27/82
WEAN: 8,300mg/L
SD: l,600mg/L
-
-
-
A
/\l\ ^^\
" /^^^ v^ \ ^^^ STRIPPER FEED
- /
•
-
i
: 6/11 - 8/27/82
MEAN: 140 kg/m3 (1.16 Ib/ga!)
SD: 2kg/m3(0.02lb/gal)
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31
-------
o
0£
ir\
O
03
(J)
ro
~CT>
JC
cT
100
99
98
97
96
«
1,600
1,200
800
400
0
40,000
38,000
36,000
34,000
' 32,000
30,000
28,000
26,000
24,000
22,000
20,000
•*•
220(1.8?
170(1.4)
120(1.0)
5/26-6AO/82
MEAN: 99%
SD: 1%
5/26-6AO/82
MEAN: 320mg/L
SD: 500mg/L
5/26-6AO/82
MEAN: 37,OOOmg/L
SD: 1.500mg/L
5/26 - 6/10/82
MEAN:200kg/m|(1.6fb/gal)
SD:_10kg/m3(0. lib/gal)
6A1-8/27/82
MEAN: 99%
SD: 0.6%
6A1-8/27/82
MEAN: 360mg/L
SDi 170mg/L
STRIPPER EFFLUENT
6A1-8/27/82
MEAN: 40,OOOmg/L
SD: 3,600mg/L
STRIPPER FEED
6/11-8/27/82
MEAN:140kg/m3(i.l6Ib/gal)
SD: 2kg/m3(0.02lb/gal)
13579
11 13 15 17
JUNE 1982
19 21 23 25 27 2930
Figure 33.
Long-term steam stripper performance - alkalinity
removals between June 1 - August 26, 1982.
87
-------
o
on
01
d.
Q
0
(D
O
100
99
98
97
96
ro
xa
I
tf.
OS.
o
1,600
1,200 - -
400
0
•i
40,000
38.000
36,000
34,000
32,000
30,000
28,000
26,000
24,000
22,000
20,000 -
220(1.8)"?
170 (1.4) -
120(1.0) -
6/11 - 8/27/82
MEAN: 99%
SD: 0.6%
6/11- 8/27/82
MEAN: 360mg/L
SD: 170mg/L
STRIPPER EFFLUENT
6/11 - 8/27/82
MEAN: 40,OOOmg/L
SD: 3,600 mg/L
STRIPPER FEED
6/11 - 8/27/82
MEAN: 140 kg/m3 (1.16 Ib/gal)
SD: 2kg/m3(0.02!b/gal)
1357
9 11 13 15 17 19 21 23 25 27 29 31
JULY 1982
Figure 33 (continued)
88
-------
100
99
£ 98
| 97
U-)
01 96
*
1,600
1,200
800
400
0
^
ci 40,OX~
01
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ITS
" 36,000
o 34,000
ff 32,000
o 30, OX
l/i
< 28, OX
z 26.0X
g 24, OX
^ 22, OX
a 20, ox
§ :
^ 220(1.8)
jl 170 (1.4)
o 120(1.0)
5
— ^^\^
6A1- 8/27/82
MEAN: 99%
SD: 0.6%
-
= 6A1 - 8/27/82
MEAN: 360mg/L
SD: 170mg/L
STRIPPER EFFLUENT
I 6A1- 8/27/82
MEAN: 40,OXmg/L
SD: 3,6Xmg/L
-
S\ ^-^/ ^"^V STRIPPER FEED
- / s^.
-
-
-
-
: 6/11 - 8/27/82
MEAN:140kg/m3(1.16lb/gal)
SD: 2kg/m3(0.02lb/gal)
AUGUST 1982
Figure 33 (continued)
89
-------
UJ
70}-
60
50
40
30
•m
2,200
1,800
1.400
1,000
600
200
*
4,400
4,000
* 3,600
3,200
2,800
2,400
2,000
s 1,600
•g 1.2TO
j| 220 (1.8)
~ 170 (1.4)
o
g 120(1.0)
ce
CD
5/26 - 6/10/82
MEAN: 83%
SD: 10%
5/26 - 6/10/82
MEAN: 310mg/L
SD: lOOmg/L
5/26 - 6/10/82
MEAN: 2,OOOmg/L
SD: 400mg/L
5/26 - 6/10/82 o
,MEAN:200kg/m,U.6lb/gal)
SD: 10 kg/nrMO. lib/gal)
i i j i i
6/11 - 8/27/8
MEAN: 56%
SD: 11%
6/11 - 8/27/82
MEAN: l,300mg/L
SD: 450mg/L
STRIPPER EFFLUENT
6/11 - 8/27/82
MEAN: 2,900 mg/L
SD: 670 mg/L
STRIPPER FEED
6A1 - 8/27/82 ;
MEAN:140kg/m3U.16lb/gal)
SD: 2kg/m3(0.02lb/gal)
JL
"I I"
1357
11 13 15 17
JUNE 1982
19 21 23 25 27 29 31
Figure 34. Long-term steam stripper performance - soluble COD
removals between June 1, 1982 and August 26, 1982.
90
-------
o
§
e
o
re
100
90
80
70
60
50
40
3£l
2,200"
1,800
1,400
1,000
600
200
•^
4,400"
4,030
3,600
3,200
2,800
2,400
2,000
1,600
1,200
JE 220 (1.8)
S. 170 (1.4)
o
g 120(1.0)
oe
6A1 - 8/27/82
MEAN: 56%
SD: 11%
STRIPPER EFFLUENT
6A1 - 8/27/82
MEAN: l,300mg/L
SD: 450mg/L
6/11 - 8/27/82
MEAN: 2,900mg/L
SD: 670 mg/L
STRIPPER FEED
6A1 - 8/27/82
MEAN:140kg/m3(1.16lb/gal)
SD: 2kg/m3(0.02lb/ga!)
1357
11 13 15 17 19 21 23 25 27 29 31
JULY 1982
Figure 34 (continued)
91
-------
I
100
90
80
70
60
50
40
30.
2,200
1,800
1,400
1,000
600
200
*•,
4,400*"
4,000
3,600
3,200
2,800
2,400
2,000
1,600
§' 1,200..
j= 220(1.8)"
• 170 (1.4)
g 120(1.0)
O£
—I
O
f
cT
o
CD
to
6A1 - 8/27/82
MEAN: 56%
SO: 11%
6/11 - 8/27/82
MEAN: l,300mg/L
SD: 450mg/L
STRIPPER EFFLUENT
6/11 - 8/27/82
MEAN: 2,900mg/L
SD: 670mg/L
STRIPPER FEED
6/11-8/27/82
MEAN:140kg/m3(1.16lb/gal)
SD: 2kg/m3(0.02lb/gal)
1357
11 13 15 17 19 21 23 25 27 29 31
AUGUST 1982
Figure 34 (continued)
92
-------
100
90
80
70
60
50
40
^
1,400
1,300
1,200
1,100
1,030
900
800
700
600 -
500 -
403 -
300 -
200 -
100 -
0
•hoi
E 220(1.8)*
. 170 (1.4)
o
g 120(1.0)
o:
o"
(9
5/26 - 6/10/82
MEAN: 94%
SD: 0.7%
5/26 - 6/11/82
MEAN: 510mg/L
SD: 290mg/L
5/26 - 6/10/82
MEAN: 94mg/L
SD: 25mg/L
5/26 - 6/10/82 ,
MEAN; 200 kg/m.(1.6 Ib/gal)
SD: 10 kg/nr (0.1 Ib/gal)
I \ i i i
_L
6/11 - 8/27/82
MEAN: 60%
SD: 13%
6/11 -8/27/82
MEAN: 930mg/L
SD: 210mg/L
STRIPPER FEED
6/11 - 8/27/82
MEAN: 370mg/L
SD: llOmg/L
STRIPPER EFFLUENT
1 3 5. 7 9
6/11 - 8/27/82
MEAN: 140 kg/m3 (1.16 Ib/gai)
SD: 2 kg/m3 (0.02 Ib/gal)
"T ~ f T r^^i T^r
11 13 15
JUNE 1982
17 19 21 23 25 27 2930
Figure 35. Long-term steam stripper performance - DOC removals
between June 1, 1982 and August 26, 1982.
93
-------
1
f
100
90
80
70
60
50
40,
1,400
1,300
1,200
1,100
1,000
900
800
700
600
500
400
300
200
100
0
JE 220(1.8)
•^ 170 (1.4)
o
g 120(1.0)
OS
6/11 - 8/27/82
MEAN: 60%
S&
STRIPPER FEED
6/11 - 8/27/82
MEAN: 930mg/L
SD: 210mg/L
STRIPPER EFFLUENT
6/11 - 8/27/82
MEAN; 370mg/L !
