Manual On Industrial Water

STP148D-EB/Jan.
1960
CHAPTER V—TREATMENT OF PROCESS WATER

AND WASTE WATER
The purification of water for industrial heavier than water and causes them to
use can be very complex or relatively move downward and settle out. Surface
simple, depending upon the properties of waters contain varying amounts of sus-
the raw water and the degree of purity pended material, and this process is used
required. There are many methods and to clarify raw water either by simple
combinations in use, but all are covered sedimentation or with addition of chemi-
in three basic processes: physical, chem- cal coagulants. The tanks in which this
ical, and physicochemical treatment. action takes place are called sedimenta-
A fourth basic process, biological treat- tion basins.
ment, is often employed where waste Particle size, weight, shape, frictional
water must be purified before it may be resistance, and viscosity play an im-
discharged. This process takes ad- portant part in the design of such tanks.
vantage of the ability of living micro- Theoretical calculations usually are
organisms to induce a variety of chemical based on modifications of Stoke's law
and physicochemical reactions. Treat- and the assumption that the particles
ment of waste water is usually a much are spheres. M a n y factors must be con-
more complicated operation than the sidered in design, and all of these must
production of process water of appro- be modified as judgment and experience
priate quality. dictate. The theory of design will not be
This chapter discusses these processes given here; it will suffice to state that
as they are used in the treatment of in- effective clarification can be accom-
dustrial water and waste water and out- plished in tanks that are properly de-
lines some of the technical problems and signed and operated.
basic considerations involved. Settling basins may be constructed of
earth, wood, concrete, or steel. They
PHYSICAL TREATMENT may be rectangular or circular. The usual
Physical treatment pertains to those period of retention ranges from 4 to 12
processes in which there is separation of hr. Where the water contains large
impurities from water without chemical amounts of settleable solids, the basins
change. The common methods are often are provided with mechanical
sedimentation, straining and filtration, scrapers which move the settled sludge
multi-liquid phase separation, degasifica- to a sump from which it is forced out by
tion, dilution, removal of entrainment, the hydraulic head of water in the basin.
distillation and stripping, underground In other instances, manual sludge dis-
discharge, and ocean discharge. charge valves are provided to remove
some of the settled material; it is neces-
Sedimentation: sary to remove such units from service
Sedimentation is the process by which at regular intervals for thorough clean-
the force of gravity acts on particles ing.
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45-48
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56 M A N U A L ON INDUSTRIAL WATER
Inlet and outlet distribution of the surface where they are skimmed off.
fluid must provide for uniform flow in Effective separation is provided at mini-
the basin if efiicient operation is to be mum cost by this method.
attained. In rectangular tanks the
influent is distributed by a trough Straining and Filtration:
equipped with adjustable sluice gates or Strainers and filters m a y be used where
plug valves, and the effluent is usually it is necessary to remove floating or
discharged over a weir or series of weirs. suspended solids from water, either as a
Circular units are provided with a center further step after sedimentation or where
distributor and an overflow launder at space precludes installation of settling
the periphery of the tank. basins.
Short circuiting often plagues the Several types of strainers are in com-
operation of rectangular basins, thereby mercial use. Cloth, metal gauze, rotary
decreasing the theoretical retention time. drum, and rotary disk are the usual
This can be overcome by improving the kinds. Cloth and metal gauze filters are
inlet distribution or by effective use of used where the suspended materials are
muffle boards at the inlet and sometimes fairly fine and in low concentration.
just ahead of the effluent weir. Cheesecloth or similar material is rolled
Depending upon the character of the around a perforated mandrel and in-
silt and suspended matter, plain sedi- stalled in a cast iron housing. The water
mentation may provide as much as 70 passes through the iiUer into the drum
per cent removal; where coagulants are and the finely suspended material is re-
employed removals may be as high as 95 tained on the cloth. When the pressure
per cent. drop reaches a predetermined value the
Many industrial waste waters contain unit is taken out of service and the cloth
organic and inorganic settleable solids washed or replaced. These units will do
that must be removed before final dis- a good job of straining but are bulky and
charge. These solids respond to the have a fairly high loss of head.
process just described, and settling basins Metal gauze is becoming popular as a
of similar design are used for the pur- strainer. Here the size of the mesh can be
pose. Retention periods are usually much rigidly controlled down to several mi-
shorter than for raw waters, rarely ex- crons and selective straining can be per-
ceeding 2 to 3 hr. Long retention periods formed.
are detrimental where the soHds are all Rotary drum and disk strainers are
organic, because bacterial action may quite widely used for coarse separations.
take place. This may result in anaerobic The drum type comprises a rotating
conditions and the generation of odors. drum covered with a screen of the proper
The settled sludge will have a tendency mesh size for the purpose and installed
to float if considerable gas is evolved, inside a housing. The drum is driven at
and this will tend to nullify the opera- slow speed by an electric motor. Valving
tion. is provided to backflush automatically a
Air flotation is very effective for re- portion of the screen in its rotation and
moving flocculent solids that settle very thereby keep it clean. These units are
slowly or have a tendency to float. The built to handle u p to several thousand
air is dispersed in the liquid under pres- gallons per minute at a low pressure drop.
sure and the pressure released just prior This unit may be modified by replacing
to discharge into a receiving basin. The the screen with perforated porcelain
finely divided air floats the solids to the disks.
45-49
TREATMENT o r PROCESS W A T E R AND W A S T E WATER 57
A drum strainer is used where floating by backwashing. In other types the filter
solids must be removed from a waste material is deposited on a rotating filter
water. This is a drum frame covered drum in a fairly thick layer-. A doctor
with screen and rotated in a concrete blade continuously scrapes off a thin
channel. The water flows through the film and thus exposes a fresh surface.
screen and out of the center of the drum. Precoated filters have the advantage of
Provision is made for backwashing the high-quality efiEluent, low weight, high
screen as it rotates. This unit is for capacity for their size, and sometimes
gravity flow only. lower first cost. They have the disad-
The disk unit is a perforated disk set vantage of high pressure drop, high
at an angle in a channel where the water operating maintenance and repair costs,
must flow through the disk. The solids and rapid depreciation and obsolescence.
are scraped or brushed off the portion of Poorly designed units are often unde-
the rotating disk t h a t is above the water pendable in operation even in the care of
surface. This is a gravity-flow unit. a competent and reliable operator. A
Filtration of water is carried out in diatomite filter must have two to four
either pressure or gravity units contain- times the filter area of a sand filter of
ing graded sand, calcite, magnetite, equivalent capacity. Even with the larger
anthracite, charcoal, or finely-divided, area, the pumping power needed may be
relatively insoluble materials such as two to four times higher than for the
diatomaceous earth. Silica sand is the equivalent sand filter. There are nu-
most common filtering medium for cold, merous types of precoat filters which
neutral waters because of low solubility, employ a variety of precoat materials.
low cost, and the relatively high specific I t should be understood that filtration
gravity of sand particles. Pressure filters will not remove true color from water.
are usually designed for a down-flow rate This can be eliminated only by use of a
of 2 to 3 gal per min (gpm) per sq ft of suitable coagulant dispersed in the water
surface area, and a reverse-flow back- prior to filtration.
wash rate up to 18 gpm. The filter
medium usually is specified on the basis Multi-Liquid Phase Separation:
of effective size and uniformity coef- One or more nonmiscible liquids can
ficient. The effective size of filter medium often be physically separated from water
is usually specified to be not more than as a result of differences in specific
1.65 and is always greater than 1.0. gravity. Gravity separations of this kind
Crushed anthracite coal, because of its are performed on a small scale in lab-
relatively low solubility, is usually speci- oratory separatory funnels and on a
fied as the filter medium where hot, commercial scale in specially designed
strongly acid, or strongly alkaline waters equipment.^ The oil and water separator
must be filtered. The anthracite filter for oil refinery waste water is an example
medium usually is backwashed at lower of one large-scale application of this
velocities than sand of the same size. process.'-^
Anthracite filter medium weighs only Frequently there is not much difference
about 50 lb per cu ft, approximately one in the specific gravities of the liquids,
half the bulk density of sand.
' C. Ingersol, " F u n d a m e n t a l s a n d P e r f o r m -
Diatomaceous earth is often used as a ance of G r a v i t y S e p a r a t i o n , " Petroleum Refiner,
filter medium. In one type the diato- J u n e , 1951, p . 1064.
^ " W a s t e W a t e r C o n t a i n i n g O i l , " Manual on
maceous earth is supported by a porous Disposal of Refinery Wastes, A m . P e t r o l e u m I n s t , ,
stone or wire mesh element and removed Section I, 4 t h E d . (1949).
4.5-49
58 MANUAL ON INDUSTRIAL WATER
and one of them may be dispersed in a Degasification:

