-------
CO
VI
7.0
6.0
I60
£ 4.0
O
O
CO
". 3.0
O
O
m
X
f 2.0
1.0
0.0
0.96
I
I
1.00
2.02
1.04 1.08
ln(M,),M, IS IN liters.
Figure 8. Desorption of acetone in water with Raschig Ring Column - BOD6 analysis
-------
8.0
I 7.0
a
2
-------
TABLE 5
Raschig Ring Experiments Linear Regression Statistical Data for Pure Components
Analysis
COD
GC
TOC
BOD
COD
GC
TOC
BOD
COD
TOC
BOD
TOC
BOD
COD
TOC
TOC
BOD
COD
TOC
BOD
COD
TOC
BOD
COD
TOC
BOD
COD
Methanol-Watpr
Standard Error Multiple Correction
Estimate Coefficient
IExp.1) (Exp. 2) (Exp.1) (Exp. 21
0.054. 0.555 0.976, 0.974
0.049. 0.081 0.973, 0.960
0.257. 0.070 0.923. 0.974
0.101. 0.114 0.885. 0.955
Acetone-Water
1.021. 0.554 0.811. 0.940
0.704. 0.439 0.777, 0.892
0.698. 0.704 0.680, 0.916
0.885. 0.474 0.909, 0.919
Phenol-Water
0.020, 0.016 0.563. 0.043
0.028, 0.053 0.279. 0.269
0.030. 0.045 0.679. 0.089
Acetic Acid
.0463 .543
.0463 .894
.0492 >.029
Formic Acid
.152 .384
Propionic Acid
.0749 .293
.129 .142
.0467 .617
Acetaldehyde
.354 .949
.665 £07
.375 .920
n-propanol
.048, 587
20} .940
.044 .992
i-propanol
.135 513
.391 .094
.110 .832
t value
for K/a - 1
-------
Simulated wastewater No. 1 consisted of -500 ppm acetone and 500 ppm phenol added to
distilled water. Simulated wastewater No. 2 and No. 3 consisted of approximately 330 ppm
acetone, 330 ppm phenol and 330 ppm methanol in distilled water. Figures 10, 11 and 12
show the test results for these two simulated wastewaters.
The above experiments with single pure components and simulated wastewater
demonstrated that the general behavior of the experiment results are as predicted by the
desorption model equations. The log log straight line behavior of single pure components
was as predicted. The volatile and nonvolatile multiple component behavior was
qualitatively correct also. The quantitative data shows much variation and this is attributed
mainly to the water evaporation lost from the apparatus. Average water loss for a 180
minute run was. 253 grams with a range of 217 to 348 grams for a percent deviation range of
-14.2% to + 37.5%. The errors inherent in accurately quantifying the water evaporated
initiated a search for a more satisfactory desorption device. Other operational problems
included; flooding due to pressure surges in air line, uncertainty in inlet air relative
humidity, inability to control column temperature, three hour run time, and equipment
bulkiness.
Intalox Saddle Packed Desorption Column Three models of a laboratory scale desorption
column were attempted before the design shown in Figure 5 was adopted. G
-------
1.0
o
z
1 0.8
<
2
ui
cc
to
u
O
tr
o
z
o
oc
o
o
u
<
oc
0.6
0.4
0.2
0.01
0.000
I
I
I
I
LEGEND
OCOO ANALYSIS
&TOC ANALYSIS
BOD ANALYSIS
I
I
0.010
0.020 0.030 0.040 0.050
1 - M,/M0. FRACTION WATER VAPORIZED.
0.060
0.070
Figure 10. Desorption of simulated wastewater No. 1 with Raschig Ring Column.
-------
NJ
0.000
LEGEND
O COD ANALYSIS
A TOC ANALYSIS
DOD ANALYSIS
J_
0.010
0.020 0.030 0.040 0.050
1-M,/M0. FRACTION WATER VAPORIZED.
Figure 11. Dcsorption of simulated wastewater No. 2 in Raschig Ring Column,
0.060
0070
-------
1.0
O
z
z
< 0.8
LU
CC
(SI
O
O 0.6
O
cc
O
LL
O 0.4
§
cc
0.2
0.0
LEGEND
OCOO ANALYSIS
A BOD ANALYSIS
I
I
I
0.00
0.01
0.02 0.03 0.04 0.05
1-M,/M0, FRACTION WATER VAPORIZED.
0.06
Figure 12. Desorption of simulated wastewater No. 3 with Raschig Ring Column.
-------
2.6
I
*
2.4
2.3
2.2
. 2.1
5
r
Z 2.0
o
3
2.4
2.3
2.2
2.1
2.0
K/a = 9.1
12-27
RUN
1-21
K/a
RUN
1-22
1 - 1 - 1 - ,
2.40 2.42 2.44 2.46 2.48 2.40 2.42 2.44 2.46 2.48
LOG M,.M, IN grams.
Figure 13.. Dcsorption of n-Butanol in Intalox Saddle Column - TOG
2.5
-------
1.6 -
*»
tn
0.8
0.6
30
60
I
I
90 120
RUN TIMEJmin.),
ISO
180
Figure 14. Oesorption of sucrose solution in Intalox Saddle Column TOC analysis
-------
hour run. Figure 15 shows the magnitude of discrepancy encountered when concentration is
employed rather than quantity on a normal one hour experirrer.t with a poultry processing
industry wastewater. As run time increases the error increases.
A series of three experiments were undertaken to determine if certain compounds
could affect the desorption test results. Since desorption is an interphase mass transfer
process, compounds were selected which have been known to interfere with the transfer
process Certain substances tend to concentrate at the interface, and may hinder the
interphase transfer of solute. Cetyl alcohol, when spread upor water in remarkably small
concentrations reduces the rate of evaporation of water into cir by as much as 95% (18).
Surfactants, such as sodium tetradecyl suliate (NaTDS) suppresses convection by inhibiting
flow at the interface (21). Goswami (11) report: that Na2 ^P04 reduces the aldehyde
desorption rate. However, this is in conflict with a referenced report that it increased COD
removal in a refinery wastfiwater from 72 to 90%. Normal hutanol was desorbed in the
Intalox Saddle device in the presences of: 30 ppm (volume) cetyl alcohol, 50 ppm (volume)
NaTDS and 30 ppm (volume) Na2HPO4, Figure 16 contains the experimental data for these
interference compounds, Cetyl alcohol appears to effect the desorption slightly. The
desorption effect of the other two compounds is not significant.
A gas-chromatogrjph (GO may be employed to determine the concentration of some
organirs in wastewater. A simulated wastewater was fabricated consisting of known volatile
and non-volatile species. Simulated wastewater No. 4 consisted of equal parts (- 165 ppm)
sucrose, phenol, n-butanol. acetic acid, acetaldehyde and acetone. Desorption was
performed in the Intalox Saddle device and GC was used to detect the total organic
concentration. The sum total area of all components was employed; no attempt was made
to obtain the concentration of individual species. The remaining organic fraction is:
f\A = tMt/M0) (22)
where Ft ^ = gas chromatograph organic fraction remaining
At = total integrator output area at time t, cm2.
AQ = total integrator output area at time initial, cm2.
Figure 17 shows the test results obtained with the 15% Chrom-W column. Sucrose, phenol
and acetic acid are non-volatile yet >9C?o of the GC-apparent organics are desorbed in a one
hour run. Gas chromatographic analysis techniques employing total integrated area output
as a measure of organic concentration will yield high values of the volatile fraction since the
non-volatile high molecular weight components may go undetected.
-46-
-------
VJ
I
0.0
10
20
I
O - C/C,,
30 40
RUN TIME, (min.).
50
60
Figure 15. Desorption of poultry processing WdStewater in Intalox Saddle Column - IOC analysis
-------
I
&
I
2.6
2.5
2.4
!
6 2.3
x~
if 2.2
o
3
2.1
2.0
CETYL
ALCOHOL
30ppm
I
I
K/a = 6.71
SODIUM
TETRADECYL
SULFATE
50 ppm
I
K/a = 7.58
I
I
SODIUM
PHOSPHATE
DIBASIC
30 ppm
I
I
K/a = 7.89
I
I
2.40 2.42 2.44 2.46 2.48 '2.40 2.42 2.44 2.46 2.48 2.40 2.42 2.44 2.46 2.48 2.50
LOG M,, M, IN grams,
Figure 16. Desorption of n-Butanol in Intalox Saddle Column - TOC analysis
-------
I
CO
10.
20.
30. 40.
RUN TIME, (min.),
50.
60.
Figure 17. Desorption of simulated wastcwatcr No. 4 with Intalox Saddle Column -GC bnalysis.
-------
Analytical Experiment Results
It was mentioned at the beginning of this section that the science of desorption in
packed columns is well established. The foregoing experimental results verify the important
predictions of the desorption model equations. In this section the mathematical equations
of packed column desorption will be employed to study aspects of the experimental
apparatus which would require prolonged laboratory experimentation to verify. Equations
(3) and (7) constitute the important desorption model relationships and will constitute the
"experimental apparatus" in this section of the report.
Raschig Ring Analytical Model Results Model equations (3) and (7) were employed with
the apparatus dimensions and operating conditions of the Raschig Ring desorption
apparatus. This device did not have mfans of temperature control. Therefore, the
calculations of K/a were performed at actual operating temperature and not at 25°C. The
inlet relative humidity for the calculations is assumed to be 0%, however there is some
doubt whether this condition was consistently maintained during all the experimental runs.
