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THE USE OF O-CLOR BENZENE
IN SEWAGE TREATMENT

Thesis for the Degree of B. 5.
Edward J. Green
1935

  

         
     
  
  
    
  

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A Thesis Submitted to
The Faculty of
Michigan State College
of

Agriculture and Applied Science

Edward J. Green

A

candidate for the Degree

Bachelor of Science

December, 1955

ACKNOWLEDGEMENT

It was with the helpful suggestions of Mr. E. F.
Eldridge that the completion of this work was made
possible. The writer, therefore, wishes to express a
sincere appreciation to Mr. E. F. Eldridge for his

guiding aids.

101427

STATEMENT OF PROBLEM

The purpose of this study is twofold:

1. To determine the desirability of using O-Clor-
Benzene in the control of odors by preventing the pro-
duction of hydrogen sulfide in sewage.

2. To determine the effect of varying amounts of

O-Clor-Benzene on the rate of digestion of sewage sludge.

DISCUSSION OF PROBLEM

The problem at hand is an attempt to find some
use for O-Clor-Benzene, commercially known as Cloroben,
in the treatment of sewage. O-Clor-Benzene is an ob-
noxious by-product of most large chemical plants. Be-
cause of its preperties, manufacturers are not allowed
to Just "dump" it, and for that reason a market fbr
O-Clor-Eenzene is trying to be created. It already has
some value as a fly exterminator, but because of its
penetrating odor, its market is very limited. The ques-
tion then resolves itself into: Just what can be done
with O-Clor-Benzene?

In England the use of O-Clor-Benzene to control
the filter fly has been tried and satisfactory results
have been obtained.. If this be the case, then perhaps
there is a possibility that O-Clor-Benzene may be used
in certain types of mosquito control growth in ponds
and lakes as well as fly control.

Because of the fact that 0-Clor-Benzene is a by-
product, arm'literature concerning its origin or its
commercial life is at a premium. However, during the
summer of 1934, W. Rudolfs of Plainfield, New Jersey,
did considerable experimenting with it as it would be
directly related to sewage treatment. His experiments
were not intended to be exhaustive, but only sufficient

to show the merits and demerits of O-Clor-Benzene.

From the start the fact must be borne in mind that,
unless Cloroben is distributed throughout the testing
samples, no satisfactory results can be obtained. Good
contract between the particles can be obtained by thirty
minutes aeration or a rapid mix using a ten per cent
Cloroben solution in alcohol.

The first phase he considered was the effect of ‘
O-Clor-Benzene on coagulation, odor control, settlebility,
and bacterial reduction of sewage.

The treatment in this case was made by the addition
of an alcoholic solution of O-Clor-Benzene to sewage for
the purpose of obtaining a more rapid and finer dispersion
of O-Clor-Benzene. This was deemed necessary because any
reaction between the water in-soluble O-Clor-Benzene and
sewage particles would be solely a surface action. Frmm
a practical point of view this means of obtaining preper
dispersion is impossible for two reasons; first, the cost
is too great; and second, because of the fact that alco-.
hol is unstable in sewage. However, by the use of a do-
mestic sewage the B. O. D. was raised from 500 ppm. to
over 400 ppm.

The addition of an alcoholic solution of 500 ppm.
of 0-Clor-Benzene caused a reduction in total bacterial
count of 99.95%; 99% of the gas forming organisms; and

99.99% of the B-Cozi. A further reduction in amount of

O-Clor-Bensene; namely, 10 ppm., had no toxic effect on
the normal bacterial pepulation.

The odor of the sewage was changed with as small an
addition as 10 ppm. This change lasted for five days.
The original sewage odor then returned, but it was not
nearly so intense as the control. If the addition added was
to be 500 ppm., its strong odor was still prevalent even
after thirty days.

0-Clor-Benzene was found to have no effect on tur-
bity and settleable solids after a four-hour contact
period.

When Just plain sewage is allowed to stand we find
a marked change in the anaerobic digestion of sewage
after thirty days. The digestion is rapid and the aci-
dity decreases until the pH is below the favorable en-
vironment for bacterial decomposition causing foul odors
to emanate from the mixture and little or no coagulation
of solids. If, however, Cloroben is added, anaerobic
digestion proceeds at a much slower rate. The rate be-
ing set by the amount of O-Clor-Benzene that is added.
With the addition of 500 ppm. anaerobic digestion is
prevented.

In considering the effect of Cloroben on the settling
rate of activated sludge, it has been found that the rate

is increased in the initial stage; that it decreases as

time goes on and is practically lost after three hours.
If the activated sludge is in good condition to begin
with, there would be no point in treating it.

