Journal of the Air Pollution Control Association

ISSN: 0002-2470 (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/uawm16

Solving a Major Odor Problem In a Chemical

Process

J. F. Byrd , H. A. Mills , C. H. Schellhase & H. E. Stokes

To cite this article: J. F. Byrd , H. A. Mills , C. H. Schellhase & H. E. Stokes (1964) Solving a
Major Odor Problem In a Chemical Process, Journal of the Air Pollution Control Association, 14:12,
509-516, DOI: 10.1080/00022470.1964.10468324

To link to this article: https://doi.org/10.1080/00022470.1964.10468324

Published online: 16 Mar 2012.

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 J. F. BYRD
Engineering Division,
H. A. MILLS,
Soap Process Development,
C. H. SCHELLHASE,
Engineering Division,
Procter and Gamble Company,
Cincinnati, Ohio,
H. E. STOKES,
Group Manager,
Procter and Gamble
Manufacturing Company,
Kansas City, Kansas
Nature of the Odorous Material
New and improved products for the
consumer requires new processes and
new chemical raw materials. Un-
fortunately, some of these new chemi-
cals have highly unpleasant odors.
This paper describes the control of a
highly objectionable odor from one of
these raw materials which we are han-
dling at our Kansas City Plant for ulti-
mate use in the manufacture of syn-
thetic detergents. Included in this
paper will be a discussion of methods
of actually placing a quantitative con-
cept on odor to determine the maximum
discharge of odorous material to the
atmosphere without creating an odor
problem. Our engineering design ap-
proaches to odor abatement, the failures
as well as successes, will be discussed
since our initial failures sired our final
successes.
The raw material we are concerned
with is di-methyl amine, [NH(CH3)2],
a gaseous material which boils at about
40°F at atmospheric pressure. The
nuiUTUil i< a fir<f cnu-in of ammonia
(XIIs) with two of tlio three hvdioiicn
:itoin< of ammonia irplured by two
"rniipiim-. ^C"IT:si.
Fig. 1. Medical syringe used for odor sampling
and measurement.
December 1964 / Volume 14, No. 12
Solving a Major Odor Problem
In a Chemical Process
CH 3
N—H
CH.3
Di-Methyl Amine (DMA)
At concentrations in excess of 100
ppm the odor of these amines are nearly
identical to that of ammonia. A slight
odor of NH3 in the process area can
appear most innocuous and harmless to
operating personnel. Unfortunately,
the material has Dr. Jekyll-Mr. Hyde
characteristics and, as its wafts its way
downwind, can take on an odor resem-
bling fish which has been too long in the
sun. As the concentration falls below
100 ppm the fish odor begins to pre-
dominate over the ammonia odor.
During the early design stages of
the chemical processing plant we were,
of course, quite aware of the unpleasant
nature of the odor. However, to design
odor control devices we needed a quan-
titative idea of the maximum allowable
Fig. 2a. Odor panel observer preparing to
eject odorous sample into nostrils.
quantities of di-methyl amine which
could be allowed to escape into the
atmosphere without causing an odor
nuisance 2500 feet away at the nearest
residential area. In essence, we had
to reduce the odor to quantitative,
objective values rather than the usual
qualitative, subjective, emotional evalu-
ations. A rational design basis is as
necessary for odor control efforts as
for any engineering project. There-
fore, the first part of this talk will
discuss our techniques for placing odor
on a quantitative basis. The first step
was to determine the concentration of
amines at the threshold odor value.
The threshold odor concentration of a
material is that concentration of the
given material in air which imparts to
the air a barely detectable odor.
Odor Measurement
Our approaches to odor measurement
and the determination of odor threshold
values are straightforward and sim-
ple.1' -• 3 From an atmosphere con-
taining a known amount of DMA we
withdraw 100 cc of the gaseous mixture
into an odor sample syringe (Fig. 1).
A small measured quantity of the
odorous gas is transferred to another
syringe—the mixing or dilution
syringe—into which a measured amount
of odor-free air has been drawn. The
dilution syringe is given to one of four
Fig. 2b. Odor panel.
509

Fig. 3. Obtaining amine gas sample of known
concentration for odor threshold determination.
or so observers on the odor panel.
The observer (Fig. 2a) inserts the tip of
the syringe into one nostril. He sus-
pends breathing and expells the 100 cc
of diluted sample into his nostril. The
observer then states whether or not he
detected any odor. Various dilutions
are made up and given to the observers
(Fig. 2b) until a concentration or level
is reached at which the observers barely
detect the odor. This by definition is
the threshold odor value. Any further
dilution results in a negative odor
pickup whereas any less dilutions will
yield an easily detectable odor. Usu-
ally no two panelists will agree on
exactly the same dilution value as the
olfactory senses vary between in-
dividuals. An average is taken of all
the panelists.
For example, let's assume we have
withdrawn from a 2000 ccflaskwith our
odor syringe a sample of gas containing
100 ppm DMA in air (Fig 3). This
quantity of DMA vapor in the flask can
be either measured directly using
straightforward analytical methods or
can be calculated fairly closely if we know
the DMA concentration in the water
solution in the flask. The calculation
is based upon the vapor pressure exerted
by DMA at various concentrations of
DMA in water. Let's say we found
that 200 parts of odor-free air was re-
quired to dilute one part of the gaseous
sample containing 100 ppm of DMA to
reach the average odor threshold of our
odor panelists. This 200 fold dilution
yielded a mixture of 0.5 ppm DMA
by volume, the odor threshold value.