Table 4 contains the calculated K/a values and are listed under the column titled:
"Theoretical K/a". In general the analytical model does a fair job in predicting the relative
volatilization rate of pure components.
Temperature and relative humidity is considered to have a large effect on the relative
volatilization rate. Equation (7) was employed to study the effect of column temperature
and inlet air relative humidity on the fraction of water lost in the column. Figure 18 shows
the effect of temperature and % relative humidity is significant. These predicted results
stimulated a search for a means of maintaining a high degree of control over the temperature
and relative humidity during the experiment.
Intalox Saddle Analytical Model Results Model equations (3) and (7) were employed with
the apparatus dimensions and operating conditions of the Intalox Saddle desorpiion device.
Column temperature is maintainc.-d at 25°C ±1 C by means of heating tape or a rheostat
controlled hotplate and dry bottled air is employed with the Intalox Saddle device. We
became concerned with the wide variation in liquid flow rate and the effect it may have on
the relative volatilization rate. We attempted to maintain a liquid flow rate at or near 150
ml./min. Uncontrollable changes in the pumping head, etc., caused the actual measured rate
to fluctuate between 130 and 160 ml./min. Employing the ana'ytical model of the
experimental desorption apparatus, the effect of L(l/min) on K/a for n-butanol was studied.
Figure 19 shows that there is only a slight variation in K/a (2.4%) for a sizable variation in
U33.3%). Figure 20 shows a similar study of the effect of the dry air rate. A 10% variation
in K/a was computed for n-butanol for an air flow variation of 75%. It appears that
moderate deviations in liquid and air flow rates will have a relatively insignificant effect on
-50-
-------
0.0022
0.0018
- 0.0014
0.0010
0.0006
0.0002
0.0000
10.0
50
15.6
60
21.1
70
26.7
80
% RELATIVE HUMIDITY
OF THE ENTERING AIR
10
70
80
90
I
32.2
90
TEMPERATURE OF THE WATER
Figure 18. Water evaporation calculations in the Raschig Ring Column.
I
37.8
100
t
°F
-51 -
-------
4.5
4.0
3 3.5
3.0
2.5
100
110
I
I
I
120 130 140
LIQUID FLOW RATE, (cc/min.).
150
Figure 19. n-Butanol desorption calculations - effect of liquid rate.
-------
U1
w
5.5
5.0
4.5
4.0
3.5
3.0
= 2.5
2.0
1.5
0.2
5.66
_]
0.3
8.49
I
0.4
11.33
I
0.5
14.16
I
0.6
16.09
I
0.7
19.82
I .
0.8 (cu. ftVr.iin.)
22.65 (litert/minj
AIR FLOW RATE. AT STP.
Figure 20. n-Butanol desorption calcufations - effect of air rate.
-------
K/a, however increased rates tend to decrease the experiment run time.
Calculated results of the relative volatilization rate of pure components for the Intalox
Saddle device are shown in Table 3. T..ese calculated results indicate that the K/a equals the
relative volatility for those components that are non-volatile in nature.
Calculations were performed to develop a correction factor relationship for ar.
experimental relative humidity other than 0%. The analytical model results indicated that
the air emerging from the Intalox Saddle packed column (15 cm. in height) was saturated
with water and makes possible the following equation:
(K/d)e @ 0%RH = »K/a)e @ E%RH x ( 1100 - E%RH>/100) (23)
where (K/a)e@0%RH = the relative volatili??tion rate at 0%RH.
(K/a)e@E%RH = the relative volatilization rate at the experiment
relative humidity,
E%RH = the experiment percent relative humidity.
The experimental K/a result obtained when humid air is employed will be iarger than the
standard condition (i.e., 0% RH) value and the above equation should be empioyed as a
correction to this standard.
Experiments With Industrial Wastewater Samples
Industry representatives responding favorably to our request (by letter) for wastewater
samples were instructed to procure and handle the sample as follows:
quantity of sample. 500 ml.
container: small mouth plastic bottle
sample point: total wastewater effluent prior to any treatment operation (i.e., raw)
sample type: single grab aliquot during daytime under normal operating conditions
sample handling: adjust pH to 3.0 or lower, seal cap to bottle with electrical tape or
other type of rubber tape that will stretch and form a vapor seal
sample information: i \\ in requested information and attach tag to bottle neck. Tag
contains return address and stamps on face and general sample information on
backside, (requested information was: industry type, major product and daily
wastewater flow)
packaging: no special packaging is necessary. Attach tag to bottle neck.
mailing: place sealed, tagged bottle in U.S. Mail (parcel post).
A total of twenty seven letters were sent to industry representatives. Eight positive
responses and three negative responses were obtained. No response was received from the
-54-
-------
sixteen remaining inquiries. Samples received were both grab and composite types. All
samples received arrived intact ami seemed "fresh". No septic odor was detected.
Eight industrial samples composited (24 hr) by personnel from the City of Springdale,
Arkansas, were obtained. Three industrial samples were obtained from McClelland
Consulting Engineers, Inc., of Fayetteville, Arkansas.
All industrial samples were processed on the Intalox Saddle device. Three hundred
gram samples were employed. Experiment run time was one hour. One milliliter samples
were withdrawn every five minutes. TOC analysis was performed on all wastewater. A
limited number of GC analysis were performed also. Fifty microliter J50 ul) samples were
employed with the TOC and ten microliter samples were employed with the G C. Odor
eminating from the desorption apparatus funnel was noted at various times during the run.
Other details of operation are as reported in the METHODS section. All test results are
reported at standard conditions (i.e., 25°C, ambient pressure, 0% R H ).
Tabie 6 contains the experimental results of the nineteen industrial samples. Table 7
contains colUbcrative published data from which reliable volatile information could be
obtained. Figures 21, 22 and 23 display the results of the desorption experiments for twelve
of the industrial waslewater samples. Also shown in these figures is the computer program
estimated ultimate non-volatile fraction (i.e., Fnv). This extrapolated Ft value is plotted at
Mt/M0 = 0.
Now, once Fnv is obtained, it is possible to compute the relative volatilization rate for
the pseudo single component fraction (see equation 15). Figure 24 shows representatix-e
results for four wastewater experiments. Drawn straight lines are computer generated.
Wastewater data exhibiting a non-linear function are interpreted to typify a mixture of
volatile components. Wastewater data exhibiting a linear function are interpreted to typify
single volatile components or several components with identical relative volatilities.
Gas chromatographic analysis were performed on three industrial wastewater samples.
Figure 25 shows the experimental data for a petroleum refinery wastewater: The GC data
tends to show a larger fraction of volatiles than the TOC data. This type of behavior also
occurred wu!i simulated wastewater No. 4 (see Figure 17). The GC analysis tends to "see"
only the low molecular weight constituents.
A significant odor reduction was noted as the run progressed on those samples which
had a detectable initial odor. No foaming occurred during any experimental run with pure
components or actual wastewater samples.
-55-
-------
TABLE 6
Air-Volatile Fractions in Industrial Wastewaters
1
s
1
Industry Type, Major Product
poultry, liquid egg products
poultry, turkey processing
poultry, chicken processing
poultry, chicken processing
poultry, chicken processing
poultry, chicken processing
metal, hand tool mfg.
oil field blowpit
canning, grape products
pharmaceutical (1)
pharmaceutical (2)
paper(unbleached kraft)
paper, tissue, plywood
food, margarine, shortening
fibers, chemicals and plastics
petroleum, refined pet. products
petrochemical, 1,3 butadiene
petrochemical, 1,2 ai-chloroethane
petrochemical, 1,2 di-chloroethane
paper(bleached) pulp & kraft paper
Wastewater
Flow 1000
ga/da
42.8
960.
360.
622.
547.
360.
76.2
?
335.
?
?
6000.
42000.
200.
12000.
20000.
2000.
43?.
diluted 2:1
22000.
Raw Cone.
mg/l
1545.
2.1
78.
122.
206.
80.
51.
102.
202.
1854.
4100.
142.
136.
236.
452.
110.
94.
92.
60.6
311.
Volatile
Fraction
%
15.6
0.
4.1
98.0
0.
6.6
0.
19.4
0.
49.1
< 32.
26.3/63.5 (GO2
24.5/66.8 (GO
22.8
35.8
58.0/87 (GO
50.6
57.5
58.7
93.5
Relative
Vol. Rate
K/a
5.0
-
-
10.6
-
-
9.3
6.8
2.9
4.4/8.33IGC)
8.5 (GO
5.4
12.9
10.7/20.6 (GO
41.6
25.1
31.0
5.8
Source
J-T1
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
J-T
Jonci-Thibodaaux this project work.
As par oa» chromatogrspri analysis.
-------
I
Nl
TABLE 7
Published Air-Volatile Fraction Data
Industry Type, Major Product
Wastewater
Flow 1000
ga/da
Raw Cone.4
mg/l
Volatile4
Fraction
Relative
Vol. Rate
K/a
Source
paper, pulp and kra't paper
I Ip, cellulose
unknown, atyrene
synthetic fiber, dacron
petrochemical, vinyl chloride
simulated, six components
domestic, Fayetteville, Ark.
domestic, Springdale, Ark.
