V O L U M E 2 1 , NO.
7, J U L Y 1 9 b 9
LITERATURE CITED
(1) Ani. SOC.Testing Materials, “A.S.T.M. Standards on Petroleum
Products and Lubricants,” Method D155-45T, November
1948.
(2) Zhid., Method Dl56-38.
( 3 ) -in,. yoc, ~~~~i~~ Llarerials, ~ ~ ~ y m p o s i u non l Color,vslLlarch
1941.
(4) Diller. I. M..Dean, J. C., DeGray, R. J., and Wilson. J. W.,
I X D . E X G . C H E Y . . . i S A L . ED.,15,367-73 (1943).
( 5 ) Diller. I. M.. DeGrq.. 11. J.. and Wilson, J. W,, Ibid., 14, 60i-14
(1942’.
Determination of Oli in Oil-Field Waste Waters
H. DARWIN KIRSCHRI.4N, Lnicersity of California, Los Angeles, Calif.,
.Montgomery and Pomeroy, Pasadena 1 , Calif.
In anal5ses of oil-field waste waters “oil” is con-
sidered as the relativelj nonvolatile liquid compo-
nent that contributes to the formation of oil films
and deposits. The nonsaponifiable hexane-soluble
fraction most closelg represents “oil content” in
this sense. In anj analjtical procedure that uses
a solvent, renioial of this so1,ent prior to weighing
or iolumetric measurement must be accomplished
in a manner to minimize evaporation of the oil.
Drging the oil at room temperature after boiling
off the solient has been found satisfactorj. In the
wet-extraction method, samples of low oil content
(below- 25 p.p.m.) jield about 9 5 q ~of the oil in two
extractions and 999’~ in three; higher percentage
recoiery is attained at higher oil contents. Naph-
T HE determination of oil in oil-field waste waters is of con-
siderable importance where pollution control agencies have
set up standards of quality for wastes discharged into bodies of
natural water, or where the efficiency of facilities for waste water
treatment must he evaluated. In general, procedures previously
recommended have not been investigated with enough thorough-
ness to provide an adequate basis for judging their accuracy and
suitability: the results of such investigations, if any have been
made, are not available in published form.
This paper reports the results of an investigation undertaken to
develop procedures that will yield valid results in terms of a
reasonable understanding of the objectives of the “oil” determi-
nation. Two basic plans, the “wet extraction” procedure and the
“flocculation” procedure, have been elaborated and compared.
C O S S T I T U E N T S CONSIDERED A S OIL
Before evaluating analytical procedures for determination
of the oil content of waste water, a decision should he made as to
what materials are to be included in the category of oil. Oil-
field waste waters contain all’the hydrocarbons of natural gas
and oil from nietharie up, plus asphaltic and resinous materials,
fatty acids, and other organic matter. The hydrocarbons having
boiling points above normal atmospheric temperature-i.e.,
isopentane (2-methylbutane) and heavier-could he considered
as constituting the oil component of the sample. \Then the oil
is separated by solvent extraction, either with or without the aid
of flocculation, there is no practical \yay of separating the solvent
from the extracted oil without the loss of highly volatile fractions.
In one published procedure for determination of oil in waste
waters an attempt is made to overcome this difficulty by partially
distilling the sample and separating the distilled oil from the
water by gravity, with a subsequent volumetric measurement
793
(6) Gardner, H. A . , and Sward, G. G., “Physical and Chemical Ex-
amination of Paints, Varnishes, Lacquers, and Colors,” 10th
ed., Washington, D. C., Institute of Paint and Varnish Re-
search, 1946.
(7) Haren, Allen,Am. Chem. J . , 14, 300-10 (1892).
(8) Osborn, R. H., and Kenyon, W.C., IND.ESG. CHEM.,;IN.~L.
ED., 18, 523-30 (1946),
(9) Story, B. W., and Kalichevsky, V. rl., Ibid.,5 , 214-17 (1933).
(10) U‘hyte, L. K., J . Am. Oil Chem. Soc.. 24, 137-40 (1947).
RECEIVED
A u g u s t 23, 1948.
4hD RICHARD POTIEROY,
thenic acids are extracted with the oil and must be
separated by saponification. -4new procedure gives
results differing by an average of less than 1 p.p.m.
on duplicate samples. Ferric chloride is unsuitable
as a flocculating agent, because it produces sulfur in
the extract if the waste w-atercontains sulfide. Zinc
salts are satisfactxy. Results by the flocculation
method are reproducible with an average difference
below 1 p.p.m. on duplicates, but the results are
about 2 p.p.m. lower than those of the wet-extraction
method, because of incomplete trapping of the oil
by the floc and incomplete removal of the oil froni
the floc. Because the wet-extraction method gives
results of superior accuracy in less elapsed time,
the authors consider it generally preferahle.