Definition of Odor Units
Well, so we have determined the odor
threshold of di-methyl amine. So
what? Is the number of mere academic
interest? What does it mean in prac-
tical engineering terms? Of course, it
is obvious that a threshold of .5 ppm
by volume says in effect that if 1/i
cubic feet of gaseous DMA is mixed
with 1,000,000 cubic feet of odor-free
air the resultant mixture will just barely
have a fishy odor at the odor threshold
for the average nose used in the odor
panel. This does not tell us whether
Mrs. Jones at her cottage 2500 feet
away will wrinkle her nose when 10
pounds per hour of material is released
510
to the atmosphere from the process
area. Using the odor threshold value
as a basis we must place some quantita-
tive value on odor in order to apply the
various atmospheric diffusion equations
for predicting odor intensities at various
downwind points. Therefore, a pre-
requisite to any such calculations is a
concept of the unit of measurement of
odor. The odor unit has been estab-
lished and defined; one odor unit is the
amount of odor necessary to con-
taminate one cubic foot of clean air to
the threshold or barely perceptible
level.1-2> 3
For instance, if a sample of an emis-
sion contained 10 odor units per cubic
foot the figure merely means that one
part of the sample can be diluted with
nine parts of odor-free air, and the
resultant mixture will still contain a
barely detectable odor. In this ex-
ample, the 10 odor units per cubic foot
is analogous to a dust loading figure,
i.e., it is a concentration but it states
nothing about the total dust emission
in pounds per hour. Therefore, as in
the case of particulate discharges, it is
necessary to know the flow in the duct
or stack. The product of the total
flow times the odor intensity gives the
total odor emission.
To be specific, if an odor source had
a concentration of 10 odor units per
cubic foot, and the rate of flow of the
odorous gases was 10 cfm, then the total
odor output would be 100 odor units
per minute.
Now let's get down to practicalities.
Calculations of Carrying
Power of Odor
What is the effect of 10 pounds per
hour emission of DMA to the atmos-
phere in terms of odor intensities at the
front porch of our hypothetical Mrs.
Jones 2500 feet away? Ten pounds per
hour of DMA is equivalent to about
85 cubic feet per hour of this material.
10 lbs DMA/hr
X 379 cu ft/mole =
45 lbs DMA/mole
85 cu ft/hr of DMA
As you recall from the measurements
of odor threshold, .5 ppm by volume
is the threshold odor value or, saying
it another way, 1/2 cubic feet is capable
of contaminating 1,000,000 cubic feet
of odor-free air to the threshold odor
value. Therefore, our 10 pounds per
hour DMA released to the atmosphere
in tnis example will contaminate 168,-
000,000 cubic feet of air per hour or
2,800,000 cubic feet per minute.
85 cu ft/hr DMA
X 106 cu ft =
V2 cu ft
168 X 106 cu ft/hr
or 2.8 X 106 cu ft/min
As you recall, this latter figure is by
definition equivalent to 2,800,000 odor
units per minute. Now we have an
actual expression for quantity of odor
discharged which can be plugged into
the various atmospheric diffusion equa-
tions.
I will now briefly discuss three of the
equations which have yielded for us
fairly reliable values. They are the
Bosanquet-Pearson stack diffusion
equation, the Halitsky expression for
discharge of gas from roof type vents,
and Sutton's equation for a continuous
point source. In very general terms
these expressions are all very similar
in several respects. The downwind
concentration of the odor (or any other
pollutant) is inversely proportional to
wind speed and inversely proportional
to some exponential function of the
distance from the source of the pollu-
tant. This exponent is somewhat less
than the power of two. However, good
approximations for the purposes of esti-
mation can be obtained by assuming the
odor concentration varies inversely as
the square of the distance from the
source of odor. The Bosanquet-
Pearson stack diffusion equation, of
course, also takes into account the
height of the emission. The ground
level concentration at any given point
at ground level being inversely pro-
portional to an exponential function
roughly the square of the height of the
emission above ground level.
(1) We have applied most frequently
in the Bosanquet-Pearson stack dif-
fusion equation which, strictly speak-
ing, is applicable to stacks. However,
assuming about a 25 foot average level
of odor emission above the ground from
our various process vessels and a ju-
dicious choice of proper atmospheric
diffusion constants, the equation checks
fairly closely observed values as well
as those calculated from Halitsky's
data on roof vents and Sutton's con-
tinuous point source equation. We
utilize the following form of the equa-
tion:
The Bosanquet-Pearson Equation (4)
1000M 1
vx* x
where
Co = "average maximum" concen-
tration odor units per cu ft
where one odor unit is threshold
odor concentration; Maximum
values of one to five minute
duration every y 2 to one hour.
This value is five to 10 times
an overall "average" value of
30 minutes duration.
M = total emission in odor units
per second
Journal of the Air Pollution Control Association
 ODOR CONCENTRATIONS AT GROUND LEVEL VS. DOWNWIND
DISTANCES ( by vorious olmospheric diffusion equations)
Fig. 4. Downwind odor concentration at
ground level comparison of various diffusion
equations.
X = distance from source—feet
V = wind velocity—feet per second
h = ht. of odor source, assume
about 25 feet for an average
figure from process area.
(2) Halitsky Vent Equation (5)—
Normally applicable to roof vents but
can be more generally applied for good
approximations quickly arrived at.
D = M(3.16 + OAR)*
D = number of dilutions at distance
R equations. However, for unusual mete-
R = distance in vent diameters—
for general cases an assumed
value of 12 inches for vent
diameter will yield realistic
dilution values and facilitates
calculations
M = turbulence coefficient—value of
three conservative except for
extreme cases of poor mixing
where one is used. Formula as-
sumes eight mph wind.
