Dissolved-air Flotation As Applied to the Treatment
of Oil-production Water and of Refinery Wastes .i
ABSTRACT
The process principles of dissolved-air flotat~ona r e .
tlescr~bed a s they a r e a p p l ~ e d to t h e treatment of
oil-contammated water. The process is a means of
removing suspended m a t t e r fiom water by a t t a c h ~ n g
small a l r bubbles to the suspended mattei. The method
1s a s u ~ t a b l emeans f o r treatment of 011-well w a t e r
prlor to ~ n j e c t ~ o na ,s well a s a means of secondary
clarificat~on of refinery wastes. A d e t a ~ l e ddlscusslon
INTRODUCTION
D~ssolved-airflotation 1s used 111 the 011 fields and oil '
refineries a s a means of removing 011 and other sus-
pended matter from water T h ~ sflotatlon method most
. commonly uses a i l a s the g a s to facilitate separation.
011-field natural g a s IS used a s the n i e d ~ ain some field
installations. The leasons foi the removal of 011 and
other matter f i o m water a l e 1 , c o n d ~ t ~ o m nfgo r ~ n j e c -
tlon ~ n t oa n 011 sand In secondary-iecoveiy projects;
and 2, treatment f o r d ~ s p o s a leither In a recelvlng body
of w a t e r or ~ n t oa d ~ s p o s a lwell (In the f o l l o w ~ n g
d ~ s c u s s ~ o ndissolved-gas
, flotat~onw ~ l lbe used ~ n t e r -
changeably w ~ t hdissolved-a~rflotat~on.)In general, the
use of t h ~ sprocess In i e f i n e l ~ e sI S conceined with the
removal of pollutants to render the waste water ame-
nable to d ~ s c h a r g eto a recelvlng body of water. When
used to t r e a t refinery wastes, d~ssolved-ail flotat~on
usually follows a g i a v ~ t y011-water separator w h ~ c h
removes the bulk of the f r e e 011.' Dissolved-a~r flotat~on
may be used with chem~calsin oldel to f a c ~ l i t a t eh ~ g h e r
degrees of removal. I t I S the purpose of thls discuss~on
to detail the piocess prlnc~plesa s well a s some of the
problems a p p l y ~ n gthls method to the tieatment of
011-beaiing waters.
Physical Factors Affecting the Process
D ~ s s o l v e d - a ~flotat~on
r 1s a process f o r removlng sus-
pended matter from water usnlg m ~ n u t ea l r bubbles
whlch have a diametei of 100 microns o r less The
m ~ n u t ebubbles a r e attached onto the suspended matter,
thereby r e d u c ~ n gthe effectwe specific gravity t o less
than t h a t of w a t e r The reductlo11 of t h e effective
*Cham Belt Co . M~lwaukee.Wle
+Presented nt the sprlna-'meet~ng of the Pacific Coast D ~ s t r ~ c t ,
D ~ v ~ s r oof
n Product~on,Los Angeles. C a l ~ f May
, 1960.
'References are at the end of the paper
is given describing the process p r ~ n c ~ p l of
e s thls method.
Some of the ploblems a p p l y ~ n gflotat~onto the renioval
of 011 from water a r e also discussed. Chemicals, such
a s alunilnum sulfate, may be used to achieve a greater
degree of tieatment than t h a t obtained using flotatlon
w ~ t h o u tchemical aids. The chem~cal dosage w h ~ c his
reqt!~red 1s related to the quantlty of 011 in the waste
water, the physio-chemlcal s t a t e o f , the 011, and the
degiee of removal needed t o meet the treatment goals.
spcc~ficgiavlty causes the particle to separate a t a
higher veloc~tyin a n upward dliect~on.Emuls~fiedoils
and soluble 011s a r e not removed by t h ~ smethod unless
cheni~caltreatment can convert these 011s t o a suspended
state. The use of chemicals also a d s In flocculat~ngf r e e
oil globules whlch a r e very small In slze. Stokes' Law
( a mod~fication of Newton's Law f o r laminar flow)
tlescl:~bed the factols a f f e c t ~ n gthe r a t e of s e p a r a t ~ o n
of a p a r t ~ c l eniovlng through a fluld, v~z.:
D = dlametei of the p a r t ~ c u l a t emattei.
g = gravity constant.
pl = d e n s ~ t yof t h e 11qu1d.
p, = tlens~tyof the p a r t ~ c l e .
p = v ~ s c o s ~ oft y the I ~ q u ~ d .