( 1 ) . But even in this procedure, a small amount of ethyl ether
is used to collect all the oil in a capillary tube. Because of the
necessity of evaporating this ether, all the pentanes and a t least
part of the hexanes are lost. Some type of distillation procedure
may he the only way to get accurate results as far as highly vola-
tile components are concerned, hut any such procedure, if exact,
is certain to he complicated and too lengthy to he of value for
routine testing. The best way out of this difficulty is to ignore
hydrocarbons that evaporate rapidly a t room temperature, and
to consider that “oil content,’’ for practical purposes, means the
oil that remains as such after moderate exposure to the air.
This is a logical view, in so far as the pollutional character of the
water is concerned, for the highly volatile oils do not contribute
to oily films on the surface of polluted streams. The volatile
hydrocarbons may contribute to explosive atmospheres in sewers,
hut this condition may result from the presence of hydrocarbon
gases as well as vaporizable oils. From an analytical standpoint
this is a problem entirely separate from oil content.
The final delimitation of the category designated as “oil”
rvill depend in part upon the practicability of laboratory proce-
dures. The objective chosen in this research Mas the separationof
the components that are ielatively nonvolatile liquidsat room tem-
perature and contribute to the formation of oil films and deposits.
With this in mind a solvent should be chosen which will dissolve
the oils effectively, hut ~villhave a minimum solvent action on
nonliquid materials. In drying the separated oil prior to weigh-
ing, a procedure should he followed in which it will he possible t o
evaporate the solvent used in the analysis, together with frac-
tions of the oil similar to the solvent in volatility, hut without
too great evaporation of heavier fractions. Solvent and drying
technique must he chosen before comparisons of extraction pro-
cedures can be made.
794
~ . ... ..
Table I. Solubilitj of JIontebello Crude Oil in Solvents
(100 ml. of solvent pliic 600 mq. of crude oil)
Insoluble Residue,
Solvent 70of Sample
Neohexane
10.3
Cyclopentane 4.8
Carbon tetrachloridr 1.4
Benzene 1.0
Chloroform 0.95
- __
CHOICE OF S O L V E N l
Ariiung the aolveiits that may be considered in the aiialysi5 of
oil-field waste waters, some-for example, benzene, the ethers,
chloroform, and carbon tetrachloride-dissolve not only the
liquid hydrocarbons but also materials of the asphaltene class.
Alkane solvents, on the other hand, have very little solvent
action on the asphaltenei. Saphthenic hydrocarbons, such as
cyclopentane, are intermediate in action. The relative strengths
of various solvents toward petroleum components are revealed
by treating small bamples of crude oil a i t h the solvents and
weighing the insoluble residue. A series of tests of this sort with
Montehello crude is shown in Table I.
When strong solvents are used in extiactions of oil-field waste
waters, and the dried extract is treated with hexane, an insoluble
residue remains, which generally amounts to about 10% of the
total exti art. These hexane-insoluble residues from crude oil
or from evtractions of oil-field waste waters are black, amorphous
solids, typically asphaltenes. Samples of these residues from
various sources have been examined many times, and have not
8hon.n an oily or tarry consistency, with the exception of a single
anomalous case ( 3 ) .
The decision as to the inclusion of asphaltenes as a part of
“oil content” depends on the purpose of the analysis. Crude
oils hold asphaltenes in solution to some extent; hence these com-
ponents might be included as possibly rontributing to the total
quantity of an oily phase separating from waste waters. I t does
uot necesbarily follow, hon ever, that such materials would always
. ANALYTICAL CHEMISTRY
-
T l i c ~oils used m r e lfontebello crude having an il.P.1. gravitl
of 25 (specific gravity 0.902) and Yanta Maria crude with a n
4.P.I. gravity of 10 (specific gravity 1.00).
Small samples of the crudes were weighed into 3OO-ml. conii.a)
Hasks, spread adequately over the bottoms of the flasks. and
~lloivedto stand at room temperature, with subsequent weighing,.
Rt appropriate intervals. In one case, 10 ml. of chloroform w r e
added to the oil with subsequent evaporation of the chloroforni
by a stream of air until it W A ~apparently all gone. Result- ? r e
-honm in Table IT.
