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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
-------
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
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t
30
(0.25)
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(0.5)
90
(0.75)
120
d.0)
150
(1.25)
183
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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
E. 38,000
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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MEAN : 430 mg/L
SD : 60 mg/L
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
•P O
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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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