THE INCINERATION OF

AQUEOUS WASTES
E. S. MONROE, JR.
E. I. du Pont de Nemours & Co., Inc.
Wilmington, Delaware
ABSTRACT
Three basic methods of treating aqueous waste by
incineration are covered. Examples of each type are gven.
A review of fammable zones is given. These are a critical
concept requirement in incinerating such wastes. Calcu
lated data are presented for the signifcant variables that
govern temperature and heat input. These can be used
to predict performance.
INTRODUCTION
The gowing emphasis on the reduction of water pol
lution in this country has had a pronounced effect upon
the feld of incineration. Once industrial incinerators
were applied primarily to fuels with self-supporting com
bustible characteristics and to a lesser degee to fuels with
only minor requirements for auxiliary fuel to satisfac
torily burn. Today H increasing number of incinerators
are being built to dispose of aqueous wastes which may
contain only traces of combustible material.
The source of these aqueous waste may include
processes which have a direct contact between the pro
duct and water, tank washings, spray condenser discharges,
etc. These wastes may vary from liquids that are essen
tially al water to liquids that are water with appreciable
percentages of other materials. The other materials
present may be toxic, materials with a high bacterial
204
oxygen demand, materials capable of producing turbidity,
or materials with excessive acidic or basic characteristics.
There are many established water treatment methods for
handling such wastes. While the many factors that affect
costs are too involved to be discussed here, there are some
situations where incineration is the economical way to
dispose of aqueous wastes.
BASIC TREATMENT METHODS
The three basic ways of incinerating aqueous wastes may
be characterized by the three states that heated water as
sumes. The frst of these may involve only the heating of
the aqueous waste. Although this is seldom a feasible dis
posal scheme, there are stripping or carbonation applica
tions. In these the contact of combustion products with
aqueous wastes, when added to other process steps, may
constitute a true incinerator system. An example is the
Schutt process shown in Fig. 1. [1]
The second basic aqueous waste incinerating method
covers the area of heating and partial or complete evap
oration. This is a very feasible operation and often covers
applications thought of only as heating. When submerged
exhaust combustion is used this method is the usual re
sult. The concentration of orgaic compounds with high
boiling points in the unevaporated water which is then
incinerated in a flame (Fig. 2) is an example of this second
basic method.
A third method of incineration is that of combining
heating and evaporation of the water and superheating of
the resultant vapor directly in a flame (Fig. 3). Combus
tibles present in the aqueous waste can be oxidized if the
necessary fundamental requirements are met.
RAW WASTE
WATER WITH
LOW BOILING
CONTAMINANTS
OFF GASES
TO FLARE STACK
COOLING
WATER
BURNER
TANK
WATER LEVEL
SUBMERGED EXHAUST DOWN COMER
WEIR
FIG. 1 SCHUTT PROCESS INCINERA TOR
STEAMING
VENT
AQUEOUS
WASTE
FEED
LIQUID LEVEL I
------ -- ------- ,----1 --
I 1
1 __ 1
PUMP
CONCENTRATED WASTE
AIR
SUBMERGED EXHAUST
WEIR
FIL TER
(IF USED)
FIG_ 2 EVAPORATING INCINERATOR
205
AIR
AQUEOU

WASTE
NATURAL
GAS
FURNACE
FIG. 3 SUPERHEATING INCINERATOR
BASIC CONCEPTS
VENT
There are certain basic conditions that must be fol
lowed in aqueous waste disposal if satisfactory results are
to be achieved. These are not always understood and
fundamental data are not generally available. If combus
tion is to be complete, the usual generalized requirements
of time, temperature, and turbulence must be within sat
isfactory limits. These are functions of burner and furnace
design and will not be dealt with here since they are well
developed in commercial designs. When water is added to