1080. 72 -8390(800) 53-94(BOD)3 8-9
? ? > 57(800)
? ? ~ 75(800)
? 85(800)
504. 1200. >8.1
9KGC) 17.0
TOO SAMPLES CONTAMINATED
6000. 254. 35.3 14.7
Estridge(1971)
Thibodeaux (1970)
Hiser (1970)
Keen (Private Comm.)
Minott (1973)
J-T
J-T
J-T
Evap. condensates 74 & 88%, decker filtrate 53%, turpentine decanter underflow 94%.
Total organic carbon unless specified otherwise.
-------
01
00
1.0
8
| 0.8
o
*5
c
01
'6
g 0.6
O
CC
U.
u
§
§ 0.2
0.0
1.0
o -
POULTRY PROCESSING (BROILER). Ks/a 10.6
PAPER (UNBLEACHED KRAFT). K$/a = 4.4
PETROCHEMICAL (1,2 UICHLOROETHANE). K$/a - 25.1
FIBER. CHEMICAL AND PLASTIC. K$/a= 12.9
J I I
.95 .90
WATER FRACTION REMAINING (M,/MO). dimensionlew.
.85
Figure 21. Desorption results for industrial wastewater I.
-------
Ol
<0
1.0
0.8
$
1
S
01
V
i 0.6
o
0.4
O
o
z 0.2
o
e
O
0.0
1.0
- POULTRY (LIQUID EGG PRODUCTS). K,/a * 5.0
-! FOOD (MARGARINE. SHORTENING). K$/a = 5.4
A -PETROLEUM REFINERY, Ks/a = 10.7
O - PETROCHEMICAL (1,3 BUTADIENE). K5/a » 41.6
I I I
.95 .90
WATER FRACTION REMAINING (M,/MO), dimensionless.
Figure 22. Desorption results for industrial wasiewater - II.
.85
-------
Figure 23. Dssorption results for industrial wastewater - III.
0.0
O -OILFIELD eLOW-ftT.Kt/a-0.3
-j- - PHARMACEUTICAL. K,/a 6.8
& - PAPER. TISSUE. PLYWOOD. K,/« - - 0.0
O -PULP,PAPER AND KRAFT PAPER.K,/«-3.1
1.0
.90
.85
H:
WATER FRACTION REMAINING (Mt/MQ), dimensionlets.
-------
O - PETROCHEMICAL (1.3 BUTADIENE). Fnv
D- FIBER. CHEMICAL AND PLASTICS. f°nv
- PHARMACEUTICAL. F
A - POULTRY (LIQUID EGG PRODUCTS). F
.03
- LOG (M,/M0).
Figure 24. Relative volatilization rates of industrial wastewaterr.
-61-
-------
o>
I
TOTAL ORGANIC CARBON ANALYZER
GAS CHROMATOGRAPHIC ANALYSIS
30 40 50
RUN TIME.Imin.).
Figure 25. Petroleum refinery wastewater T 0 C and G C results.
60
-------
SECTION VIII
DISCUSSION
Experiments with pure components established that a batch recirculating packed
column with counter-current air flow can be an effective desorption device. Good
comparison of experimental data with theoretical equations and calculated values instilled a
degree of confidence in the analytical model developed for the desorption apparatus. Table
4 shjws the extent to which the experimental results agree with the aralytical model for the
Rdschig Ring apparatus.
The experimental results of tests run with pure components appear in Table 4. The
data is u-auiated in order of decreasing relative volatility and the experimental K/a values
display thij tr.me decreasing trend. There is general quantitative agreement on K/a results
between the various test methods. The data treatment techniques (i.e., slope from a log-log
plot) is sensitive to er ors >n the test methods and may account for the relative wide range of
K/a values. Figures 6 ,ind 7 show that the least square algorithm will yield biased results if
some data are ir strong deviation from the trend. Ideally all test methods should yield
identical experimental values of K/a for pure components.
Although the Raschig Ring apparatus displayed sizable errors in water loss, which will
in turn effect K/a. there are instances of agreement between test methods worth noting in
Table 4. The acetaldehyde results show good agreement between test methods. The BOD5,
COD and GC results for acetone (run 2) and methanol (run 1) are in fair agreement. All four
test results for methanol (run 2) are in fair agreement. The results of both phenol runs are
exceptionally good. Phenol has approximately the same relative volatilization rate as water
and all six test results indicate this with a high degree of absolute accuracy. Considering the
sensitivity of the log-log correlation to experimental test error it is doubtful that the most
error free data will yield a K/a value with a range of uncertainty less than ±1. K/a unit.
The agreement between repetitive runs for the Raschig Ring column is generally poor.
The GC data for acetone in Table 4 is in fair agreement. The COO data for methanol is in
good agreement. The phenol data is good in an absolute sense.
Statistical results (Table 5} of pure component experiments with the Raschig Ring
column for K/a reveal that no test method emerges as being superior, however the standard
error is usually less for the TOC and COD tests. Non-zero (with 95% confidence) K/a values
were observed for methanol, acetone, acetaldehyde, n-butanol and i-butanol. K/a values not
significantly different from zero were observed for phenol, acetic acid, formic acid and
propionic acid. This is in general agreement with the theoretical K/a column of Table 4. An
exhaustive set of experiments was not carried out with the Intalox Saddle device.
Recommended Test - An Intalox Saddle device was developed (Figure 5) that displayed the
same experimental behavior as the Raschig Ring device. This modified apparatus required
-63-
-------
less sample, a shorter run time, was simpler to operate and gave considerably more accurate
results. Water evaporation in a one hour run averaged 40.4 grams with a range of 38.4 to
42.4 grams for a percentage deviation range of -5.0% to 5.0%. The correspondence of
repetitive runs with n-butanol (shown in Figure 13) is indicative of the reproducibility of
the Intalox Saddle device results.
Experiments with selected pure chemicals revealed some information about desorption
of solution* containing both volatile and non-volatile components. Desorption of simulated
wastewater revealc-o that the non-volatile fraction remains in the aqueous phase and a
volatile fraction i:. stripped out by the air (see Figure 10, 11 and 12). These simu'ated
wastewater runs further suggest that the volatile fraction observed depends upon the test
method. For example "Simulated Wastewater No. 2" (Figure 11) was found to contain a
50% volati e BOD5 fraction.
-------
concentrations to be measured on the total carbon analyzer. In general all the industrial
sample results display a behavior predicted by Equation (14). Some samples contain
volatile-; which display low K/a values and a sixty minute run time is too short for
accurately determining Fv. The poultry sample in Figure 21 and the paper and
pharmaceutical samples in Figure 23 are examples. Figure 24 shows that relatively
consis ant values of Ks/a can be obtained from a uesorption experiment. This figure
rep.esents the results of only the most consistant data results. Plots of this type are possible
only if the wastewater test methods are penormed with extreme care and utmost accuracy.
No operating problems were encounterea with any of the experimental runs. Significant
odor reduction was noted during the experiment.
The Intalox Saddle device as described abo/e appears to be ideally suited to perform
desorption studies on industrial wastewater samples. It has a number of inherent advantages
over sparged vessel type devices and hollow fiber devices (see Appendix C). The foremost
advantage is that it simulates the desorption (or stripping) process as it occurs in cooling
towers. The main advantages of packed column desorption are:
a) the apparatus is simple and the elements are readily available
b) the operation is simple to control and the experiment run time is short
c) standard wastewater test methods ca.^ be employed with the experiment
d) data handling and interpretation require elementary graphical or mathematical
techniques.
e) a correction is available for air with a humidity other than 0% R H
f) the results are somewhat insensitive to operating conditions (except for
temperature)
g) samples that have a tendency to foarr. when contacted with air can be readily
handled.
The main disadvantages of the packed column desorp J?n device are:
a) column temperature must be maintained constant (i.e., at 25°C, cooling tower
inlet temperature, etc.)
b) samples should be kept in a chilled state before and after desorption
c) run times of greater than one hour may be desirable on some samples
The apparatus design and the organic concentration test method are somewhat related.
The TOC (instrumental) test is possibly the best technique for measuring Fv and Ks/a due to
the present accuracy of these devices. If COD or BOD is employed, relatively large samples
will be required from the desorption apparatus. A large flask (- 1 liter) should be employed.
COD and BOD are both useful for measuring Fv and Kj/a. The GC should not be employed
for Fv measurements. Ks/a measurements can possible be estimated from GC results.
One most important use of this device is the simulation of stripping of volatile
components from wastewater in industrial size cooling towers. An experimental value of
-65-
-------
Ks/a is obtained from the Intalox Saddle dcsorption device operated at the proposed inlet
water temperature. This relative volatilization rate is employed with an equation developed
by McAhster. Turner and Estridge (1) to obtain the percentage extent of treatment by
stripping in a cooling tower. The equation is
(Ks/a)aCT(1 +B/L)
R = (Ks/a) aCT + B/L <24)
where R = percentage of treatment by stripping
aCT = fraction of water loss in cooling tower
B - blowdown rate from tower basin, l./min.
L = water flow rate to tower, l./min.