One of the most important phases of this subject is
O-Clor-Benzene's effect on aerobic decomposition in re-
spect to suspended solids, oxygen consumed, B. 0. D.,
and nitrification; and to determine the effect of larger
quantities of Cloroben on retarding or the inhibitation
of these activities. Any reduction in suspended solids
is negligible no matter what quantity of the chemical
is added. In oxygen consumed tests samples treated with
200 ppm. to 500 ppm. show marked increases (5% to 55%).
This indicates that Cloroben does have an inhibitory
effect on aerobic organisms. The effect is lost, how-
ever, on prolonged digestion.

By increasing the quantities of O-Clor-Benzene, a
slight inhibitory effect can be realized. The maximwn
reduction for 500 ppm. is about 17% which.persists from
five to fifteen days.

Nitrite formation is very active upon the addition
of small additions (0 to 200 ppm.) of Cloroben in the
early stages, but plays out as time progresses (twenty
days). With the addition of larger amounts (500 ppm.)
that activity is inhibited until the twentieth day when

it is extremely active.

If Cloroben is to break into the sewage treatment
program, it will be used as a substitute in most cases
for chlorine. For that reason it is interesting to note
Just what a comparison of the two chemicals will indicate.
An experiment on the comparative effect of chlorine and
O-Clor-Benzene on the prevention of hydrogen sulfide
production has been carried on and with interesting re-
sults. As far as possible the experiment was conducted
to more or less duplicate what normally occurs in a sewer.
That is, the treatment with O-Clor-Benzene and chlorine
was made after one hour of detention by "re-seeding", or
the addition of organisms capable of reducing sulfates
to hydrogen sulfide which normally are present in the
film surrounding a sewer pipe.

It was found that Cloroben treatment of 5 ppm. had
a slightly greater initial effect in the reduction of
sulfide production which remained for a longer period
than did the same amount of chlorine. This advantage
was lost, however, when the amount of chemical added was
increased to 10 ppm. and 15 ppm. at which points they
rode at practically even terms. Any increase in the do-
sage above those points was found to have little or no
effect on the Q-Clor-Benzene sulfide reduction while an
increase in chlorine treatments decreased the sulfides

produced in direct preportion. The sulfides produced

amounted to 1/2 to 1/3 as that produced by the control
indicating a fairly persistent retardation.

Thus for rapid flowing small sewerage systems chlorine
treatment from 33.3 % to 100% of the chlorine demand ap-
pears to be as effective as equivalent weights of O-Clor-
Benzene, and treatment to 200% of chlorine demand is
somewhat more effective than Cloroben whereas over longer

periods of contract O-Clor-Benzene appears more effective.

M ETHOD OF PROCEEDURE

Part I. Fresh samples of a typical domestic sew-
age (3.0082 ppm HzS) obtained from the East Lansing
sewage plant wcssused. Six three-liter samples were
used; (1) Control, (2) 10 ppm. of 07010r-Benzene,

(5) 20 ppm., (4) 50 ppm., (5) 40 ppm., (6) 50 ppm. These
samples were tested daily over a period of seven days

for the production of hydrogen sulfide. At the end of

the period of experimentation the other preperties, namely,
odor and appearance were also noted and the results re-
corded. Two such analyses were made.

The method of testing the samples for H23 was as
follows:

‘1. Pipette 10 ml of standard iodine (.025 n) solu-

tion into a 400 ml Erlenmeyer flask.

2. Add about 1 gm of pottassium iodine crystals to

flask.

3. From 5 liter sample pipette 200 ml sewage into

flask.

4. Titrate with .025 N standard sodium.thiosu1fate

using starch solution as the indicator.
Calculations:

10 - 3 3 #ml of sodium.thiosulfate used
#ml of distilled water used

10 - D

ppm. of HIS 3 S - D x 426
o o samp e

Part II. Six #10 cans were suspended at different
points in the settling channels of the East Lansing sew-
age plant for a period of one week. The samples were
then collected and intimately mixed in a large container.
Four portions of two liters each wereremoved and placed
in stoppered bottles so hooked up as to capture and re-
cord the production of any gases.

This experiment was allowed to run forti period of
four weeks with readings on the production of gases re-

corded daily.

control
10 ppm.
20 ppm.
50 ppm.
40 ppm.

50 ppm.

control

10 ppm.
20 ppm.
50 ppm.
40 ppm.
50 ppm.

Data - Part I

Trial I

Fresh Sewage 5.088 ppm. HIS

1 day
1.704

1.704

1.584 ,

1.598
1.598
1.704

5.515 6.688 5.645 5.645 4.567

2.556 5.452 2.806 2.728 4.785

5.621 1.971 1.555 2.875 2.257

2.172 2.252 2.150 1.917 2.769

2.620 2.252 1.598 1.661 2.876

2.875 2.252 2.545 1.704 1.917
Trial II

Fresh Sewage 2.982 ppm. 5‘s

1 day 2 day 5 day 4 day 5 day 6 day 7 day

‘2.875
5.725
5.500
2.770
5.085
2.770

5.255 4.575 4.620 5.725

5.085 5.725 5.680 5.085

2.150 2.555 1.855 0.960

2.445 2.555 2.490 1.855

2.660 1.811 1.980 1.540

2.875 2.555 2.555 1.490

5.854
5.514
1.065
1.278
1.278
1.065

2.449
5.854
1.176
1.490.
1.490
1.490

First Week
1

001903

Second Week

H

03015303

Data - Part II

Production of Gases

Typical of Sewerage

Chiefly'Q‘H4 and 0 02

Control

400
1600
2170
2900
5900

4420
5060
6100
6560
7240
8540

0
$00
800

1240
1660
2560

2760
5960
4780
5580
5860
7580

 