!
A
-----
v
IETAE ("
W
FIG. 4 FLAMMABLE ZONES AND WATER INJECTION
8

the combustion fame the requ

i
rement of fammability
limits (or more properly zones) assumes importance and
must be understood for successful results.
Fig. 4 shows a plot of fammable zones for methane
and oxygen. The Line AB represents the possible
methane-oxygen combinations in air. The point L77
represents the usually reported lean limit and the point
R77 represents the usually reported rich limit. Point S
represents the stoichiometric mixture. The points L, R,
and S are usually available from the literature (i.e., [2 and
3] ) but are usually based upon am bien t conditions. Once
combustion is achieved these limits are changed. The lean
limit will generally shift only a slight amount such as
shown by the subscripts on L1400 which represents the
lean limit at 1400 F. The rich limit will expand at
1400 F a greater amount as shown by the relationship
of R
1
400 to R77. There is a third point on the fam
mable zone which is of importance and this is the point
M. This point represents the minimum oxygen content
at which igition can be achieved at the indicated tem
perature. It usually lies on or near a line drawn from
point S, which is the stoichiometric air/fuel ratio, to the
zero ordinate and abcissa point. Point M is readily avail
able from the literature at 77 F but there is little or no
background information on this minimum oxygen limit
at higher temperatures. The point drawn as M
1
400 is
from the author's own experience.
It can readily be seen that once igition is achieved
and the operating temperature of the fame and its fur
nace increased, there is a much geater range of fam
mable limits and zones than occurs at the time of initial
ignition. In other words, a mixture which might not
ignite at all at room temperature will burn satisfactorily
after ignition is established and a higher temperaure is
attained.
Point C was selected for demonstration of another
important feature. It represents the air/fuel mixture for
methane with 30 percent excess air. On a dry basis the
combustion products would contain 5 percent oxygen
and no fuel and a line is drawn to this point from point C
to represent the combustion process. The gases at C are
within the 77 F flammable zone and wlreadily ignite and
burn. If we assume the same air/fuel ratio of point C but
with varying amounts of water added, we can investigate
the burning of aqueous wastes in fames. In order to plot
points similar to point C, the water was assumed to be
evaporated as steam.
Point D on Fig. 4 was assumed to have lIb of water
added for every 6000 Btu of gross calorifc value in the
fuel. The resulting decrease in the percentage of oxygen
206
and fuel present in the overall mixture of fuel, air, and
steam is shown by the location of the point D outside the
77 F flammable zone. If the steam, air, and fuel were
supplied well mixed, igition would be diffcult if not
impossible. The adiabatic fame temperature of this mix
ture is 1750 F and since point D is well within the 1400 F
fammable zone, the mixture should burn once furnace
temperature is established. It is necessary, therefore, to
ignite the fuel and air alone and then add water slowly as
represented by line CD to achieve a stable fame.
If more water is added until a ratio of 1 lb of water per
4000 Btu of fuel is achieved, the condition shown by
point E on Fig. 4 is reached. At this condition the adia
batic combustion temperature is 1400 F and theoretically
stable combustion can be maintained. While this is true,
in practice, the equipment must be well designed and
carefully operated.
If even more water is added until a ratio of lIb per
3000 Btu is reached, the condition shown by point F
results. Although point F is within the 1400 F fammable
zone, its adiabatic combustion temperature is only 1100 F
and combustion cannot be maintained. If the water in
jected in cases D and E contains traces of combustible
materials and the burner and furnace design are correct,
the combustible traces can be expected to be burned com
pletely if they are injected directly into the combustion
reaction. The water cannot be sprayed into the products
of complete combustion with any results other than
evaporation and pyrolysis of the waste.
This important and little understood point can be ex
plained as follows. Referring again to Fig. 4 and reassum
ing a 30 percent excess air mixture of methane (point C),
it was stated that the products of complete combustion
would be represented by the 5 percent oxygen and 0 per
cent fuel point. From this point it is possible to construct
the dash line marked fuel and dry combustion gas dilution
line. This line represents the possible combinations of
methane and the dry combustion products. Since no
point on this line intersects the known fammable zones,
combustion of the methane cannot and will not occur.
If the water used in case D is added an even lower line re
sults which has a maximum of 3.3 percent oxygen. If me
thane or other organics are present in the water added,
they will not burn if the water is injected after the initial
methane and air combustion is completed since no fam
mable mixture occurs.
In terms of the example gven, it can be stated that if
1 percent organics are added to the stream D and injected
with the methane and air in a single combustion reaction
of good design, the organics will be incinerated. It can