-66-
-------
SECTION «X
REFERENCES
1. McAlister, J.A.. B.C. Turner, and R.B. Estridge. Treatment of Selected Internal Kraft
Mill Wastes in a Cooling Tower. Environmental Protection Agency, Water Pollution
Control Research Series. Publication Number 12040 EEK. August, 1971.
2. Prather, V. Advanced Treatment of Petroleum Refinery Wastewater by Autoxidation.
Journal Water Pollution Control Federation. 42 (4): 596 - 603, April 1970.
3. Mohler, E.F.. H.F. Elkin, and L.R. Kumnick. Experience with Reuse and Bio-oxidation
of Refinery Wastewater in Cooling Tower Systems. Journal Water Pollution Control
Federation. 36 (11): 1380 - 1392, November 1964.
4. Burn;, O.B., Jr. and W.W. Eckenfelder, Jr. Aeration Improvement and the Adaptation
of a Cooling Tower to an Activated Sludge Plant. TAPPI 48 (11):96A(1965). Pilot
Plant Evaluation of Plastic Trickling Filters in Series with Activated Sludge. TAPPI 48
(11:42(1965).
5. Cohn, R.G. and Tonn, FIT., Use of a Cooling Tower in Black Liquor Evaporation.
TAPPI 4Z (3): 163AH964).
6. Engelbrecht. R.S., A.F. Gaudy. Jr. and J.M. Cederstrand. Diffused Air Stripping of
Volatile Waste Components from Petrochemical Wastes. Jo. W.P.C.F.^3. (2): 127-135
Feb., 1961.
7. Gaudy, A.F. Jr., R.S. Engelbrecht, and B.C. Turner. Stripping Kinetics of Volatile
Components of Petrochemical Wastes. Jo. W.P.C.F..33. (4) 382 - 392, April, 1961.
8. Gaudy, A.F., Jr., B.C. Turner and S. Pusztaszeri. Biological Treatment of Volatile
Waste Components. Jo. W.P.C.F..3JL(1): 75 - 93. January, 1963.
9. Eckenfelder. W.W., Jr. Industrial Water Pollution Control. McGraw-Hill Book
Company, New York, 1966, p. 82.
10. Hiser, L.L. Selecting a Wastewater Treatment Process. Chemical Engineering Nov. 30,
1970.p. 79.
-67-
-------
11. Goswan.i, S.R.. Treatment of Strippable and Nonstrippable Substrates by the
Activated Sludge Process. P!i.D. Thesis. Oklahoma State University. 1969.
12. Thibodeaux. L.J. and D.G. Parker. Desorption of Selected Gases and Liquids from
Aerated Basins. (Presented at 76th National Meeting American Institute Chemical
Engineers. Tulsa. Oklahoma. March 10-13. 1974.) Paper No. 30d.
13. Horton, J.H., J.C. Corey and R.M. Wallace. Tritium Losses from Water Exposed to the
Atmosphere. Environmental Science and Technology_5_<4): 388 - 343, April, 1971.
14. Mackay, D. and A.W. Wolkoff. Rate of Evaporation of Low-Solubility Contaminants
from Water Bodies to the Atmosphere. Environmental Science and Technology J7 (7)
611 -614, July, 1973.
15. Weimer, W.C. and G.F. Lee. Method for the Storage of Samples for Dissolved Gas
Analyses. Environmental Science and Technology 5_ (11): 1136 - 1138, November.
1971.
16. Pierotti, G.J.. C.H. Deal and E.L. Derr. Activity Coefficients and Molecular Structure.
Industrial and Engineering Chemistry, jjl (1): 95102, January, 1959.
17. Thibodeaux. L.J.. R.B. Estridge and B.G. Turner. Measurement of the Relative
Volatilization of the Water-Miscible Fractions in an Aqueous Effluent. New York,
American Institute of Chemical Engineers, Symposium Series 124. Volume 68, 1972.
18. Treybal, R.E. Mass-Transfer Operations, 2nd Edition. McGraw-Hill Book Company,
New York. 1968. p. 164-171.
19. Reinhardt. J.A. An Experimental Apparatus for Measurement of Volatile Components
in Aqueous Phases. Thesis (M.S.). University of Arkansas, Fayetteville, 1972.
20. American Public Health Association, Standard Methods for the Examination of Water
and Waste Water, 13th Edition, New York, APHA Inc., 1971.
21. Emory, S.F. The Effect of Surface Active Agents on Interfacial Convection. New York,
American Institute of Chemical Engineers Student Bulletin, p. 37, 1972.
-68-
-------
SECTION X
PUBLICATIONS AND PATENTS
Two pending publications have been written at a result of this study.
1. Jones, Jack Ray; "Air Stripping of Volatile Components .- Industrial
Wastewater" University of Arkansas. Thesis, May. 1974.
2. Thibodeaux, LJ. rnd Jones, J.R.; "A Desorption Test for Quantifying the
Volatile Organic* in Industrial Wastewater" (proposal accepted for presentation at
AlChE Meeting, Salt Lake City. Utah. Aug.. 1974)
No patents have been produced or applied for under this project.
-60-
-------
SECTION XI
GLOSSARY OF SYMBOLS
FREQUENTLY USED ABBREVIATIONS
ac = alternating current
BOD6 = biological oxygen demand (5 i ay, 20"C)
°C = degrees Celsius
cm = centimeters
COD = chemical oxygen demand, mgOj/l.
da = day
Exp = experiment
EXP = exponent (e = 2.71828)
°F = degrees Fahrenheit
ft = feet
ga = gallons
G C = gas chromatograph
Hg = mercury
in = inches
I = liters
log = common logarithm (i.e., base ten)
m = meters
mg = milligrams
mgC/l = milligrams carbon per liter
mgO2/l = milligrams oxygen per liter
min = minutes
ml = milliliters
n = normal
PCBS = polychlorinated biphenyls
pH = log[hydrogen ion concentration in gram ions per liter]
ppm = parts per million
RH = relative humidity
SCF = standard cubic feet (i.e.. ft3 at 32°F. and 1 atmosphere)
STP = standard temperature and pressure (i.e., 0°C and 760 mmHg or 32°F and 1
atmosphere)
TOC = total organic carbon
v = volts
wrt = with respect to
-70-
-------
% = percent
> = greater than
» > = much greater than
- = approximately
~ - approximately equal
H = a definition
<> » infinity
SYMBOLS
Roman
A = integrator area, cm2.
a - fraction water lost in column (dimensionless), regression equation constant
B = blowdown rate from cooling tower, l./min.
b = regression equation slope
C = concentration of gross organic pollutant measures (i.«;., BOD5, COO, and TOO,
mg/l.
CV = coefficient ol variation (standard error -:- mean)
E = experimental percent relative humidity, %
F = organic fraction {0 < F < 1), dimensionless
G = gas flow rate through column, (g-nioles)/{min)(cm2)
H = height of a transfer unit, cm.
K = fraction of a volatile component lost in column, dimensionless
K/a = relative volatilization rate of a volatile component wrt water, dimensionless
L = liquid flow rate through column, (s-moles)/(min)(cm2) or (g moLs)/(min)
M = quantity of liquor, grams. &M = change in quantity of liquor, grams.
m = sample size, grams. Am = individual sample size, grams.
n = number of samples
p = vapor pressure, torr. or mmHg.
R - removal of BOD, COD, TOC in a cooling tower as a fraction or as a percent of it in
feed liquor.
S = stripping factor, dimensionless
SE = standard error of estimate of regression equation
t = time, min. or statistical t-value.
W = weight, grams
X = independent linear regression variable
x = mole fraction in liquid, dimensionless. liquid phase concentration (same dimensions
-------
Y - dependent linear regression variable
y = note fraction in gas, dimensionless
Z = iieiyht of packed section of desorption column, cm.
Greek
« = relative volatility, dimensionless
Y = activity coefficient, dimensionless
<*> = fraction of the original volatile fraction remaining, dimensionless
SUBSCRIPTS
CT = cooling tower
e = experimental
f = final
i = volatile component
ii = inlet concentration of component i
io = outlet concentration of component i
j = non-volatile component
jo = initial concentration
m = total number of non-volatile components or designates a molar quantity (i.e.,
moles)
n = total number of volatile components
nv = non-volatile
o = original or initial
OG = overall gas phase
R = ratio (i.e., stripping factor ratio)
s = a pseudo volatile component
T = tower or column
t = at time t (i.e., one of many sample times)
v = volatile
w = water
x = liquid phase
SUPERSCRIPTS
o = original or pure component
* = in equilibrium
-72-
-------
SECTION XII
APPENDICES
Page
A. Raw Experimental Data 74
B. Computer Program to Calculate F^ and Kj/a fof Industrial Wastewater
Samples 119
C. A Hollow Fiber Device as a Desorption Apparatus 126
-73-
-------
APPENDIX A
RAW EXPERIMENTAL DATA
- 74 -
-------
Experiment 1
component(s) methanol-water
initial concentration approx. 1000 ppm methanol in H_0
initial ci^xrge volume 2876 ml
water vaporized 245 m^
^\
liquid flow rate 700 ral/min (4t340 Ibs/HR-ft )
^ac flow rate 1.82.8 ftV^in AP = 11" Hg
1:1 xet dry bulb tomperaturc of air 77 °?