(S) Sutton's equation (6)—Ground
level point source
2Q
X =
irCyCzUX2-"
where
3
X = odor units/cm —odor thresh-
old is still one whether ex-
pressed in odor units per cm3
or odor units per cu ft3
Q = odor units/sec—for use in this
equation multiply by 2.7 X 10"
to convert to cm3 from cubic
feet—Odor units is defined as
the amount of odor which
can contaminate one cubic foot
of odor-free gas to threshold
odor level. This same odor
unit can contaminate 2.7 X 104
cm3 of gas
U = wind velocity in cm/sec
X = distance from point source in cm
Cy = 0.4 cm1/8 (diffusion coefficient-y
direction-normal atm. condi-
ditions)
Cz = 0.2 cm1/s(diffusion coefficient-z
direction-normal atm. condi-
tions)
n = V8 (atm stability factor-nor-
mal atm conditions)
December 1964 / Volume 14, No. 12
Now let's see what happens to our
10 pounds per hour DMA as it drifts
downwind using these three equations.
Figure 4 reveals graphically the travels
of our whiff of odor, the 10 pounds per
hour DMA, which was discharged from
the process using the three expressions
discussed above. For something as rel-
atively inexact as atmospheric diffusion
equations, the calculated values of the
three equations are fairly close to each
other. You will note that up to about
1000 feet away from the odor source, the
odor is detectable. Beyond about 1500
feet the odor concentration under nor-
mal atmospheric conditions and moder-
ate winds (eight mph in this example)
is below the odor threshold of people
whose odor sensitivity is equivalent to
our odor panel which determined the
threshold odor of DMA. The calcu-
lated values obtained prior to start-up
checked fairly closely the observed
values of our many odor patrols through-
out the neighborhood under most condi-
tions. Our experience elsewhere prior
to this time confirmed the validity
of calculating downwind odor con-
centrations using atmospheric diffusion
orological conditions such as extremely
light winds (one to two mph) the odors
could be detected several times the
calculated distance, as far as 2000 feet
to 4000 feet away. So our hypothetical
Mrs. Jones should be free of the fishy
odor even during most abnormal con-
ditions although it is conceivable that
she could on occasion pick up a brief,
stray sensation from 10 pounds per hour
emission. Since downwind odor con-
centration is directly proportional to the
quantities of emission at our source,
observe what happens if our discharge
of DMA increased to say, 10 pounds
per hour to the atmosphere. The odor
2500 feet away is well above the thresh-
old. Mrs. Jones is no longer hypotheti-
cal but an irate reality as she calls the
plant manager to register her quite
valid complaint.
We must point out that these cal-
culations are, at best, very good ap-
proximations based upon equations
which were never designed to be exact.
Meteorological conditions and the hu-
man olfactory senses do not yield to
rigorous mathematics. However, we
at least have from these curves reason-
able design criteria based upon valid
calculations.
Process Odor Control—Phase I
You will note my use of the term
"Phase I." This Phase I of our odor
control efforts assumed that control
devices with usual conventional pre-
cautions would suffice to avoid a neigh-
borhood nuisance. Let's review our
engineering approach and take a look
at the results.
Basically, two waste streams are dis-
charged from the process. One is a
relatively small hydrogen stream rich in
amines and the other is a large hydrogen
stream rather lean in amines. The
first stream contains about 35% by
volume of amines and 65% hydrogen.
This mixture passes through a packed
water scrubber. The scrubber water
from the packed scrubber containing
about 15 to 20% DMA is discharged
to an amine recovery column. The
packed scrubber removes about 95%
DMA from the gas stream. It operates
at 50 psi. There is nothing unique
about this column. Conventional cal-
culations of mass transfer were em-
ployed. Coefficients of diffusion and
heights of transfer units for NH3 were
found applicable for amines.
A 95% removal of DMA in the water
scrubber is absolutely inadequate and
a severe odor problem would result from
the discharge of this material to the
atmosphere. Hence, the gaseous efflu-
ent from this water scrubber combined
with a stream of hydrogen mentioned
above containing only small amounts
of DMA was further treated in an acid
scrubber (Fig. 5). DMA reacts with
the acid forming a sulfate of di-methyl
amine which exerts no vapor pressure.
Therefore, practically complete DMA
removal and odor elimination was
realized. The spent acid solution bled
off from the acid scrubber was neutral-
ized with caustic. This reaction re-
leased DMA back to its pure state for
recovery in the recovery column. Na2-
SO4 was formed as a side reaction. The
effectiveness of this approach was estab-
lished by laboratory work.
So much for the actual control equip-
ment which was quite simple. There
is nothing extraordinary in our approach
at this point. We, of course, realized
that if allowable DMA discharge was
to be limited to 10 pounds per hour,
the performance of the scrubber was not
the only factor to be scrutinized. Amine
losses from leaking flanges, pump pack-
ings, and other potential sources must
be eliminated through proper equipment
design and maintenance. Routine in-
spection and maintenance procedures
were established which we hoped would
minimize the chances for major odor dis-
Fig. 5. Acid scrubber.
511

Fig. 6. Typical portions of processing area
handling amines.
charges. Figures 6 and 7 are evidence
of the extremely complex nature of the
process consisting of many potential
sources of amine leaks and chances for
misoperation as well as malfunctioning
of equipment.
You will recall that amines in higher
concentrations have a weak ammonia-
like odor which rapidly fatigues the
olfactory senses. Amidst many amine
leaks the operators of the process can be
living in a fool's paradise oblivious of
the neighborhood nuisance they may be
creating. Therefore, it was planned to
check for leaks on a routine basis several
times per week using SO2 bottles.