Z

also be stated that if the same water and organic are

sprayed into the products of combustion of the same
methane air fame, little or no incineration will take place
and the stack products will include the vaporized orgnic
and its pyrolysis products. If the aqueous stream impinges
on the walls of the incinerator, sufcient pyrolysis prod
ucts may accumulate to appear as aparks from the unit
when they are dislodged.
TREATMENT BY HEATING ONLY
Calculations were made to determine the variables in
volved when the aqueous waste was only to be heated with
combustion products. These calculations are relatively
simple thermodynamically but are tedious since a trial and
error solution involving the partial pressure of the water
vapor is involved. A computer progam was written to
perform the calculations for each of the three states of
water in equilibrium with combustion products. It was
found that only the heat input in Btu/lb H20 was a sig
nifcant factor and the results are show in Fig. 5. Where
dilute organic wastes are involved with water and they
have low boiling temperature characteristics, the Schutt
system shown in Fig. 1 has application. This system is
Il

0
I

/
-

NITI L T F
. .
20 3 4 50 6 70
BTu/LB WATR
FIG. 5 TEMPERA TURE VERSUS HEAT INPUT FOR
HEATING WATER
8
207
described in detail in [1]. Combustion products from
submerged exhaust burners strip the organics from the
waste liquid. A partial condenser removes the evaporated
water and the orgnics are passed off to a fare stack or
other combustion process to be burned. If the flare stack
has the proper combustion conditions which produce a
fammable mixture, the gaseous organics will be incin
erated. Since a minimum of auxiliary fuel is used to heat
the water, this system is advantageous where other com
bustion processes, flames, or fares are available to dispose
of the off-gas.
Submerged combustion can also be applied to aqueous
wastes to carbonate them. Carbonation, pH control, or
both, may be used to achieve desirable chemical reactions
which improve the aqueous stream before it is discharged
or treated further. While the choice of fuel does not af
fect the Btu/lb water required to heat the water, it does
affect the CO2 produced and should be taken into con
sideration.
It should be noted on Fig. 5 that with 100 percent ex
cess combustion a, evaporation wlstart to occur at
about 109 F while a temperature of 132 F can be achieved
without evaporation at zero excess combustion a. Fig. 5
should not be used at heat inputs above the excess a
limits shown in the dotted portion of the curve.
TREATMENT BY SATURATED VAPOR HEATING
When evaporation with combustion products occurs, a
second variable becomes signifcant in addition to heat
input in determining the fnal temperature. This is
excess air. The reason that excess air is important is that
the increased partial pressure of the unconsumed oxygen
and its accompanying nitrogen reduce the partial pres
sure of the water vapor being evaporated. The computed
results for the evaporation condition are shown on Fig. 6.
The type of fuel used was not found to be signifcant.
At atmospheric pressure and with no excess combus
tion a, a maximum boiling temperature of 191 F wl
occur and with 100 percent excess combustion a, the
maximum boiling temperature will be 176 F. For all
practical purposes a maximum heat input of 1400 Btu/
lb water wl achieve complete evaporation regardless of
the excess a used. This is shown by the vertical line at
the upper rigt of alexcess air cures where evaporation
is complete. There are many incinerator applications for
the operating range shown on Fig. 6. If an aqueous waste
contains organics with high boiling temperatures and the
orgnic wlnot evaporate at the temperatures shown,
then the organic can be concentrated as shown in Fig. 2
and sprayed into the combustion fame to burn the or
ganic. The heating value of the organic will reduce the
amount of auxiliary fuel required to provide the 1400
Btu/lb water needed for complete evaporation. For ex
ample, under adiabatic conditions, a mixture of 5 gallons
of No. 6 fuel oil and 95 gallons of water could be evap
orated and incinerated with an auxiliary fuel input of
only 455 Btu/lb water.
. _ 5 gal x150,000Btu/gal
Heat RequI
red
-
1400
-
95 gal x 8.34
5Ib/gal
455 Btu/lb water
Another area of application for saturated vapor heat
ing is that of solids emission control and recovery. If the
I