71, = r a t e of rlse of the p a r t ~ c l e .
I t may be seen t h a t the r a t e of rise 1s t l ~ ~ e c t lpropor-
y
tional to the d~fferenceof the density of the 11qu1dand
t h a t of the particle. A f t e r s e p a r a t ~ o n of the a l r -
suspended p a r t ~ c l eh a s occurred, t h e floated m a t e r ~ a lis
iemoved by a propelly deslgned scum collector.
The mechanism a t t r a c t ~ n gand h o l d ~ n gthe a l r bubble
to the suspended globule o r p a ~ t ~ c may l e be cons~dered
a s am adsorption phenomenon. The surface character-
1st~ of the particle 1s a primary fact01 ~nfluencingthe
operation of the flotation process. Surface-actwe agents
may be added t o alter t h e adsorption c h a r a c t e r ~ s t ~ c s ,
a s is done In ore beneficiation. I n waste treatment,
however, t h e use of surface-active agents m a y be
economically proh~bltlve.
The r a t e of separation also may be increased by
Inc?easlag the slze of the suspended particles. According
 to Stokes' Law, the rate of separation is a f u n c t ~ o nof
diameter size raised to the second power. One of the
purposes f o r using chemical flocculants is to increase
the p a ~ t i c l eslze. The suspended matter 1s adsorbed,
trapped, 01 chemically united by the precipitated chemi-
cal coagulant. One o r more of the preceding attachment
mecha~lisins may contribute to the coalescence of sus-
pended mattel 111, w a t e ~ .Aluiii, ferrous sulfate, ferric
chlo~lde,and coppel Sulfate a r e commonly used floc-
culants. Alum IS, however, the most popular of those
llsted
Chemical Aids
When chemlcal flocculattng agents a r e added, pl:ec;pt-
tat1011 of soluble, colloidal, and e-mulsified matter may
be effected. The degree of removal of these materials
depends upon envr~onmentalfactors a s well a s the type
of floccularit used. Generally, the use of chemical floc- AVERAGE PARTICLE SIZE
- culants will not facilitate removal of soluble organic
(mm)

material othei than oil. Biological treatment 1s needed Fig. 2 - Effect of

Average Particle Size
to accompl lsh the removal of d~ssolvedorganic sollds. on Rate of Rise
Flocculation a s a means of promot~ngparticle growth 100 Ppm L~rne- 20 Ppm Bentonite
~ ~ ~ e c e c l tflotat~on
ng may contribute to the effectiveness 20-percent Recycle
of the flotat~onprocess where flocculants a l e used. The inc~easecl with mixing tlme to a constant value. I n
term flocculation implies a means of paiticle growth summaly, flocculation serves two purposes when chem-
uslng cont~olledagitation f o r a sufficient length of time lcal flocculants a l e used to treat water. The first is t o
t e sepalation. It h a s
to obtaun a n opt~nlump r e c ~ p ~ t a for inclease particle size to f a c ~ l i t a t ea more rapid separa-
been shown"11at a s the flocculation time is increased, tlon. The second 1s the maximum use of flocculants
the particle size of the flocculant was also increased resulting In lowel chemical dosages and, therefore,
(see Fig. 1). It was also demonst~atedt h a t the rate lowel. piocesslng costs.
of rise Increases with partlcle size a s shown in F i g 2.
T ~ I experimental
S work was carried out on a bench
- scale model under controlled condlt~ons a s noted in
Fig. 1 and 2. I t is also shown t h a t to obtaln maxlmum
1 1 Kay.