SD: llOmg/L
6/11 - 8/27/82
MEAN:140kg/m3(1.16lb/gal)
SD: 2kg/m3(0.02lb/ga!)
1357
9 11 13 15 17 19 21 23 25 27 29 31
JULY 1982
Figure 35 (continued)
94
-------
•§
100
90
80
70
60
50
40,
1.400
1,300
1,200
1,100
1,000
900
800
700
600
500
400
300
200
100 -
0
JE 220 (1.8)
S. 170 (1.4)
o
£ 120(1.0)
6A1 - 8/27/82
MEAN: 60%
SD: 13%
6/11 - 8/27/82
MEAN: 930 mg/L
SD: 210 mg/L
STRIPPER FEED
STRIPPER
EFFLUENT
6/11 - 8/27/82
MEAN: 370mg/L
SD: 110 mg/L
6/11- 8/27/82
MEAN:140kg/m,(1.16lb/ga!)
SD: 2kg/nr><0.02lb/gal)
3 5 7
11 13 15 17 19 21 23 25 27 29 31
AUGUST 1982
Figure 35 (continued)
95
-------
I
er>
E
n>
50
40
30
20
10
0
«
150
140
130
120
110
100
90
80
70
60
50
220 (1.8)"
170 (1.4)
120(1.0)
6/11 - 8/27/82
MEAN: 29%
SD:-11*
STRIPPER FEED 6/11-8/27JS
MEAN: 13ifflg/L
SD: 22 iig/L
STRIPPER EFFLUENT 6/11 - 8/27/S
MEAN: 91ffl§/L
SD: 11
STRIPPER FEED
STRIPPER EFFLUENT
5/26 - 6/10/82
: MEAN; 200 kg/m3 (1.6 Ib/gal)
6/11 - 8/27/82
^ v MEAN: 140 kg/m3 (1.16 Ib/gal)
SD: 10kg/m3 (0.1 Ib/galPv SD; 2 kg/m3 (0.02 Ib/gal)
ii i i i i i V| i • i i" r —r~•' i' t*m
5/31 1 3 5 79
11 13 15 17 19 21 23 25 27 29
JUNE 1982
Figure 36.
Long-term steam stripper performance - phenols removals
between June 1, 1982 and August 26, 1982.
96
-------
50
40
30
20
10
0
•
150
140
130
120
110
100
90
80
70
60
50
^E 220 (1.8)
~ 170 (1.4)
e>
g 120(1.0)
K
6A1 - 8/27/82
MEAN: 29%
SD:
6A1 - 8/27/82
MEAN: 130mg/L
SD: 22mg/L
6/11 - 8/27/82
MEAN: 91mg/L
SD: llmg/L
STRIPPER
FEED
STRIPPER EFFLUENT
6/11 - 8/27/82
MEAN:140kg/m3(1.16lb/gal)
SD: 2kg/m3(0.02lb/gal)
_
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31
JULY 1982
Figure 36 (continued)
97
-------
I
50
40
30
20
10
(^
150*
140
130
120
110
100
90
80
70
60
50
JE 220(1.8)
•^ 170 (1.4)
Cn
t/f
O.
120 (1.0)
6/11-
MEAN: 29%
SD: 11%
6/11 - 8/27/82
MEAN: 130mg/L
SO-' 22mg/L
6/11 - 8/27/82
MEAN: 91 mg/L
SD: 11 mg/L
STRIPPER FEED
STRIPPER
EFFLUENT
6/11 - 8/27/82
MEAN:140kg/m3(1.16lb/gal)
SD: 2kg/m3(0.02lb/gal)
1357 9 11
13 15 17 19
AUGUST 1982
21 23 25 27 29 31
Figure 36 (continued)
98
-------
Ammonia, alkalinity, TKN, and sulfide removals were excellent
(greater than 95%) during the entire period. The range of
percent removal was narrow, indicating very good long-range
stability of the steam stripper operation and performance.
Over the test period from June 11 to August 26, 1982, COD removals
ranged from 36% to 78%, and DOC removals ranged for 34% to 89%.
The removal efficiency for both parameters decreased steadily dur-
ing the period even though G/L ratios remained constant. This
could have resulted from the steadily increasing COD and DOC
levels in the gas condensate (stripper feed) produced by Retorts 7
and 8 during the test period.
Removal of phenols varied from 7% to 42% and averaged 29%. As
indicated in Figure 36, phenols removals did not follow any
specific trend over the test period.
Because a continuous supply of cooling water was not available at
the Logan Wash test site, the stripper was operated most of the
time with the overhead uncondensed and vented to the atmosphere.
The difference between a parameter concentration in the stripper
feed and the stripper effluent was used to evaluate stripper
removals. Feed and bottom rates to and from the stripper were
essentially the same (a constant level was maintained in the
stripper column, thus, the flow out equalled the flow in) and
this percent removal calculation is similar to calculations based
on mass alone. However, no calculations based on mass were made.
To provide some indication of pollutant distribution between the
stripper effluent and stripper overhead, the stripper was operated
at a constant liquid feedrate of 158 cms/s (2.5 gal/min) with
constant steam-to-liquid ratio of 144 kg/m3 (1.2 Ib/gal). For
approximately two hours, municipal water was used to condense the
stripper overhead and this overhead was collected as a condensate
sample. Simultaneous grab samples of the stripper feed, stripper
effluent, and stripper overhead were taken and analyzed for
99
-------
ammonia, metals and organics (by GC/MS and DOC fractionation).
During this time period, stripper bottoms maintained an average
flow rate equal to the column feed rate (158 cm3/s or 2.5 gal/min)
and the overhead rate was approximately 19 cms/s (0.3 gal/min).
The test results for GC/MS organics, metals, and DOC fractions
are summarized in Tables 24 through 26. Table 27 shows ammonia
grab sample results and present a material balance for thei
stripper system.
Phenolic and pyridine compounds (50% and 20%, respectively) con-
stituted 70% of the organics in the stripper feed, while phenolic
compounds constituted 73% of the organics in the stripper bottoms.
The major constituents of the overhead vapor condensate organics
were pyridine compounds (28%) and unidentifiable compounds (58%).
The stripper bottoms and the overhead vapor condensate contained
some compounds that were not found in the stripper feed. This
discrepancy was caused by the different matrixes in which the
compounds were present in the feed, bottoms, and overhead vapor
condensate.
The stripper feed had a low metal content, and many metals were
present at concentrations below the detection limit of the analyt-
ical method. The concentrations of metals detected in the three
streams sampled varied little from stream to stream and were at
very low levels or below the detection limits.
A review of DOC fractions data shows that 63% of the hydrophobic and
69% of the hydrophilic compounds (refer to Table 8 for a list of
the compounds) were removed by the steam stripper. As indicated in
Table 26, base and neutral fraction removals in both :
categories were greater than 60%.
100
-------
TABLE 24. STEAM STRIPPER PERFORMANCE DATA FOJ
PURGEABLE AND EXTRACTABLE ORGANICS0
Concentration, mg/L
Organic compound
Base/Neutral Extraction Fraction
Pyridine compounds and their isomers
Trichlorome thane
Benzene
Cyclohexene
Methylcyclopentenone
Phenolic compounds and their isomers
Trimethylcyclohexanone
Quinoline and/ or isoquinoline
IH-Indole or benzeneacetonitrile
Methyl quinoline or methyl isoquinoline
Unknown
2-Cyclopenten-l-one, 3-methyl
Pyrrole compounds
Benzamine
Methyl indole and/or methyl
indolizine (isomer)
Acid Extraction Fraction
Trichlorome thane
Benzene
Cyclohexane
Carboxylic acid
Phenols
Alkene >C8
Unknown
Furanone, 5-hexyldihydro
Furanone , 5-ethyldihydro-5-methyl
Possible chlorine-containing unknown
Silicon-containing unknown
Sulfur
Unknown phthalate
Feed
100
3.2
5.4
9.3
2.6
150
3.9
2.9
2.1
3.4
67
1.9
4.2
10
20
110
0.81
7.2
Bottoms
4.9
4.9
11
230
1.9
10
3.1
19
22
3.3
6.3
5.4
12
73
Overhead
vapor
condensate
140
1.3
4.8
2.5
11
2.1
11
140
5.9
5.5
13
0.12
150
0.13
0.35
0.3
0.18
7.3
2.2
One grab sample taken on June 16, 1982.
Blanks indicate compound below detection limits.