250ppm. 500 ppm.
0 0
200 40
740 110
1020 150
1200 140
1540 140
1800 140
2440 140
2580 160
2810 200
5070 200
5850 220

Third week
1
2
5
4
5
6
Fourth week

1

2
5
4
5
6

Control

8540
8620
9520
9620
9920

10,100

10,250
10,440
10,760
10,940
11,000
11,050

7580
7960
9080
9540
9920
10,220

10,480
10,810
11,150
11,570
11,410
11,440

Production of Gases - Continued

5850
4150
4950
5550
5950
6570

6740
7250
7950
8550
8770
9190

500 ppm.

220
250
240
240
240
240

240
260
260
260
260
260

 

 

 

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DISCUSSION OF DATA

A fresh sample of East Lansing sewerage was found
to contain about 5 ppm. of Has. In running sulfide
tests on the day following collection a considerable
reduction in the sulfide content was found. This re-
duction was due to the presence of combined sulfides.
From that time on the control sulfide content was
steadily increased, the enichment being due to the
reducing of inorganic sulfates. In a region where cal-
cium and iron are present in greater quantities a change
such as this will be even more marked.

A similar procedure was evident in the 10 ppm.
sample, but in the other samples 0~Clor~benzene left the
sulfides in a combined state. This was due to the steri-
lization of the samples by Cloroben. From this it is
obvious that organisms appearing in the sewage are not
resistant to dosages of 0-Clor-Benzene greater than
20 ppm. This is not true of organisms present in sludge.
It was found there thatciosages up to 250 ppm. could be
resisted. They do, however, fall victim to dosages of
500 ppm.

Cloroben does remove the typical odor of sewage in
samples greater than 30 ppm. in the sewage and 300 ppm.
in the sludge. In the place of sewage odor we have the

penetrating odor of O-Clor-Benzene, and it is a question

of tastes as to which of these two is the least desirable.

Another observation that can be made is that ap—
roximately equal retardation in sulfide production is
obtained in samples containing 20-50 ppm. of O-Clor-
Benzene. The sulfides produced in those samples amounted
to 1/2 to 1/4 of the amount obtained from the control
which does indicate a fairly persistent retardation.

The digestion of the sludge which was inhibited at
a dosage of 500 ppm. does not mean very much so far as
sewage treatment is concerned. Before any significance
can be attached to the results, it must be decided whether
a stunted digestion is worth while. A prolonged storage
of sludge may be desired before disposal. If such be the
case, 0-Clor-Benzene in a quantity great enough to pro-

duce 500 ppm. could be added.

G ICNEFAL C~')NCLUS IONS

From Part I.

l. O-Clor-Benzene is effective in holding down the
production of H 8 for a period of six to seven days in
dosages greater than 10 ppm.

2. It was found that somewhere between the dosages
of 10 ppm. and 20 ppm. was the line of demarcation where
0-Clor-Bensene has a sterilizing effect on sewerage. A
black sludgy percipitate was present in the 10 ppm. sam-
ple but absent in the so ppm. sample.

In the control, 10 ppm. and 20 ppm., only the
clear liquer persisted While in 30 ppm., 40 ppm., 50 ppm.,
the colloidal material remained in suspension. This would
indicate a growth of organisms able to remove any colloidal
material present.

5. In the control, 10 ppm., 20 ppm., and 50 ppm.
samples, there was present the sewerage odor in varying
degrees. It was very strong in control and dwindled down
to merely a trace at 30 ppm.

From.Part II.

1. It was found the O-Clor-Benzene present in amownts
greater than 250 ppm. prevented the digestion of sewage
for a period of four weeks.

The sample containing 250 ppm. was held back con-
siderably for four weeks, but at the end of that time it

was throwing off the effect of O~Clor~Benzene at a fairly

rapid rate. One hundred ppm. is retarded only in a small
degree throwing off all effects in seventeen days. Five
hundred ppm. may be termed an outer limit, inhibiting any
digestion what-so-ever.

The differences in the amounts of gas collected in
the control and 100 ppm. sample may be contributed to an
experimental error. An error was made in setting up the
control the first day which would compensate for any marked

difference.

BIBLIOGRAPHY

Reports of w. Rudolfs
July 1954
August 1934

October 1934

 

 

 

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