I
A h Dosage
(PPm)
blbHy Bentonite
Doswe
IPPm)
usage of flocculant (alum), suffic~entflocculation time
must be provlded (see Fig. 3 ) . It may be noted t h a t f o r
a constant chemical dosage, the alum flocculant removal I

TOTAL FLOCCULATION TINE

(m~nutec)
TOTAL MIXING TIME
Fig. 1 - The Effect of Flocculation Time on (minutes)
Average Particle Size Fig. 3 - Effect of Flocculation Time on Removal of
'
125 Pprn Alum - 10 Ppm Bentonite a n Alum-bentonite Flocculant by Flotation
 CHEMICAL FEEDER
ttr I RECYCLE DBTR!BJO
lN
I )IEMER
F L M A T K U TANK
PRESSURE TANK
AIR SUPPLY
I I
RECIRWLAlED EFFLUENT
SCUM COLLECTOR
Fig. 4'- Flow Diagram of a Dissolved-air
Flotation System
Process Elements , 2. P r o v ~ d e splessule drop to facilitate the formation
Basically, tlie process elements 01 flow diagram of
dissolved-air flotation is a step-wise plocess. These
stations a r e pressurized a e l a t ~ o n ,foimation of a i r (or
g a s ) bubbles of suitable size, attachment of tlie bubbles
on the partlculate matter, and the s e p a i a t ~ o nof t h e
suspended m a t t e r f l o m waste watel. In commercial
~ ) l a nunits
t thele a r e two metl~odsby which g a s bubbles
a r e i n t ~ o d u c e dto the water bearing suspended matter.
I n one system, a i r IS intioduced and dissolved In the
waste stream A g l e a t e r volume of ail can be dissolved
in the water by utihzing this method. I n tlie othei
system a portion of the cla~ifiedwaste watel in whlch
a i r IS dlssolved 1s reintroduced to the flotation tank.
The second n~etllocl (recycle) iequiies less pump
c a p a c ~ t yand h a s a lower o p e r a t ~ n gcost T h ~ smethod
a v o ~ d saddit~oilalpumping of the 011-bea~ingwaste to
f a c ~ l i t a t ebubble f o r m a t ~ o nPumping may tend to eniul-
sify t h e 011"s well a s bleak up flocculants A floccu-
l a t ~ o n basin p r e c e d ~ n g flotation may be used more
advantageously when a iecycle system is used
A flow diagram of a flotation system using ~ e c y c l e
effluent a s a means of intiociucing all is shown in
Fig. 4 The waste water may be treated with chem~cals
followed by a period of flocculat~on01 tlie waste w a t e r
may be subjected t o flotation d ~ r e c t l y ,w ~ t h o u ta d c l ~ t ~ o n
of cl~e~nicals. In t h e mixing zone of the flotation basin,
the waste w a t e r 1s mixed with a n all-charged stream
(iecycle). Here the minute a i r bubbles a r e attached to
tlie suspended m a t t e r This mlxture flows through a
distribution baffle ~ n t othe s e p a l a t ~ o nzone. The sus-
pended m a t t e r moves t o the top of the tank whele a
s u ~ t a b l eremoval means 1s plovided The clarified water
flows underneath the scum tlough and out of the
flotation basin
Application
F o r oil wastes, a recycle l a t e of 20 to 33 pelcent of
the waste flow 1s generally used The recycle flow 1s
piessurized to from 30 to 50 p s ~ gwith a centrifugal
pump. The amount of a i r (01 g a s ) which may be
dlssolved increases with the cluant~tyof w a t e r recycled
a s well a s t h e process pressure. With a process pressure
of 40 psig, 1 0 to 1.3 std cu f t of a i r 1s used pel 100 gal
of recycle flow. (Saturation f o r a i r a t 40 pslg and 64 F.
is approximately 0.95 cu f t per 100 gal F o r t h e same
condition the saturation value of CH, IS 70 percent
h ~ g h e r . )A~f t e r the inlection of a i r the air-water nilx-
t u r e flows t o a t a n k where the a i r is d~ssolvedin the
water. Valious pressure-tank deslgns a r e used. A pres-
s u l e tank provid~ngmeans f o r c r e a t ~ n gmore air-water
~ n t e r f a c e~ 1 1 1inclease the a~r-solution rate. The a l r
requ~renientf o r t h e f o r m a t ~ o nof a i r bubbles will depend
upon the method of a l r ~njection, t h e pressule-tank
design, effective holdmg time in the pressure tank, the
process pressure, the dissolvecl s o l ~ d scontent of the
water, and the temperature of the water
From the plessule tank, the recycle stream whlch
c o n t a ~ n sthe dissolvecl a i r flows through a pneumatic -
control valve w h ~ c hh a s three functions, viz:
1. Controls process pressure.
of a i r bubbles
3 P i o v ~ d e stulbulence necessary to c ~ e a t eminute a i r
bubbles
Not only is a reduction In pressure necessary to form
the a l r bubbles, but turbulence 1s also necessary.