When SO2 is sprayed on an amine leak,
a visible cloud results. In addition,
routine odor tours at a distance of V2 to
one mile downwind were initially
planned on a twice weekly basis.
Pressure relief valves were discharged
directly to the atmosphere. It was
believed that enough instrumentation
and alarms were available to prevent
over-pressure.
The Results
Our approach seemed reasonable.
Normal precautions were taken for what
we believed was an average odorous
process. However, this was not a
normal "business as usual" type of
process but in some respects bordered
on the unique. During our start-up
period the usual minor malfunctions and
misoperations associated with getting
new equipment on the line created a
major odor incident. On some of our
worst days when the wind was not
favoring us we received over a half
dozen calls a day, some as far as several
miles away.
During the succeeding six weeks the
process was operated on a "stop and go"
basis as we tried to plug the gaps in our
odor control defense. During this pe-
riod of travail, the public relations as-
pects of the problem were as important
as the engineering approaches to solve
the problem. We made every effort to
keep the press informed of our actions
to correct the odor nuisance. The day
512
Fig. 7. Typical portions of processing area
handling amines.
the odor problem developed we called
the press before the odor was traced to
our premises.
We also took the initiative in making
sure the local government was informed
of developments at all times. We in-
vited the city, county, and state public
health officers to the plant to review the
situation with us. We were able to
assure these officials that the odors were
not toxic and in no way constituted a
health problem. We engineers de-
scribed the nature of the raw material
to the governmental authorities. The
maximum allowable concentration
(MAC) of di-methyl amine for personnel
safety is several hundred times higher
than the levels which were creating an
odor nuisance. Our factory Commu-
nity Relations Supervisor personally
visited every individual who called the
factory and would identify himself.
The public relations facets of this
odor problem would be a story in itself.
This paper concerns the engineering
approach to abating the odor nuisance.
I have merely touched upon the public
relations angle to emphasize its impor-
tance in a nuisance problem of this sort.
It is difficult to divorce the engineering
aspects and the public relations aspects
in a nuisance situation of this nature.
We had to have the indulgence of the
community to limp along for sufficient
time to identify our problems. Our
public relations people performed a
yeoman service for us.
Back to the Drawing Board—
Phase II of Process Odor Control
Just what did occur which created
the odor nuisance? I will discuss each
cause and the solution.
A side reaction aggravated by the
intermittent nature of the start-up
produced much larger quantities of
ammonia than originally predicted.
The recovery of ammonia along with
di-methyl amine in the water and acid
scrubbers resulted in a build-up of NH3
in the system. The ammonia did not
condense in recovery systems nor, once
formed, did it enter into further re-
FLARE STACK
Fig. 8. Pilot plant flare stack '/soo scale model.
actions. In effect, the NH3 acted as
an inert, noncondensible gas building
up in the system. The result was
over-pressuring of various vessels and
popping of pressure relief valves which
released to the atmosphere large
amounts of di-methyl amine along with
the ammonia. There are few, if any,
relief valves available on the market
which remain absolutely tight once they
discharge. Therefore, once opened re-
lief valves became chronic sources of
odor until the valves were reset.
As a temporary expedient during the
initial run, some waste gas streams
were routed to a separate once-through
water scrubber to remove this build-up
of inert ammonia in the system which
contributed to the discharging of relief
valves. The spent scrubber waters were
disposed directly to the nearby Kaw
River.
However, this water absorption was
impractical over the long haul for
several good reasons. The quantities
of DMA discharged with the NH3 were
great enough to render the scrubber
water excessively odorous in the sewer
lines until dilution in the Kaw River was
achieved. Neutralization of the amines
with H2SO4 could control the odor
evolved from the scrubber water but
the acid usage would be costly. More
important, the pollution load on the
Kaw River would exceed the proposed
legal limit in terms of biochemical oxy-
gen demand (50 ppm upper limit) and
dissolved solids (300 ppm upper limit).
These facts emphasize one concept
which we have become more and more
aware of—the close relationship of
problems of air pollution and water
pollution. Removal of air pollutants
by water scrubbing frequently merely
transfers a problem from the realm of
the air pollution control officer to the
stream sanitation commission. The
reverse is also true. This was no ex-
ception. We could discharge our wastes
neither up nor down. We were left with
one alternative—destruction of the
pollutants to innocuous compounds. In
a word, our only feasible alternative
was combustion. We decided that a
flare stack was our 1)est bet. A ground
flare as well as a furnace had certain
built-in risks of explosions due to
Journal of the Air Pollution Control Association

Total — H<, % . DMA
SCFM SCFM % Vol. SCFM
3.8 2.0 52.5 0.36
7.0 3.4 48.5 0.76
5.0 _ — 2.16
3.4 _ — 0.4
5.0 _ — .—.
fluctuating loads from our process flows.
A flare stack obviated these objections.
However, for effective elimination of
the nuisance problem, almost total de-
struction of the amines is necessary
because of the extremely low odor
threshold of DMA.
Flare Stack Design—
Pilot Plant Work
To determine the effectiveness of a
flare stack we built a small model pilot
stack for test purposes. A bunsen
burner was rigged to the stack to simu-
late the pilot flame. This model handled
flows of Vsoo the actual design flows.
A maximum of 7.0 cfm of the several
constituents of the exhaust gases were
metered to the pilot model flare stack.