finely divided, globular state. Thermal Stripping operations, such as physical
convection currents under such condi- deaeration and aeration, are processes
tions may be strong enough to prevent for removing undesirable dissolved gases
efficient operation of the equipment. It from water. One or more dissolved gases,
is therefore always desirable to mini- such as oxygen,* carbon dioxide,^ am-
mize thermal currents by careful design monia, or hydrogen sulfide, are removed
of gravity separator systems. An equal- by exposing large surfaces of the liquid
izing basin ahead of the treatment unit to a vapor phase deficient in the gases to
will minimize temperature and other be eliminated.
fluctuations that may disturb proper
operation. Agglomeration of the dis- Degasifying equipment can be classi-
persed phase by chemical or physical fied as ebullition, tray or drip, and spray
means will greatly increase the efficiency units. In the ebulhtion type, a suitable
of the separator. gas is bubbled through the liquid for a
period sufficient to change the vapor
Centrifugal equipment is used for pressure equilibrium and enlarge the
multi-liquid phase separations where the liquid surface. This principle was widely
value of the separated product justifies used in the past for hydrogen sulfide and
the relatively high capital cost of the carbon dioxide removal; it is now mainly
equipment. Use of a centrifugal separator employed to separate carbon dioxide and
to remove traces of suspended water and oxygen in deaerating feedwater heaters
solids from lubricating oil is an econom- usually operating under a few pounds
ical application of this process. The pressure.
differential separating force between the
two or more liquids can be greatly in- Tray or drip gas-stripping equipment
creased with such equipment. The exposes large surface areas to the desired
strength and cost of the materials from vapor pressure conditions by slowly
which centrifugal separators are con- flowing the water in thin layers over
structed place a limit on their size and plates, channels, slats, or packing and
capacity. allowing it to fall or trickle in droplets
or thin sheets. Deaerating feedwater
Air flotation is widely used in this type heaters operate on this principle to re-
of separation. The oily water is put under move dissolved oxygen and carbon di-
a pressure of 30 to 50 psi and air is dif- oxide from boiler feedwater. The heaters
fused into the liquid. The pressure is re- are usually operated under a few pounds
leased just prior to discharge into a sep- pressure and at temperatures above
arating tank where the fine air bubbles 212 F. Degasifiers used to remove carbon
rise to the surface carrying the particles dioxide where alkalinity is controlled by
of oil with them. A rotating skimmer acid addition, or by blending hydrogen
sweeps the floated oil to a collecting zeolite effluent with sodium effluent or
trough from which it flows into a receiv- after cation exchange, operate on this
ing tank. These systems can easily pro- principle. Closed wooden tanks contain-
duce 90 per cent separation with very ing many stacks of trays allow the water
short retention periods, sometimes of no
more than 30 min duration.^ ^ J. R. McDermet, "The Separation of Dis-
solved Gases from Water," Transactions, Am,
Soc. Mechanical Engrs., Vol, 42, p, 267 (1920).
' A. M. Amorosi and J. R. McDermet, "The
2 A. H. Beebe, "Soluble Oil Waste Treatment Calculation of the Distribution of Carbon Diox-
by Pressure Flotation," Sewage and Industrial ide Between Water and Steam," Proceedings,
Wastes 7ol. 25, p. 1314 (1953). Am. Soc. Testing Mats,, Vol, 39, p. 1204 (1939).
45-50
TREATMENT OF PROCESS W A T E R AND W A S T E WATER 59
to drip down while air blown up through where the waste stream is small and
the tank escapes at the top. there is available considerable uncon-
Spray and spray-ebullition gas strip- taminated waste water (for example,
pers utilizing atomizing nozzles, ebulh- from cooling operations), the two are
tion, and entrainment to divide the water blended to conform with the concentra-
into fine droplets for exposure to the tion allowable in the plant discharge.
desired vapor pressure conditions are Where the amount of clean water is in-
finding wide use, not only in deaerating sufficient for diluting all the concentrated
feedwater heaters, but also with vacuum waste, any surplus of the latter is held
deaeration of carbon dioxide and oxygen for controlled discharge.
from cold water and ammonia from hot Controlled discharge takes advantage
water. Vacuum deaeration is carried on of the increased stream flows during
in one or two stages, usually in vertical winter months or rainy seasons to dispose
steel tanks where the vacuum is main- of concentrated wastes that would other-
tained by steam-jet ejectors. wise overload the receiving water. The
With the exception of vacuum deaera- wastes are stored in ponds and released
tion, some means must be employed to during periods of heavy runoff at a rate
maintain the partial pressure of the un- that will not exceed the allowable con-
desirable gases well below the point at centration in the river. This operation
which stripping will cease. In a gas- may require large areas of land for
stripping basin or tower, the air that is storage lagoons, but it is often the most
pumped or blown through the equip- economical method of handling the
ment carries the undesirable gas away to problem.
the atmosphere. Steam with a low partial When there is sufficient flow in the
pressure of free oxygen is the stripping receiving stream to assimilate the bio-
agent in deaerating feedwater heaters. A chemical oxygen demand (BOD) load
vent condenser is usually included to per- from high concentrations of organic mat-
mit the incoming feedwater to absorb ter, dilution can be utilized to provide
most of the heat in the stripping steam. satisfactory stream assimilation and to
eliminate areas of heavy oxygen deple-
Dilution: tion. This method has certain limitations
High salt concentrations in waste b u t it has been used successfully in some
water from the oil and alkali industries areas.
present a difiicult disposal problem. The dissolved salts and sludge in
Similar problems occur in other chemical evaporators, boilers, and cooling towers
plants where sodium sulfate and organic are concentrated in the circulating water
solids are present in high concentrations and these concentrations must be con-
in efSuents. Most regulatory agencies trolled by blowdown. Slowdown is thus
have set limiting concentrations in the a dilution process whereby concentrated
receiving streams that restrict the solutions and suspensions are replaced by
amount of effluent that may be dis- more dilute water. Intermittent boiler
charged. blowdown usually discharges directly to
Where inorganic salts such as sodium an atmospheric drain tank, with the re-
chloride, calcium chloride, and sodium sult that all of the heat of the liquid and
sulfate must be discharged, there are two of the flashed steam are lost. Continuous
methods in use. One is by dilution with blowdown systems make it possible to
uncontaminated water, and the other is recover this heat. Heat recovery systems
by controlled discharge. In those plants are available for both high- and low-
45-50
Flashed , per cent

54 50 45 40 35 30 25 20
800 1500
1 1 \j 1
\™ \ \A
700
\\\ /v 1 1400
1—\f
Flash Pressure
Curve s, psig
600 1300
500 1200
yf / \
400
'A \ I 100 ^
* \ CD
1 \
1 \
1 \
300
ii \ 1000
\ \ IOo\l50
1501
loo/ *///fy\\W" l\50 \
200 1 \\ 900
25///j 1 \
y^ /ciV-\A\\
100
5 10
/o
15
5\n \y
"WW
20 25
l\ 30
\
35
800
F l a s h e d , per cent
FIG. 1.- - F l a s h e d S t e a m R e c o v e r a b l e from C o n t i n u o u s B l o w d o w n S y s t e m s .
N O T E . — F o r boiler pressures b e t w e e n 100 a n d 800 psig, use " f l a s h " p r e s s u r e curves s l a n t i n g from
lower left-hand t o u p p e r r i g h t - h a n d corner a n d t h e b o t t o m axis. F o r boiler p r e s s u r e s a b o v e 800 psig,
use "flash" pressure curves slanting from lower r i g h t - h a n d t o u p p e r left-hand corner a n d t o p axis.
T h i s c h a r t is used t o calculate t h e p e r c e n t a g e of boiler w a t e r d i s c h a r g e d b y a c o n t i n u o u s b l o w d o w n
s y s t e m t h a t can be flashed i n t o s t e a m a t a r e d u c e d p r e s s u r e a n d recoverable a s low p r e s s u r e s t e a m
for h e a t i n g or process.
E X A M P L E . — A boiler o p e r a t e s a t a pressure of 450 psig. C o n t i n u o u s b l o w d o w n a m o u n t s t o 10,000
lb per hr. W h a t j^ercentage of b l o w d o w n w a t e r c a n be recovered as flashed s t e a m a t 5 psig pressure?
S O L U T I O N . — L o c a t e 450 psi on left-hand axis. Follow h o r i z o n t a l l y t o w a r d t h e r i g h t t o t h e i n t e r -
section w i t h 5 psi "flash" curve (point A). D r o p vertically d o w n w a r d t o t h e b o t t o m axis a n d r e a d
25.5 per cent. Twenty-five a n d a half per c e n t of 10,000 l b per h r b l o w d o w n = 2550 lb p e r hr of
flash s t e a m a t 5 psig pressure.
T h e s e curves h a v e been p r e p a r e d from t h e f o r m u l a :
Flashed steam, per cent = X 100
where;
HB = h e a t of liquid a t boiler pressure in B t u per lb,
Hp = h e a t of liquid a t flash pressure in B t u p e r lb, a n d
VF = l a t e n t h e a t of v a p o r i z a t i o n a t flash p r e s s u r e in B t u p e r l b .
45-51
T R E A T M E N T OF PROCESS W A T E R AND W A S T E W A T E R 61
temperature operation. Heat-recovery bination of these forces to remove liquid

equipment for high-temperature blow- and solid contamination. Preliminary
down may consist of a flask tank to washing of the steam by feedwater or
salvage flash steam or of a surface heat steam condensate may be used in steam
exchanger for transferring the blowdown separating equipment. Devices for over-
heat to the feedwater just before it enters coming entrainment of liquids in gas will
the boiler. Heat-recovery flash tanks or not appreciably separate a mixture of
surface exchangers for low-temperature gases, such as steam and carbon dioxide,
blowdown usually transfer the blowdown or steam and hydrocarbon vapors.
heat to the cold feedwater in or ahead of Entrainment separation efficiency in a
the deaerating feedwater heater. Heat- steam boiler is controlled not only by
recovery systems for high and low level the mechanical equipment, the steaming
blowdown can be used in series where the rate, and the water level in the boiler
over-all heat balance of the plant makes drum, but also by the surface tension of
such equipment economical. the dissolved solids and the liquids in
Figure 1 shows the percentage of the the boiler water. There is usually a limit
boiler water that is flashed to steam as it for dissolved solids above which, at nor-
is throttled from various pressures to mal steaming rates, priming and carry-
atmospheric pressure. I t also shows the over will occur. No general standard for
total heat of the boiler water at various allowable dissolved solids can cover all
pressures. types of steam generators. While oper-
Blowdown from cooling towers is often ators at one plant will insist that con-
called purge water. Windage or other centrations must be kept below 1000
water losses are sufficient in some cases to ppm dissolved solids, operators at an-
limit the concentration of salts of the other plant with identical equipment, but
cooling tower water. Where additional with different water conditions, m a y be
dilution is required, a continuous stream able to operate satisfactorily with 5000
of concentrated water is run to the waste ppm.
water system. The same general principles apply to
reduction of solids carry-over in the
Removal of Enlrainment: vapor from evaporators in process opera-
One of the fundamental problems in tions. This is especially important where
boiler design and operation is the me- barometric condensers are used to pro-
chanical separation of solutions and solids vide vacuum, because the tail water is
from the steam. All boilers must include usually discharged directly to the sewer
entrainment separators. The simplest and minimum solids are desirable to keep
method is to provide sufficient disen- product losses and the BOD of the waste
gaging space above the normal water line water to a minimum.
in the steam drum. I t is economical for
industrial steam generators to use dry Distillation:
pipes, baffles, or special types of sep- Distillation is the time-honored
arating devices to reduce the size of the method for preparing high-quality pure
steam drum. Most modern steam drums water. Both dissolved and suspended
are furnished with carefully designed and solids can be removed almost completely
proved internal equipment. Steam sep- by this purely physical process of evap-
arator equipment is mechanical in nature oration and condensation. The con-
and operates by gravity, centrifugal densate from a water distillation unit
force, and surface tension or by a com- with good steam separator equipment,
45-51
and at normal evaporating rates, should Distillation equipment should be so

contain no more than a few parts per designed that the scale and sludge pro b -
million of dissolved solids and may con- lem can be handled with minimum labor.
tain only a fraction of one part per mil- The problem is similar to that of a boiler
lion. The suspended and dissolved solids except that the temperature usually is
of the feedwater remain in the evaporator lower. Heat transfer rates at lower tem-
salines and are removed by blowdown peratures are more vulnerable to the
and descaling operations. insulating effects of scale and sludge de-
The high quality of its product gave posits.
the distillation process an initial ad- Extremely high quality distilled water
vantage over other processes for the can be obtained by multiple or fractional
preparation of boiler feedwater. Distilla- distillation. In the latter process, p a r t of
tion transfers a large part of the boiler the product is condensed and refluxed to
water treatment problem from the plant scrub entrained salts and solids from the
boilers to low pressure evaporators where steam being produced in the vapor
it can be more successfully handled. generator. I t is doubtful whether this
Single-effect and multiple-effect evap- quality will surpass that from a well-
orators have found wide use in plants operated mixed-bed deionizer.
where large quantities of low level heat
or exhaust steam otherwise would be Underground Discharge:
wasted. Low level, or so-called waste Underground discharge is a method for
heat, is not worthless; its cost is too often disposal of liquid wastes into permeable
underestimated in the over-all plant heat
strata in the earth. I t is a satisfactory
balance and in the original plant design.
method only in areas where other
Compression distillation equipment methods are extremely expensive or un-
may be economical where low level heat available. The permeable strata must be
is not available in sufficient quantity or so located that the liquid waste pumped
is being put to more valuable use. These into them will not contaminate strata
units, employing the heat-pump principle
used for water supply. These permeable
of salvaging the latent heat of evapora-
layers are very deep, 4000 to 5000 ft
tion, have the heat economy of 15 or more
being usual. Furthermore, injection wells
effects of multiple-effect evaporation.
are very expensive.
Compression stills may be electrically
driven or may be powered by prime The waste water must be sterile and
movers. Diesel-driven compression dis- free from suspended solids. Extensive
tillation units can produce from 150 to pretreatment is essential to remove silt,
250 lb of distilled water per pound of fuel suspended solids, oil, and emulsions.
oil. With diesel fuel at ten cents per Chlorination is generally provided to
gallon, compression distillation can pro- make sure that it is free from micro-
duce distilled water with a fuel cost of organisms. Additional pressure above
approximately 65 cents per 100 gal. that developed by the depth to the
In industries where only a few parts aquifer is necessary to force the water
per million of dissolved soHds are allow- into the strata; this may be as high as
able in the process water, either distilla- 200 to 300 psi.
tion or one of the deionizing processes This method has been used in only a
(discussed under Chemical Treatment) few locations because of the extensive
can be used. The choice will depend study required and the high cost of the
largely upon the concentration of dis- installation. I t does have its applications,
solved solids in the raw water. however, and should not be overlooked.
45-50
TREATMENT OF PROCESS WATER AND WASTE WATER 63
Ocean Discharge: ness to relatively insoluble calcium car-