101
-------
TABLE 25. STEAM STRIPPER PERFORMANCE DATA FOR METALSla
Metal
Concentration, mg/L
Feed
Bottoms
Overhead
vapor
condensate
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
K
Mg
Mn
Mo
Na
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
<0.19
0.20
<0.01
0.36
<0.01
<0.01
1.91
<0.01
<0.04
<0.02
<0.03
0.16
<0.01
<2.6
0.18
<0.01
<0.05
<10
<0.08
<0 . 1
<0.38
<0.01
<0.5
<0.01
<0.02
<0.03
0.19
<0.19
0.15
<0.01
0.42
<0.01
<0.01
2.19
<0.01
<0.04
<0.02
<0.03
0.16
<0.01
<2.6
0.23
0.02
<0.05
<10
<0.08
<0 . 1
<0.38
<0.01
<0.5
<0.01
,<0.02
<0.03
0.03
<0.19
0.25
0.01
0.10
0.01
<0.01
2.67
<0.01
<0.04
0.02
0.07
0.75
0.02
<2.6
0.20
<0.01
<0.05
<10
0.14
<0 . 1
<0.38
<0.01
<0.5
0.01
<0.02
<0.03
0.08
Grab sample taken on June 16, 1983.
Ammonia concentration in the condensed overhead was approximately
77,000 ppm (see Table 27). Flow rates in Ib/hr are based on gal/
min rates and measured stream temperatures. The material balance
closure for ammonia is excellent (103%). ;
Every 7 to 10 days the liquid throughput to the stripper column
decreased from 190 cm3/s (3.0 gal/min) to 127-158 cms/s (2JO-2.5
gal/min) as a result of partial clogging of the overhead vapor
102
-------
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lines with condensed ammonium carbonate. This increased the
pressure in the stripper column and eventually resulted in column
flooding. Blowing steam through the packing for several hours did
not completely eliminate the clogging problem, but it did riaise
the liquid throughput to 190 cm3/s (3.0 gal/min) again. Despite
this problem, the stripper performed very well, required minimal
attention, and supplied a steady feed for biological treatment.
The stripper packing was inspected at the end of the study and a
black deposit was observed. The deposit was analyzed and found
to contain 66% nickel and 25% copper.
4.3.4 Conventional Activated Sludge Treatment '
The feasibility of removing organics from steam-stripped gas con-
dens ate by the conventional activated sludge process was evaluated
from May 25 to August 10, 1982. This subsection describes the
treatment and the results obtained.
4.3.4.1 Bioreactor Startup and Acclimation ;
Operation of a continuous-flow, completely mixed activated ;sludge
reactor system was begun on May 25, 1982, using the following
startup operating conditions and the aeration basin and clarifier
described in Section 3.5: . .
Reactor hydraulic loading rate: 41.7 cm3/s
Reactor hydraulic retention time: 24 hours
Mean cell residence time (sludge age): 30 days ;
Clarifier overflow rate: 9.3 x 10~6 m3/m2-s
Operating tank liquid volume: 3.6m3 , ;
Operation: Complete mix ,
104
-------
Raw gas condensate water had an average ammonia concentration of
approximately 8,600 mg/L. Since this value is considerably higher
than the concentration that begins to inhibit the activated sludge
process (480 mg/L) [5], the raw gas condensate required pretreat-
ment for ammonia removal; this was done using the steam stripper.
Section 4.3.3 presents performance data on the stripper and
describes the quality of the stripper bottoms generated for use
as feed to the activated sludge reactor.
Nutrients were added to the activated sludge reactor to sustain
microorganism growth in the biological system. Nutrient addition
requirements were determined from bench-scale activated sludge
treatment of Occidental Retort No. 6 gas condensate and were
based upon approximate values of cell composition and assumed
maximum values of sludge wastage rate. Phosphoric acid (H3PO4),
magnesium sulfate (MgS04•7H20), and ferric chloride (FeCl3-6H2O)
were found to be deficient and were added to the steam-stripped
wastewater in quantities sufficient to maintain phosphorus,
magnesium, and iron concentrations of 7.5, 1.25, and 0.50 mg/L,
respectively.
The reactor was seeded with sludge obtained from the secondary
clarifier of an activated sludge treatment plant treating coke
plant wastewater at a steel mill. This sludge was added to each
of the 4 sections in a sufficient amount to result in 17,000 mg/L
of mixed liquor volatile suspended solids (MLVSS) in the aeration
basin. The stripped gas condensate flow was then gradually
adjusted to 41.7 cm3/s within the following 24 hours of reactor
operation.
A number of operational problems were encountered during the
acclimation period. They are summarized below (additional
details are provided in Appendix A):
105
-------
• The\high mixed liquor suspended solids (MLSS) concentration
(28,000 mg/L) caused rapid accumulation of thick sludge at
the inlet to the secondary clarifier and resulted in frequent
plugging of the aeration basin overflow line. This problem,
prevalent over the first two days, was resolved by periodical-
ly unclogging the aeration basin overflow line, and by solids
loss from sludge overflow from the secondary clarifier, which
decreased the mixed liquor solids level in the bioreactbr.
• The overflow from the aeration basin was saturated with air.
As the liquid flowed into the overflow pipe from the basin
the air separated from the liquid, causing an air lock (or
air pockets) in the overflow pipe and severely reducing the
flow through the pipe and hose connecting the aeration basin
with the secondary clarifier; this caused the aeration basin
to overflow. This problem was corrected by installing an
aeration basin overflow chamber or holding tank, which
allowed the air to separate from the water prior to the
liquid entry into the hose connecting line and the ;
secondary clarifier. '•
• The aeration basin overflow was characterized by poor sludge
settling characteristics. Hence, the sludge did not settle
in the secondary clarifier and was lost in the clarifier
overflow. Alum was added to the aeration basin overflow to
i
improve sludge settleability. Also, during the poor sludge
settling period, fresh seed sludge was periodically added to
the aeration basin to prevent rapid depletion of biological
solids.
• Uniform operation of the aeration basin could not be maintain-
ed. The aeration basin comprised four sections of unequal
volumes, as described in Section 3.5, and was to be operated
as a completely mixed homogeneous reactor. To achieve; uni-
form operation of each section, it was necessary that leach
106
-------
section be fed with stripped effluent flow in proportion
to its volume. This could not be done because the section
flow distribution tubes built sludge deposits as the mixed
liquor splashed against them; this, in turn, made the flow
distribution unpredictable. Similarly, sludge returning
from the clarifier had to be distributed in proportion to
the volume of each section; this distribution could not suc-
cessfully be done owing to system design limitations. Cut-
ting holes into the walls between the sections to facilitate
intersectional mixing and thus equalize the aeration basin
operating conditions improved but did not correct the situa-
tion. Thus, the aeration basin operated as four distinct
reactors rather than as one homogeneous reactor until three
of the sections were removed from use as described below.
From May 25 to June 10, the steam stripper was operated to
produce an effluent with an ammonia concentration of 20-25
mg/L. As noted earlier, this resulted in a COD concentration
that was believed to be too low based on decreasing MLVSS
concentrations and dissolved oxygen uptake rates to sustain
a viable biological treatment. Although raising the ammonia
level to 80-120 mg/L increased the COD levels, a further
increase in the organic loading of the system was believed
to be necessary based on the above criteria and conversations
with several biological treatment experts. This was done by
decreasing the hydraulic retention time, from 24 hours to
16 hours. The retention time was reduced by taking out of
service the three smallest sections in the aeration basin
and decreasing the inlet flow to this basin.
On June 5 (the tenth day of reactor operation) stripped re-
tort water rather than stripped gas condensate was inadvert-
ently fed to the aeration basin (operator error). This upset
the system and interrupted its acclimation. Several days
were needed to restore equilibrium.
107
-------
During July 4 to July 8, owing to development of a leak in
the aeration basin overflow line, most of the biological
solids from aeration basin Section 4 flowed into Sections 2
and 3 instead of the secondary clarifier. Sections 2 ,and 3
were out of operation during this period. This caused a
large drop in MLSS and MLVSS levels in Section 4, and .neces-
sitated transfer of large quantities of sludge from Sections 2
and 3, as shown in Table 28.
TABLE 28. SEEDING SCHEDULE FOR BIOSYSTEM >
Date Quantity of sludge added,
1982 m3 (gallons)
6/21
6/29
6/30
7/1
7/2
7/3
7/4
7/7
7/8
7/9
7/10
7/11
7/12
0.380
0.060
0.020
0.020
0.040
0.040
0.040
0.060
0.095
0.360
0.400
0.285
0.130
(100)
(15)
(5)
(5)
(10)
(10)
(10)
(20)
(25)
(95)
(105)
(75)
(35)
• Foaming problems were occasionally encountered in the aeration
basin, and were eliminated by adjusting the air flow rate and/
or agitator speed of the aeration basin.