,
| |
|
,
.,..... . +

+
'
| I
| ,
,
--. '' + . ..
,

- - + - + = ..
:, - ~- +-<
IIRM
E
M I1ARTS.

= _

_
.... -

E
!CS
AIR

:_ 1 j
A I R
4V AIR

,
,

. AIR
.i-

|
B

W
:
;
I

'

' IHIIIAL JMF

lX
|
,
, '
lM

^^ =
'
1
,
** ~ .,

I
|
,
~ ~ ^ ^ + +

.
. Air
|

:
|
l
_
W .r W .m
BTULB. WAlR
FIG. 6 TEMERATUREVERSUSHEAT INUT FOR
EVAORATlNG WATER
208
aqueous waste contains a metallic ion it w generally be
come an oxide particle of submicron size in a combustion
fame. Such particles are difficult to trap but submerged
exhaust combustion can often reduce the emission level
to 0.2 gr/cu ft. If submerged exhaust combustion is fol
lowed by a high efficiency scrubber, good recovery of the
metallic particles is possible. It is frequently desirable to
recover these particles either because they are toxic and
cannot be discharged into watersheds or because they are
valuable materials. High efciency separators or filters
are expensive and if the arrangement shown in Fig. 2 is
employed, the size of the separating equipment can be re
duced since the residual oxides are concentrated in the
small amount of aqueous waste that is recirculated and
Hltered.
These two examples are only indicative of the many
applications possible for evaporative incinerators without
superheat. They should always be considered when pos
sible because they require a maximum of 1400 Btu/lb of
water and frequently less. They are often criticized be
cause the evaporated water at 191 F or less results in a
visible plume of steam. This water vapor is not an air pol
lutant and should not be considered one any more than
the vapor plume from a cooling tower or a steam jet ejector.
HLNLN Y 5ULHHLN VOH
If the aqueous waste is injected into a fame properly
according to the principles previously stressed, the water
will be superheated as well as evaporated. For this con
dition a third factor was found to be significant. This third
factor is the hydrogen content of the fuel burned. The
relatively high specifc heat of superheated water formed
by the combustion of the fuel's hydrogen cannot be ig
nored. Figs. 7a, 7b, and 7c represent the computed results
with three carbon to hydrogen fuel ratios by weight. Fig.
3 shows a typical burner which can obtain equilibrium
combustion of organics in aqueous streams. A perusal of
any of the three Figs. 7 show the relatively high auxiliary
fuel requirements. If we re-examine our previous example
of a waste consisting of 5 gallons of No.6 fuel oil and 95
gallons of water and assume it is to be fired with auxiliary
natural gas fuel to provide 1750 F with 30 percent excess
air, we find from Fig. 7b that 4700 Btu/lb of water are re
quired. The credit for the fuel oil is the same as previous
ly and 3755 Btu/lb of water are required from the auxiliary
fuel. This is 8.0 times as much auxiliary fuel as the evap
orative incinerator required. This example emphasizes the
problem of fuel consumption for direct fame incineration.
With 100 percent water the ratio is over 5 and it increases
4w
W
W
lW
!w
#W
6w
W
4w
W
M
r-
\W
/

I
lBS CIBS
I''"A , ..
W
BlllB kTEk
FI6.Tk
W
W
EXC S$+|
9
I0
'

80

I.M
=

W
W
8W
W
W
W
W
M
\W
11

f
1
I
l

y
4w
Jw
M
W
W
W
6W
W
W

W
EX

w

f-
lBS CIB Kg
I J
\W
BTUIB kTEk
FI6.(L
.0
.