The a~r-cliaigedstlearn (recycle) flows through a clis-
t ~ i b u t ~ oheader
n and nilxes w ~ t hthe lncomlng waste in
the nlising zone Here the mlnute bubbles a r e attached
to the suspended mattel. The d e t e n t ~ o n time in the
lnlxing zone langes from 30 to 60 sec.
The flotation basin design, a s indicated in F l g 4,,
follows the plocedure suggested f o r gravity-type oil-
w a t e ~separatols in Vol. I, APZ dlanztul 011 Dzsposc~l of
Rcfij~eqy1'I:astes.G The r a t e of rise of p a r t ~ c l e sis deter-
mined by labolatory tests' and with proper application
of the tuibulence and short-circu~tingfactors, a proper
tank slze may be calculatecl
As with all plocesses, flotat~oil is not universally
appl~cable Howevei, where it 1s aclvantageously used,
the l e t e n t ~ o n times a l e less t h a n those f o r gravity
sepalatois to obtaln equivalent results. Generally, the
designed holding tinie f o r flotation ranges from 10 to
20 min G r a v ~ t yseparators a r e designed w ~ t ha deten-
tion t ~ m evai ying from 40 to 90 nun
A second advantage of this inetliod is t h a t tlie
s e p a ~ a t ~ ocharacteristics
n of the suspended m a t t e r a r e
s t a b ~ l ~ z e Chemical
d flocculants assoc~atedwith varying
amounts of oil may have widely d ~ f f e r e n tseparation
v e l o c ~ t ~ e sSome
. particles niay settle, some m a y float,
and some may have a zero s e p a ~ a t ~ ov~~?l o c i t y . By
attaching a n a i r bubble, ~t niay be a n t ~ c i p a t e dt h a t all
of tlie paiticles ~ 1 1 1float. A tllild advantage may be
the lowel chemical dosages ~ e q u i r e d Chemicals need
not be added to Increase the specific gravity of t h e
flocculant a s m a y be necessary in a g r a v ~ t ys e p a r a t ~ o n
basin to achieve sufficiently h ~ g hs e p a l a t ~ o nlates.
Dissolved-air flotat~oncan be used in the preparation
of watei f o r injection into the pioducing strata. Flota-
tion in co~nbinationwith che~nicalt l e a t ~ n e n carries
t out
the following functions.
 1. Removes 011.
2. Removes other suspended matter.
3. Alds In tlie removal of ferrous Ion.
I t 1s also necessary t o n i a l n t a ~ n a proper caibonate
balance to prevent prec~pitatlonnl the sand a s well a s
f o r C O ~ O S I O I I control. The use of n a t u r a l g a s In flotatlon
~ n h ~ b l tthe s pleclp~tatlon of ferrous Ion, a s well a s
corroslon. Ferrous Ion 1s precip~tateda s ferric hydroxide
when oxldlzed by oxygen If a l r 1s used In flotat~on,it
may be necessary, when Iron 1s present, t o o s l d ~ z ethe
11on by aeration prlor t o s e p a r a t ~ o n111 the flotatlon unit.
A f t e r F e ( O H ) 3 1s formed by a e r a t ~ o n a, chelnlcal such
a s alum may be added t o form larger flocculant p a r t ~ c l e s
to a ~ dIII separation. When n a t u r a l g a s is used, the
~nstallatlon of the treatment system becomes more
costly because ~t should be deslgnecl to plovide a n
explosion-proof system. The flotatlon t a n k must be
covered and prov~cledw ~ t hthe necessary safety clevlces.