inlet wet buib temperature of air 68 °P
iitruid temperature 68 °K
?ime into axperiment Analysis Concentrations
COD GC TCC BOD
(min) (ppm HeOH) (ppm MeOH) (ppai MeOH) (ppm MeCH)
0
15
30
45
60
75
90
105
120
135
150
165
130
805
734
718
685
636
615
598
528
496
474
442
421
399
405
550
538
522
492
442
432
423
401
390
365
340
325
i'X)
312
570
424
320
251
251
251
214
181
165
101
67
120
120
67
520
530
493
560
487
477
447
453
333
420
350
400
300
300
-75-
-------
Experiment 2
components . nethanol-water
initial concentration approx 100 ppm methanol in water
initial charge voxune 2913 nil.
water vaporized 245 ml.
liquid 2'iow rate 700 ml/mm. (4,840 lb3/HR-ft2)
(,-as flow rate 1.828 ft^/min.
inlet dry bulb temperature of air 78 F
ii; let wet bulb temperature of air 66 F
liquid temperature 66 F
rj-ne ir. V.Q Experiment Analysis Concentrations
CCD CC TOG BOD
(min) (ppm MeOH) (ppm MeOH) (ppm MeOH) (ppm MeOH)
0
15
30
''.5
75
)0
105
120
135
150
165
130
195
916
826
787
723
686
632
611
630
563
546
499
4V3
429
434
1030
970
925
842
812
820
595
710
630
610
560
512
470
438
4U
395
347
347
288
288
238
248
237
206
197
206
181
160
580
510
440
410
460
340
340
330
280
220
260
220
180
200
-76-
-------
Experiment 3
components
initial concentration
initial charge volume
water vaporized
liquid flow rate
gas flow rate
inlet dry bulb temperature
inlet wet bulb temperature
liquid temperature
Time into Experiment
(minutes)
0
15
30
45
60
75
90
105
120
135
150
165
180
195
acetone-water
approz 1000 ppm acetone in water
2912 ml
174 ml
700 ml/rain (4,840 lbs/Hr-ft2)
1.828 ft
COD
1223
734
470
258
179
111
89
11
14
0
11
0
0
0
75°
63°
63°
Analysis
GC
1000
866
410
281
160
108
68
83
0
0
0
0
0
0
P
P
P
Concentration
TOC
851
515
298
185
106
0
0
0
0
0
C
0
0
0
(ppm ACETONE)
BOD
554
412
256
142
106
62
31
27
10
3
2
2
0
2
-77-
-------
Lbcperiment 4
co;rporier.tD
initial concci.tration
initial charge volurw
water vaporised
liquid flow rate
air flow rate
inlet dry bulb temperature
.nlet wet bulb temperature
liquid temperature
acetone-water
appro* 1000 ppm Acetone in water
3013 m.
268 ml
700 mi/min (4,840 lbs/Hr-ft2)
1.828 ft*
82° F
64° F
64° :-'
Time into bxnenment
Analysis Concentrations (pp:n Acetone)
(min)
0
15
30
45
60
75
90
105
120
135
150
165
130
1^5
(XD
757
433
225
133
79
55
0
14
0
14
12
13
11
11
GC
940
545
300
210
145
85
100
0
0
0
0
0
0
0
TOC
563
245
145
56
24
8
3
3
0
0
0
0
0
0
BOD
353
126
149
85
51
41
34
24
24
7
17
17
7
14
-76-
-------
iixperiment 5
components
initial concentration
initial charge volume
water vaporized
liquid flow rate
air flow rate
inlet dry. bulb temperature
inlet wst bulb temperature
liquid temperature
Phenolwater
approx 1000 ppra Phenol in water
2937 ml
251 ml
700 ml/min
1.575ft3/min. 9-5" Hg
" F
F
83°
67°
67° F
Time into i^cneriment
Analysis Concentrations (ppm Phenol)
(min. )
0
15
30
45
60
75
90
105
120
135
150
165
130
195
COD CC
973
950
949
922
937
969
960
967
979
953
994
975
993
1002
TOG
509
477
490
490
473
465
496
487
487
487
514
487
490
509
BOD
636
636
611
623
598
579
611
579
566
611
579
611
579
578
-79-
-------
£xperiment 6
initial concentration
ii.itiul char^ vola'.io
water vaporizeu
liquid flow rate
air flow rate
ir.let ury bulb temperature
Pher.oi-water
approx 1000 ppm Phenol in water
2355 n>i
241 ral
700 ml/mir.
1.545 ft
80° F
ir.iet wet bulb temperature
liquid temperature
Time into i^xpem.nent
(min )
O
15
30
45
60
75
90
105
120
135
150
165
130
195
Col.
X3
we
940
^34
>32
;J17
?40
941
'934
913
943
944
932
964
67° P
67° V
Analysis Concentrations
GC TOG
336
400
433
409
419
419
426
419
354
386
401
401
400
400
(ppm Phenol)
BCD
648
604
679
686
611
661
686
673
626
635
641
667
617
654
-80-
-------
Experiment 7
components
initial concentration
initial charje voiii,T»
i;ater vaporised
liquiu flow rate
air flow rate
ir.-et ary bulb temperature
inlet wet bulb temperature
liquid te.-.iperature
Acetone-Phenol-V.'ater
approx 500 PPrt Acetone + 5^0 PPm Phenol in water
3027 nl
215 ml
700 nl/nin
1.828 ft
75° P
64° V
64° K
Tine into iixperimer.t
Analysis Concentrations
(nir.)
0
15
30
45
60
75
20
105
120
135
150
165
130
195
COD
^ppin ^xy£cn)
2064
1741
1564
1412
1332
1255
1259
1263
1340
1296
1244
1276
1292
1268
TOC
(ppm C)
378
310
275
250
253
253
250
248
233
232
225
225
200
208
BOD
(ppm Oxygen)
1450
1275
1030
935
955
930
890
840
860
840
865
855
825
845
-81-
-------
Kxperimnt 8
components
ir.itial concentration
initial vclu,Tic charts
water vaporized
liquid flow rate
air flow rate
inlet dry buib temperature
iniet wet bulb tcnperaturc
liquid temperature
Acetone, Phenol, Hethanol, and Water
approx 332 i-pm of each organic co**pon«nt In
0 -., , the water
2-jM ml
211 nl
7OO ml/mm
1.828 ft
74° y
1'inc i-.'.tc K
(nin)
0
'5
30
45
60
75
oo
105
120
135
150
165
130
195
(ppr. oxygen)
2032
1650
1521
1335
1304
1242
1137
1022
1007
960
934
920
91?
923
Anaii'sis Concentrations
TCC
(pnm carbon)
350
670
590
570
545
470
451
435
396
355
375
330
330
305
BCD
(pprn oxygen)
1330
1155
1020
915
900
795
310
795
765
720
680
675
675
705
-82-
-------
licperiroent
components
initial concentration
initial volume charge
water vaporized
liquid flow rate
air flow rate
ir.let dry bulb temperature
inlet wet bulb temperature
liquid temperature
Acetone, Phenol, I-'ethanol, and Water
appro* 333
2970 mi
134 nl
700 ml/min
1.828 ft
73° P
68° y
68° 1'
of each orcar.ic compond in water
ir.to Experiment
Analysis Concentration
0
5
10
15
20
25
30
35
40
45
50
55
CO
65
70
75
30
35
(ppm
COD
i oxyGcn)
1943
1313
1695
1433
1446
M30
1332
1333
1238
1267
1134
1197
1173
1138
1135
11C1
1100
1075
1104
BOD
(ppm oxygen)
1350
1250
1140
1050
360
330
810
870
750
810
750
750
630
690
720
780
660
630
810
-83-
-------
toperime.it 1-18-73
components formic acid - water
initial concentration approx 1000 ppm
initial volume charge 3?QO ml
water vaporized 223 ml
liquid flow rate 610 ml/min
air flow rate 1.65 ft /rain
in lot air humidity lees than 30$
Time into i^xperiment Ana lysis Concentrations
1WP COD TCC BOD
(min) ( F° } (ppm 02) (ppm c) (ppm 02)
0 68 967.7
15 66 652.0
30 66 757.0
45 64 767.0
60 64 . 748.0
-84-
-------
Experiment 2-26-73
components
initial concentration
initial volume charge
water vaporized
liquid flow rate
air flow rate
inlet air humidity
acetic acid - water
approx 1000 ppm
3367 ml
233 ml
570 ml/min
1 .65 ftV»in
less than 30J&
Time into Experiment
Analysis Concentrations
(rain)
0
15
30
45
60
75
90
105
120
135
150
165
180
TtMP
( P° )
77
69.5
68
65-5
64
63
63
63
63
63
63
63
63
COD
(ppm 02)
1223.0
1079.3
1092.4
1076.7
1063.6
1208.1
1120.9
1178.0
1064.4
1131.3
1157.2
1131.3
1120.9
TOC
(ppm C)
950.0
787.5
850.0
837.5
837.5
775.0
787.5
812.5
800.0
800.0
806.3
800.0
800.0
301)
(ppm C
1410
1305
1305
1335
1350
1335
1260
1290
1200
1065
1080
1125
1065
-86-
-------
Experiment 3-3-73
components
initial concentration
initial volaae
water vaponrea
liquid flow ra.lt
air flow rate
inlet air
propionic acid - water
approx 1000 ppra
3723 ml
348 ml
570 mJ/min
1 .65 ft3/min
less than 30$
Tiae into
Analysis Concentrations
(mm)
0
15
30
45
60
yO
120
150
1iiO
TEMP
( 1'° )
75
70
63
67
66
66
66
66
66
COD
(ppn 02)