These flows included various combina-
tions of hydrogen, di-methyl amine,
ammonia, nitrogen, and fuel gas. Fuel
gas is considered a necessary ingredient
at all times. Hydrogen normally pres-
ent would support combustion. How-
ever, we could foresee various process
conditions where the waste gases might
consist of no hydrogen but merely
purging nitrogen containing enough
amines to create a major odor problem
but not enough to support combustion.
These conditions could occur at any
time. Therefore, sweetening fuel gas is
required on a continuous basis in the
total effluent streams discharged to the
flare stack.
The various gases were fed from high
pressure gas bottles through calibrated
rotameters into a manifold and thence
to the model flare stack (Fig. 8). Feed
rates of the constituents discharged to
the flare during several test conditions
are shown in Fig. 9.
We checked the efficiency of odor
removal of the amines by three
approaches:
(1) Direct a small stream of SO2 at
the tip of the flame to determine vis-
ually if there were any remnants of
unburned amines. Amines combine
with SO2 to form a thick, white visible
fume. The test is a rather sensitive
qualitative approach. At the tip of the
ilame and around the periphery no
white fumes were noticed. At the
cooler base there was only the slightest
indication of the presence of amines.
{2) Odor tests—Observers in the im-
mediate area of the flame noticed no
sign of the distinctive fish odor. How-
December 1964 / Volume 14, No. 12
Pilot Plant Flare Stack Tests
FLOW (SCFM to Burner)
. •TMA- . — NH,
% Vol. SCFM
i %Vol. SCFM % Vol.
9.5 — 0 0.36 9.5
10.9 0.36 5.1
43.2 0.36 7.2
11.8
—
— 2.16 43.2 0.36 7.2
Fig. 9. Various test conditions for model flare stack.
ever, it was possible that due to certain
incomplete products of combustion of
the amines such as, say, oxides of nitro-
gen, a mild odor problem could remain.
We, therefore, took gas samples from
the periphery of the flame with our odor
syringe. These samples were taken to
an odor-free room for dilution as neces-
sary and observation by our odor panel.
A barely discernible odor was noted,
probably some oxide of nitrogen, but
the fish odor was, fortunately, con-
spicuous by its absence.
(3) Being engineers, however, we were
not completely satisfied with subjective
approaches. Engineers like to express
facts with numbers. So we actually
drew samples from the outer periphery
of the flame through a midget impinger
sampling train consisting of a midget
impinger containing .01 normality HC1,
a rotameter for measuring the gas sam-
pling rate, and an eductor to provide the
motivating force for the gas sample
(Fig. 10). Amine hydrochlorides were
formed in the impingers. In the labo-
ratory, these amines were evolved over
solid KOH in large excess within a
sealed chamber. The evolved gas was
then chromatographed. This techni-
que did show thy presence of several
parts per million amines in the gases of
combustion. While this quantity would
be too insignificant to be an odor prob-
lem at the closest homes and represented
a better than 99.9% removal, we still
should have detected this odor with our
noses since the odor threshold of amines
is much less than one ppm.
The reason for this apparent but
slight inconsistency is simple. The
gas sample collection tube had to be
manually held in the flame since the
Fig. 10. Midget impinger test unit for measur-
ing amine concentrations.
Fuel Gas
SCFM % Vol. SCFM % Vol.
0.08 2.0 1.0 26.5
1.48 21. 1.0 14.5
1.48 29.6 1.0 20.
2.0 58.7 1.0 29.5
1.48 29.6 1.0 20.
flame whipped about in the wind (the
tests were run outdoors for safety
reasons). Inadvertently, as the tube
was moved around in an attempt to
keep it in the dancing flame, some of the
sample was drawn from the cool inner
core of the flame where the amines still
existed in an undecomposed state.
Nevertheless, these quantitative anal-
yses for the amines with all their short
comings did confirm at least the near-
absence of amine. The possibility of
the formation of a black plume at our
flare stack consisting of unburned carbon
particles formed from thermal decom-
postition of the gaseous compounds and
incomplete combustion of these parti-
cles appeared to us as highly unlikely
because of the small ratio of carbon
atoms to hydrogen atoms and the low
molecular weight of the gaseous com-
pounds.7- 9 In practice this assump-
tion proved entirely correct. The flare
stack has not smoked.
Flare Stack Design
So we installed a flare stack in place
of the acid scrubber and never regretted
the decision (Fig. 11). The flare stack
purchased from the John Zink Company
is 100 feet high. The bottom section
is six feet in diameter by 10 feet high
and acts as a knock-out drum to remove
liquid material. The top two feet of
the stack is lined with castable refrac-
tory on the inside for protection against
heat from the flame. Similarly, the
upper eight feet is stainless steel. The
stack is designed to handle various
combinations of amines, ammonia, hy-
drogen, and nitrogen plus sweetening
gas, i.e., natural gas, to assure a com-
bustible mixture under worst conditions.
Fig. 1 1 . Sketch—full scale flare stack as
designed.
513
 Fig. 12. Flare stack in operation.
The addition of natural gas provides a
minimum of 350 to 400 Btu/cubic feet
of exhaust gases entering the flare stack.
We had been advised that 250 Btu/cubic
feet of exhaust gases is probably ade-
quate but our pilot plant tests showed
the need of a higher heat value to be
sure of combustion. We did not want
to risk a flame-out and a major odor
nuisance again. The stack was
equipped with four natural gas pilot
lights to assure ignition of all combus-
tibles released from the stack. Ignition
of the pilots is accomplished by a remote
"flame front" ignition system. About
400 feet of pipeline to the pilot light
isfilledwith a proper mixture of natural
gas and air. A spark is generated by a
spark plug and the flame is propogated
along the length of the pipe line to the
pilot lights. About 25 cfm of natural gas
is fed to the four pilots (Fig. 12 to 14).