bonate:
Ocean discharge of waste water is
practiced by plants in coastal locations. Ca(0H)2 -I- Ca(HC03)2 -> 2CaC03 -|- 2H2O
Actually, it is a dilution method. Con- The process can be carried out in either
sideration must be given to the path of batch or continuous equipment. In
ocean currents in the area of the outfall either type, close control of the lime
to insure that the waste water will not dosage is necessary to approach the
be carried to the shore and contaminate theoretical minimum hardness. Chemical
bathing beaches. The major cost for this cost is usually low if the lime particles
method is construction of an outfall to are sufficiently small and good agitation
such distance that safe disposal will re- is provided. Fine particles result from
sult. Toxic wastes or those with a high proper slaking of quicklime or thorough
BOD are usually transported by barge dispersion of hydrated lime.'
for release in deep water. Removal of carbonate hardness by
heating the water to drive off the dis-
CHEMICAL TREATMENT solved and half-bound carbon dioxide
Chemical treatment pertains to those accomplishes the same result as adding
processes in which separation of the im- lime:
purities from water involves chemical Ca(HC03)2 -f Heat -^ CaCOs -|- H2O + CO2
alteration of the contaminating material.
It may include precipitation, ion ex- Water containing noncarbonate hard-
change, sequestering reactions, gas re- ness is only partially softened by adding
moval, oxidation and reduction reactions, lime alone. Noncarbonate hardness can
chemical control of biological growths, be removed by adding soda ash (sodium
and sterilization. carbonate):
CaCk + Na2C03 ^ CaCOj -|- 2NaCl
Precipitalion: Soda ash usually is combined with lime
When certain soluble salts are added to remove both kinds of hardness in one
to an aqueous solution, some of the step. The two reactions can be carried
free ions may react to form compara- out simultaneously, hot or cold, in batch
tively insoluble compounds. The pre- or continuous equipment. A coagulant
cipitate can be separated by filtration or generally is used to improve the separa-
by decanting the clear liquid after tion of the solid phase.
settling. Precipitation occurs in ac- INIagnesium can be precipitated in a
cordance with definite laws governing lime-soda softener by increasing the
the combining weights of the reactants hydroxide alkalinity of the effluent to the
and their solubility products.' Many of point at which magnesium hydroxide is
the methods described below depend relatively insoluble. This can be ac-
upon precipitation of impurities. complished with hydrated lime or caustic
Softening.—The earliest commercial soda:
chemical precipitation process was the MgClj + Ca(0H)2 -^ Mg(0H)2 -t- CaClj
addition of hydrated lime (Ca(0H)2) to
MgCl2 -t- 2NaOH ^ Mg(0H)2 -|- 2NaCl
water for removal of bicarbonate hard-
ness. Lime converts bicarbonate hard- If magnesium is precipitated by lime,
there is no appreciable reduction in
" D. S. McKinney, "The Calculation of Equi-
libria in Dilute Water Solutions," Proceedings, ' R. D. Hoak, "How to Buy and Use Lime,"
Am. Soc. Testing Mats., Vol. 39, p. 1191 (1939). Water & Sewage Works, Vol. 100, p. 468 (1953).
45-50
64 M A N U A L ON INDUSTRIAL W A T E R
hardness unless additional soda is used but this can be reduced to about 25 to
to precipitate the calcium that replaces 30 ppm at 220 and to 10 at 295 F.
the magnesium. I t is economical in some Zero hardness is desired for boiler feed
locations to use caustic soda alone instead makeup, and it is evident that the lime
of lime and soda for precipitating mag- or lime-soda method will not provide
nesium. This eliminates lime-slurry feed- this. Phosphate softening following hot
ing problems and particle size difficulties. lime-soda treatment is often used as a
Theoretically, magnesium can be pre- second softening stage; it is used for
cipitated only as described above. At single-stage softening when the initial
several installations, however, where hardness is 30 ppm or less." The theory
high-calcium hydrated lime alone was involved is the precipitation of the
being used for calcium bicarbonate pre- calcium ion as the triphosphate, and in-
cipitation, it has been found that about soluble material:
60 per cent of the magnesium was being
3Ca(HC03)2 -f- 2H3P04 ^
precipitated, even though only a few
ppm hydroxide alkalinity was present. Ca3(PO,)2 -f 6H2O + 6CO2
This small amount was insufficient to
precipitate the magnesium as the hy- Any of the phosphates may be used;
drate, but certain unusual equilibrium they are added in aqueous solution.
conditions produced the unexpected re- Where the calcium hardness is mainly
sult. Total reduction of hardness was bicarbonate, phosphoric acid provides
within normal limits in these instances, alkalinity control as well as lower total
but the amount of calcium precipitated solids in the effluent. T h e reaction is
was less than normal. The operations carried out at a p H of 10 or higher with
were carried out in the cold in sludge- maintenance of a few ppm of hydroxide
blanket units. residual. The resultant hardness in the
treated water is about 1 p p m CaCO^ by
Most continuous process installations
gravimetric analysis. Caustic soda is used
for lime-soda or caustic soda softening
for precipitation of magnesium ion when
utilize accumulated sludge in suspension
phosphates are used to precipitate cal-
to promote growth of larger precipitation
cium.
particles. This arrangement carries the
chemical reaction and absorption pro- In the past, especially in European
cesses to practical completion in a short practice, barium carbonate was used in-
time. The unit for performing this opera- stead of lime for softening. This method
tion is known as a sludge-blanket pre- has not found favor in America where it
cipitator. In older plants, settled sludge is used in only a few specific instances.
was mixed vv'ith the incoming water to Internal Boiler-Water Softening.—Us-
produce the same effect. However, ef- ually it is unsatisfactory to depend upon
ficiencies were not as high as with the external softening alone for boiler
new units and the older method has been makeup water, especially for high pres-
more or less abandoned. sure boilers. Internal boiler water treat-
ment may be required to convert scale-
Temperature plays a very important
forming salts to soft sludges to be
part in chemical reaction. Where low
removed by boiler blowdown. Chemical
hardness is desired and hot water can be
compounds whose solubilities increase
used, as in boiler feed, temperatures from
with a rise in temperature can be made
220 to 295 F are employed. A hardness
of about 70 ppm is the best that can be ' E. W. Feller, "Fundamentals of Feedwater
produced at temperatures of 50 to 80 F, Treatment," Power. Vol. 91, p. 71, December, 1947.
45-51
T R E A T M E N T OE PROCESS W A T E R AND W A S T E W A T E R 65
to form nonadherent sludges;^ those During the decomposition of the bi-