-4comparison of the t h o ~ a i n p l a sof Montebello crude >how.
that the percentage loss of a eight is greater for the smaller sample
as would be expected, yet the difference is relatively slight. The
rhxperinient also shows relativdy little difference in behavior of
the two crudes. Rather surprisingly, the heavy Santa Maria
crude shows a slightly greater loss in n eight than the less dense
Montehello crude. A greater range of behavior would n o d ( ~ u b t
he found if a greater variety of crudes were tested.
The fourth test shows that some of the added solvent raiiiained
with the oil for an hour or more, but after 2 hours the figuret for
percentage of loss are the same as for the sample to w h i v h rir
rhloroform had been added.
VOLATILITY LOSSES DURING DISTILLATION OF SOLYE17
The losses attending the proresr; of distillation of the soh-rnt
were studied.
In each test a sample of Montehello crude was weighed iiitu a
300-ml. conical flask, and a 200-ml. portion of solvent’was added,
and then distilled off. I n the distillation process, a water bath
was used for heating and the flask was connected to t,he con-
denser by corks and a glass angle tube 10 mm. in diameter. The
solvent was dist’illed down to a volume of 3 to 5 ml. The flask
was then disconnected and the last of the solvent removed by
tilting to pour out the vapor, reheating, if necessary, by a momen..
tary immersion in the water bath and tilting again, until removat
of the solvent appeared to be complete. The flask was theis
placed upright near the balance and wrighed at interval. The
results are .shown in Tahle 111.
l h e losses are substantially grritttlr than when the saiiipler
I ,

be a part of the oily phase. Hecause they are not themselves \yere merely exposed to the air, aiid generally increase with
oils, and the objective is to determine, as nearly as possible increasing boiling point of the solvent used. Exceptions are
the “relatively nonvolatile liquids,” the decision in this research noted in the case of benzrne u t 1 and 2 hours, but this WAS prole-
was to consider only the alkanr-boluble material as oil. ThcI :ibly due to incomplete removal of the txnzene.
solvent selected for this purpov is rssentially a mixtulr of iso- The last line of Table I11 shows the results of re-use of a solvent
meric hexanes, \old as “mivetl hpxanrs” anti hereinafter referreti previously used in a similar experiment. The accumulation in the
to a i “hevarir.” In certain Y i e p of the procedures stronger solvent of volatile fractions of the crude oil evidently diminishek
solvent9 are usrd, hut the final vparatiori is made a i t h hexant, dmequeiit lossrs. This wis obsrrvrd also with other solvents
T h r standard procedure of thr Inieiiran Public Health .issocia- in preliminary experiments. After this behavior became ap-
tion for determining “grease” i l l +w:ige ( 2 ) tilw II+* a n alkane parent, all solvents were redistilled before reuse, and roughly 20%
solvrrit (petroleum ether)
<!iscarded at the end of the distillation. When seeking the mos1
:tccurate results on small quantities of oil, it is desirable to purify
I)KYI1(: O I L PREPAH \ I’OHY ‘IO WEIC;HI?(.
the dolvents by two successive distillations.
111 ariy practical analytical procrdure, the oil will be separatrtl Thci object of the analysis is to heparate relatively nonvolacilr
in the form of a dilute solution in an organic solvent. The solverii oils. Hence it is desirable to hold the losses of volatile fractione
must then be removed by distillation 0.i- evaporation and the clowii t o the minimum consisterit \Tit ti complete removal of the
containing vessel brought to equilibrium with the laboratory air. nolvent. The loss of these fractions. however, does not diininish
To secure information about the loaves of oil due to evaporatioii the usefulness of the result.: it’ t h t , [)rwwIure gives rra*m:3hl>-
and to develop a suitable technique for drying the extracted oil reproducible values.
prior to weighing, a study was made of the evaporation losseq of The foregoing experinlent?;led to the adoption of a procedure
small samples of crude oil when expospd to thP air. ,*iihstantially :is outlined ahorr-distillation on a water bat’h.
with reinoval of the last of the solvent
~ . . -. . . _____
~ ___ by gentle warmirig and tipping of t’he
Table 11. Loss of Oil I h r to E\aporatinri flask. Subsryuently the flask is sup-
Original ported in the balance room for 1 to 2
Weight of
’I’ypeof Crude Oil, 0.25 0.5 1 Time,
2 tIours
3 .. 4 6 ......24~- hours i n an inverted position. When the
Crude Oil RIg. Per Cent Change of Weight quantity of oil is too great to permit this.