Because of some of these problems and the changes needed to deal
with them, the biological reactor performance was not evaluated
from May 25 to June 15. From June 16 to July 12, one section of
the aeration basin was operated at a hydraulic detention time of
16 hours;. A sludge settling problem was still present, and a
significant quantity of biological solids was being lost in the
secondary clarifier overflow. This prevented development 6f a
108 •
-------
viable population of organisms in the bioreactor. To combat this
problem, no sludge other than the overflow sludge was discarded,
and fresh seed sludge was periodically added to the aeration basin,
as noted in Table 28. Also, alum (at 120-150 mg/L) was added con-
tinuously to the aeration basin effluent to help sludge settling.
Although these measures resulted in considerable improvement, the
TSS and VSS levels in the clarifier overflow continued to be high,
as shown in Figure 37. Also, the MLSS and MLVSS concentrations
varied significantly, as shown in Figure 38, owing to sludge addi-
tion and loss of biological solids from the clarifier overflow.
Plots of dissolved oxygen (DO) concentration and uptake rate dur-
ing the acclimation period are presented in Figure 39. The DO
concentration was maintained well above 2 mg/L so that growth
would not be oxygen-limited. The DO uptake rate varied from 1.4
to 7 mg/ms/s and was generally erratic due to the addition of new
seed sludge.
Soluble COD was used as an indication of the ability of the
system to remove organics. Influent and effluent soluble COD
values, along with percent removal, are presented in Figure 40.
After June 22, removal rates were generally greater than 50%,
except for July 4 and 5 when the biological solids level in the
aeration basin was low. These removals remained relatively
unchanged despite the fact that influent and effluent COD
concentrations were gradually increasing over the acclimation
period.
Influent and effluent also were analyzed for DOC and soluble BOD5.
The DOC and BOD5 data, along with removal rates, are plotted in
Figures 41 and 42, respectively. DOC influent and effluent con-
centrations increased with time, and removal rates were general-
ly greater than 50%, except for July 4 and 5 when MLVSS level was
low in the aeration basin. BOD5 concentrations increased with
109
-------
16 18 20 22 24 26 28 30 2 46 8
JUNE JULY
1982
10 12
Figure 37, TSS and VSS concentration in secondary
clarifier effluent during biological
reactor acclimation period.
110
-------
o
I
UJ
1,600
1.500
1,400
1,300
1,200
1,100
1,000
900
800
700
600
500
400
300
200
100
0
MLVSS
16 18 20 22 24 26 28 30 2
JUNE
1982
4 6 8 10 12
JULY
Figure 38. MLSS and MLVSS concentrations in biological
reactor during acclimation period.a
Seed sludge was added several times during acclimation phase.
Ill
-------
"5.
I'
UJ
8
7
6
5
4
3
2
1
0
7.5
-------
I
•
o
I-H
I—
UJ
O
70
60
50
40
30
20
«*i
1,050
950
850
750
650
550
450
350
2501-
150
EFFLUENT
Figure 40.
16 18 20 22 24 26 18 30 2 4 6 8 10 12
JUNE JULY
1982
Soluble COD concentration and removal in biological
reactor during acclimation period.
113
-------
79
16 18 20 22 24 26 28 30 2 4 6 8 10 12
JUNE
JULY
1982
Figure 41. DOC concentration and removal in biological
reactor during acclimation period. ;
114
-------
time, and the average removal rate was approximately 80% during
the acclimation period. The BOD5 removal rate varied with MLVSS
level in the aeration basin.
Influent and effluent concentrations for phenols, along with
removal rates, are plotted in Figure 43. Over 95% removals
were obtained except when the MLVSS concentration in the
aeration basin was low.
Bioreactor influent and effluent pH values are plotted in Figure
44. The effluent pH was generally one unit lower than the influ-
ent pH and in the 7.0-8.0 range. Influent pH adjustment was not
required to maintain the bioreactor pH in the desired range of
7.0-8.0.
4.3.4.2 Bioreactor Steady-State Performance
After the acclimation period (May 25 - June 15), the dissolved
oxygen uptake remained greater than 6 x 10~6 kg/ms/s (22 mg/L/hr)
and COD and BOD5 removals remained rather constant. This did not
necessarily indicate that steady-state was achieved but rather
than consistently high removals of organics could be obtained and
that a bilogical system could be sustained. Bioreactor perform-
ance monitoring data collected after the acclimation period are
summarized in Tables 29 through 31 and in Figures 45 through 50.
The data summarize bioreactor performance monitoring records.
Bioreactor operating conditions and performance are discussed
below, for each parameter.
Retention times - The hydraulic retention time (HRT) and the
sludge age or solids retention time (SRT) are the two parameters
that were used to control the activated sludge process. For the
data collection period, the average HRT was 16 hours with minimal
variation [±1 S.D. (standard deviation) where S.D. = <0.1h] in HRT
115
-------
100
90
: 80
70
* 60
< 50
1 40
05 30
20
! 10
0
*•
500"
400
6 300
P
z 200
o
§
o
100
INFLUENT
EFFLUENT
16 18 20 22 24 26 28 30 2 4 6 8 10 12
JUNE JULY
1982
Figure 42. Soluble BODS concentration and removal in1
biological reactor during acclimation
period.
116
-------
100
90
80
70
I 50
a: 40
30
20
10
0
^
«*
100
90
^ 80
E
z 70
o
5 60
1 50
40
30
O
z
8
20
10
INFLUENT
16 18 20 22 24 26 28
JUNE
30 2 4
1982
6 8 10
JULY
12
Figure 43. Phenols concentration and removal in biological
reactor during acclimation period.
117
-------
11
10
1 •
S
IS)
MEAN : 8.6 STD. UNITS
SD:0.1 STD. UNITS
INFLUENT
EFFLUENT
MEAN : 7.4 STD. UNITS
SD : 0.3 STD. UNITS
16 18 20 22 24 26 28 30. 2 4 6 8 10 12
JUNE JULY
1982
Figure 44. pH in biological reactor during
acclimation period.
as indicated by the flowrate data in Appendix C. The SRT is de-
fined as the total quantity of active microbial mass in the ;aera-
tion basin divided by the total quantity withdrawn daily. The
total quantity withdrawn daily includes the microbial mass lost
in the secondary clarifier effluent as well as that purposely re-
moved by disposal of settled sludge from the secondary clarifier.
The total volatile suspended solids indicative of the active
microbial mass concentration are used to compute the SRT. The
average SRT was 32 days for the period July 12 to July 30. :High
SRT's (>20 days) are typical of extended aeration processes.; The
system was designed to operate at an SRT of 30 days (refer to
Section 4.3.4.1), and it performed very near this desired value.
Although the system operated for approximately 1/2 an SRT (J,uly 12
to July 30) and steady-state was not achieved, data was collected
118
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TABLE 30. BIOREACTOR DATA3 FOR PURGEABLE AND EXTRACTABLE ORGANICS
Parameter
Base/Neutral Extraction Fraction
Trichlorome thane
Benzene
Cyclohexene
Quinoline and/or isoguinoline
Unknown
2-Cyclopenten-l-one, 3-methyl
Acid Extraction Fraction
Trichlorome thane
Benzene
Cyclohexene
Phenols
Concentration ,
Influent
4.9
4.9
11
1.9
9.8
3.1
6.3
5.4
12
73.5
mg/L
Effluent
4.1
, 5.5
12b
1 7.4
• 2.8
4.5
5.3
, 17
2.5
are for one composite sample for both the influent and
effluent taken on August 4, 1982. '.
Blank indicates compound not detected.
during this time period to show the levels of organics removal
that can be obtained. The SRT for the period July 31 to August 10
is not included for the reason discussed in the following
subsection.
MLSS and MLVSS - MLSS and MLVSS levels varied significantly, as
shown in Table 29 and Figure 45. This was partly due to inade-
quate mixing in the aeration basin and partly to the loss pf
solids in the secondary clarifier effluent, requiring that no
sludge be disposed of from the system [except for the 0.02 m3
(5 gallons) disposed of on July 23]. On July 30, 1,800 grams
of powdered activated carbon was added by mistake to the aeration
basin. This caused the MLSS and MLVSS levels to increase ;on
August 1. Although data was collected from August 1 to 10, it
is not presented in this report as inconsistent levels of ;organic
removals, MLVSS concentrations, and DO uptake rates indicate
120
-------
TABLE 31. BIOREACTOR DATA FOR METALSa
Metal
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
K
Mg
Mn
Mo
Na
Ni.