whose solubiUties decrease with increase carbonates and carbonates, some of the
in temperature often form hard, ad- calcium of the boiler water is precipitated
herent scale. Internal boiler-water treat- as calcium carbonate:
ment in actual practice is far more
Ca++ -I- C O 3 - • CaCOs
complex than these general principles
indicate. This results from the wide The rate of decomposition of the bi-
variety of compounds and mixtures of carbonates and carbonates may be so
compounds that can be formed in the rapid at boiler pressures above 5 psig that
boiler, and from the effects of organic the calcium hardness is entirely precip-
matter and rates of evaporation on itated and the hydroxide concentration
crystal structure.'"' "• ^^- ^^ becomes excessive. This difficulty is
It is not desirable to precipitate large solved by using phosphates." Internal
quantities of minerals in a boiler, and softening with phosphates under proper
internal boiler-water treatment pref- conditions precipitates calcium hardness
erably should be applied as a supplement as tricalcium phosphate sludge.
to external chemical or physical treat- Iron, Manganese, and Chromium Re-
ment. Internal treatment alone may be moval.—Iron and manganese can be re-
satisfactory for low pressure boilers for moved by precipitation, using lime or
which only moderate amounts of reason- caustic soda to adjust the p H to the
ably soft feedwater are required. proper range. Ground waters often con-
Bicarbonates and carbonates intro- tain iron and manganese that must be
duced with the feedwater or with internal removed. These waters usually have very
treatment decompose in the boiler to little color or turbidity except that due
produce carbon dioxide in the steam and to those minerals. The iron is generally
to form hydroxides in the concentrated bound with carbon dioxide as the bi-
boiler water: carbonate, and aeration is a necessary
pretreatment to release the CO2 and
2HCO3- + Heat -^ H2O -t- CO3- - -1- CO2
precipitate some of the iron. The addi-
C O r -^ -h H2O -1- Heat -^ 20H~ + CO2 tion of alkali converts the ferric iron to
The hydroxides produced in this manner a hydroxide which settles out. For iron
can precipitate the magnesium in the alone, a p H in the range of 8.5 is suf-
boiler water as magnesium hydroxide: ficient, but when manganese is present a
2 0 H - -I- Mg++ -^ Mg(0H)2 p H above 9 is required. A coagulant is
generally required to aid subsidence of
^ Ralph E. Hall, et al., Industrial and En-
gineering Chemistry, Vol. 17, p. 283 (1925); Ibid., the precipitate. Chlorine is often used to
Vol. 21, p. 826 (1929); Technical Bulletin, Car- accelerate the rate of oxidation. Reten-
negie Inst., Vol. 24 (1927). tion basins are necessary for separation
^^ J. F . Barkley, "Questions and Answers on
Boiler Feedwater Conditioning," Bureau of of the precipitate. These may be followed
Mines, U. S. Government Printing Office, Wash- by sand filters to provide a satisfactory
ington, D.C. (1943). final effluent.
" "Central Boiler Plants," Technical Manual
TM5-660, Chap. 4, War Dept., U.S. Government Waste waters from plating operations
Printing Office, Washington, D.C. (1947).
^^ "Boiler Feedwater and Feedwater Appara- may contain chromium, usually in the
tus," Bureau of Ships Manual, Chap. 56, Navy hexavalent form. Chromium in this form
Department, U.S. Government Printing Office, is toxic to aquatic and human life; it
p. 56 (1948).
" D. S. McKinney, "Water for Steam Genera- must be removed prior to final discharge.
tion," Chemistry ol Engineering Materials,
McGraw Hill Book Co., New York, pp. 1-32 " R. E. Hall and H. A. Jackson, U.S. Patent
(1942). No. 1,903,041 (1933).
The chromium is first converted to the provide a satisfactory supply for process
trivalent form by lowering the p H to 2 and boiler feed uses. A preceding section
with acid and adding reducing agent described removal of cations by pre-
such as ferrous sulfate, sodium bisulfite, cipitation; this process had no effect on
or sulfur dioxide. The chemical reaction the anions present, and other means are
is as follows: required to remove them.
Certain insoluble substances possess a
2 C r O r - + 3SO2 + 4H+ ->
capacity for exchanging ions bound in
2Cr+++ + 3SO4- - + 2H2O their molecular structure with other ions
in water. The exchanged ions are released
The trivalent chromium is then pre- by regeneration of the exchange resin.
cipitated as the hydroxide with lime and Negatively or positively charged ions
p H adjustment to some value between may be exchanged, depending upon the
7.8 and 8.5. Residual chromium can be nature of the resin. A wide variety of
reduced to very low limits by this solid materials possess this reversible
method. property. A characteristic difference be-
tween ion exchange and precipitation
Emulsion Breaking or De-emulsificaiion: processes is that the frmer produces
Organic oil emulsions in waste waters only solutions for waste disposal while
present a disposal problem because the the latter yields both liquid and solids.
emulsion will contain considerable or- This important difference m a y be the
ganic matter with a high biochemical deciding factor in a choice of process.
oxygen demand (BOD), and breaking Disposal of sludge from a precipitation
the emulsion will release free oil which process may make it uneconomical as
may not be discharged to surface streams. compared with ion exchange. On the
In many cases these emulsions can be other hand, waste water from an ion
broken by acidification below p H 4, but exchange process may present a disposal
the resultant acid water is extremely problem.
corrosive and must be handled in acid- Natural and synthetic substances
resisting structures. p H correction is re- (zeolites) have been used for many years
quired after sedimentation and before to remove calcium and magnesium ions
discharge to the receiving stream. from water. These ions are then replaced
De-emulsification with calcium chlo- by sodium ions when the zeolite is re-
ride and adjustment to p H 9 with soda generated :
ash is a method that has gained accept-
Softening:
ance. The calcium chloride dosage is
high, about 2000 ppm, but exceptional Sodium zeolite -f- Ca++ ^ •
breaking and precipitation of the emul- Calcium zeolite -|- 2Na+
sion has been obtained with a resultant
high percentage recovery of oil. The Regeneration:
chemistry of this procedure is not fully Calcium zeolite + excess Na"*" - ^
understood, but full-scale installations
Sodium zeolite + Ca^'*'
have proved the feasibility of the proc-
The process will operate equally well if
the calcium and magnesium ions are re-
lon Exchange: placed with potassium ions or with any
I t may be necessary to remove the other positive ions t h a t can exist in a
cations or anions, or both, from water to relatively concentrated neutral solution.
45-52
In the early years of the industry, Where the anions must be removed
zeolites were developed from natural from the water, the process is operated
greensand. Suitable treatment opened in two stages. The water first flows
up the pores in the grains and hardened through a hydrogen regenerated cation
the surface. Exchange capacity, which unit and the acid effluent is then passed
was dependent upon pore area, was rela- through an acid-absorber anion ex-
tively low, about 2.8 kilograins (kgr) per changer.
cu ft. Capacities of 4.5 kgr were de- In this two-step process the acid
veloped by either acid or heat treat- effluent is usually degassed to remove
ment. The natural zeolites were not re- free carbon dioxide before passing
sistant to high or low pH water, and through the acid-absorbent exchanger to
pretreatment of the raw water was often complete the deionization. The degassing
necessary because they were easily step can be eliminated if a strongly basic,
fouled by iron or organic matter. Syn- acid-absorbent exchange medium is used.
thetic gel zeolites were later produced If the hydrogen exchange of the first
and had very high capacities, but their step is complete, the product from the
use was rather restricted and they have final unit will be neutral and low in
gradually been abandoned in favor of the ionized solids. If the effluent from the
newer synthetic resins. hydrogen cycle contains positive ions,
With advances in the art of ion ex- these ions with their negative com-
change, carbonaceous and synthetic resin ponents will pass through the acid-ab-
zeolites were developed that would with- sorbent units and appear in the final
stand both acid and alkaline solutions effluent. It is therefore essential to have
and provide both cation and anion re- good operation of the hydrogen cycle in
moval. Carbonaceous zeolites are limited this process. Depending upon the solids
to about 8 kgr per cu ft while the resins in water, the two-step units will produce
have a maximum of about 30 kgr. an effluent with a conductivity of about
In hydrogen cycle operation, the ma- 1 mho. Two or more stages, or a mixed-
terial exchanges hydrogen ions for cal- bed unit, will be necessary if higher
cium, magnesium, sodium, and other purity is required.
positive ions; it is regenerated with Weakly ionized materials in water
sulfuric or hydrochloric acid: passed unaffected through the older type
Hydrogen zeolite -|- Ca"'""*" —> of ion exchangers. Thus, silica was not
removed by the original two-step hy-
Calcium zeolite -|- 2H+
drogen exchanger and weakly basic add
The effluent from hydrogen ion ex- absorber. If the silica is converted into
changers contains free mineral acidity, the strongly ionized fluosilicic acid by
and it may be desirable to operate such addition of fluorine compounds at some
installations in parallel with sodium point in the process, the fluosilicic acid
cycle exchangers or to mix the effluent can be removed by the weakly basic acid
with untreated water to neutralize the absorber. The development of strongly
acidity. The combination of sodium and basic acid absorbers has economically
hydrogen cycle ion exchange makes it solved the problem of ion exchange re-
possible to remove the hardness and removal of silica without the use of fluorine
duce alkalinity at the same time. The compounds.
bicarbonate hardness is converted into In general, silica removal has been
dissolved carbon dioxide which can be carried on along with anion removal using
removed by degasification. highly basic anion resins. Where soften-
45-62
ing and silica removal are required b u t sodium and chloride exchange, in which
not complete demineralization, the use of both kinds of ions in the regenerating
strongly basic anion exchangers following solution serve a purpose. The sodium ions
normal sodium regenerated cation ex- regenerate the cation exchange material,
changers has served the purpose eco- liberating calcium and magnesium ions,
nomically. The capacity of anion resins while the chloride ions regenerate the
for silica removal has been found to be a anion exchange material, liberating bi-
function of the caustic soda dosage used carbonate ions. These units will replace
for regeneration. Silica reductions to 1 hardness with sodium ions and bicar-
ppm from 35 ppm have been obtained by bonates with chloride ions. The two ion
this method.'^ exchange materials need not be com-
Initial cost, process, and control prob- pletely mixed; the unit can be operated
lems of two-step deionization are now with the material in the layers t h a t de-
being reduced by the use of mixed-bed velop during backwashing.
deionizers. The hydrogen exchange and This method is feasible, but it is not
acid absorbing materials are mixed widely used. Two stages are employed
intimately in a single bed in these units. more often, the first to remove calcium
A mixed-bed unit performs like multiple and magnesium, utilizing sodium chlo-
stages of the two-step process and can ride for regeneration. I n the second stage,
deliver water with extremely low ion the anion material absorbs the bicar-
content. The break-through of ions at the bonate ion and replaces it with chloride
end of the operating cycle can be made ion. Here a mixture of sodium chloride
extremely sharp with mixed bed units. and caustic soda is used for regeneration.
During backwashing the two media Although the salt performs the regenera-
separate by differential density, with the tion, the caustic has been found to
hydrogen exchanger below the acid ab- lengthen the life of the resin, which re-
sorber. The acid absorber can be regen- sults in higher capacity.'^
erated with caustic soda and rinsed Ion Exchange in Waste Treatment.—
through the spent hydrogen exchange Ion exchange is being used to recover
material. The hydrogen exchanger is then chromium from waste waters. T h e
regenerated by introducing acid through chromic acid waste is first passed through
a distributor located just below the anion an anion exchanger to remove the
absorber medium. chromium in accordance with the equa-
Ion exchange must compete with dis- tion:
tillation for the production of high-purity
HjCrzO, -h R O H ^ R C r O a -\- H^O
industrial water. The choice between the
two processes depends largely upon the The anion material is regenerated with
total concentration of ionized and non- caustic soda which releases the chromium
ionized substances in the water supply, as sodium chromate:
and whether sterile water is required
from the process. R-CrOs -f- 2NaOH ^ R O H -J- NazCrjOv
Other forms of mixed-bed or multiple- The products of regeneration are then
bed ion exchangers are of commercial passed through a cation exchanger to
importance. One involves simultaneous
" S. B. Applebaum, "Experiences with
' ' S. B. Applebaum and B. W. Dickerson, Chloride Anion Exchangers for Reducing Al-
"Silica Removal by Salt Splitting Without De- kalinity Without Acid," 13th Annual Water
mineralization," 16th Annual Meeting, Am. Conference, Engineering Soc. Western Pa., Octo-
Power Conference, March 24-26, 1954. ber 20, 1952.
45HJ3
convert the sodium chromate back to separation of the ionic material from the
chromic acid: nonionic material may be quite sharp.
Separations of this kind are possible
NajCrjO, + 2 H R -> 2 N a R + HjCrjO, because of the peculiar behavior of an
This treatment recovers the chromic acid ion-exchange bead in an aqueous solution
and concentrates it for re-use. of a mixture of an electrolyte and a non-
The chromic acid content of plating electrolyte. In such solutions the electro-
lyte tends to be more concentrated
waste waters varies from 100 to 500 ppm
around the bead, while the nonelectro-
CrOs. The recovered chromic acid has a
lyte tends to have the same concentration
concentration of about 30,000 ppm or 3
within and outside the bead. This dif-
per cent CrOs, which is sufficiently high
ference in concentration between the two
for re-use. The waste water has been rid
solutes is the basis for the process. T h e
of dilute chromic acid and it can be re-
ionic material appears to be rapidly
used or discharged to a stream.
flushed through the void spaces between
Ion exchange has also been used for
the individual ion beads, while the non-
recovery of certain ionized organic com- ionic material is retained in the column
pounds. These include nicotine from for a longer period since it diffuses
water used to wash the gases from through the resin beads as well as around
cigarette drying, and tartaric acid from them.
winery wastes. Nonionized fruit sugars
Resins used in ion exclusion do not
have been recovered from cannery wastes
need to be regenerated because they
and citrus peels, and pectins from grape-
never become exhausted; the only
fruit wastes, by ion exchange. These are
operating cost is for water and pumping."
special applications but show the wide
Ion Retardation.—Another new ion-
range of applicability of this process to
exchange process for separating water-
the treatment of waste waters for product
soluble materials is ion retardation. This
recovery.
has resulted from development of a resin
Ion Exclusion.—A new technique,
that has both anionic and cationic ex-
known as ion exclusion, has been evolved
change sites located in the same bead.
which has many possibilities in waste The resin will therefore adsorb both
water treatment and certain process anions and cations from the feed solu-
operations. It allows separation of ionic tion. The resin sites are so closely as-
and nonionic materials, such as sodium sociated, however, that they partially
chloride from ethyl alcohol, sodium neutralize the electrical charges in each
chloride from formaldehyde, and sodium other; the adsorbed ions are thus weakly
sulfate from glycerine. Thus, separations held and may be displaced from the resin
that were never economically possible by water alone.
are now quite feasible.
Ion retardation is a column operation
The method provides for alternate
in which alternate portions of feed and
feeding of the aqueous solution of ionic rinse water are passed through the
and nonionic materials and water into column, as in ion exclusion. I t permits
an exchange column. One volume of feed separation of two electrolytes, such as
solution is usually followed by one or ferrous sulfate from zinc sulfate, sodium
more volumes of water. An aqueous
solution of ionic material comes out of " R . M . W h e a t o n a n d W . C. B a u m a n , " I o n
the column first, followed by an aqueous Exclusion, a U n i t Operation Utilizing I o n E x -
solution of the nonionic material. The change M a t e r i a l s , " Industrial and Engineering
Chemistry, Vol. 4 5 , p . 228 (1953).
45-.W
hydroxide from sodium chloride, and complexes. Polysilicates are available