Montebello 530.1 -1.2 -1.9 -2.4 -2.9 -3.5 ... the flask is left on its side for approxi-
Montebello 48.4 -1.2 -1.6 -3.1 -3.5 -4.5 .. ... . ,
BantaMaria 544.3 -1.2 -2.2 -3.1 -3.6 -4.1 -4.8 -4.5 ... mately one day. The tare weight
Santa Maria + the flask is determined after w-eighing
chloroform 593.7 +28 +8 -1.8 -3.5 -4.1 -4.3 -4.5 -5.0
-. -- -__ flask plus oil, hy rinsing out t h r nil
V O L U M E 21, NO. 7, J U L Y 1 9 4 9 79s
a subsequelit separation of these acids by saponification. The
Tahle TIT. Loss of Oil During Distillation of Solvent details are given in the elaboration of the procedure below.
Boiling Original Time, Hours
Point of Weight 1 2 3 24 COMPLETENESS OF EXTRACTION OF OIL BY DIFFEREh'I
Solvent, of Oil, % Change from Original Weight
Solvent c. hIg. of Oil TECHXQUES

Ethyl ether 35 497.1 -7.0 -8.5 -

8,- -
9.2 .ittempts to extract oil from oil-field waste water by niaim
Methylene chloride 40 498.4 -7.5 -8.6 -
8. -
9.8
ally shaking with hexane gave unsatisfactory results (Table VI).
Chloroform 61 505.7 -7.8 -9.6 -1O.U -10.7
Benzene 80 :04. -3.4 -9.0 , . . . -11.00
Methylene chlorideu 40 ~ 2 8 . 8 -4.4 -4.7 ... . , ..
Complete extraction could not he a,ttained with a reasonnhle
" Sample re-used as ret-overed b y distillation from previous analysis rxpenditure of time and energy.
If the oil were present i n the waste waters entirely ill the foriii
Table 1V. Effect of acidification upon Quantity of Hexane o f colloidal droplets, complete ext,raction should be readily
Extract attained. Much of the difficulty is no doubt due to the fact that
Acidified Not R considerable amount of the oil is bound up with particle& of
Sample .Icidified Difference :Isphalt and other solid material, ,so that effective contact betweell
Parts p e r million of extract
wlvent and oil is not easily attained. With a solvent, such ar
kirat extrnction 261 141 123
Second extraction 12 15 27 htinzene or chloroform, which will dissolve asphaltic materials.
Third extraction 19 6 13 the extraction end point ~hould.be more rapidly approached.
Total 3325 162 163 'To determine the correc*triess of this concept, samples of oil-
. -. .... . . ... -. . . . . ..
~

t i ~ l dwaste water were subjected to successive extractions Lvitl:

rhloroform, employing manual shakiiig (Table VII).
with the solvent and allowing the flask to stand in the balance Comparison of Tables VI and VI1 shows, as expected, that the
rnnm for 2 hours or more. eixtraction by manual shaking approaches an end point niore
rapidly when using chloroform than when using hexane.
UET-EXTRACTION PROCEDURE .illthough the oil can be quantitativelj- recovered by manua!
-haking with chloroform, this requires considerable expenditure
The wet-extraction method has been shown to be suitable for of time and effort. ZIec-hilnicaI agitation was then tried as R I
the determination of grease in sewage and certain industrial wqier method.
wastes ( 3 ) . Detailed examination of its performance as applied
to oil-field waste waters revealed two problems requiring special Aisewing-machine iiiutur wac equipped with a Monel stirrrr
35 mm. in diameter which could be loivered int'o a wide-mouthed
investigation: possible extraction of organic acids from the water 1-gallon bottle. Use of a rheostat controlled the speed of rota-
arid attaining complete extraction of the oil. tion to about 2000 to 1000 r.1i.m. Hot,h hexane and chloroforni
The magnitude of the first effect became apparent when suc- were tried: 200 to 300-ml. portioiiu of solvent were used in each
cessive extractions were made of two identical samples of Santa extraction with similar liut n o t idmtical water samples of 2 to 3
liters.