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Concentration, mg/L
Influent
<0.19
0.15
<0.01
0.42
<0.01
<0.01
2.2
<0.01
<0.04
<0.02
<0.03
0.16
<0.01
<2.6
0.23
0.02
<0.05
<10
<0.08
<0.1
<0.38
<0.01
<0.5
<0.01
<0.02
<0.03
0.03
Effluent
<0.19
4.5
<0.01
0.42
<0.01
<0.01
6.0
<0.01
<0.04
<0.02
0.03
0.28
<0.01
<2.6
2.32
<0.02
<0.05
11.8
<0.08
<0.1
<0.38
<0.01
<0.5
0.02
<0.02
<0.03
0.23
Data are for one composite
sample for both the influent
and effluent taken on
August 4, 1983.
bioreactor upset conditions. The ratio of MLVSS to MLSS averaged
about 0.63 for the July 12-30 time period, which is within the
range of 0.5 to 1.0 for typical activated sludge systems.
Chemical Oxygen Demand - Soluble COD was the key parameter used
to monitor removal of organics in the bioreactor. Influent and
effluent COD values along with the corresponding percent removals
are presented in Figure 46. The influent COD level varied from
121
-------
O
O
5,800
5,600
5,400
5,200
5,000
4,800
4,600
4,400
4,200
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
MISS
MEAN: 2,810mg/L
SD: 446 mg/L
MLVSS
MEAN: 1,780 mg/L
SD: 306 mg/L
12 14 16 18 20 22 24 26 28 30
JULY
1982
Figure 45.
MLSS and MLVSS concentration in biological
reactor during July. ;
122
-------
I
LU
o
1
70
60
50
40
30
20 h
16
**
1,800
1,700
1,600
1,500
1,400
1,300
1,200
1,100
1,000
900
800
700
600-
500-
400
300
MEAN :l,380mg/L
SD : 200 mg/L
INFLUENT
MEAN : 580 mg/L
SD : 100 mg/L
MEAN: 57%
SD: 5%
12 14 16 18 20 22 24 26 28 30
JULY
1982
Figure 46.
Soluble COD concentration and removal in
biological reactor during July.
123
-------
«C
on
UJ
o
100
90
80
70
60
900 -
Figure 47.
700
600
500
400
300
200
100
MEAN: 91%
SD: 5%
INFLUENT
MEAN: 510 mg/L
SD: 100 mg/L
MEAN: 60 mg/L
SD: 30 mg/L
12 14 16 18 20 22 24 16 28 30
JULY
1982
Soluble BOD5 concentration and removal in
biological reactor during July.
124
-------
o
oc
O
f—i
<
CJ
o
70
60
50
40
«••.
510
490
470
450
430
410
390
370
350
330
310
290
270
250
230
210
190
170
150
130
MEAN: 52%
SD: 8%
MEAN: 420 mg/L
SD: 50 mg/L
EFFLUENT
MEAN: 190 mg/L
SD: 40mg/L
I I I
12 14 16 18 20 22 24 26 28 30
JULY
1982
Figure 48. DOC concentration and removal in biological
reactor during July.
125
-------
1,100 mg/L to 1,750 mg/L, averaging 1,380 mg/L (S.D. = 200 :mg/L).
The effluent COD level varied from 400 mg/L to 740 mg/L, averaging
580 mg/L (S.D. = 100 mg/L). COD removal rates varied from |54% to
63%, averaging 57% (S.D. = 5%) as average. Data after August 1
are not included because of the PAC addition. The influent and
effluent' COD was 99+% soluble. Although the MLVSS level varied
significantly during the test period, the standard deviation
(S.D.) was only 5% for COD removal.
BODS and DOC - BOD5 and DOC were used to supplement the COD data
to monitor bioreactor organics removal. Influent and effluent
BOD5 and DOC values along with the corresponding percent removals
are presented in Figures 47 and 48, respectively, as well as in
Table 29. The average BOD5 removal was 91% (S.D. = 5%) and the
DOC removal was 52% (S.D. = 8%). BOD5 removal varied from ;84%
to 98%, and DOC removal varied from 38% to 60%. The DOC removal
rate variation might have been due to changes in the organic
compounds in the influent water with time.
DO Level and DO Uptake Rate - Dissolved oxygen (DO) and DO ;uptake
rate data are summarized in Table 29 and Figure 49. The DO concen-
tration ranged from 0.5 to 4.5 mg/L, averaging 2.3 mg/L (S^D. = 1.1
mg/L). Except for five days, DO concentrations usually were kept
significantly higher than 1.5 mg/L so that growth would not be
oxygen-limited. The DO uptake rate varied from 2.5 x 10"6 !to
14.7 x 10~6 kg/m3/s, averaging 7.5 x 10~6, kg/m3/s (S.D. =
2.2 x 10~6 kg/m3/s). Since the DO uptake rate was consistently
greater than zero throughout the entire test period, the reactor
microorganism population was active and viable. '"
Phenols - The activated sludge system achieved excellent removal'
of phenols as shown in Table 29 and Figure 50. The average influ-
ent phenols concentration was 101 mg/L (S.D. = 7.1 mg/L), and the
effluent concentration was 6.0 mg/L (S.D. = 3.2 mg/L). Removal
126
-------
^
^ 5
| 4
ce 3
H- •*
LU o
o 2
I 1
on
__i
S
^E 15
MEAN: 2.3mg/L
SO: l.lmg/L
MEAN:7.5X10~6kg/m3/s
SD: 2. ZXlO^g/m^s
12 14 16 18 20 22 24 26 28 30
JULY
1982
Figure 49.
DO concentration and DO-uptake rate in
biological reactor during July.
127
-------
I
en
E
o
I—I
s
UJ
o
100
95
SO
85
80
+»
14
12
10
8
6
4
2
0
*.
120
110
100
90
70
MEAN: 95%
SD: .2%
MEAN: 6.0mg/L
SD: 3.2mg/L
EFFLUENT
MEAN: 101 mg/L
SD: 7.1 mg/L
INFLUENT
I _t I
12 14 16 18 20 22 24 26 28 30
JULY
1982
Figure 50. Phenols concentration and removal in biological
reactor during July.
128
-------
for this parameter varied from 93% to 97% and averaged 95% (S.D. =
2%), showing that the system microorganisms could readily degrade
phenols.
Ammonia-Nitrogen and Nitrate-Nitrogen - The average influent and
effluent ammonia-nitrogen concentrations were 96 mg/L (S.D. = 26
mg/L) and 80 mg/L (S.D. = 10 mg/L), respectively, as shown in
Table 29. Ammonia-nitrogen removal by the system was insignif-
icant. In addition, the influent and effluent contained an
insignificant amount of nitrate-nitrogen. These low nitrogen
concentrations demonstrate that nitrification did not occur in
the bioreactor. The bioreactor sludge age of 32 days was
considerably in excess of the 10 days generally required to
achieve nitrification [5].
p_H - The influent pH averaged 8.6 (S.D. = 0.1), and the effluent
pH averaged 7.4 (S.D. = 0.3). This indicates that pH decreased
approximately 1.2 units across the aeration basin. During the
bioreactor operation, influent pH adjustment was not required;
the pH in the bioreactor was generally in the desired range of
7.0 to 8.0.
Organic Compounds and Metals - Except for phenols, the concentra-
tion of all other organic compounds detected (Table 30) did not
change significantly across the biological reactor. Bioreactor
influent and effluent metal concentrations were very low (Table 31)
and did not affect bioreactor performance.
4.3.4.3 Effect of Powdered Activated Carbon (PAC) Addition on
Conventional Activated Sludge System
On July 30, 1982 a quantity of PAC equivalent to a 1,000-mg/L dose
was inadvertently added to the steady-state conventional activated
sludge system. Prior to this addition, the average COD removal
by the bioreactor was 60%. After the PAC addition, COD removals
129
-------
increased to 74%, 68%, and 62% during the first, second, and third
day of operation, respectively. Later, this information was used
in determining the PAC dosage for a PAC-activated sludge system.
4.3.5 PAC-Activated Sludge Treatment
' ' I
!
Activated sludge treatment with powdered activated carbon (PAC)
addition was not originally scheduled for testing at Logan Wash.
For financial reasons only one biological system, the conventional
activated sludge treatment, was to be tested. However, the opport-
iunity arose to test the PAC-activated sludge treatment, and a
system was set up and operated for 16 days. They provide' the
information reported in this section.
On August 11, 1982, the conventional activated sludge system that
had an inadvertant PAC addition on July 30 was converted to! a
PAC-activated sludge treatment system, and it was operated from
August 11 to August 22 using stripped gas condensate as feed.