ammonium chloride from zinc chloride. that form soluble complexes with iron.^"
I t will also separate electrolytes from Relatively large concentrations of
nonelectrolytes, and salts from very treating chemicals usually are required
large nonelectrolyte molecules. to sequester effectively even moderate
Like ion exclusion, this technique holds concentrations of undesirable constit-
promise of adding another tool to the uents. Thus the sequestering process
fractionation of process streams and finds its most economic application as a
treatment of waste waters. supplementary or final treatment after
the bulk of the undesirable constituents
Sequestering: have been removed by a process having
a lower unit cost.
The sections above have been devoted
to water-treating processes in which Oxidation:
chemical constituents are removed as
Surface and ground waters m a y con-
precipitates or by ion exchange. A third
tain odor- and taste-producing sub-
chemical method is that of sequestering
stances that make them unfit for drink-
the impurity into soluble complexes. I n
ing water and for some process uses.
the sequestering process, certain nor- These substances are usually organic,
mally positive ions, such as calcium and and often they can be removed by oxida-
magnesium, are so strongly held in a tion.
complex negative ion that the equilib- Spray ponds provide one method for
rium concentration of the free metal ion accomplishing this. Water is dispersed in
is extremely low. The concentration of the air as fine droplets by spraying it
free metal ions can be depressed by this over a pond through nozzles. The inti-
process to the point where insoluble mate contact between water and air pro-
soaps will not form. Water so treated vides the desired oxidation. Usually any
may have a soap hardness of zero, and dissolved gases are released at the same
it can even redissolve precipitated cal- time. A forced-draft degassing tower m a y
cium soap. be used in place of a spray pond; it
Nearly 100 years were required be- should provide about the same efficiency.
tween Thomas Graham's first studies of Oxidation with chlorine, chlorine di-
sodium metaphosphate and the general oxide, or ozone can be used to convert
recognition that a soluble negative objectionable organic m a t t e r into in-
complex ion of calcium does exist. The nocuous compounds. A short contact
discovery^*''' of the soluble phosphate- period, usually not over 10 min, is re-
calcium complex was made with sodium quired for complete oxidation. Certain
hexametaphosphate. Many of the poly- waste waters may contain taste-pro-
phosphates display this property in ducing materials, such as phenol, in
various degrees. Other chemicals have small volume b u t high concentration.
been found in recent years which are Biological treatment under these condi-
able to sequester hardness in true soluble tions would entail a very large capital
expenditure, b u t the operating cost would
be low. The capital investment can be
i « R . E . Hall, U . S . P a t e n t N o . 1,956,515
(1934), reissue 19,719 (1935); U . S . P a t e n t N o . reduced materially by using chlorine or
2,087,089 (1937).
' ' Industrial and Engineering Chemistry, Vol. ^^ C. R . H e n r y , " P r e v e n t i o n of S e t t l e m e n t of
29, p . 584 (1937); Ibid., Vol. 3 1 , p . 51 (1939); I r o n , " Journal, A m . W a t e r W o r k s Assn.. Sep-
Ibid., Vol. 32, p . 1572 (1940). t e m b e r , 1950.
45-52
chlorine dioxide, because the operation reaction is exothermic and means must
would be the equivalent of a waste treat- be provided to remove enough heat to
ment unit. The waste water flow would hold the catalyst at 600 C. Conversion
be the water supply to the chlorinator efficiencies of 90 per cent and above can
and it would be discharged as a treated be achieved by this method with organic
effluent. The operating cost for such an concentrations as high as 8 per cent; the
arrangement might be rather high, but method is uneconomical at concentra-
the low capital investment would make tions below 1 per cent.
it attractive in many instances. The
Iron in water above 0.3 ppm and
effluent will contain excess chlorine, and
manganese over 0.2 ppm are generally
some retention is necessary before release
objectionable. Both can be removed from
to a stream.
most waters by lime-soda or caustic soda
Normal biological methods are usually
precipitation process. They also can be
prohibitive where waste waters contain
removed by oxidation, precipitation, and
more than about 3 per cent of soluble
filtration because of the comparative
organic matter, because of the large
insolubility of hydrated ferric and
dilution necessary for effective purifica-
tion. A method known as wet combustion manganic oxides. Aerated water is passed
has been developed which provides ef- through contact filters in which the filter
ficient air oxidation through operation at medium acts as a catalyst for the oxida-
elevated pressure and temperature.^' The tion reaction. Manganese is more de-
waste water is heated to not less than pendent on catalytic contact than is iron
350 C and the pressure raised to 2000 in this process. Silica sand is often a
psi. Air is blown through the liquid under suitable contact medium for iron re-
these conditions, and effective oxidation moval, but complete manganese removal
of the organic material takes place with usually requires pyrolusite (manganic
purification efflciency well above 90 per oxide) or special manganese zeolite.
cent. Power requirements for this process These manganese zeolite units are not
are very high, but with effective power cation exchangers but are contact oxi-
and heat recovery, the economics of the dizers that are regenerated by treating
operation are satisfactory. zeolite with manganous sulfate and po-
A catalytic oxidation method has been tassium permanganate. The higher oxides
developed for organic ^wastes plus water of manganese are deposited on the zeolite
that are produced in the vapor phase and granules during regeneration. Contact
that can be prevented from condensing with this material oxidizes ferrous and
prior to treatment.^^ f h e waste feed is manganous ions to insoluble hydrated
raised to 300 C and together with air in oxides which are then removed by filtra-
the ratio of 300 to 700 per cent of the tion. Such units are employed most
requirement for oxidation, also heated economically as a final treatment to re-
to 300 C, is fed into a converter contain- move the last trace of iron and manga-
ing copper or manganese chromite nese from effluents that already have
catalyst maintained at about 600 C. The been treated by a less expensive, but less
efficient, process.
^' F . J. Z i m m e r m a n , " N e w W a s t e Disposal
P r o c e s s , " Chemical Engineering, August 25, 1958« The sodium-cycle ion-exchange process
p . 117.
^^ R . V. Green a n d D . V. Moses, " D e s t r u c t i v e will remove ferrous and manganous salts
C a t a l y t i c Oxidation of Aqueous W a s t e M a - simultaneously with hardness if these
t e r i a l s , " Sewage and Industrial Wastes, p . 288
(1952). metals are present as bivalent ions.
45-53
Neutralization: of dry material is weighed continuously.