Fc Springs waste water, one of which had been acidified, while the
othtar was left at its normal p H value of 7.6. R e s u h are shown I t is evident that mechauical agitation gives much better
in Table I\-. recovery in each extraction than manual shaking, and that there
The increase of extracted material in the acidified sample is little difference in this case hetween the two solvents. (How-
aniounted to 163 p.p.m. in three extractions, which indicates ever, longer periods of agitation employed with hexane may liavr
that organic acids are potentially a source of large errors when thik winpensated for some difference in solvent action.) Eaclb
pH is low enough to perinit their extraction. extraction yielded 75 to 80% of the oil remaining in the sainple:
111 another test, a sample of Wilmingtoii oil-field waste wat(Jr thus substantially complete removal can be effected in four ex-
was extracted with hexane, using high speed stirring. The total tractions and for approximate piirposes two or three extraction*
extract recovered was dissolved in an ether-alcohol solution and would be satisfactory.
titrated lvith sodium hydroxide. Subsequently hexane and
water were added and the mixture was shaken, thus transferring
the oil t o the hexane layer and leaving the saponified acids in the Table V. Quantity and Acidity of Extracts
aquwus phase. Two additional extractions were also made of Weight of Me. oj
Extract, M g . Aside
t'he original waste water sample using chloroform, with sub-
Firat extraction, hexane a t p H 7.2 16.8" 0.028
sequent titration with base. For comparison purposes, the Two additional extractions, with chloroform 30.3 0.13
weights of extract obtained by :ihexane extraction at pH 11, Hexane extraction of identical sample at P H 11 12.4 0.005
Flocculation method, hexane extraction 13.0
by the flocculation method, and hy a hesane ext,raction of the Chloroform extraction with saponification a n d
hexane extraction of unsaponified oil 12.5
saponified chloroform estract are inrluded i n t h e quantit:atire
Saponification left 11.8 mg. of oil.
result,s summarized in Table \-.
The result obtained by hexwile extraction at pH 11 led to the
Table VI, Hexane Extraction Using Manual Shaking
hope that this might afford a simple way t o prevent extraction
Extraction No. Shaking Time Oil Recovered
of the acids. An attempt was made to analyze Saiita F'e Springy
.Win. P.p.m. "IC
waste water by this means, but if wili impossible to prevent 1 2 15 28
the extraction of fatt'y acids until the pH TWS raised to such a 2 2 13 25
3 2 9 17
value that the voluminous precipitate of calcium carbonate and 4 30 15 28
magnesium hydroxide prevented coniplete recovery of the oil.
Corrections for extracted acids might be made on the basis of a Tahle VII. Removal of Oil by Successive Extractions.
titration of the extract, using an assumed equivalent weight for Using Chloroform
the acids. This equivalent n-eight is variahle, however, and if the Method of Agitation Sample 1 Samplr. 2
acid con ten^ is high and the oil content is lowl as in the case of the P.p.m. % P.p.m. LI

Kilmingtori water (Table I-),uncertainty of the correction will he Alnnual shaking, 5 min. 28.8 70.5 26.8 53.5
Second manual shaking, 5 min. 6.7 16.3 13.7 27.3
large relative to the true oil content. Third manual shaking, 5 min. 3.2 7.8 7.8 l5~.5
Additional motor stirrer extraction
The most practical way to overcome this difficulty appears to
be extraction under ronditions suitable for complete recovery of
.5 min.
Total extract
-2.2
40.9
- 6.4
100.00
-1.9
50.2
- 3.7
100.00
the oil, regardless of the a m o u n t of organic acids extracted. and
796 ANALYTICAL CHEMISTRY

With the usual oil-field waste waters of moderate oil content

Table YIII. Hexane and Chloroform Extractions Using this sludge layer appears very light in color after the second
Mechanical Stirring extraction. The small fraction of the original oil content of the
sample remaining in this layer may be neglected in most cases,
but when more voluminous than usual and when maximum
accuracy is desired, a third extraction may be indicated or this
95.4 81 102.2 . 82 sludge layer may be separately extracted with a small portion of
16.8 14 15.7 13 solvent.
4.3 4 5.8 4
4 1.1 1 (1.3)a At the conclusion of an analysis, a small amount of emulsified
__ __
la
chloroform remains in the water and settles to the bottom of the
Total 117.6 100 125.0 100
a Assuming that a n additional 1% would be recovered in fourth extraction. vessel after a few hours’ standing. The amount is generally so
small that additional operations to recover its oil content are not
Table IX. Extraction of Oil by High-speed Mixing with worth while.