The v a r l a t ~ o n sin the charactei ~ s t ~ of c sthe 011-bear 111g
waste water, a s well a s the conditions f o r the cllsi~osal.
of the waste water, wlll result nl v a r ~ a t l o n s In the
degree of treatment. F o r example, the presence of
sulfide In refinery waste water may Increase the reclulred
chemical dosage. The optimum p H f o r cheni~caltreat-
ment may vary. Bench scale tests a r e necessary before
it 1s posslble t o p r e d ~ c tt h e t r e a t a b ~ l l t y of a waste
water. These tests should be conducted w ~ t l isuficlent
frequency and cluratlon to observe the optimum treat-
ment f o r the results deslred. This approach 1s par-
ticularly necessary f o r refinery waste water. F o r the
study of 011-field w a t e r a lesser program of testing 1s
requlred Bench scale test equipment is available fr0.m
manufacturers of flotatlon equ~pment.When bench- scale
tests ~ n d l c a t et h a t chemical treatment 1s necessary, tlie
most effectwe chemical, chemical dosage, and o p t ~ m u m
pH may be determlried through these tests.
Pllot-plant tests a r e helpful III t h e deslgn of large-
scale plants based on a flow-through capaclty. P a r t ~ c -
ularly a r e these tests helpful when considering the
treatment of a refinery waste. It is poss~bleto predict
more a c c ~ ~ r a t e tlie l y degree of varlatlon of performance
of a prototype u m t because of the usually large varla-
tlons w h ~ c hoccur In t h ~ stype waste water.
CONCLUSIONS
I n summary, d ~ s s o l v k d - a ~flotation
r 1s a means f o r
the removal of suspended m a t t e r from water. F r e e 011
may be removed w ~ t h o u tthe use of chemlcals I n order
to remove emulsified o r soluble oil, chemlcals a r e
lequlred to convert these constituents t o particulate
matter. When chemicals a r e requlred, flocculation a s a
step preceding flotation appears t o be advantageous.
Universal a p p l ~ c a t ~ o1sn not ~ n d l c a t e d ;each waste must
be examined on ~ t own s merits.
REFERENCES
lRohl~cli, G. A . A p p h c a t ~ o n of Alr F l o t a t ~ o n to
Refinery Waste Waters, Ind. ctntl Eng. Clienz., 46,
F e b 1954.
Qrown, G. B : Utlit 0 p e v a t i o . t ~John
~. Wlley & Sons,
Inc., New York, 1950.
SIiatz, W. J. and Wullsclileger, R: Studles of Some
Variables W h ~ c hAffect Chemlcal Flocculation When
Used wltli Dlssolvecl-Air Flotation, Proc , P?tv(hie
Tl~lelftltItttlttst~sctl Ii'ctstes C o ? l f t , v ~ ~ ~May
c t , , 1957
-'Eldrldge, E . F I~rtlicstv?ctl117ciste Trecctnrel~tPrrtc-
tlce, 1' 317, McGiam-H111, Inc., New York, 1942.
1st Edn.
Wougen, 0 A. ancl Watson, K M : Chet~~lcnl Process
Prl~tclpleb,p 117, John Wiley & Sons, Inc , New York,
1046.
6hIn~ll~ctl 071 I)tspvsnl of Refitlevy TVctstcs, Cliapt. 2 ,
Vol. I, Amellcan Petloleuni Instrtute, New York, 19.59,
6th Ecln.
;nIttt~itrtl Dtupu\~il ot Refi~lvryTl'(t~tt,,s,Chapt. 3,
Vol. I , Amellcan Petrole~umI n s t ~ t u t e ,New Yolk, 1959,
6th Ecln.
I \
DISCUSSION
I C. F P a r e n t (Petloleum D l v , Long Beach Harbor
Dept , Long Beach, Ca!if.) (wiltten) : Thls paper 1s a
complel~enslvetieatlse on the latest theory and appll-
c a t ~ o nof flotatlon ;s a means of cleamng waste water
to increasingly i l g ~ dstandards -
Natural g a s is b a n g used In tlie Wllm~ngtonFleld
because ~t loweis costs thlough e l ~ m l n a t ~ o nof a l r
complessols ancl ieductlon 111 corroslon Added expense
to provide a n explos~on-ploof system 1s 11n11ted to the
s l ~ g l i te x t r a cost of a n esploslon-proof e l e c t i ~ cmotor
fol the s k ~ m m e r Calbon dloxlcle In the form of engliie
exhaust g a s 1s bemg coiis~clerecla s a n addltlve to the
flotatlon cell effluent to plevent scale forniatlon, but ~ t s
extreme corios1r7it.y l)recludes use In t h e flotatlon cell
lndected water f o r the W~lnimgtonflood 1s sea water
obtamed floni shallow source wells. When thls 1s pro-
duced m combination wlth connate ivater, ~t IS harder
to clean because of the different cliem~calcomplex. -4
slow increase in lion sulfide IS symptomatic of sulfate-
reduclng bacteria ~nfestatlon,and 1s b e ~ n gtreated by
preveiitatlve bacteilc~des l a t h e r than curative meas-
ui es In the flotation cell.