Neutralization of acidity or basicity The dry chemical discharges into a mix-
may be necessary to provide satisfactory ing box where it forms a solution or a
process water or for treatment of waste suspension. I t is then allowed to flow by
water. Many ground waters contain such gravity, or pumped, to the point of ap-
high concentrations of carbon dioxide plication. These machines can be made
that the water is quite acidic. Aeration to operate in proportion to flow rate or
will remove most of the carbon dioxide, to p H response. Hoppers over the
but not all of it, and the p H may still be machines provide chemical storage of 8
so low that the water is corrosive for to 24 hr.
general purposes. Accordingly, neutral- Where lime or lime and soda methods
ization is provided to raise the p H to the of softening are employed, the effluent
desired value. will contain caustic alkalinity. This ex-
Calcite filters, which consist of pres- cess alkalinity generally must be neu-
sure vessels filled with pulverized marble, tralized. This is done by adding acid,
can be used if the quantity of water is usually sulfuric or carbonic. The amount
small. The carbonic acid is neutralized of acid fed is determined by the resultant
by the calcium carbonate and the water p H value desired. The usual control is
is stabilized at the same time. Stabiliza- by a p H recorder-controller.
tion means that the alkalinity-pH ratio A 10 per cent acid solution is normally
is automatically adjusted to provide a used to treat relatively small volumes of
water neither corrosive nor scale-form- water. Concentrated acid is fed if the
ing. volume is large. A metering p u m p is to
Alkali feeds are used where large be preferred for acid feed in Idrge-volume
volumes of water are needed. The solu- operations. The pump can be controlled
tion feeder comprises euipment for con- for ratio-flow control, p H control, or a
tinuously feeding a water solution of combination of both. Acid-resistant
caustic soda, soda ash, or lime slurry. storage tanks, piping, and pumps must
Provision is made for controlling the rate be used.
of chemical addition to maintain the Both alkaline and acidic waters are
desired p H value. The control may be encountered in waste treatment. Free
manual or automatic, through a p H re- mineral acids and free alkalies must be
corder-controller. Neutralization is not neutralized before discharging such
instantaneous and a contact period must waters. This means neutralization to the
be provided, usually not more than 5 min. methyl orange or the phenolphthalein
The alkali solution may be fed by gravity end point, respectively. Rarely is it neces-
or by pumping into the stream to be sary to go above p H 4.6 or below p H 8.3.
treated. Liquid storage tanks are usually The neutralized waste water will not re-
designed for 12- to 24-hr operation be- duce the total alkalinity in the receiving
tween refills. stream. I t is very difficult to maintain
Chemicals may also be fed dry. Only p H values above 5 since slight increments
soda ash or lime may be used in dry in alkali feed cause wide swings in p H as
feeders because caustic soda is too neutrality is approached.
hygroscopic to permit uniform feeding. Where acid and alkali waste waters
The dry-feed machines operate either on are discharged in the same plant, blend-
the volumetric principle, in which a ing these may be all t h a t is necessary for
measured amount is displaced each satisfactory neutralization. Any defi-
stroke, or gravimetric, whereby the flow ciency of one waste can be made up by a
separate chemical feed and the final vary widely. The multistage neutralizer^^
blended efHuent can be discharged at the can be used to deal with this difficulty.
desired p H . The blending should be The neutralizer consists of several cham-
carried out in an acidproof tank provid- bers in series, up to 6 in number, each
ing sufficient time for full reaction. provided with a mechanical mixer. The
Neutralization studies in the laboratory waste water flows from the top of one
will establish the period of retention re- chamber to the bottom of the next one,
quired. thereby providing ample reaction time
Consideration must be given to the without short-circuiting. Lime slurry is
type as well as the concentration of acids fed at alternate chambers; the feed rate
in waste waters that must be neutralized. is governed by p H recorder-controllers.
Such acids as hydrochloric or nitric can The first chambers of the multi-neu-
be neutralized with lime without trouble tralizer function as equalizing units and
since the salts produced are soluble in the alternate ones as reaction vessels.
high concentrations. With sulfuric acid, Detailed reaction-rate studies must be
there is a very definite limit if high- made before designing such a system to
calcium lime is to be used; the acid con- establish total retention time, reaction
centration must be held below 0.3 per time, and rate dosage.
cent if calcium sulfate deposits are to be Silo storage of burned lime is usually
avoided. Concentrations up to 1 per cent provided together with gravimetric
can be handled successfully if dolomitic feeders and slakers and effective slurry
lime is used. If other acids are present, storage. The slurry, usually 10 per cent,
the resultant depression of calcium sul- is circulated past the feed valves and
fate solubility must be taken into ac- back to the slurry storage by centrifugal
count. An example of this is a blend of pumps. Provision must be made for
neutralized nitric and sulfuric acids in holding constant back pressure on the
which the calcium sulfate solubility was feed valves. Excellent effluent control can
reduced to 1100 ppm from about 2000 be achieved with an installation of this
ppm. kind for treating waste flows as high as
Acids can be neutralized by upward 10 to 15 mgd with lime requirements of
flow through granular limestone beds.^^ 120 tons per day.
The flow rate is usually 25 to 40 gpm
per sq ft of bed, and beds 3 to 5 ft in Degassing:
depth are placed in acid-resistant tanks. Dissolved Carbon Dioxide.—Dissolved
These beds are quite effective because of carbon dioxide can be chemically re-
the turbulence created as the water is moved by adding lime, soda ash, or
forced to flow upward. Sulfation must be caustic soda to form soluble bicarbonates
avoided where sulfuric acid is neutralized or relatively insoluble carbonates. This
or the limestone particles will cement method requires careful chemical control.
together. Approximately the same result can be
Gravity flow is necessary for handling obtained with less control and super-
large water volumes if high pumping vision by passing the water through a bed
costs are to be avoided. Usually both of material with which the dissolved
rate of flow and acid concentration will carbon dioxide will react chemically to
form a neutral or alkaline product. The
^ ^ H . W . G e h m , " N e u t r a l i z a t i o n of Acid
W a s t e s with U p - F l o w E x p a n d e d Limestone 2* B . W . Dickerson and 11. M . Brooks, " N e u -
B e d s , " Sewage Works Journal, V o t 16, p. 104 tralization of Acid W a s t e s , " Industrial and En-
(1944). gineering Chemistry, Vol. 42, p . 599 (1950).
45-53
most common material for this process is moval through oxidation of the metal,
crystalline or granular calcium carbonate, the products of corrosion largely remain-
such as crushed calcite or limestone. The ing in the filter. Steel wool filters in some
calcium carbonate slowly dissolves by waters liberate ferrous salts which con-
reaction with the carbon dioxide to form sume additional dissolved oxygen be-
additional bicarbonate hardness in the yond the filter. The slow rate of oxygen
water: consumption by steel wool contact filters
has limited their commercial use. Contact
CO2 + H2O + C a C O s - ^ C a ( H C 0 3 ) 2
reduction of dissolved oxygen can be
Such a unit also acts as a filter, and brought about by a reversible oxidation
periodic backwashing may be required. reduction process using an amine ex-
T h e initial investment is the principal change resin. Inasmuch as this material
cost of the process; chemical replace- can be regenerated by chemicals it is
ment and operating costs are small. The similar to ion exchange.
additional hardness added to the water Dechlorination and Removal of Gases by
by the process may be objectionable.^^ Chlorine.—Sulfite, sulfur dioxide, and
Chemical Removal of Dissolved Oxygen. thiosulfate or bisulfite can combine with
— T o supplement physical deaeration, dissolved chlorine in a dechlorination
dissolved oxygen also can be removed process. The reactions may be repre-
from water by chemical means. Sodium sented by the equations:
sulfite is used extensively as a final treat-
NajSOs + H2O -I- CI2 - > Na2S04 -|- 2 H C 1
ment to consume the small trace of dis-
solved oxygen which is not removed b y SO2 -1- 2H2O -I- CI2 ^ H2SO4 -I- 2 H C 1
deaeraling feedwater heaters. Sulfite re- 2Na2S203 + Clj - ^ Na^SiOe + 2NaCl
acts rapidly with dissolved oxygen at
boiler water temperature to form sulfate: Chemical methods usually are em-
ployed only for removing low chlorine
2Na2S03 + O2 - > 2Na2S04 residuals. Chlorine gas, on the other
I t is easy to determine sulfite in boiler hand, may be used to convert ammonia
water, and the concentration and con- or ammonium ions to chloramine, which
sumption of sulfite can be used as a can be removed from solution by aera-
convenient chemical integrator for check- tion.
ing the performance of the physical
Sterilization and Disinfection:
deaerating equipment. Sulfite at boiler
water temperature may reduce certain In general, all waters, whether surface
chemicals, however, such as iron and or ground, contain bacteria, the type and
copper salts, and a material balance may number depending upon existing condi-
be slightly inaccurate. Ferrous iron salts tions. Ground waters taken from sand
and hydrazine have been used as oxygen strata usually are free of pathogens but
scavengers. Colloidal iron, tannin, and may contain a fairly high count of soil
other chemicals are also used for their organisms not harmful to man. Water
oxygen-consuming properties. taken from rock wells m a y or m a y not
contain pathogenic organisms.
Contact Reduction of Dissolved Oxygen.
—Steel wool contact filters have been Surface streams are prone to bacterial
used in the past for dissolved oxygen re- contamination from both soil and man,
the amount of the latter increasing
^* W . J. K y a n , " W a t e r T r e a t m e n t a n d Purifi-
cation " M c G r a w Hill Book Co., N e w Y o r k , p .
greatly with sewage discharges. Other
221 (1937). types of bacteria can be present in large
45-54
T R E A T M E N T OF PROCESS W A T E R AND W A S T E W A T E R 75
numbers where industrial pollution is ter, and the effluent from a filter plant is
present. usually very low. Feed of 0.5 to 1 p p m
Soil bacteria must be more or less under such conditions will provide a
completely removed from water for residual of 0.2 ppm as combined chlorine.
municipal supply, and pathogenic or- Feed rates of 10 to 40 ppm may be re-
ganisms must be absent. In industrial quired if the organic matter is high.
waters, small numbers of organisms can Chloramines are used where there is a
usually be tolerated, dependent upon large distribution system or a reservoir
process use. I t is thus apparent that these open to the sunlight, because chlorine
organisms must be eliminated if satis- alone may be dissipated too quickly to
factory potable water supplies are to be insure sterile water. Chloramines are
provided. formed by adding ammonia in a 1:4 ratio
Where small volumes require steriliza- of ammonia to chlorine. The chloramines
tion, as in the laboratory, heating to are not as active as free chlorine, and a
boiling temperature is sufficient. When minimum contact time of 15 min is re-
continuous treatment is necessary, as in quired. Chloramines are very persistent,
a water purification plant, bactericidal however, and they provide more satis-
agents are employed. The most common factory sterilization in long distribution
of these is chlorine, either as a gas or as systems.
hypochlorite. I t has been found that a combined-
Feeding gaseous chlorine requires chlorine residual will not always destroy
specially constructed equipment and, all of the microorganisms in the system
while the gas may be diffused into the and that tastes and odors sometimes oc-
water to be treated, the general practice cur in sequence. This problem is com-
is to feed an aqueous solution of it. This bated by maintaining a free-chlorine
results in full utilization of the gas and residual. This is done by feeding suf-
better control. Gas chlorination is gen- ficient chlorine to oxidize all the organic
erally employed when 15 lb or more is matter, thereby to provide a residual of
required per day, because there is no free chlorine. This practice is now fol-
saving in the cost of the feeding equip- lowed a t most waterworks.
m e n t below this quantity. Chlorine dioxide is a product that is
Bleaching powder, high-test calcium finding favor in eliminating tastes and
hypochlorite powder, or sodium hypo- odors, for it is also an excellent sterilizing
chlorite solution are used where only agent. This is produced by reacting
small amounts of chlorine are needed. sodium chlorite solution with a chlorine
These solutions are fed by gravity or solution at p H 3.0. The resultant solu-
pumped into the system by a diaphragm tion contains both chlorine and chlorine
pump. The available chlorine in these dioxide. Its use has been successful in
compounds is much more expensive than eliminating tastes and odors in many
gaseous chlorine, but the low equipment cases when other methods have failed,
cost and simplicity of operation more and the residual appears to persist well.
than offset the difference. Accessory equipment is required for
The amount required to provide a making a solution of the chlorite and for
residual for sterilization is in general de- feeding it. Furthermore, a reaction cham-
pendent upon the amount of organic ber is necessary for mixing the two solu-
matter in the water because this must be tions. The chlorine dioxide and chlorine
oxidized before there can be a residual. combination is more expensive in terms
Most ground water is low in organic mat- of actual available chlorine, but with a
difficult taste and odor problem it pro- Chlorination processes are effective for
vides the only way to eliminate it. control of most biological growths in
Sterilization of water is also effected water.^^ Chromates and salts of copper,
with ozone generated by passing an zinc, and silver also are used for this
electrical discharge through dry air. I t purpose. Organic compounds such as
must be generated at the site in expensive phenol, chlorinated phenol derivatives,
equipment with a high electrical demand. naphthenates, quaternaries, and many
The gas and air mixture is bubbled others under a wide variety of trade-
through the water as in a normal aeration names are available for biological growth
system. The cost of installation and inhibition. Copper sulfate, with or with-
operation is considerably higher than for out aliphatics such as citrates to keep the
chlorinators except in large waterworks. copper in dilute neutral solution, is used
In addition, measurement of residual for the economical control of algae in
ozone is nearly impossible; as a result, it large bodies of water such as reservoirs
has been used in very few locations. and lakes. Treatment with considerably
Bromine possesses the same sterilizing less than 1 ppm of copper sulfate is
properties as chlorine but it is a more usually satisfactory, depending upon the
difficult material to feed and control. So type of algae^' and the care that must be
far, it has been used experimentally in taken not to kill fish. The amount of the
some swimming pool installations. treatment need only be sufficient for a
Ultraviolet light can kill bacteria in limited top water layer and not for all of
clear water. The light must be generated the water in the reservoir. For large
at the point of use and the equipment is quantities of water used only once, the
complex. A few experimental units have economic choice for biological growth
been installed in the past but the method control is usually limited to copper sul-
has not been generally accepted. fate, chlorination, and ozonation.
Silver iodide has excellent disinfection I n smaller bodies where the water is
properties when fed as a soluble salt. Its re-used, as in circulating cooling water
high cost precludes its use except during basins, treatment with other chemicals
war emergencies. I t was made in tablet may be economical. Intermittent chlo-
form during World War I I and was ex- rination may be economically satis-
tensively used by the armed forces. factory for control of biological fouling
in cooling water systems. Residual free
Control of Biological Growths: chlorine in the order of 0.5 to 2 p p m in
Various biological growths in water most cases is satisfactory for control of
may require chemical treatment, either slimes and the spat or larval stage of
to inhibit their growth, to kill them by larger organisms. Intermittent treat-
sterilization, or to stimulate them with ment with bromine also is used to a
hydroponics. The objectionable organic limited extent, especially for the control
growths in industrial water systems may of such macroscopic organisms as mus-
include pathogenic and nonpathogenic sels, which are resistant to chlorine.
bacteria, algae, slimes, iron and man-
ganese bacteria, sulfur bacteria, and a
host of other microscopic and macro- 2« J. G. Dobson, "The Control of Fouling Or-
ganisms in Fresh and Salt Water Circuits,"
scopic organisms. Some organic growths Transactions, Am. Soc. Mechanical Engrs., April,
are dangerous to health, others cause bad 1946.
tastes and odors, and still others cause " F. E. Hale, "The Use of Copper Sulfate in
Control of Microscopic Organisms," Phelps
clogging of equipment and piping. Dodge Refining Corp. (1939).
45-55
Incineration: particles, called floe, which will settle