FIG. 7 TEMPERATURE VERSUS HEAT INPUT FOR
SUPERHEATING WATER
7a - C/H= 233
7b- C/H = 4.0
7c- C/H= 9.0
209

E CESSAl

~
0

B

L
40
60
80

F-

lBS CIBS +.0

IhlT|kL TEW = W
9.W
BTUIB. kTEk
FI6.Y8
to infinity as the heating value of the aqueous waste in
creases.
Another short-cut method for predicting the auxiliary
fuel requirement for direct flame incineration can be made
by using Fig. 8. This Figure shows the percent of a fuel's
heating value that is available at various combustion con
ditions. For 1750 F and 30 percent excess air an avail
ability of 40 percent is read from Fig. 8. If lIb of water
is heated to 212 F from 60 F it will require 152 Btu. To
evaporate at 212 F an additional 970 Btu are required. To
superheat to 1750 F with a specific heat of 0.5 requires
769 more Btu for a total of 1891 Btu/lb water. Using the
availability figure of 40 percent from Fig. 8 we fnd that
4730 Btu/lb of water are required. This answer is in good
ageement with the result of 4700 Btu/lb obtained from
Fig. 7b.
It is not to be concluded that superheated vapor incin
eration should not be used because the fuel cost w be
hig. In fact the system shown in Fig. 2 uses it at the
burner. It is also quite applicable for small streams where
I0
w
,

O
7
O
* "
-
7

%
O
c
C0w IcuI8tM
Wlth EE$$ 8lr
P `U
08t0r8I @
0
l0
|
|

lw X w
C0Y805Tl0h RYPEkkT0kE ~!
FIG. 8 EFFICIENCYOFAUXILIARYFUEL
X

210
the relatively high fuel costs may be less than equipment
depreciation and maintenance costs required for more
complex systems. For large size streams a careful evalua
tion of the superheated vapor incineration versus the
evaporating incinerator should be made.
The choice of auxiliary fuels for superheating vapor
incinerators is a subject of debate. It is relatively easy to
install dual gas guns and water atomizing nozzles in a
single air regster and to obtain quality combustion. Dual
oil and water nozzles in a singe regster suffer some de
terioration in performance since the two atomized sprays
interfere with one another. This can be compensated for
in units with a flame holding diffuser at the end of the
atomizing nozzles by greater turbulence produced by
higher than normal burner regster mpressure drops. The
author has also had some success with direct mixing of
either No. 2 fuel oil or solvents directly with the aqueous
waste into a singe line prior to atomization m a single
nozzle. Oils requiring heating for proper atomization can
not be used in such an arrangement.
UONULU5lON5
1) Every effort should be made to apply proper com
bustion fundamentas when aqueous wastes are disposed

of by incineration. These include the flammability zones

for which there is need of more fundamental knowledge
in the vitiated regon.
2) Of the three methods of treating aqueous wastes,
viz., heating evaporation, and superheating, none w
serve all applications. Each must be evaluated for each
specifc application.
HLLHLNUL5
[1] Schutt, . C., and Loftus, Jordan, "Waste Water Recon
ditioned by Carrier Gas," O/andLm]cutna/, Vol. 64, No. 32,
August, 1966.
[2] Coward, . F., and Jones, G. W., "Limits of Flammability
of Gases and Vapors," Bureau of Mines, u//etnNc. 50J, U. S.
Government Printing Offce, 1952.
[3] Zabetaris, M. G., "Flammability Characteristics of Com
bustible Gases and Vapors," Bureau of Mines, u//etnNc. 627,
U. S. Government Printing Office, 1965.