Aside from the elimination of a stream
pollution problem and total destruction
of odorous compounds the flare stack
proved far more reliable than the pre-
vious odor control device, the acid
scrubber. The latter was, of course, a
chemical process requiring some atten-
tion. Several odor episodes were cre-
ated by malfunctioning or misoperation
of the scrubber. The troubles included
malfunctioning of the pH control,
failure to deliver acid to the scrubber,
flooding of the scrubber, clogging of the
recirculation pump with broken bits of
berl saddles, ad infinitum. Much oper-
ating and maintenance attention was
required by the acid scrubber. On the
other hand, the flare stack is given only
a bare minimum of maintenance and
operational time. It just keeps on
burning. After a year on the line there
has been no period of misoperation or
malfunctioning, resulting in flame out
and an odor nuisance. The amines
entering the flare stack have been to-
tally destroyed.
Pressure Relief Valve Discharges
Our earlier troubles during the first
runs (Phase I) involved frequent pop-
ping of pressure relief valves. We par-
tially solved the problem by bleeding
514
Fig. 1 3. Flare stack in operation.
from the system the NH3 which built
up in the system from a side reaction
and over-pressured some of the pro-
cessing and storage tanks. During our
first run we installed additional inter-
locks and alarms to avoid those mis-
operations which could over-pressure
the process vessels. However, in even
the best managed of families, relief
valves do discharge and once opened do
not reset well. We just could not af-
ford the risk of further major nuisance
espisodes. Therefore, in our revised
system (Phase II) the discharges from
all major relief valves are fed into a
16 inch collection header and thence to
two large storage tanks which act as
surge tanks to contain the discharges
from the relief valves. These relief
valve surge tanks meter their contents
slowly into the flare stack for destruc-
tion of the odorous organic material.
The normal emissions also pass through
these surge tanks which constitutes a
wide place in the line and therefore serve
the purpose of a knock-out drum to
remove any liquid from the gaseous
stream prior to discharge to the flare
stack. We wanted to avoid the possi-
bility of flaming particles of liquid
dropping down toward the ground.
One might be tempted to ask why
the surge tank for the relief valve dis-
charges. Why not pipe the relief
valves directly to the flare stack?
These relief valves were designed for
large peak flows and the discharge
from a number of these valves could
peak simultaneously. To have de-
signed the flare stack to burn the in-
stantaneous peaking of all these sources
at once would have resulted in a flare
stack of record breaking height, diam-
eter, and cost. One of the key cal-
culations in flare stack heights in-
volves flame lengths for given heat
loads.7'8 Safety dictates a flare stack
be of such height that the flame length
for the design heat load will not en-
danger life or property. A surge tank
to receive the relief valve discharges
obviates the necessity for the flare stack
to be so large and costly. Just as an
aside, toxic concentrations at ground
Fig. 14. Base of flare stack.
level in case of flame failure was not a
design criteria for the height of our
stack because of the relatively innocuous
nature of the waste gases.
These relief valve surge tanks nor-
mally operated at two psig or so. How-
ever, the maximum allowable pressure
of the tanks was set at 30 psig by our
safety people for various process safety
considerations. Combined surge tank
capacity was 3200 cubic feet. There-
fore, at 30 psig they were capable of
handling 6400 standard cubic feet of
emission from the relief valves. The
contents of these surge tanks could be
discharged to the flare stack at a con-
trolled rate so as not to exceed the
design capacity of the flare stack.
The one Achilles heel in this scheme of
things is the large relief valve protecting
these surge tanks. It discharges to the
atmosphere. The theoretical rate of
discharge from this relief valve was
tremendous, too large for a flare stack
of reasonable dimensions. However,
with our alarm and interlock system for
vessel over-pressures, we believed that
the over-pressure of our surge tanks
would rarely, if ever, occur. A year's
operation confirms this reasoning.
Storage Tank Vent System
A number of storage tanks operating
at or near atmospheric pressure con-
tain stocks normally free of odorous
amines. However, misoperation could
result in amine contamination of the
stocks in the tanks and odor discharges
to the atmosphere from the vents of
the tanks. We therefore collect the
vents of various groupings of tanks
and discharge them to the atmosphere
through a water scrubber. The spent
scrubber water normally is clean and,
therefore, sent directly to the sewer and
thence to the river at an outfall near a
heavily trafficked bridge. However,
short and infrequent periods of mis-
operation could result in a scrubber
water discharge contaminated with
enough amines to render the odor of the
spent water objectionable. Therefore,
all spent scrubber water passes through
Journal of the Air Pollution Control Association

Fig. 1 5. Flare stack control panel including ig-
nition points for four pilot lights.
a sewer neutralization system (Fig. 15).
Amines, begin similar to ammonia, are
basic and small amounts in the range of
perhaps a 1000 ppm can raise the pH
to nine or ten. Consequently, a pH
sensing device effectively monitors the
spent waters. Should amine be pres-
ent, sulfuric acid is automatically
metered into the spent water thus
neutralizing the amines and rendering
them innocuous as to odors.
Odor Inspections and Odor Tours
One of the chief sources of odor during
our first start-up was leaks from pump
packing, valve packing, flanges, etc.
Re-design of pumps and stuffing boxes
of pumps and agitators helped alleviate
this problem. Nevertheless, we decided
to have one man full time do nothing
else but police the equipment for leaks
using the highly sensitive SO2 test. The
intensity of leaks could be estimated
using the midget impinger unit described
above. Knowing the carrying power
per pound of di-methyl amine, we could
make some good educated guesses as to
how far the odor might be detected by
a given leak. Most leaks could be
fixed on the run. However, if the leak
was major and could be detected ac-
cording to our calculations over 2000
feet to 2500 feet away but could not
be repaired while the process was on the
line, our management's established
policy was immediate shut-down for
repairs.