Incineration is not usually considered rapidly. A flocculent precipitate which
as a waste disposal method but there are has enormous surface area per unit of
certain cases where it is applicable. When volume is produced by coagulants. This
the volume of waste water is under 10 precipitate removes suspended and col-
gpm and the soluble organic concentra- loidal matter from the water by electro-
tion above 4 per cent on a BOD basis, physical attraction, adsorption, absorp-
the waste can be sprayed into the boiler tion, and physical entanglement. For
furnace for evaporation of water and example, aluminum sulfate reacts with
combustion of organics. The boiler fur- hydroxyl ions in water to form complex
nace must be large enough to handle the aluminum hydroxides that are relatively
vapor load. Some additional fuel will be insoluble in the pH range from 6 to 8.
required, and the fuel-feed and burners The particles of precipitated aluminum
must be of sufficient size to handle this hydroxide, with the help of suitable mild
increase. This method can generally be agitation, agglomerate into visible
used only with oil-fired boilers. If the clumps which settle by gravity. The
waste water contains toxic materials a simultaneous formation, agglomeration,
modified unit provided with its own adsorption, and inclusion of the sus-
burner and fuel supply can be used ef- pended matter and color into the floe is
fectively for destroying the compounds. the physicochemical process of coagula-
tion.
A great deal of study is necessary,
followed by pilot operation, before in- Each coagulant has a pH range in
cineration can be used effectively, but which it is most effective. The addition
the technique does provide a satisfactory of the coagulant usually changes the pH
answer for certain waste water problems. of the solution at the time the floe is
formed. Acidic coagulants such as alu-
PHYSICOCHEMICAL PROCESSES minum and ferrous and ferric sulfates
precipitate as basic compounds and re-
Several important water treatment duce the pH of the water. When the
processes depend upon combined chem- natural alkalinity of the water is not
ical and physical action. These are co- sufficient to maintain the minimum pH
agulation, adsorption and absorption, requirement after coagulation, it is neces-
crystal growth deactivators, additives sary to add lime or soda. The optimum
for changing surface tension, and cor- range for coagulation with aluminum
rosion inhibition. sulfate is between pH 5.5 and 7.0. Above
7.0 there is a tendency for some of the
Coagulation: alum to remain unprecipitated and a
Most surface waters contain suspended small amount of residual aluminum will
matter and color. Much of the suspended remain in the final filtered water. When
matter consists of particles too small to the pH of the raw water gets above 7.2,
settle rapidly, even in quiet water. Color the amount of coagulant necessary to
is caused by absorption of light by sus- drop the pH into the optimum band may
pended and dissolved organic and mineral be too great economically, especially if
substances. A chemical coagulant, such the coagulation pH is 6.3 to 6.4 for the
as alum, ferrous or ferric sulfate, or water. Accordingly, sulfuric acid is added
sodium aluminate, will cause the finely ahead of or with the aluminum sulfate to
divided and coUoidally suspended ma- reduce the pH to the proper range for
terials to be gathered together into larger good coagulation. Sulfuric acid will lower
45-S5
the pH much faster and at less expense dispersion, the finely formed floes require
than the coagulant. agglomeration by very gentle agitation
Ferric sulfate is an effective coagulant so they can develop into large masses.
over the wide pH range of 5.5 to 10. It Slowly revolving paddles in a chamber
has an acidic reaction and lowers the providing from 40 to 60 min retention
alkalinity of the water. Ferrous sulfate, will bring the floe to maximum develop-
while effective over a wide range, is ment and produce one that will settle
generally used between pH 8.5 to 10. In rapidly and provide a satisfactory super-
addition to requiring alkalinity for co- natant for filtration.
agulation, there must be an oxidizing
agent to convert the ferrous iron to the Adsorption and Absorption:
ferric state. Usually there is enough dis- The processes of adsorption and ab-
solved oxygen in the water to complete sorption of organic and colloidal ma-
the oxidation; if insufficient, some form terials into flocculent precipitates with a
of aerating device is employed to in- resultant increase in sedimentation rate
crease the oxygen content. Chlorine also are used to remove color, taste, and odors
is frequently added for this purpose. from water. High silica concentrations
Many factors affect the amount of co- also can be economically decreased by
agulant needed for optimum results. ferric and magnesium floes. These proc-
Among these are type and amount of esses are more efficient in terms of chem-
suspended matter, water temperature, ical consumption when the flocculent
rate of mixing, and retention time. Co- precipitate develops in the water than
agulant dosage may vary from 5 ppm when a preformed precipitate is added.
for a good water very low in turbidity Adsorption on ferric hydroxide can
and color to 100 ppm or more for a reduce the silica content to 2 or 3 ppm.
highly turbid one. Presettling is usually The initial reduction occurs rapidly, but
provided when turbidities continually suitable mixing and retention time are
run over 400 to 500 ppm, to reduce the required to attain minimum concentra-
coagulant requirement. tions. The process operates best in the
Continuous and proportionate feeding cold. Magnesium hydroxide also will re-
of the coagulating chemical is necessary move silica and often is used in the lime-
for effective coagulation. In addition, soda precipitation process for silica
control of the pH in the optimum range adsorption and precipitation. Magnesium
is essential. The coagulant can be fed dry can be added to the water as magnesium
or in solution, depending upon the carbonate, magnesium bicarbonate, or
amount to be fed and specific conditions. magnesium oxide. Magnesium hydroxide
Usually quantities up to 100 lb per day requires a longer contact time than ferric
are fed as a solution. Above this, dry hydroxide for maximum silica reduction.
feed machines are employed with a dis- It differs from the ferric hydroxide proc-
solving tank so that a dilute solution is ess in that warming the water improves
fed; with proper physical arrangement silica reduction. The pH for magnesium
the dry material can be fed directly into hydroxide formation must be above 10.2,
the water. which is the usual condition with lime-
The coagulant should first be thor- soda softening. On the other hand, the
oughly dispersed in the stream to be ferric hydroxide process is usually carried
treated. This is accomplished in a high- out separately because the pH for its
speed mixing chamber having a reten- most economical silica reduction is about
tion of from 0.5 to 1.0 min. After the 9.0.
45-54
TREATMENT OF PROCESS W A T E R AND W A S T E W A T E R 79
Taste, odor, and some dissolved gases Additives for Surface Tension Changes:
often can be removed from water by ad- Numerous chemicals have the property
sorption on activated carbon. This mate- of significantly changing the natural
rial can be added as a powder to the filter surface tension of water. Chemicals which
influent and removed from the filter bed markedly decrease surface tension are
during backwashing. Activated carbon called wetting agents, and those which
filters of granular or powdered activated materially increase surface tension are
carbon are available for filtered water often spoken of as foam suppressors. Wet-
service. Activated carbon may be ting agents in a w ide variety of commercial
partially regenerated by steam or other forms are available for many industrial
gases. Activated carbon filters are also uses, such as ore-separation processes,
used for dechlorinating water. laundry operation, fire fighting, acid
cleaning, and a host of others. Numerous
Crystal Growth Deactivators: chemicals that increase the surface
The surface deactivation properties of tension of water also are commercially
numerous chemicals are employed in a available for reduction of foaming and
variety of treatment processes for re- priming difficulties in steam generators.
tarding or inhibiting crystal growth. The
polyphosphates have this property in Corrosion Inhibition:
various degrees. Organic materials, such Water conditioning for corrosion con-
as tannin, lignin, and many others, have trol involves both physical and chemical
surface deactivation properties. Crystal processes operating together. Protective
surfaces are believed to be covered with films that inhibit metal deterioration are
molecular or submicroscopic films of the physical barriers. The formation and
surface deactivator, thereby reducing, maintenance of such films may be the
altering, or inhibiting further crystal result of chemical reactions. These physi-
growth. cochemical corrosion inhibition processes
Threshold treatment is an example in are briefly described in the following
which calcium carbonate deposits are three sections.
inhibited, although concentrations above Calhodic Protection.—The electrolytic
the normal solubility of the scale-forming theory of iron corrosion, as postulated by
material are present. Calcium phosphate Whitney-' and demonstrated by Walker
precipitation in feedwater equipment can and associates,^' is essential for under-
be inhibited in the same manner. This standing the process of cathodic protec-
technique is also used to retard precipitation.^" According to this theory, metals
tion of ferric iron in water containing in contact with water tend to go into
dissolved oxygen; thus red-water troubles solution, forming positively charged ions.
frequently can be reduced by crystal Positive ions can go into solution in an
electrically neutral system only if an
deactivation.
equivalent number of positive ions of
Surface deactivation is used as an aid some other element are plated out. In
in keeping trace elements in solution for
hydroponics, in limiting crystal size, and ^'W. R. Whitney, "The Corrosion of Iron,"
Journal, Am, Chemical Soc, Vol, 25, p. 395
for many other special uses. An ever- (1903),
increasing number of surface active 2' W. H. Walker, A, M, Cederholm, and L. N.
Bent, "The Corrosion of Iron and Steel," Jour-
chemicals, under a wide variety of trade nal, Am. Chemical Soc,, Vol, 29, p. 1251 (1907).
names, are available to the water con- ^^ J, M. Pearson, "Fundamentals of Cathodic
ditioning engineer. Protection," Corrosion Handbook, p. 923, John
Wiley & Sons, Inc., New York (1948).
45-51
the case of pure water in contact with a chemically inactive in water and is
metal, such as iron, hydrogen ions are tenaciously attached to the metal will
plated out at the interface. The reaction inhibit aqueous corrosion. Painting and
may be written: molten-metal plating are examples of
physicochemical corrosion barriers. A
Fe + 2H+ ^ Fe++ + 2H
corrosion-inhibiting film also can be
Metal Ions Ion Atoms developed from the metal itself by
chemical action. Metal oxide finishes and
The liberated hydrogen forms a thin,
chromate, silicate, phosphate, and tan-
insulating film on the metal which pre-
nate films are examples of chemically
vents further corrosion. Thereafter the
produced corrosion barriers. T h e art of
corrosion reaction proceeds at a rate that
chemically producing and maintaining
is a function of the rate of removal of the
uniform corrosion-resistant films on the
layer of atomic hydrogen. The observed
various engineering materials is a com-
effects of dissolved oxygen, temperature,
plex field.
pH, salt concentration, and turbulence
on this protective hydrogen film on iron A well-maintained steel boiler might
and steel have been found to agree with be defined as a clean, thin, continuous
this theory.5^ Any method for maintain- film of water-insoluble material, rein-
ing the protective hydrogen film will forced by steel, and used to generate
reduce corrosion. vapors. The development and mainte-
nance of this thin continuous film, usually
Galvanizing steel provides a form of
consisting of metal reaction products,
cathodic protection. Here the protective
depend on many factors. Raising the p H
hydrogen film is maintained on the ex-
of the water in contact with steel to
posed steel cathode at the expense of the
between 10.5 and 11.7 to develop a more
zinc anode, which slowly goes into solu-
uniform protective film is common
tion. Magnesium and zinc rods or plates
practice for steam boilers. Other condi-
suspended in water and electrically
tions such as the removal of dissolved
connected to the steel tank are further
oxygen and carbon dioxide by physical
examples of cathodic protection. In other
or chemical deaeration will improve the
forms of this process, direct current is
uniformity and tenacity of the protective
supplied from an outside source to main-
film. Filming amines are also used to pro-
tain the protective hydrogen film on the
vide a monomolecular protective film.'^ '^^
steel cathode and a corrosion-resistant
Venting of such gases as carbon dioxide''*
anode is used. A sacrificial anode, such as
from steam condensate systems results
an abandoned pipe line, also can be used.
in an increased p H and improves the
Various types of commercial equipment
protective film. I n open cooling-water
are available to provide cathodic protec-
systems, chromates^^ and silicates'^ are
tion. Cathodic protection often is used
to inhibit corrosion in cold-water tanks ^^ F. N. Speller, Proceedings, Nat. District
and pipe lines. By a variation of this Heating Assn., Vol. 24, p. 203 (1933).
process, hulls of steel ships can be pro- " A. A. Berk, U.S. Bureau of Mines, Report
of Investigation No. 3754.
tected from electrolytic corrosion caused ^^ E. W. Guernsey, Transactions. Am. Soc.
by copper-alloy propellers. Heating and Ventilating Engrs., Vol. 51 (1945).
'^ Marc Darrin, "Chromate Corrosion Inhibi-
Physicochemical Corrosion Barriers.— tors in Binaetallic Systems." Industrial and En-
Any type of continuous film that is gineering Chemistry, Vol. 37, p. 741 (1945).
•'* L. Lehrroan and H. L. Shuldener, "The Hole
^1 F. N. Speller, "Corrosion, Causes and Pre- of Sodium Silicate in Inhibiting Corrosion by
vention," MoGraw Hill Book Co., New York, Film Formation on Water Piping," Journal, Am.
3rd Ed. (1951). Water Works Assn., Vol. 43, March, 1951.
45-55
TREATMENT OF PROCESS W A T E R AND W A S T E W A T E R 81
widely used for the development of thin, of alternating cationic and ionic selective
uniform protective films on steel. Organic membranes which provides a series of
materials such as tannin and lignin com- parallel cells through which the raw water
pounds are also used for this purpose. flows. An electric potential across the
The polyphosphates^^ under controlled stack causes the cations and anions to
conditions can form protective films on move in opposite directions and to pass
steel and cast iron. Polyphosphates, through the appropriate selective mem-
organics, and chromates are often used branes. As a result, ions tend to leave
together for cooling-tower corrosion in- alternate cells and to concentrate in the
hibition. Where serious deposits of cells between them. Thus the stack con-
calcium carbonate scale will not develop, tinuously discharges two streams, one
it is sometimes desirable to increase the relatively demineralized and the other
p H in cold, hard-water lines'' by a con- proportionately concentrated in the ab-
trolled lime treatment to reduce corro- stracted ions. The process shows prom-
sion. All the above processes are used for ise as an economical method for desalt-
the purpose of developing and maintaining brackish water.
ing a thin, uniform, tenacious film to keep Osmoionic demineralization is another
corrosion of pipe and equipment at method being studied for purifying salt
minimum levels. water with ion-selective membranes. N o
Inhibition of Biological Corrosion.— electricity is required, because the
The chemistry of biological corrosion is method uses osmotic pressure to move
still in its infancy. I t is believed that ions through the membrane. The proce-
dilute sulfuric and nitric acids can be dure is effective for desalting brines with
produced on the surface of metals by chloride concentrations in the range of
biological reactions in polluted waters. 3000 ppm.
Elimination of the acid-producing or- Dialysis and electrodialysis have been
ganisms should prevent biochemical used in the treatment of certain waste
corrosion of ferrous and copper-alloy waters. These methods separate ionizable
tubing. These organisms can be con- salts from colloidal suspensions. The
trolled by the same general processes ionized salt passes through a membrane
used in physical and chemical regulation and leaves the colloidal material behind.
of biological growths. Depending upon the material to be
separated and the conditions at hand,
Liquid-Phase Separation: electricity may be used as an additional
With the steadily increasing demand driving force. These methods are being
for water, considerable thought has been used for alkali and acid separation and
given to the purification of sea water, recovery from process liquors.
and it is here that the liquid-phase sepa-
ration is being widely investigated. BIOLOGICAL TREATMENT
The development of ion-selective mem- Percolation of raw surface water
branes has led to their use in this work. through a bed of fine, graded sand is one
Membrane electrolysis employs a stack of the oldest methods of water purifica-
" G. B. Hatch and Owen Rice, "Factors in tion. These units, after a period known
Formation of Protective Films upon Steel by as seasoning or ripening, had the ability
Waters Treated with Glassy Phosphates," In-
dustrial and Engineering Chemistry, Vol. 37
to remove turbidity, color, and bacteria.
(1945). Although primarily a straining device,
™ S. T. Powell, "Corrosion Inhibition by Lime the ability of these beds to remove
Treatment." Industrial and Engineering Chem- bacteria, finely divided material, and
istry, Vol. 26 (1934).
45-55
color resulted from a gelatinous growth waste water on the bed. The underdrain
on the surface of the bed. This coating system has air ducts which allow air to
was known as schmutzdecke and com- circulate through the bed by natural
prised organic material derived from draft; this provides the oxygen necessary
living and dead organisms such as bac- for good biological action. The stone
teria, diatoms, algae, and lower forms of provides a large surface for growth of the
life. This material provided the major organisms that accomplish aerobic de-
purification; the bed of sand was es- composition. The units are classed high
sentially a support for the schmutzdecke. or low rate depending upon the rate of
Excellent purification resulted, although operation. Up to 5 mgad is considered
at very low rates of flow, the normal low rate, while 10 to 30 mgad is high
being 2.5 to 3.0 million gal per acre per rate. Biochemical oxygen demand (BOD)
day (mgad). These slow-sand filters have is the design criterion. The volume of the
been almost completely supplanted by filter is based upon decomposition of 1
mechanical sand filters which are sup- to 5 lb of BOD per cu yd of stone per
plied with water from which the bulk of day. The diameter is fixed by the rate of
the suspended matter has been removed application and volume of waste water
by chemical pretreatment. to be handled per day. Actual design
. Biological purification is widely used should be developed only after pilot plant
for treatment of waste water containing studies of the waste water in question.
dissolved organic matter. Bacteria break Efficiencies of single filter units range
down the complex compounds into from 35 to 85 per cent removal of BOD.
simple, stable ones; the usual end prod- Where higher efficiencies must be pro-
ucts are carbon dioxide, water, nitrate, vided, a second unit is installed to oper-
and sulfate. This change is brought about ate in series with the first to provide
through the metabolism and cell synthe- two-stage treatment. Under such condi-
sis of the microorganisms present. tions, 80 to 95 per cent purification can
Usually these processes are carried out usually be obtained.
in the presence of excess dissolved oxy- In the activated sludge process the
gen, and the operation is then known as waste water to be treated is held for a
aerobic decomposition. Another group of period of time in a tank in which air is
microorganisms can thrive in an environ- blown through the liquid. This develops
ment devoid of dissolved oxygen. Under a lush bacterial suspension which brings
these conditions the process is known as about aerobic decomposition. The reten-
anaerobic decomposition. Although most tion time is dependent upon the waste
biological treatment today is aerobic, treated but will usually range between 4
there are some wastes which respond and 24 hr. BOD in lb per day is the
better to anaerobic decomposition. design criteria for these units and the
There are two broad types of bio- loading will vary between 15 and 150
oxidation equipment, trickling filters and lb per 1000 cu ft of aeration tank volume.
activated sludge. The trickling filter is a The air required is supplied by rotary
bed of graded rock, usually 3 to 6 ft deep, compressors or centrifugal blowers. The
but sometimes as deep as 10 ft. The bed diffuser system may be perforated pipe,
diameter may vary from 15 to 200 ft. nozzles, carborundum plates or tubes,
The rock is supported by an underdrain and, just recently, turbo-mixers provided
system for collection of the liquid flowing with a sparge ring. Purification effi-
over it. A rotary distributor on the top ciencies will range from 75 to 95 per cent
provides for uniform spreading of the depending upon the waste water and the
45-56
concentration of bacteria in the aeration particular purposes. Among the best