1149.1
1210.8
1237.9
1313.8
13*5.0
1324.3
1279.7
130y.4
1354.1
TOC
(ppn C)
662.9
713.7
353.2
713.7
745.1
796.5
750.3
765.3
755-4
BOD
(ppm (
960
810
990
1020
810
735
990
975
810
-86-
-------
Experiment 3-23-73
compeonents
initial concentration
initial volume charge
water vaporized
liquid flow rate
air flow rate
inlet air humidity
Time into Experiment
acetaldehyde - water
approx 1000 ppm
3501 ml
260 ml
570 ml/min
1 .65 ft
less than
Analysis Concentrations
(min)
0
3
.6
9
12
15
20
25
30
Temp
(F°)
75
74
72
72
71
70
69
63
63
COD
(ppm 02)
1467.3
1287.4
1139.3
992.2
844.6
721.6
590.4
475.6
377.2
TOC
(ppm C)
599.5
462.0
416.2
397.8
297.0
242.0
150.3
141.2
95-3
BGJ
(ppm <
1050
810
690
630
450
510
630
330
30
-87-
-------
Kxperiment 4-13-73
components
initial concentration
initial volume charge
water vaporized
liquid flow rate
air flow rate
inlet air humidity
Time into Experiment
propar.ol water
approx 1000 ppm
3341 ml
237 ml
540 ml/min
A £.£. C*A. ~> II «
1 .op it /mm
less than 30$
Analysis Concentrations
(min)
0
5
10
15
25
35
45
60
75
yo
105
120
135
150
165
180
' TEMP
( F° )
72
68
68
67
67
66.5
66
66
66
66
66
66
66
66
66
66
COD
(ppm 02)
1822.2
1802.2
1762.1
1722.1
16
-------
Experiment 4-18-73
compor.cr.tc
in. cial concentration
initial volume charge
water vaporized
liquid flow rate
air flow rate
inlet air humidity
t'ime into Experiment
isopropanol - water
appro* 1COO ppm
3546 ml
211 ml
540 ml/iin
1 .65 ffVniin
less than 30jS
Analysis Concentrations
(sain)
0
5
10
15
25
35
45
60
75
50
105
120
135
150
165
130
TiMP
( I'° )
80
74
72
70
53
63
67
66
66
66
66
66
66
66
66
COD
(ppm U2)
1360.0
15.10.0
1520.0
1380.0
131/4.0
1316.5
1220.0
1142.2
1006.7
1232.4
1175.5
1175.5
10W.7
1030.7
777.4
815.3
TCC
(ppa C)
617
600
550
500
533
500
667
467
450
350
330
300
267
317
250
317
BOD
(ppm (
150
60
150
60
90
90
60
150
90
60
60
90
60
60
90
150
-89-
-------
Experiment 6-1-73
components
initial concentration
initial volume charge
water vaporised
liquid flow rate
air flow rate
inlet air humidity
Time into Kxperitncr.t
(nin)
0
30
60
jo
120
150
130
210
?70
300
330
360
3;o
420
420
450
4PO
510
540
'J70
TKHP
( F°
72
$>
63
63
68
f:&
63
~f-
66
65
66
^ *
66
66
74
68
66
56
66
(5
sucrose water
approx 2000 ppm
3612 ml
542 ml
540 ral/min
1 .65 ft 3/min
lesc than
537
Analysis Concentrations
CCD TOC BOD
(ppm 02) (ppm C) (ppm 02)
-90-
-------
Experiment 7-17-73
industry
initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
ary air
liquid temperature
i'lrie into Experiment
(minutes)
0
5
10
15
20
25
30
35
40
poultry - broiler processing
pure waste
300 gm
41.1 gm
112 ml/rain
0.6 ftV
-------
Experiment 7-18-73
ir.ciu-jtry
initial concentration
initial weight charce
v;ater vaporised
liquid I'low rate
air flov; rate
ary air
temperature
Tine into Experiment
0
60
metal - force and plating
pure waste
300 gin
33.7 em
125 mi/min
0.6 ft3/mn
air bottle
25° c
.alycis Concentrations
TOG
(ppm Carbon)
367
378
-92-
-------
iicperi.-ncnt 7-19-73
uuiustry
initial concentration
initial weight charge
water vaporized
liquid flow rate
air fiov; rale
dry air
^.iquiu temperature
P:rr,e into hxperi:no:'.t
(ninutec)
0
60
feed grape products
pure waste
300 gm
33«5 5*"
122 ml/rain
0.6 ftV-nin
air bottle
25° c
Analysis Concentrations
TOC
(ppm Carbon)
6*5
722
-93-
-------
Experiment 7-23-73
inductry
initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
dry air
liquid temperature
Time into Experiment
(min)
O
5
10
15
20
2?
30
35
40
45
50
55
60
poultry - liquid egg products
pure waste
300 gro
37.2 gm
112 ml/min
0.6 ft3/min
air bottle
25 °C
Analysis Concentrations
TOC
(ppm Carbon)
1545
: 1540
1560
1620
-94-
-------
Experiment 7-31-73
components
initial concentration
initial weight charcc
water vaporized
liquid flow rate
air flow rate
dry aid
liquid tenperature
Time into Llxperi^er.t
(seconds)
0
45
>o
150
210
235
360
-35
530
660
720
730
340
otyrene - water
approx 1000 ppra
300.3 gm
10.6 gin
1?^.5 ml/nin
0.6 ft /min
air bottle
25° c
Analysis Concentrations
TOG
(ppra Carbon)
76
137
111
65
U7
455
41
24
325
-95-
-------
jJxpenner.t 8-1-73
components
initial concentration
ir.itiai weic«t ciuir^je
water vaporized
liquid flow rate
air Mow rate
dry air
~i':ui
-------
Experiment 8-16-73
..components
initial concentrations
initial weight charge
water vsporized
liquid flow rate
air flow rate
dry air
liquid temperature
Tine into rlxperinct'it
(nin)
0
5
10
15
20
25
30
35
40
46
50
55
60
sucrose, phenol, acetone,
acetaldehyde, styrene,
n-butanol, acetic acid,
water
50/tl of each component
303.5 gm
42.3 cm
144 ml/min
0.6 ft/fain
air bottle
25 °c
Analysis Concentrations
GC
(average weight, gm)
0.018
0.013
0.011
0.008
0.009
0.008
0.008
0.009
0.009
0.009
0.011
0.009
0.012
-97-
-------
Experiment 8-22-73
industry
intitai concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
ary air
iiqu.iu temperature
Time into _Expenreer.t
(minutes)
0
5
10
15
20
25
30
poultry broiler processing
pure waste
300 gm
37.8 m
129 ml/rain
0.6 i
air bottle
25° C
Ar. 'lysis Concentrations
TOC
(ppm Carbon)
122
33
111
84.5
135
72
40
45
50
55
60
60
44
40
47
49
-98-
-------
Experiment 8-23-73
industry
initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
dry air
liquid temperature
poultry - broiler processing
pure waste
300 gm
41.7 gm
153 nil/min
0.6 ft^/min
air bottle
25 °c
Tine into Ilxpcrr.rent
(min)
0
5
10
15
20
25
30
35
40
45
50
55
60
Analysio Concentrations
TOG
(ppm Carbon)
80
62
78
91
93
37
109
82
98
96
-99-
-------
Kxpcriment 3-24-73
co.-.ipcnents
initir.i concentration
initial weight charge
water vaporised
liquid flow rate
air flow rate
dry air
liquid temperature
Tirnc into Experiment
(minutes)
0
3
at.iraor.iun chloride, sodium
. 11 hydroxide, water
301.3 pa
3^.5 6"
123.rni/nin
0.6 ft3/min
air bottle
25° C
Analysis Concentrations
Spectrophotometer
(pprn annnonia)
'J
12
15
20
25
30
35
40
45
50
55
60
380
363
852
325
733
735
710
630
431
45?
-100-
-------
lixperiraent 8-23-73
components ;
'initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
dry air
liquid temperature
Time into Experiment
(minutes)
0
15
33
45
60
75
90
105
120
135
150
165
180
sucrose - water
appro* 2000 ppm
3CD.6 gm
138 gm
138 ml/min
0.6 ft^/min
air bottle
25° c
Analysis Concentrations
TOG
(ppm Carbon)
J210
1310
1360
1460
1520
1640
1640
1730
1790
1910
- 101-
-------
Experiment ->-1073
i;iuoj ury
initial concentration
initial weirrht charge
water vaporizeu
. iquiJ flov; rate
air flow rale
tiry air
ii<[Uiu temperaturo
Time into h'xperincr.t
(minutes)
O
10
?0
paper pulp, unbleached kraft paper
pure waste
300.1 em
33.6 cm
132 nl/nin
0.6 ft
50
55
60
air bottle
25° c
Analysis Concentration
TOC r,c
(ppm Carbon) (average weight, grams)
311 0.027
282 0.021
224 0.021
216 0.020
233 0.019
244 0.017
2-J6 0.016
13,' 0.014
222 0.012
218 0.012
240 0.011
187
153
-102-
-------
experiment ^-11-73
i:iuiu; try
initial concentration
initial weight ct\as r;e
water vaporised
± i.iuiii flow rate
air flow rate
dry air
temperature
i'i:,ic ii! to Kxperi.-.ner.t
(minute;;)
0
5
10
1';
30
35
50
55
paper - unbleached kraft paper
pure wacte
300 pn
40.5 cfit
132 ml/iiiir.