Clarlty of cell eflluent 1s almost n dlrect f u n c t ~ o nof
p a r t s per mlll~onof mflux. F o r example, suppose wash
tank water l u n s over 200 1)pm; a f t e r the gravlty skim
pits thls would be ieclucecl t o 50 pl>m; then cell effluent
would a p p r o u ~ m a t e17 ppm Should cell niflux Increase
to 100, effluent would Inclease proport~onatelyto some
31 ppm Voluliie of thoughtput seems t o have llttle
effect on clailty until t h e cell 1s overloaded, although
thls may take place well below rated capaclty if severe
scallng has occulled. Another vltal factor 1s a reason-
ably steady influx l a t e , usually effected by a surge tank.
Use of flotatlon cells t o acli~evethe final clanficatlon
t o a n acceptable c o n d ~ t ~ ohas n the d ~ s t l n c tadvantages
of low cost, compactness, and rellab~llty;and t h e elmi-
~ n a t l o nof the escelsloi plol)len!s galns the deep g l a t -
itucle of opeiatlng men
Waste cl~sposal of all kinds 1s a serlous econonnc
ploblem foi many ~ n d u s t l ~ eand s tlils paper delineates
a n excellent solution to the c l a r ~ t yfactor *
Howarcl F. Kellel, Jr. (Jones & Keller, Iiic., Long
Beach, Callf.) (written) : We w ~ s hto thank th.e author
f o r a n excellent presentation of the dissolved-a~rflota-
tlon treatment of waste waters. I t was very interesting
to note the difference in overall treatlng econommcs and
effectlveness wlth unlts w111ch use recycle water f o r
solutlon of gas rather than solutton of gas 111 the full
stiealn Because we a r e mterestecl In knowlng more of
the efiect~veness of laboratory evaluatlon of waste
waters, we submit the following qnest~ons.
1. I s evaluatlon of waste waters best done with
samples of the wateis taken to a laboratory or IS the
evaluatlon best calriecl out 111 the field?
2. Woultl the additional amount of methane whlch 1s
soluble 111 water effect greater removal of oil and sus-
pended sohds o r IS ~ t solub~lity
s too great t o form an
addlttonal quantity of bubbles?
3. Would ~t be possible to clescrlbe more fully the
method of deterin~nlng"rate of rise"?
4 I s ~t iecommended that f o r removal of oil to below
5 ppm 111 011-field waste waters that flocculating agents
be a general rule?
We wlsh to agall; thank the author for the tlme and
e f f o t~ he put into the preparation of thls paper.
Mr. Katz (written): With reference t o Mr. Keller's
first question, the tests would best be carried out In
the field because there 1s the possiblllty of the test
samples changlng during transportation to a laboratory.
This characteristic IS common in lnany olly waters.
I n regard to the second quest~on,I do not believe t h a t
the Ilmitlng factor on the degree of treatnlent 1s neces-
sarlly a functton of the quantity of g a s bubbles formed.
Rather, the physical state - suspended, collo~clal, o r
dissolved-wlll determlne the degree of treatinent whlch
will be obtained without the addltion of chemicals. If
the quantity of oil III soluble or collo~clalstate exceeds
the concentration \\.hich IS deslrecl a f t e r treatment, ~t
wlll be necessary to use chemlcal atds to achleve satls-
factory treatment
The method f o r d e t e r m ~ m n ga rate of rise vla obser-
vatlon of a n Interface, a s quest1011 3 mentions, IS .
. described In reference 'iof this paper.
In answer to quest1011 4, flocculating agents generally
will.be required where 011-field waste'waters niust be
treated to below 5 ppin of oil I would assume t h a t there
wlll be esceptlons 111 some waste waters where the oil
content can be redaced to below 5 ppm wlthout t h e use
of chemicals.