To check on the effectiveness of our
operational and maintenance proce-
dures, we instituted an odor tour on a
twice per shift basis. These six daily
odor tours were conducted by trained
individuals from other departments with
no axe to grind. The odor patrols re-
mained objective and clinical in their
observations. If an odor is detected
over 2500 feet away and appeared major
in nature, the odor patrol has been in-
structed to use the radio-telephone
system provided in the company car
to inform the process foreman about the
situation. Otherwise, the report awaits
the patrol's arrival back into the plant.
December 1964 / Volume 14, No. 12
The plant manager, group manager, and
the department manager review the re-
ports regularly. This review tends to
spur the efforts to abate odor. One of
the key elements to our ultimate success
in eliminating our odor nuisance is the
attitude of the process operating per-
sonnel, both supervisory and hourly
people, toward odor control. Our
people have taken a personal interest
in maintaining an odor-free operation.
Summary
What were the results of all these
efforts to solve the odor nuisance prob-
lem? Our first start-up previously de-
scribed (Phase I) resulted in complaints
reaching upwards of perhaps 100 or so
in six weeks. We identified the prob-
lems and then shut down to take all
the actions which I have just described.
It was not in vain! In a period span-
ning one year we have to date received
perhaps a half dozen mild complaints.
Our improvement was by a margin of
several hundred fold. We decreased
the odor by at least several orders of
magnitude. The odor problem is either
negligible or nonexistent at the present
time. I think we can and should draw
some conclusions of a general nature to
serve as guide lines for odor control in
any complex process based upon the
experiences during our first abortive
run followed by our successful elimina-
tion of the problem.
(1) Odor should be placed as much as
possible on an objective, quantitative
basis rather than an emotional, qualita-
tive, subjective basis. This approach
proved invaluable to us in establishing
goals for the proper degree of odor con-
trol and indicating to us the extent of
an odor problem which might develop
from leaking equipment.
{2) All process equipment such as
pumps, valves, etc. should be designed
with odor control considerations loom-
ing as important in the minds of the
designer as the conventional considera-
tions of corrosion, maintenance, ease
of operation, cost, etc. Lavish use of
odor control equipment alone is not the
answer.
(3) Vigilant supervision must be con-
stantly exercised over both operation
and maintenance phases of the process.
Indoctrination of hourly as well as
supervisory people is indispensible to
successful nuisance abatement. Fre-
quent inspection of equipment and
neighborhood odor tours are excellent
checks on the effectiveness of an odor
control program. Our successful runs
after the first abortive start should be
credited to the efforts and attitudes of
the operating people, both supervisory
as well as hourly.
(4) Air pollution control equipment
must be designed as trouble-free as
possible. There is always an under-
standable tendency to neglect pollution
STORAGE a WORK TANK VENT SYSTEMS
X .,mKnM...nn
Fig. 16. Tank vent odor control and sewer
neutralization system.
abatement equipment because of the
pressures to meet production schedules
and quality control standards. This
leads to the need for consideration of the
normally much simpler combustion pro-
cesses as a means of odor eliminat'on
over the more complex chemical
methods.
(5) Solving an air pollution problem
can create a water pollution problem.
The two are frequently inseparable.
Again, destruction by combustion may
solve both problems.
(6) Sometimes an air pollution prob-
lem can be solved more cheaply and
effectively by certain revisions in the
process rather than by installation of
control equipment. This approach
should be investigated in the early
stages of design.
(7) Lab and pilot plant tests are
necessary pre-requisites to many forms
of odor control except the most con-
ventional approaches. Combustion
process must be checked out on a small
scale to ascertain whether complete
combustion of organic materials in a
given time at a given temperature is
possible. Furthermore, it is necessary
to determine if combustion results in
complete decomposition of the material
to CO2, H2O, N2, etc. If not, a knowl-
edge of the products of combustion is
necessary. The partially decomposed
compounds might constitute as much
of a nuisance as the original compound.
(8) Last, but not least, are the
public relations facets of the problem.
During nuisance episodes every effort
must be made to keep the citizens, the
press, and the regulatory agencies in-
formed of the situation. A candid
presentation of facts in the long run is
far more effective than a secretive, cloak
and dagger approach. However, words
are cheap. Ultimately, action and
progress toward solving the problem are
the best public relations of all. The
excellent handling of the situation by
our plant management and public rela-
tions people, however, allowed us time
to "cripple" along to pin-point our prob-
lems so that we could effectively and
quickly solve them without lawsuits and
injunctions.
It is hoped that our initial failures as
well as our ultimate successes as de-
515
scribed in this paper will be of help to
others in solving their particular odor
problems by the exercise of sound basic
principles applicable to any process.
Acknowledgments
Credit is due to Messrs. R. A. Hent-
ges, J. R. Smith, R. D. Walker, L.
Altamirano, R. K. Guthrie, R. C.
Peterson, Hugh Tassey, Ladd Duryea,
W. Daly, and others of the Procter and
Gamble Company for their contribu-
tions to the Odor Abatement Program
described in this paper.
REFERENCES
1. J. F. Byrd, "Demonstration—Syringe
Odor Measurement Technique," J. of
Air Poll. Control Assoc, 7: 58-59 (May
1957).
2. J. F. Byrd, E. L. Dewey, "Venturi
Scrubber in Odor Control," Chem. Eng.