tank water. Higher efficiencies can known of these are the Guggenheim,
generally be obtained with higher bac- Kraus, contact aeration, dispersed-
terial concentrations, but this must be growth aeration, and biosorption meth-
balanced against an increased air require- ods. These have all been described in
ment. The concentration of bacterial various texts and they will not be dis-
slime (reported as suspended solids) will cussed here.
range from 2000 to 5000 ppm. Where the effluent from the treatment
Biological purification produces sludge, plant must discharge into a very small
whether by trickling filters or by ac- stream, the amount of organic material
tivated sludge. This must be removed remaining in the treated water may be
from the effluent before final disposal. too large for inoffensive assimilation; in
Settling basins providing from I j to 5 such cases additional purification be-
hr retention permit the solids to settle. comes necessary. Here use is made of the
Scrapers move the settled material to a oldest type of biological unit, the slow
central point for removal. The sludge sand filter. This is simply a sand bed
produced by trickling filters is removed which is dosed intermittently with the
completely from the system. In the effluent from the treatment plant. Slime
activated sludge process, a portion is growths develop on the sand and addi-
returned and mixed with the raw waste tional purification and straining take
water entering the aeration tank. The place. The effluent flowing from the
excess over that necessary to maintain a underdrains is clear and has a very low
satisfactory concentration of suspended BOD. The rate of flow through these
solids in the aeration tank is removed filters is extremely low and extensive
from the system. land areas are required, but they can do
The wasted sludge must be disposed of a most effective job.
in some manner. This can be a problem Modifications of the slow sand filter
because of its fairly large volume, in- are the percolation bed and spray irriga-
ability to dry readily on a sand bed, and tion. These use large areas of land where
evolution of offensive odors. Bacterial the soil is sandy and little or no clay is
decomposition of the wet sludge under present. Percolation beds make use of the
anaerobic conditions will yield a sludge sandy soil above the ground water table
that dries well and has little odor; this and require 5 to 8 ft of depth for good
process is widely used for sludge treat- operation. Low dikes are built and means
ment. Closed concrete tanks providing provided for dosing the areas once a day.
from 25 to 60 days retention and heated Dosing is normally equivalent to flooding
to about 90 F hold the raw sludge and to a depth of about 2 in.
allow bacterial decomposition to occur. The waste is usually diluted with water
The volatile solids are broken down from to provide a BOD of 300 to 500 ppm and
about 75 to 80 per cent to about 50 per applied to give a BOD loading of 100 to
cent and in so doing CO2, methane, and 200 lb per acre per day. Under such
nitrogen are given off as gases. If a conditions, purification efficiencies of 90
sufficient volume of gas is evolved it can to 98 per cent have been obtained.
be burned for heating the tanks and also Biological growths develop in the sand
used for operating gas engines in the which utilize the soluble organic material
plant. in the waste water as food and thereby
There have been many adaptations of provide purification. Air is drawn into
the activated sludge process to serve the soil during the dosing period; this
45-56
provides the oxygen needed by the bacterial growths develop. These ponds
organisms. can remove 95 per cent of the BOD and
Spray irrigation utilizes the same kill 99 per cent of the coliform bacteria;
general principle. Rotating sprays or thus purification is generally sufficient to
fixed sprays spread the diluted waste allow discharge of the efHuent into
over a large area, which can be crop land streams. These stabilization ponds have
or wooded areas. The spray period been quite widely used in the paper
usually lasts from 8 to 12 hr per 24 hr. industry and they are gaining acceptance
Sandy soil is a requisite, and purification in the textile and chemical industries.
is effected by biological growths in the They are used as a low cost method for
soil. The sprayed waste water should be municipal sewage treatment.
low in suspended solids to avoid plugging
of the soil. While this method has been SUMMARY
primarily developed for disposal of can- An attempt has been made to enumer-
nery and milk wastes, it is applicable ate the principal water treatment proc-
to almost any easily oxidized, nontoxic esses serving industry at the present
waste. time. New processes will undoubtedly be
A modification of the activated sludge developed in the future. The discussion
process is the oxidation pond. In this has been limited to the main technical
adaptation the waste water is held in a and economic features. Literature refer-
shallow pond for a period of days. Agra- ences have been given for readers desir-
tion from the atmosphere takes place and ing greater detail.
43-57

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STP148D-EB/Jan.

CHAPTER V—TREATMENT OF PROCESS WATER

and one of them may be dispersed in a Degasification:

Flashed , per cent

Flashed steam, per cent = X 100

temperature operation. Heat-recovery bination of these forces to remove liquid

and at normal evaporating rates, should Distillation equipment should be so

Ocean Discharge: ness to relatively insoluble calcium car-

to form nonadherent sludges;^ those During the decomposition of the bi-

hydroxide from sodium chloride, and complexes. Polysilicates are available

Neutralization: of dry material is weighed continuously.

Incineration: particles, called floe, which will settle

concentration of bacteria in the aeration particular purposes. Among the best

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