Hexane
Oil in First Oil in Emulsion Total LABOR4TORY DIRECTIONS FOR WET-EXTRACTION PROCEDURE
Time, Extraction. Layer, Extracted, %,Remaining
Minutes % of Total % of Total % in 1% ater Transfer the sample of water (about 2.5 liters) to a 1-gallon
1 70 2 7 73 27
bottle with a sufficiently wide mouth to admit a motor-driven
5 83 7.3 90 10 stirrer but not wider than necessary, so that loss by spray during
15 81 12.7 94 6 agitation may be kept down. Add a 30 to 50-ml. portion of
30 90 2.0 92 8 chloroform to the original sample bottle, taking care to rinse
off the stopper, and shake. Add this solvent to the water sample
Table X. Duplication of Results by Wet-Extraction and repeat the process with fresh portions of chloroform until tile
Method bottle is sufficiently cleaned for the accurary desired in the
Oil Content, Parts per Million
analysis. Add to the water enough more chloroform to make a
First Second total of about 200 ml. and then subject it to 5 minutes’ stirring
Water KO, analssis analysis Ar. Difference with a motor-driven agitator a t sufficient velocity of rotation
to keep the solvent and water well mixed.
Decant most of the supernatant water back into the original
sample bottle and pour the chloroform with the remaining tvater
into a 500-ml. separatory funnel. Run the unclear solvent layer
off into a second separatory funnel. I t mill usuitlly become clear
with a small amount of viscous sludge at the solvent-water inter-
face. If the solvent layer is not cleared by this procedure, allow
Ar. difference hetween 1st and 2nd analyses 0.86 the second funnel to stand for a fetv minutes and give it a single,
sharp shake which will usually break the “emulsioii” and give a
clear solvent layer. With care to keep the stem of the separatory
funnel free from water, run the clear chloroform througn a filter
I n contrast to sewage, in which the sample yields its grease paper into a 300-ml. conical flask.
Add the water remaining in the first separatory funnel to the
content readily on moderate shaking with the solvent for short original sample bottle. \“ash the sludge in the second funnel
periods of time, the oil-field waters require vigorous agitation. out of the funnel top into the water and repeat the extraction
During this agitation, a certain amount of viscous emulsion is process as previously outlined.
produced which accumulates between the water and solvent While the second extraction is being made, connect a condenser
to the flask containing the filtered cdoroform solution and distill
layers when the mixture is allowed to settle. I n the experiments the chloroform by partially surrounding the flask with hot water.
shown in Table VIII, this emulsion layer was left with the water When the volume is reduced to 10 to 20 ml., add the second
to be subjected to subsequent extractions. It appeared likely extract to the same flask and distill in a similar fashion down to a
that a substantial portion of the oil unrecovered after each suc- volume of about 1 ml. Remove the last portion of solvent by
pouring the vapor out of the flask. To the cooled flask, add 5 ml.
cessive extraction by high speed motor stirring might be present of ethyl ether, followed bv 10 ml. of ethanol or 2-propanol, about
in this emulsion layer. .kccordingly, a series of tests was run n i t h 1 ml. of 1 S sodium hydroxide, and 2 drops of phenolphthalein
four identical samples, in which the emulsion layers were in each indicator solution. S o w wash the contents of the flask with 200
case separately extracted. The time of stirring was also varied. ml. of hevane into a separatory funnel containing about 200 ml.
of distilled water. Gently shake the mixture, then draw off the
Table I X presents the results. water layer. Repeat this washing with water until the water
After agitation for 5 minutes or more the amount of the oil shows no color of the phenolphthalein.
remaining in the water is 10% or less of the total oil content. Draw off the last portion of wash water and filter the hexane
Agitation for 1 minute gives poorer removal, but there is relatively layer into a 300-ml. conical flask. h 50-ml. pipet equipped with a
rubber suction bulb IS convenient for the transfer of hexane to the
little advantage in times longer than 5 minutes. filter. Wash the filter paper well with small portions of hexane.