Westvaco Nuchar S-A powdered activated carbon was added batchwise
to the bioreactor contents every four hours at the rate of 400
mg/L of feed for the 11 day test duration while an equivalent
amount of sludge from the secondary clarifier was simultaneously
removed and disposed of. The reactor was operated at a 16-hour
hydraulic retention time and at a feed rate of 31.7 cms/s
(0.5 gal/min).
From August 23 to August 27, this system was operated with fLncreas-
ing PAC dosage rates. The dosage was increased every 24 hours,
reaching 1,900 mg/L on the last day of operation. Carbon was
added on a batch basis every six hours to maintain the desired
concentration. An equivalent amount of sludge from the secondary
clarifier was simultaneously removed and wasted. To observe the
effect of carbon dosage on pollutant removal, four grab samples
130
-------
(one sample taken every 6 hours) and one 24-hour composite sample
of influent and effluent were collected and analyzed for soluble
COD, DOC, soluble BOD5, and phenols.
The results obtained with this PAC-bioreactor from August 11
to August 22 are summarized in Table 32 and discussed below.
Retention Times - The average hydraulic retention time (HRT) was
16 hours, with minimal variation. The average solids retention
time (SRT) or sludge age was 44 days. Due to time and financial
limitations, the PAC system did operate one complete sludge age
cycle indicating a steady-state PAC was not achieved. However,
data is presented to indicate removals which can be obtained by
a PAC system.
MLSS and MLVSS - MLSS and MLVSS levels varied significantly as
shown in Table 32 and Figure 51. This is believed to be due
largely to inadequate mixing in the aeration basin which resulted
in variations in solids measurements, and to some extent to the
batch PAC addition and the sludge wasting schedule. - The ratio of
MLVSS to MLSS averaged about 0.64.
Chemical Oxygen Demand - Soluble COD was the key parameter used
to monitor bioreactor performance. Influent and effluent COD
values, along with corresponding percent removals, are presented
in Figure 52. The influent COD varied from 1,600 mg/L to 2,100
mg/L, averaging 1,700 mg/L (S.D. = 140 mg/L). The effluent
COD varied from 410-870 mg/L and averaged 530 mg/L (S.D. = 120
mg/L). The COD removal rate varied from 54% to 74%, averaging 70%
(S.D. = 5%). COD removal was greater than 65% during the first
ten days of operation, but it dropped significantly in the last
two days, from 72% to 54%.
131
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6,000
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MEAN : 59%
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INFLUENT
MEAN : 170 mg/L
SD : 20 mg/L
EFFLUENT
1 1
11 12 13 14 15 16 17 18 19 20 21 22 23
AUGUST, 1982
Figure 53. DOC concentration and removal in PAC bioreactor,
August 11 through August 22.
135
-------
10.6
oo
CO
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uu
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6.0
4.5
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MEAN:
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11 12 13 14 15 16 17 18 19 20 21 22 23 24
AUGUST, 1982
Figure 54. DO concentration and DO-uptake rate in PAC
bioreactor, August 11 through August 22.
136
-------
DOC and BOD5 - DOC and BOD5 data were collected to supplement the
COD data in monitoring bioreactor performance. Influent and
effluent DOC values, along with corresponding percent removals,
are plotted in Figure 53. As shown in Table 32 and Figure 53,
DOC removal varied from 50% to 65%, averaging 59% (S.D. = 7%).
DOC removal gradually decreased with time. Soluble BOD5 removal
averaged 96%, and an effluent BOD5 concentration as low as 13
mg/L was achieved.
DO Concentration and DO Uptake Rate - Dissolved oxygen (DO) con-
centration and DO uptake rate results are summarized in Table 32
and Figure 54. The DO concentration ranged from 3.7 to 5.0 mg/L,
and averaged 4.5 mg/L (S.D. = 0.4 mg/L), assuring aerobic con-
ditions in the bioreactor. The DO uptake rate varied from 3.6 x
10~6 to 8.3 x 10"6 kg/m3/s, averaging 6.4 x 10~6 kg/m3/s (S.D. =
1.1 x 10~6 kg/ms/s). DO uptake data indicate that the reactor
microorganism population was viable during the test period. During
the last four days of operation, the DO uptake rate dropped signi-
ficantly, from 10 x 10~6 to 4.3 x 10~6 kg/ms/s, indicating a
gradual decrease in biological activity. This could have resulted
from a decrease in the biological solids and an increase in the
PAC solids in the reactor as PAC was added and sludge was wasted.
Phenols - As shown in Table 32, the average removal of phenols
was 99% (S.D. = 0.4%); the effluent contained less than 2 mg/L
of phenols. This demonstrates excellent capability of the PAC-
activated sludge system for removal of phenols from stripped gas
condensate.
Ammonia-Nitrogen and Nitrate-Nitrogen - The average influent and
effluent ammonia-nitrogen concentrations were 100 mg/L (S.D. =
12 mg/L) and 94 mg/L (S.D. = 6 mg/L), respectively, as shown
in Table 32. Thus, ammonia-nitrogen removal by the PAC system
was insignificant. The influent and effluent also contained an
137
-------
insignificant amount of nitrate-nitrogen. These low nitrogen
concentrations demonstrate that nitrification did not occur
during the short bioreactor operation. '
- Influent pH averaged 8.5 (S.D. = 0.1), whereas effluent pH
averaged 7.3 (S.D. = 0.1). Thus, pH dropped by 1.2 units across
the aeration basin. During the test period, influent pH adjust-
ment was not required. The pH in the bioreactor ranged from
7.1 to 7.5 standard units. ;
I
The results of increasing PAC dosage experiments (August 23
through 27) are summarized in Table 33, and removal rates are
plotted in Figure 55. These data show that removal of DOC,
soluble COD and BOD5 , and phenols increases with an increase in
PAC dosage as expected, but the incremental increases are not
proportional to the dosage increase.
4.3.6 Sand Filtration
The purpose of the sand filters was to remove suspended solids
from the secondary clarifier effluent and thus prevent clogging
of the granular activated carbon (GAG) columns used in subsequent
treatment of the effluent. The sand filters were used so that
only one filter was in operation at a time. Water feed rate to
the 1.7-m (5.5 ft) deep sand filters was 31.5 cms/s (0.5 gal/min)
from July 12-27 and reduced to 25.2 cms/s (0.4 gal/min) from
July 28 to August 11. The filter was backwashed as needed,
generally every 16 to 20 hours. The performance data for the
sand filters are presented in Table 34. ;
The data show that except for July 19 and 21, the sand filtier
effluent had a TSS level equal to or lower than 20 mg/L. This
indicates that the sand filter successfully removed suspended
138
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90
80
70
60
3 5°
o lOCT
90
locr
99
98
400 600
SOLUBLE COD
DOC
SOLUBLE BOD5
PHENOLS
1,000 1,200 1,400 1,600 1,800 2,000
PAC DOSAGE, mg/L
Figure 55. PAC bioreactor removal performance with
increasing dosage.
140
-------
TABLE 34. SAND FILTER PERFORMANCE DATA SUMMARY
Date, 1982
7/12
7/12
7/12
7/14
7/15
7/16
7/17
7/17
7/18
7/18
7/19
7/19
7/20
7/21
7/22
7/24
7/25
7/25
7/26
7/27
7/29
7/30
7/31
8/1
8/2
8/3
8/4
8/5
8/7
8/8
8/9
8/10
8/10
Average
Type of
sample9
G
G
G
G
G
G
G
G
G
C
G
G
C
G
C
G
G
C
C
C
C
C
G
C
C
C
G
C
C
G
C
C
G
TSS
concentration
Influent
58
87
53
43
14
15
70
200
43
172
124
c
93
233
25^
c
13
114
100
154
381
390
70
33
53
27
33
29
29
64
30
61
78
93
, mg/L
Effluent
NSb
NS
NS
NS
<5
<5
NS
NS
NS
NS
9
84
NS
75
NS
7
<5
NS
NS
NS
NS
NS
14
NS
NS
NS
13
NS
NS
13
NS
NS
20
23
Percent
removal
_
»
_^
>64
>67
w
^
_
—
83
_
68
^
_
>62
—
—
«
_
_
80
_
_
_
61
_
•H
80
M
«.
74
71
G - grab
C - composite.
NS - not sampled.
•*
"Sample lost.
141
-------
solids from the secondary clarifier effluent. The reasons for
the high effluent concentrations obtained on July 19 and 21: may
be attributed to high influent TSS concentration.
4.3.7 GAG Adsorption :
Granular activated carbon (GAG) adsorption tests were conducted
on two types of effluents: (1) the stream stripper effluent, and
(2) the effluent from the secondary clarifier of the conventional
activated sludge treatment system after sand filtration.