Progress, 3 : 9, 447-451 (September
1957).
3. V. E. Gex, E. A. Fox, "Method of
Determining Odor Concentrations in
Air and Gases," / . Air Poll. Control
Assoc, 7: 60-61 (May 1957).
4. C. H. Bosanquet, J. L. Pearson, "The
Spread of Smoke and Gases from
Chimneys," Transactions of the Fara-
day Society, 32 : 1249-1264 (1936).
5. J. Halitsky, "Diffusion of Vented Gas
Around Buildings," / . Air Poll. Control
Assoc, 12: 2, 74-80.
6. O. G. Sutton, "Micrometeorology,"
McGraw-Hill, New York (1953).
7. F. T. Bodurtha, "Flare Stacks—How
Tall," Chem. Eng. Progress, 177-180
(December 15, 1958).
8. G. E. McElroy, C. E. Brown, L. B.
Berger, and H. H. Schoenk, "Dilution
of Stack Effluents," Technical papers
657, U. S. Dept. of Interior, Bureau of
Mines (1944).
9. A. G. Gaydon and H. G. Wolfherd,
"Flames, Their Structure, Radiation,
and Temperature," London, Chapman
and Hall, Ltd. (1953).
The Staff
At APCA Headquarters
Extends Best Wishes
For a Merry Christmas
And a Happy New Year
CLASSIFIED
ASSOCIATE AIR POLLUTION
CONTROL ENGINEER $677 to $842—
Fast growing area. Requires chemical,
mechanical or related engineering degree
plus 2 yrs. exp. in similar field.
CIVIL SERVICE DEPT.—Court-
house, San Bernardino, California
5T6
NEWS FROM THE CONTROL DISTRICTS
Bay Area
A new regulation to control organic emissions in the six county Bay Area Air
Pollution Control District was urged by the District's Advisory Council.
The need for such a regulation, which will affect industrial, commercial, residential
and agricultural interests in the Bay Area was determined after exhaustive studies by
the Council's Technical Committee and Ad Hoc Committee on Organic Emissions.
The Council approved the committees' report and directed the District's staff
to prepare a draft of a regulation for submission to the Technical Committee by
January, 1965.
According to the report 49% of the organic compounds that form Bay Area
smog conies from gasoline-powered automobiles, diesels and aircraft. Forty-one
percent is emitted by organic solvent
users, backyard burning, commercial Columbia University Drafting Re-
and apartment house incinerators, and search, under a U. S. Public Health
agricultural operations. The remaining Service grant, with the co-operation of
10% comes from petroleum marketing air pollution control authorities both
here and in other sections of the coun-
and refining, combustion of natural
gases, chemical and metallurgical opera- try. It became official after its adop-
tions, and ships and railroads. tion by the Air Pollution Control
In order to attack the smog problem Board and it is expected to become a
model for the nation.
effectively, the Council recommended
that the proposed regulation be timed The complete code is distributed by
so that all of the major sources would the office of: The City Record, 2213
be controlled concurrently. Municipal Building, New York, New
York 10007, at a price of Si.00; by
mail $1.10.
New York City
The Text of New York City's new
Air Pollution Control Code which be- MVPCB GIVES OUTLINE
came effective October 1 has been made
public by Commissioner Arthur J. OF FIVE WARNINGS
Benline. RE CRANKCASE CHECK-UP
By far the most sweeping provision
in the new code is that which restricts Five warning signals that call for
the sulfur content of fuel used in most checking of crankcase ventilation sys-
tems now on most newer model cars
apartment buildings and commercial
and industrial establishments. The have been outlined by Donald A.
provision spells out a staggered program Jensen, Executive Officer of the State
over a five-year period which requires Motor Vehicle Pollution Control Board.
"The things to watch for," Mr. Jensen
the reduction in sulfur in fuel oil and
solid fuel to three percent in the first said, "are fumes coming out of the
year. In 1965 the allowable content engine when the car is idling (lift the
will be 2.8 percent. By 1968 the per- hood to check), oil on top of the engine,
centage will drop to 2.5 and by 1969 it rough idle, excessive stalling in traffic,
will have been reduced to 2.2 percent. and engine hesitation.
The code, which expands the powers "If any of these are present, ask your
of the Commissioner in numerous ways, mechanic or service station man to
contains scores of changes. Some of check the crankcase ventilation system
the important ones which affect a large valve and tubes. This can be done- in
majority of the city's residents follow: a moment or two and save unnecessary
(1) Expands the jurisdiction of the concern over engine performance."
department to include air contaminants He said all that may be needed is to
such as smoke, dust, fumes and vapors. clean or replace the valve. Cost for
The department was originally created this work averages about $2.50.
solely for the control of smoke. Approved crankcase devices have
(2) Limits smoke from boilers, in- been on all new cars registered in Cali-
cinerators, etc., to a period of four fornia, starting with the 1961 model.
minutes per hour. This refers to No. Many used cars are also equipped, but
1 smoke, or smoke that is 20 % visible. the bulk of the used car population will
Previously there was no limitation on come under the mandatory installation
this degree of smoke, though smoke of phase of the law next year.
higher density was totally banned. Mr. Jensen said that starting in 1966
(3) Prohibits the idling of any motor every car with a crankcase device, and
vehicle for a period of more than three registered in a metropolitan county will
minutes. Idling motors, it was ex- require an annual inspection at an offi-
plained, emit prodigious amounts of cial station.
toxic and injurious gases. He pointed out that the device is like
Commissioner Benline said that the any other part of the car needing peri-
exhaustive code was drafted by the odic servicing.
Journal of the Air Pollution Control Association