When chloroform is used as the first extracting solvent, the Distill off the hexane down to a volume of about 1 ml. Remove
problems of sludge or emulsion layers become somewhat different the flask from the water bath, and remove the vapor by tipping.
than when hexane is used. mhen chloroform and waste water Wipe o f f the outside of the flask with lintless cloth or paper and
place it neck down through an iron ring on a stand near tile
are vigorously agitated, and allowed to settle for a few minutes, balance; weigh after 1 to 2 hours. (If the quantity of oil is so
three principal layers separate: an aqueous phase on the top; large that it may run out of the flask, lay the flask on its side and
a bottom layer which generally consists of droplets of chloro- weigh the next day.) To obtain the tare weight of the flask, warn
form separated by aqueous films; and, between the two, a it out with several portions of hevane and again bring to equilib-
rium with the atmosphere. Inasmuch as the flask is now cool,
“sludge” layer of water, solvent, air, and solid matter. I n the a longer time is needed; 2 hours are adequate.
recommended procedure set forth below the water is poured from
the top of the bottle used for agitation and the lower layers are Reproducibility of results attainable by this procedure is in-
transferred to a separatory funnel. Subsequently, the bottom dicated by the series of analyses of duplicate samples shown in
layer in the funnel, consisting principally of chloroform, is run Table X.
into a second separatory funnel. This operation usually causes
the separation of clear chloroform, apparently by disrupting the FLOCCULATION METHOD
films that separate the chloroform droplets. The sludge layer is The flocculation procedure as developed by the Committee
returned to the water for a second extraction, whereby any oil on Waste Disposal of the American Petroleum Industry ( I )
that it contains is largely removed by dilution in successive ex- recommends that the final measurement of the separated oil be
tractions. made volumetrically in a special apparatus. This volumetric
V O L U M E 21, NO. 7, J U L Y 1 9 4 9 797

a d d i t i o n a l . From the re-

Table XI. Wet Extraction Versus Flocculation with Zinc Carbonate maining water, another 22%
(Comparison of wet-extraction a n d flocculation methods. All figures in parts per million) was recovered by a single - wet
Samples ~ e x t r a c t i o n . The total re-
Line Oil Recovered from 1 2 3 4 5 6 7 8 9
covery averaged 110% of the
1 First extraction, first floc 3.21 4.15 1.89 5.70 3.41 2.Y8 4.26 19,68 2 9 . 7
2 Second extraction, first amount found by the proposed
floc 0.88 0.69 0.85 0.06 0.00 1.00 0.65 1.38 ... wet procedure, using two ex-
3 Extraction of second floc 0.05 0.75 0.06 0.70 0.06 0.29 1.19 0.52 1.5
4 Total by floc 4.14 5.59 2.80 6.46 3.47 4.27 6.10 21.68 31.2 tractions. ; i third extraction
5 Wet extraction of filtered
water 2.10 L54 0.61 2.00 2.16 0.23 0.43 1.04 3.6 presumably would have yielded
6 Total recovered 6.24 7.13 3.41 8.46 5,63 4.50 6.53 22.62 31.8 an additional 5%, leaving a
7 By standard wet extrac-
tion 4.60 7.10 4.05 6.22 5.48 3.92 6 . 6 2 22.20 3 5 , l d i s c r e p a n c y of 5 % . This
8 Difference, line 7 - line 1 - 1 . 3 9 -2.95 -2.16 -0.52 -2.07 -0.94 -2.36 -2.52 -5.4
9 Difference, line 6 - line 7 + 1 . 6 4 + 0 . 0 3 - 0 . 6 4 +2.24 +O.l5 +0.58 -0.09 +0.42 +0.30 difference p r o b a b l y is n o t
significant, as it would average
only 0.5 + 1.5 mg. of oil in
the samples taken. This may
measurement is only slightly faster than weighing and is decidedly be considered satisfactory agreement, in vie\\- of the fact that
less accurate. In the present research it was desired to secure the two groups of analyses involve five operations and ten flask
results of maximum accuracy, often using samples from which the weighings on each sample.
yield of oil was only a few milligrams, and to obtain results suit- With samples of higher oil content, the discrepancy between the
able for comparison with gravimetric results secured by the wet- two methods is relatively less, but nevertheless substantial.
extraction method. Hence the extraction of the floc was fol- Thus sample 8, containing 22.2 p.p.m. as determined by two wet
lowed by the removal of solvent, drying, and weighing of oil extractions, yielded 89% of this amount by a single flocculation
in the manner previously described for the wet-extraction pro- and extraction, and 106% by t x o flocculations, re-extraction,
cedure. and wet.extraction of the water. Sample 9, showing 35.1 p.p.m.