0.6 ft /rain
air bottle
25° c
Analysis Concentrationa
GC
(average area, grama)
0.018
0.018
0.016
0.017
0.016
0.015
0.015
0.020
0.013
0.0V;
0.018
0.015
0.015
- 103-
-------
industry
initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
dry air
liquid temperature
Time into Experiment
(minutes)
0
5
10
15
20
25
30
35
40
45
50
55
60
food shortening & oargerin*
37*3 g» pur* w*at«
300*4 fin
40.2 em
147 ml/mm
0.6 ft^/ain
air bottle
25° C
Analysis Concentration
OC
(average heights, units)
96
85
82
7?
70
68
54
53
47
44
42
40
40
-104-
-------
Lxperimcnt 9-17-73
i nciuc t ry
iniliaj. concentratioi:
ir.itial wei,-ht charge
water vaporized
liquid flow rate
air flow rate
dry air
paper tissue, paper, & plywood.
pure waste
300.2 gin
41 gm
154 ml/.7iin
0.6 ft
air bottle
liquid temperature
Tine ir.to Lxperirr.snt
(minutec)
0
5
10
15
20
25
30
35
40
45
50
55
60
fuC
(ppm Carbon)
173
73
162
1*5
224
156
167
124
3#>
238
v;8
25° c
Analysis Concentrations
CC
(average area, units)
0.020
0.018
0.015
0.014
0.013
0.012
0.012
0.011
0.010
0.010
0.003
0.007
0.00?
-105-
-------
Experiment 10-29-73
i;:du^try
initial concentration
initial weight, charge
water vaporized
liquid flow rate
air flow rate
ury air
liquid temperature
petroleum - refined petroleum producta
pure waste
300 gn
40.1 em
136 nl/njin
0.6 ft
air bottle
25° c
Tine into Experiment
(minutes)
0
5
10
15
20
25
30
35
40
45
50
55
60
TOC
(ppn Carbon)
74
'I)
y6
60
68
-
54
69
Analysis Concentrations
CC
(average height, cm.)
7.63
5.07
4.23
5.77
6.10
4.73
5.67
5.60
3.73
4.50
4.60
5.30
5.20
- 106-
-------
Experiment 12-18-73
indoetry
initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
dry air
liquid temperature
i'ime into .Lxpcrinent
(minutes)
0
5
10
petrochemical - fibers( chemicals, A plastics
pure waste
300 gra
42 gra
: .
143 ml/min
0.6 ftVnin
air bottle
25° c
Analysis Concentrations
TOC
(ppra Carbon)
464
430
413 .
20
25
30
33
<0
'5
50
55
CO
393
380
374
362
364
368
-- 107 -
-------
iixperinent 12-21-73
industry
initial concentrations
initial weight charje
water vaporized
ii'Miic. TJ.CV; rate
air I'.vv; rate
dry air
temperature
I'line into r^cpcr incut,
(ninutcc)
0
s
10
petrochemical - 1,3 butadiene
135 0^ pure ivacte
300 cjm
42 gm
133 mi/in in
0.6 ft /inin
air Lottie
25° c
Ar.al.ysia Concentrations
TCC
(ppm Carbor.)
53
50
40
34
34
33
50
55
60
51
44
33
-108-
-------
i^cperiment 12-27-73
components
initial concentration
initial weight charge
water vaporized
-i^uiu i'low rate
air fiov; rate
cry air
tiquid temperature
Time ir.to K
(minutes)
0
5
10
15
n-butonol water
approx 1000 ppm
300.3 em
40.6 gm
144 ml/min
0.6 ftV^m
dry air
25° c
Analysis Concentrations
I\.C
(ppn Carbon)
302
266
216
25
30
35
40
45
50
55
60
156
120
116
94
-109-
-------
Experiment 1-2-74
i i. due try
initial concentr.ition
initial weight charce
water vaporised
iiquiu flow rate
air l'iow rate
dry air
liquid temperature
Time into Experiment
(.niimtc'j)
0
r,
J
10
petrochemical *,2 dichloroethane
920.7 gm pure waste
300.4 gm
40 gm
1 S6 ml/min
0.6 ft /min
air bottle
25° c
Analyais Concentrations
TOO
(ppn Carbon)
60.6
48.9
33.5
20
30.6
30
35
40
45
50
55
60
30.4
29.7
28.8
30.4
34.1
- 110-
-------
iixper intent 1-16-74
industry
initial concentration
initial weight char£b
water vaporized
liquid flow rate
air flow rate
dry air
liquid temperature
J.TM into
(minutec)
0
5
10
15
20
25
30
35
40
pharmaceutical waste (?)
pure waste
300.7 en
40.7 gm
123 ml/rain
0.6 ft3/min
air bottle
25° C
Analysis Concentrations
TOG
(ppra Carbon)
1854
1846
^760
1680
1586
1564
50
55
60
1.538
1516
1470
- Ill -
-------
Experiment 1-18-74
industry
initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
dry air
liquid temperature
Time into experiment
(minutes)
0
5
10
oilfield - natural gas blow pit waste
pure waste
300 gm
41.5 era
1 30 rai/min
0.6 ft
air bottle
25° c
Ana lysis Concentrations
TOC
(ppm Carbon)
102.4
*5.4
97.2
20
25
30
35
40
45
50
55
60
i/8.6
99.0
101.4
102.0
101.4
100.6
-112-
-------
Experiment 1-20-74
compor.onts
Initial concentration
initial weight charge
water vaporized
liquid flow rate
eir flow rate
dry air
liquid temperature
Tine into ^
(min)
0
5
10
20
30
40
50
55
60
n-butanol water
tpprojc 1000
300.6 gm
46*6 gn
144 nl/min
0.6 t
air bottle
25 cc
An*ly»ie Concentrations
TOO
(cpn Carbon)
388
302
268
224
190
156
130
112
96
-113-
-------
Experiment 1-21-74
components
initial concentration
initial wej^ht charge
water vaporised
liquid fj.ow rate
air 1'low rate
ury air
liquid te.Tipe rat lire
1'ime into Ocperi.~e;.t
(mir.utec)
0
5
10
15
20
25
30
35
40
45
50
55
60
n-butanol - water
approx 1000 ppra
300.3
-------
Hxperinent 1-22-74
concentrations
initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
dry air
liquid temperature
Tine into Experiment
(min)
0
5
10
20
30
40
50
55
60
n butanol water
apprcx 100O ppm
300.3 gm
54.1 em
158 ml/min
0.6 ft
air bottle
25 °c
Analysis Concentrations
TOC
(ppm Carbon)
396
353
328
284
258
210
178
144
108
-115-
-------
tixpericcnt 1-25-74
component:;
initial concentration
initial weight charge
i/ater vaporised
.Liquid flow rate
air flow rate
dry air
liquid temperature
Time into IX
(nin)
0
5
10
20
30
40
50
55
60
n-butanol - acetyl alcohol
- water
approx 1000 ppm (n-butanol)
50 ppm (acetyl alcohol)
300.3 gm
40.6 c"i
154 ml/min
0.6 ft
air bot»le
25 °c
AnaXvais Concentrations
TOO
(ppm Carbon)
342
370
338
266
250
216
183
150
150
- 116-
-------
iicpcriment 1-28-74
components
initial concentration
initial weight charge
water vaporised
liquid f.'.ow rate
air flow rate
dry air
liquid temperature
Tine into rlxperiner.t
(min)
0
5-5
10
20
30
40
50
55
60
n-butanol - water
- sodium tetradecyl Bulfate
approx 100U ppm (n-C.HQOH)
50 ppm (NaTIE) 4 *
300.7 en
40.1 gn
156 ml/nin
0.6 ft
air bottle
25 °c
Analysis Concentrations
TOC
(ppn Carbon)
398
366
352
300
254
220
180
172
156
- 117-
-------
Experiment 1-29-74
components
initial concentration
initial weight charge
water vaporized
liquid flow rate
air flow rate
dry air
liquid tenperature
into Experiment
(min)
0
5
10
20
30
40
50
55
60
n butanol water
sodium phosphate
- dibasic htpt a pi
appro* 1000 p^ra
10/*1 (sodiun phos
(DB
te),
300.3 gm
40.1 gm
154 ml/min
0.6 tt
air to i tie
25 °c
AnaXysis Concentrations
TOG
(ppm Carbon)
374
360
338
288
236
222
168
166
146
-118-
-------
APPENDIX B
COMPUTER PROGRAM TO CALCULATE F° AND K$/a
FOR INDUSTRIAL WASTEWATER SAMPLES
Reproduced from
best available copy. \3Sjp
-119-
-------
r *
T t \i~
r <~ ' P" r r <; THf-~ l'| Tj'i
f--,' t M >'."-. A .| » r p-> «r * T,-v( T . " . , f "* Tfvr ptc»-||iy) « *> Tl'~ c
ATIVr V 11 AT »|. 1 7 «T' TO "AT= | <»- ».T \( .-) '.