Tests with GAG were conducted using the two carbon columns
shown in Figure 56.
The columns were operated in a downflow mode. Column influent
and effluent samples were taken for performance evaluation at the
locations shown in Figure 56.
4.3.7.1 GAG Adsorption of Stripper Effluent
Treatment of stripper effluent with granular activated carbon (GAG)
was not scheduled for testing at Logan Wash. However, to maximize
the benefit of the Logan Wash trial results, such testing was con-
ducted simultaneously with the conventional activated sludge treat-
ment. The capacity of the steam stripper was adequate to supply
both treatment processes with stripper effluent. i
Stripper effluent was passed directly through the columns (i.e.,
no prefiltration was used) at an average flow rate of 41.7 cm3/s
(0.66 gal/min) ranging from 39.2 to 44.2 cm3/s. This flow rate
corresponds to a hydraulic loading rate of 0.22 ms/s-m2 (3.;3
gpm/ft2) and an empty bed contact time of 660 s per columns. Grab
samples of the stripper effluent (which was the column 1 influent),
the column 1 effluent, and the column 2 effluent were collected
142
-------
E u=!
" 5
^ 1
W
fi
O •
u co
4->
d w
O 0)
m c
u o
•H
iw 4.)
e o
fO M
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O
u
-H M
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rs
en
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143
-------
approximately twice per day and analyzed for soluble COD, DOC,
phenols, and soluble BOD5. Analytical results are presented in.
Table 35, The columns operated continuously for the duration of
the stripper effluent run (233 hr) and did not require backwashing.
Soluble COD breakthrough curves for columns 1 and 2 are plotted
in Figure 57. The curves are not very steep, and breakthrough is
reached immediately in both columns, indicating a relatively poor
adsorption for some of the components. Soluble COD concentrations
in the column influent ranged from 490 mg/L to 970 mg/L and
averaged approximately 800 mg/L during the test period. Soluble
COD removals were equal to or greater than 90% for only the first
7.2 m3 throughput (48 hours) with average influent and No. '2
effluent concentrations of 630 mg/L and 60 mg/L, respectively.
DOC concentrations in the column influent during the test period
ranged from 190 mg/L to 250 mg/L and averaged approximately 210
mg/L. DOC removals were equal to or greater than 86% for the
first 9 m3 throughput (60 hours) with average influent and ;No. 2
effluent concentrations of 210 mg/L and 24 mg/L, respectively.
During the test period, influent phenols concentrations varied
from 69 mg/L to 96 mg/L and averaged 82 mg/L. Initial removal of
phenols was high (approximately 99%). However, a significant
increase (breakthrough) in phenols concentration from column 1
occurred after 14.4 m3 throughput (95 hours) and from column 2
after 25.2 m3 throughput (168 hours). Influent soluble BOD5
concentrations varied from 240 mg/L to 410 mg/L during the :test
period with 340 mg/L as average. Soluble BOD5 removal rate was
greater than 84% during the first 18 m3 throughput (120 hours)
with the carbon column average effluent soluble BOD5 level at
50 mg/L.
144
-------
TABLE 35. PERFORMANCE DATA FOR CARBON COLUMN TESTING OF GAS CON-
DENSATE STEAM STRIPPER EFFLUENT, JUNE 22-JULY 2, 1982a
Through-
put
volume ,
o
m3
<0.1
1.8
3.6
5.4
7.2
8.1
9.0
10.8
12.6
14.4
16.2
17.1
18.0
19.8
21.6
23.4
24.3
25.2
27.0
27.9
28.8
30.6
31.5
32.4
34.2
35.1
<0.1
1.8
3.6
5.4
7.2
8.1
9.0
10.8
12.6
14.4
Concentration, mg/L
Stripper
effluent
660
510
580
770
620
610
U
640
710
720
660
670
670
680
680
800
970
800
490
760
680
770
890
960
Stripper
effluent
80
69
74
80
81
70
72
70
Soluble COD
Column 1
effluent
100
40
57
86
100
130
150
200
310
380
510
530
470
530
540
570
710
560
360
700
730
810
770
720
Phenols
Column 1
effluent
0.026
<0.005
<0.005
<0.005
0.025
0.06
10
44
Column 2
effluent
_c
c
c
42
64
83
87
91
110
110
140
140
140
200
220
280
390
290
280
470
570
510
630
590
Concentrati
Column 2
effluent
_c
_c
_c
<0.005
<0.005
<0.005
<0.005
<0.005
Stripper
effluent
**'•' 210
200
200
210
200
210
200
190
200
190
200
220
210
220
220
250
240
250
on, mg/L
Stripper
effluent
_b
350
280
240
370
DOC
Column 1
effluent
11
28
29
33
39
50
72
85
120
160
150
170
200
190
220
220
210
230
Soluble BOD
Column 1
effluent
35
90
81
170
Column 2
effluent
b
"b
~b
19
27
30
35
37
41
50
34
49
78
100
140
150
160
170
5
Column 2
effluent
39
i
50 .
56
(continued)
145
-------
TABLE 35 (continued)
Through-
put
volume ,
m3
16.2
17.1
18.0
19.8
21.6
23.4
24.3
25.2
27.0
27.9
28.8
30.6
31.5
32.4
34.2
35.1
Concentration, mg/L '
Stripper
effluent
89
80
: 90
96
93
96
87
Phenols
Column 1
effluent
87
83
83
96
90
104
98
Column 2
effluent
0.14
0.14
1.06
36
59
110
109
1
Soluble BOD5
Stripper Column 1 Column 2
effluent effluent effluent
330 230 , 53
300 290
••
410 350
310 380 ; 230
390 :
330
410 370
Steam stripper operated according to Table 23. :
Blanks indicate that either no sample was taken or sample was lost.
£j
Column 2 not in operation for initial 30.5 hours. :
4.3.7.2 GAG Adsorption of Biologically Treated Effluent ;
Two tests were conducted using the two GAC columns in series to
treat effluent from the conventional biological treatment system.
The two carbon columns, were preceded by two sand filters. \ Two
tests were conducted to study the effects of different contact
times on removals. The operating conditions for each are shown
in Table 36. Grab samples of the filtered biological effluent
(i.e., carbon column 1 influent) and carbon column 1 and 2
effluents were collected once a day for soluble COD analysis arid
approximately once every two days for DOC, phenols, and soluble
BOD5 analyses. The results of these analyses are shown in:
Tables 37 and 38 for tests 1 and 2, respectively. The carbon
146
-------
1.0
0.9
0.8
0.7
0.6
0.5
0.4
= 0.3
0.2
0.1 -
o
o
o
8
COLUMN 1
Average throughput - 41.7 cm-/s.
Steam-stripped gas condensate used
as influent.
10 15 20 , 25
VOLUME THROUGHPUT, nr
30 35
Figure 57.
Soluble COD breakthrough curves for GAC columns 1
and 2 using stripped gas condensate as influent.
147
-------
TABLE 36. OPERATING CONDITIONS FOR GAG COLUMN TESTS
WITH BIOLOGICALLY TREATED EFFLUENT I
Parameter, units Test 1 Test 2
Average wastewater influent rate: cm3/s (gal/min) 31.5 25.2
(0.5) : (0.4)
Hydraulic loading rate: m3/s-m2 (gpm/ft2) 1.63 x 10~3 1.36'x 10~3
(2.4) > (2.0)
Empty bed contact time, s: Column 1 930 : 1,120
Columns I and 2 1,860 ; 2,240
columes were operated continuously:for the duration of the run
(Test 1 = 309 hr; Test 2 = 275 hr) and did not require ;
backwashing. ;
Soluble COD breakthrough curves for columns 1 and 2 and tests 1
and 2 are plotted in Figures 58 and 59, respectively. In bbth
tests column 1 curves are not very steep. Comparison of column 2
curves for both tests indicates that at the lower feed rate or
longer contact time, the time until breakthrough was longer, in
test 2 than in test 1.
During test 1, column influent soluble COD concentrations ranged
from 400 mg/L to 670 mg/L and averaged approximately 560 mg/L.
Soluble COD removals were equal to or greater than 90% for the
first 22.2 m3 throughput (200 hours) with average influent and No.
2 effluent concentrations of 520 mg/L and 20 mg/L, respectively.
During the test period, column influent DOC concentrations ranged
from 180 mg/L to 230 mg/L and averaged 200 mg/L. DOC removals were
equal to or greater than 84% for the first 27.5 m3 throughput (247
hours) with average influent and No. 2 effluent concentrations of
200 mg/L and 20 mg/L, respectively. Phenols removal was greater
than 97% during the test period with average influent and #2
effluent concentrations of 7 mg/L and 0.03 mg/L, respectively.