Tests of the flocculation method were first made with ferric by two wet extractions, yielded 85% of this amount by the simple
chloride as the flocculating agent. I t was found that if the waste flocculation procedure, and 99% by double flocculation and wet
water sample contained sulfide, the material extracted from the extraction of filtrate.
dried ferric hydroxide floc included sulfur. Other flocculating
agents were then tried. -4luminum hydroxide and zinc car- REL4TIVE MERITS O F FLOCCULATIOY 4 Y D WET-EXTR4CTION
bonate appeared most suitable. Both trapped the oil just as METHODS
well as iron hydroxide and neither yielded sulfur vrhen used with The wet-extraction method, as previously shown, gives results
sulfide-containing aaters. Zinc carbonate is more compact (Table X ) which, on samples with 3 to 125 p,p.m. of oil, are
and filters much more easily than aluminum hydroxide and duplicable within an average difference less than 1 p.p.m. On
therefore was used in most of the flocculation experiments. samples of oil content up to 35 p,p.m. a comparison of the results
A number of tests for acidity in the material extracted from the of the wet-extraction procedure with those obtained by two suc-
floc by hexane showed no evidence of the presence of organic cessive flocculations followed by a wet extraction showed differ-
acids. ences averaging less than 1 p.p.m. (Table S I ) . These facts
The procedure finally adopted for the flocculation method is as indicate that the wet extraction method gives a reliable measure
folloR s: of the oil content of the sample; “oil” is understood to mean the
T o a sample of 2 to 3 liters, add 5 millimoles each of zinc hexane-soluble, nonsaponifiable, relatively nonvolatile liquid
acetate and sodium carbonate in solution. -4fter thorough component of the n-aste water.
mixing, allow the floc of zinc carbonate to settle and filter the The flocculation method gives results that are similarly repro-
supernatant liquid through a qualitative paper. Toward the end ducible and consistent among themsevles, but in waters of low oil
of the filtration, transfer the floc to the filter paper and allow the
paper to stand in the air until thoroughly dry. Wash out the content are about 2 p.p.m. lower than the Ret-extraction method.
oiiginal sample bottle with 50 to 100 ml. of hexane to remoye any As it has been demonstrated that this amount of additional oil
oil on the walls and stopper. Separate the water with a separa- actually can be recovered from the water by an additional
tory funnel and transfer the hexane to a Soxhlet apparatus, taking wet-extraction operation, it may be concluded that the dis-
care that no drops of water arc included. Place the dried filter
paper and floc in a Soxhlet thimble and extract for 2 to 3 hours crepancy is due to incomplete recovery hy the flocculation method.
with hexane. At the end of the extraction period, reduce the K i t h adequate equipment, the working time per analysis is
volume of solvent in the receiving vessel to 2 to 3 ml. Dis- about the same for the two methods. However, results can be
connert the flask and remove this last portion of solvent as di- obtained in considerably less elapsed time by the wet-extraction
rected in the wet-extraction procedure. After removal of the
solvent, place the flask in an inverted position near the bslance for method. Six hours of elapsed time are adequate for a wet-
1 to 2 hours; then weigh. Wash the oil out of the flask with estraction analysis, but in the flocculation method the precipi-
several small portions of solvent and dry the flask as before to tated floc must be dried at least overnight, so that results cannot
secure its tare weight. be secured in less than 2 1 hours.
Early tests on duplicate samples by the two methods showed
ACKYOWLEDGMEYT
that results were generally somewhat lower by the flocculation
method. This discrepancy was found to be due to incomplete The authors acknowledge the sponsorship of the Los .4ngeles
removal of the oil by the floc and incomplete extraction of the County Sanitation Districts and the Santa Fe Springs Waste
oil from the floc by hexane. This is well demonstrated by the Water Disposal Company for research on this subject.
series of comparative experiments shown in Table S I , in which
repeated flocculations of the water, repeated extractions of the LITERATURE CITED
floc, and a wet extraction of the water after flocculation give a (1) .lm.Petroleum Inst., “Report on Disposal of Refining Wastes,”
basis for comparison with the results secured by the wet-extrac- 3rd ed., Sec. I, ;ippendix 5, Sheets 1-5. April 1941.
tion method as previously described. (2) Am. Public Health Assoc., “Standard Methods for Examination
The first group of seven waters had oil contents below 10 p.p.m. of Water and Sewage,” 9th ed., p . 155, 1946.
(3) Pomeroy, Richard, and Wakeman, C. M.,ISD EX. CHEY.,
For these, on the average, a single flocculation and extraction ANAL.ED.,13, i95 (1941).
yielded 6170 of the total oil recovered. A re-extraction of the
first floc yielded another lo%, and second flocculation gave i % RECEIVED October 29, 1948