PUT ;y T.|cr) rt-r-i ncr ,->-.«OT j ~v sync? » vcs T J|TL< ^ »: «!>!' "''
!?'rIJ'\T;M M rri '«f<"ci^r v^<; T r«-; *s TCO ,
r = T;>?- n|_ T ' ' T r f ' .*" . . "3» TMII-J) » V|-U;t| r 1 1 r r?^r T t '
T-.|r. \fi|4Tf|C £: f, r r i*?i vr.y nr. roT»j\;cr -»/ ^t | JT " > r » T r
p r-jrki II-ITTV, T!-^ WI'^IL1" Fc-*r.T»f'» ' "i TM'- 1 1| 1 t -. ' c
O'I\*ITITV -"I1" Ti.r '">r,-.-1>|r j-r» ]M~or;\»n«- .-/- .«_.^ T j 7- tr « T c t-i
C = ro;r> T- r^ir T '. v CT'/i
L-
A
.IT 1 «; 11 -;° Tf -i --e. trr r .1
| «n/oi »*«" I-.-.HT ,jr T in'-. T|.i
fx/rTr-T ei. M'l*"". T r> i >- m t -jr pti_
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7 K «i o.».Tr. Tijt^ |*,M.'' -c.
fS fW" '. * I ' '- T -«" P'lT- -T»-" '"!F^ronT| ,-:, :ir t-L.-r , o r > * I
TV T'! T .>.:!' rr voi ii CMT T^» TI.C O'.TC -ip r /.>''" *.T » r ir
u.^Tfo^ r.ji; ;» » r "^ Tr '> t 5 fv
ir K / « i -_ r>r«Tf.% TJ*.. .,MiTv
: iv^i'ii T:. r I\T .jE'iT -'. JPu - T--» P.--;; t>T\- >i/f».--tr » »- ^ >.' -| *"»i -
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i^ rr.-iM TI n»-tTV ' lr«<: **-*.»: :l%llTy '-4'-»i />.!«> n .> F > o t >.;
''|'-.; ' <;> | ^ ^ -nr p."fTi
t -i A--V inc i- A T T v.i TU-T
vt-n -.70 M.r.. '"r-
f«-rr-j «; T.;-I ? i ' / T' -?
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vT f : i: : | '.VT f "!? c. "T f *"; r
:!: '; ..... : : ft « 'r » ' * f 1^
i \'fi / T «
» r-tr r>-«rr c r , ' i Tic T I -' IT ^ Tl r- » * - .» > Y "'
r
r
r
r
, .. t . i ,
r f "..^T -c -i ( -" i :*, rr ';i~ f « >«» ( cr 5-«.\T : I ^ . /« I . "I' r. ' t " |
li^r ^r^.^tv/, *-i| * T ! f. T j c f i_<; ^M'* r>.-rric..^ r>i: -"liTntiT frxll|
t r i" T ''Ti r.o"; »<-: tf<"--\T <"f5f* i-'.'j T1-" v j**.'t r. > 'T <'. TA
"-!<; in cr.nri. ( ^rs 4» r : f i ) , TM= cas-.'c. -._ ...f = -> v^»''»" T 7«-f>
r:|Tfvr, rue ryntn |vr.,r (riCMJT. riT.M, Tut J.Mf'tM <-.'-ft"s
re :'\rct rn^rrr, T" TMC r»p cnppr j r -\f *>» V ^Ti|<; |r~,r>-.«iT; C 1
«» t -\.f oi|^ T|MC T»I 'ifiMT.--^ fctr>4»r« c\
riitT *\r» cniirapir; c^en r IMT,\ |-- TU=
:rt. T t M= T*T^ IHTitVr" «=*"« ^»»ii|-.c
r ^YOCI? tMrf. t , THr TT.»t \iifjut > -v
r.- fv TI.IC
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TMC
PI
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-120-
-------
t t .
/. i 7 r » 7 ' r (", i
r, >r> ? T - r .-.,.:-, u ^ «" i i ». i - i . '«»)
f, . s = ": \r t i»i , i -.'.»
7 -- ''< S.n i 1 i, «.> ' .--r . -JT
'r.^fi \~; t.--t '*'> ": *« i rrr*1. 4\pi I.;AT-^
J : » "> | i T < " » I T J i r; f c i»c y , r ~r; r I
M Tt
1 1
ve; I Tc»r . A7 )
rno-«»7(/jv«
fin <:/. t .-. 1 . !-
-1 »« t I T f C f '
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-125-
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APPENDIX C
Hollow Fiber Device As A Desorption Apparatus
Preliminary investigative tests were performed on a device that may be an alternative to
the packed column desorption apparatus. A Dow Hollow fiber Gas Permeator was
purchased. The device consists of a U-shaped bundle of hollow silicone (dimethyl silicone)
rubber copolymer fibers in a 100ml. poly-methyl-pentene beaker (Fig. C1). This device is
designed for bubble free transfer of a wide variety of common gases in gas-liquid transfer
operations. Common applications include: O2 enrichment from an air stream, oxygenation
or carbonation of fermentation broth, and removal of waste gases (i.e., CO2) from sealed
environments.
The gas permeator has several characteristics that makes it attractive for desorbing
gases from wastewater samples. The device is compact and can be weighed on laboratory
scales to obtain water loss information. A simple apparatus is possible since o pump is not
necessary for the liquid. A stirrer-bar keeps the liquid sample well mixed at all times. Figure
C2 shows the equipment arrangement employed to test the gas permeator as a gas
desorption apparatus for wastewater samples.
The operating procedure employed was as follows:
1) The test solution was prepared with an approximate concentration of 1000 to 1500
parts per million ot the desired volatile component in distilled water.
2) The permeator was filled with test solution (-75 ml.)
3) The permeator, with magnetic stir-bar, was weighed.
4) The permeator was set in place, ano inlet and outlet air lines were connected.
5) The magnetic stirrer was activated to a reading of four to five.
6) The air was turned on and regulated to a pressure of ten to twelve psig. The rotarreter
was set at a constant rate of 80 on a scale yf 100.
7) One mitliliter samples were taken initially, after 15 minutes, 30 minutes, one hour, and
at appropriate intervals thereafter (usually one or one and a half hours). ''
8) Finally, the permeator and contents wore weighed again to find the water loss.
Three components were employed in the preliminary test on the gas permeator. Table
C-1 shows the total organic carbon results for the three components tested. It is apparent
from these results that this device may have limited use on gas desorption studies of
wastewater. Experimental results on these three volatile components with the 46 cm. X 5
cm. raschig ring packed column allow a comparison of desorption rites between the gas
permeator and a packed column (Table C-2'i.
It is also apparent from this data that the tube wall (40 micron) may be providing an
added resistance to the transfer ot me volatile cpecies from the liquid to the gas phase. High
molecular weight components may not be able to permeate the tube wall or may react or he
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Polyurethane 1 ube Sheet
Recirculation Port (Open to Beaker)
Silicons Rubber Copolymer
Hollow Fiber Bundle
Nominal Diameters
180x260 Microns
Nominal Wdi Thickness
40 Microns
Nominal Area500 cm1
Beaker Container
(Poly Methyl Pentene)
Nominal Volume - 100 ml
Protective Screen
Magnetic Stir-bar Chamber
Recommended Stir-bar
I'/z" Cylindrical
(Stir-bar not included)
Gasket
Bottom Cap
Figure C 1. The Dow hollow fiber beaker gas permeator b/HFG-1.
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PRESSURE PRESSURE GAUGE
REGULATOR
I , , 1
AIR SOURCE
DRYING
FILTER
*- ROTAMETER
» TO HOOD
A A
SAMPLE PORT
__ HOLLOW FIBER
APPARATUS
MAGNETIC STIR-BAR
MAGNETIC STIRRER
Figure C2. Schematic diagram of equipment arrangement for gas permeator desorption experiment.
-------
TABLE C-1
Test Results Volatile Component Desorption in Gas Permeator
Component
Acetaldehyde
-
Methanol
Propanol
"
Time (hrs)
0.0
0.25
0.5
1.0
2.0
3.0
4.0
0.0
0.25
0.5
1.0
2.0
3.0
4.0
5.0
6.5
8.0
0.0
0.25
0.5
1.0
2.0
3.0
4.0
5.0
6.5
8.0
Per Cent Stripped Water Evaporated (g)
0.0
47.1
535
57.8
60.7
85.1
100.0
0.0
11.8
11.8
125
19.0
22.9
26.9
32.1
37.4
46.0 19.1
rate * 2.39 cc/hr
0.0
7.05
7.8
155
26.1
35.0
45.6
59.4
64.7 95
rate- 1.15 cc/hr
TABLE C-2
Relative Dteorptton Rates in 1-Hour Run Tim*
Component
acetaldehyde
n-propanol
methanol
Gn Permeetor
575%
7.8%
12.5%
Packed Column
73.5%
155%
21.0%
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absorbed by the silicone rubber copolymcr. Another disadvantage is that the tube device
does not simulate industrial stripping operations, as dees a desorption apparatus for
wastewater samples, however further detailed testing is indicated.
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