148
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VOULJME THROUGHPUT, m
35
Figure 58.
Soluble COD breakthrough curves for GAG columns 1 and 2
using filtered biologically treated effluent, Test 1.
153
-------
0220-1/A-107
1.0
0.9
0.8
0.7
-------
During test 2, soluble COD concentrations in the column influent
ranged from 470 mg/L to 740 mg/L and averaged approximately 600
mg/L. Soluble COD removals were equal to or greater than 92% for
the first 18.3 m3 throughput (203 hours) with average influent and
#2 effluent concentrations of 600 mg/L and 30 mg/L, respectively.
During the test period, column influent DOC concentrations ranged
from 120 mg/L to 300 mg/L and averaged 210 mg/L. DOC removals
were equal to or greater than 92% for the first 17.5 m3 throughput
(227 hours) with average influent and #2 effluent concentrations
of 210 mg/L and 15 mg/L, respectively. Phenols removal was greater
than 99% during 20.5 L throughput with average influent and #2
effluent concentrations of 5.5 mg/L and 0.02 mg/L, respectively.
The spent carbon was analyzed according to RCRA requirements. The
results of these analyses indicated that the spent carbon was
nonhazardous.
During the first eight hours of Test 2 GAG column operation, 8 hr
composite samples of column 1 influent and column 2 effluent were
collected and analysed for metals and organics using GC/MS. The
analytical results, presented in Tables 39 and 40, indicate that
metals concentrations were very low and about the same in both the
influent and the effluent. Eight organic compounds were present
in the influent at concentrations ranging from 2.5 to 17 mg/L.
Of these, phenols and 3-methyl-2-cyclopenten-l-one were completely
removed. The concentrations of the others did not change
significantly.
4.3.8 Overall Treatment
Filter coalescing, steam stripping, conventional activated sludge
treatment, sand filtration, and GAG adsorption comprised the over-
all treatment scheme for the gas condensate. The scheme was very
effective in removing ammonia, organics, sulfide, alkalinity, and
155
-------
TABLE 39. CARBON COLUMN PERFORMANCE DATA FOR METALSa
Concentration, mg/L
Metal
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
K
Mg
Mn
Mo
Na
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Column 1,
influent
<0.19
4.53
<0.01
0.42
<0.01
<0.01
6
<0.01
<0.04
<0.02
<0.03
0.28
<0.01i
<2.e :
2.32
0.02
<0.05
11.8
<0.08
<0.1
<0.38
<0.01
<0.5
0.02
<0.02
<0.03
0.23
Column 2 ,
effluent
<0.19
0.23
0.03
0.45
0.04
<0.01
13.9
<0.01
<0.04
<0.02
<0.03
0.20
<0.01
<2.6
3.38
0.03
<0.05
14.7
<0.08
<0.1
<0.38
<0.01
0.94
0.20
<0.02
<0.03
0.04
a8-hr composite sample taken dur-
ing first 8 hours of test 2.
156
-------
TABLE 40. CARBON COLUMN PERFORMANCE DATA FOR
PURGEABLE AND EXTRACTABLE ORGANICS*
Parameter
Base/Neutral Extraction Fraction
Trichloromethane
Benzene
Cyclohexene
Unknown
2-Cyclopenten-l-one, 3-methyl
Acid Extraction Fraction
Trichloromethane
Benzene
Cyclohexene
Phenols
Concentration ,
Column 1,
influent
4.1
5.5
12
7.4
2.8
4.5
5.3
17
2.5
mg/L
Column 2,
effluent
3 6
5 4
10
1 ?
_b
5 5
5 7
~\ 6
8-hr composite sample taken during first 8 hours of test 2.
Blanks indicate compounds were below detection limit.
solids from the gas condensate. Assuming the following average
operating conditions, the scheme would be expected to produce a
final effluent with the composition presented in Table 41:
Steam stripper G/L ratio: 140 kg steam/m3 water
(1.20 Ib steam/gal water)
Activated sludge system HRT: 16 hours
Activated sludge system SRT: 32 days
GAC column contact time: 1,120 seconds
157
-------
TABLE 41. OVERALL TREATMENT SCHEME PERFORMANCE DATA SUMMARY
FOR CONVENTIONAL POLLUTANTS AND OTHER PARAMETERS
Concentration, mg/L
Parameter
Raw
wastewater
Final
effluent
Percent
removal
NH3-N
TKN
NO3-N
Soluble COD
Soluble BOD5
DOC
Phenols
Sulfide
TSS
VSS
Alkalinity as CaCO3
to pH:4.5
pH
9,000
6,800
1.1
2,700
800
890
120
72
7
5
31,000.
8.5'
90
180
0.4
50
20
25
0.02
2
20
20
350
7.5'
'99
97
!64
•98
98
i97
>;99
;97
29
i 0
•99
^Standard pH units.
158
-------
SECTION 5
QA/QC DATA SUMMARY
A summary of the quality assurance/quality control (QA/QC) data
for all analyses conducted in this program is presented in
Table 42. This summary has been prepared from the detailed QA/QC
data. The data in Table 42 suggest minimal analytical discrepanc-
ies, but corrective actions were taken whenever such discrepancies
occurred. These actions included review of the critical steps in
the analytical methods with analytical technicians, discarding of
unreliable data based on QA/QC problems, or outlier tests, and
repeating the analyses until reliable data were obtained, as
confirmed by satisfactory QA/QC results.
159
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REFERENCES
1. Assessment of Oil Shale Retort;Wastewater Treatment and
Control Technology - Phases I and II. EPA 600/7-81-081,
U.S. Environmental Protection Agency, Cincinnati, Ohio.
1981. 99 pp. i
i
2. Experimental Plan for Wastewater Treatability Studies at
Occidental Retorts 7 and 8 (Preliminary Draft - Experimental
Plan). U.S. Environmental Protection Agency, Cincinnati,
Ohio. July 24, 1981. 40 pp. ; i
3. Occidental Petroleum Corporation. Shale Oil, (undated
informational document). 28 pp. :
4. Hicks, R. E., et al. Wastewater Treatment and Management at
Oil Shale Plants. In: Thirteenth Oil Shale Symposium
Proceedings, Colorado School of Mines, Laramie Energy
Technology Center, Golden, Colorado, 1980. pp. 321-334.
5. Water Pollution Control Federation and American Society of
Civil Engineers. Wastewater Treatment Plant Design, Manual
of Practice Number 8. Lancaster Press, Inc., Lancaster.
164
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Logan Wash Field Treatability Studies of
Wastewaters From Oil Shale Retorting Processes
5. REPORT DATE
May 1983
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
B. 0. Desai, D. R. Day,
and T. E. Ctvrtnicek
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, Ohio 45418
10. PROGRAM ELEMENT NO.
DU Ml 04
11. CONTRACT/GRANT NO.
68-03-2801
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory
Office of Research and Development
Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPp OF REPORT AND PERIOD COVERED
Project Report
14. SPONSORING AGENCY CODE
EPA 600/2
15. SUPPLEMENTARY NOTES
16.
ABSTRACT
treatability studies were conducted on retort water and gas condensate wastewater
from modified in-situ oil shale retorts to evaluate the effectiveness of selected
treatment technologies for removing organic and inorganic contaminants. At retorts
operated by Occidental Oil Shale, Inc., at Logan Wash, Colorado, treatability studies
were conducted on retort water using filter coalescing, steam stripping, activated
sludge treatment (both with and without powdered activated carbon addition), sand
filtration, and granular activated carbon adsorption. Retort water had high con- .
centrations of ammonia-nitrogen, total Kjeldahl nitrogen, alkalinity, dissolved
organics, phenols, sulfide, total dissolved solids, boron, potassium and sodium.
Steam stripping removed ammonia-nitrogen, alkalinity, and sulfide from retort water
and organics removal was low. Gas condensate wastewater had high
of ammonia-nitrogen, total Kjeldahl nitrogen, dissolved organics,
phenols, sulfide, and pyridine compounds. The overall scheme for
sate treatment removed ammonia-nitrogen, total Kjeldahl nitrogen,
concentrations
alkalinity,
the gas conden-
alkalinity,
sulfi de, Diochemical oxygen "demand,
demand, and phenols.
di ssolved organi c carbon; chemi cal oxygen
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
Oil Shale Pollution, Fossil Fuels,
Oil Shale Wastewater, Steam
Stripping, Oil Shale, Wastewater,
Synthetic Fuels, Energy
NTIS Terms: 97F
Fuel Conver.
97R £nergy, En-
vironmental
Studies, 99A
Analytical
Chemistry
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
184
2O. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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