1042 INDUSTRIAL A N D ENGINEERING CHEMISTRY Vol. 19. No.

Solubility of Paraffin W a x in Oil

By F. W. Sullivan, Jr., W. J. McGill, and August French

STANDARD
OIL COMPANY
(INDIANA),
WHITIKO,IND.

A KNOWLEDGE of the
solubilities of paraffin
wax in petroleum oils
a t various temperatures, and
Paraffin waxes of 111" F., (43.9'C.), 125" F. (51.7"C.),
and 145' F. (63.8' C.) Saybolt melting points and con-
taining relatively few individual hydrocarbons have
been obtained by the repeated fractionation of 125' F.
midcontinent, and hence its
value is doubtful for calcula-
tions involving this crude,
(51.7' C.) Saybolt melting point commercial paraffin Preparation of Waxes
of the effect of viscosity of
solvent and the melting point wax from midcontinent crude. The solubilities of The waxes used in these
of the wax upon solubility, is these fractionated waxes and of the 125' F. (51.7' C.) experiments were f r a c t i o n s
of considerable practical value melting point commercial wax itself have been de- from the vacuum distillation
in filter-pressing wax distil- termined in petroleum ether (boiling point 21.0° to of 50 liters of 125" F. (51.7'
lates to remove the wax. It 82.0' C.) and in a number of midcontinent petroleum C.) melting point wax ob-
is also useful in making cal- oils of varying viscosities. Some of the oils represent tained from the wax refinery.
c u l a t i o n s involving the re- narrow cuts from a fractional vacuum distillation; This wax had been sweated
f r i g e r a t i o n of wax-bearing others are blends of oils of widely separated viscosities. from intermediates, and con-
oils. Solubility data in the Solubilities were determined a t various concentrations sequently did not contain the
literature consist principally and curves were constructed showing the variation of highest melting waxes sepa-
of figures for supposedly pure these solubilities with temperature, viscosity, and rated in pressing.
h y d r o c a r b o n s from either melting point. -- the fractional distilla-
-ffnr
synthetic or natural sources, tion of the wax, a still of 10
in the usual organic solvents. Such figures have little or no liters capacity was made. The body of the still consisted
direct value in plant operation. Prac&ally all of the meager of a 9-inch (23-cm.) length of 10-inch (25-cm.) pipe with
information upon solubilities in petroleum oils which is avail- plates welded at either end and appropriate openings for
able was obtained on oils and waxes from crudes other than charging and draining. The fractionating column was a
1 Presented before the Division of Petroleum Chemistry at the73rd Meet- Z1/2-inch (6-cm.) pipe 18 inches (46 cm.) long, filled with
ing of the American Chemical Society, Richmond, Va., April 11 t o 16, 1927. plates of 3/8-inch (1-cm.) mesh wire screen spot-welded a t
2-inch (5-cm.) intervals on a thin rod running through the
center of the tower. An iron pipe '/z inch (1.3 cm.) in
diameter and 30 inches (76 cm.) long served M an air con-
denser. The receiving system consisted of a 500-c~.balloon
Aaek with a stopcock outlet. Two Cenco oil pumps were
used to maintain the vacuum at 5 111111. When all the fittings
had been carefully tightened after the threads had been
painted with graphite paste, a 5-mm. vacuum was readily
maintained under operating conditions. I n fact, one pump
was at times sufficient. From one to four Meker burners
supplied the heat. The tower was wound with electrical
resistance wire. It was found convenient to heat the tower
a t the beginning of the run, both tosave time and to break
any foaming caused a t the beginning of the distillation by the
evolution of gas and moisture from the wax on the application
of heat and vacuum. After the distillation had once started
I I / I 1
September, 1927 I L D U S T R I A LAAVD ENGINEERING CHELVISTR Y 1043

I I
I
I I
PUTE V
SOLUBILITY c+
IIlF1438CIMP -~
PARAFFINE W M

SAYBCCT IOOF VECc)51TY

OF OIL %LENTS

3 ; , \ _____

ali heating of the tower was found to be unnecessary and was

therefore discontinued.
PLATE V I
Five such distillations of 10-liter charges of 125" F. (51.7' SOLUWLITY OF
C.) melting point refined wax were made. I n general, the IPST<51.?21 MI?
PARAFFINE WAX
melting points of like cuts checked each other fairly well.
The 0-10 per cent and 10-20 per cent cuts from the five SAYBOLT DOF VISCOSITY
OF OIL SOLVENTS
~

distillations were combined to give 10 liters of material to

be distilled B second time. Likewise the 20-40 per cent cuts,
the 40-60 per cent cuts, and 60-80 per cent cuts were com-
bined to give 10 liters of material for the second fractionation.
The 80-90 per cent cuts combined gave another 5 liters.
Thus six more distillations were made. Ten per cent cuts
-
were taken again. These cuts represented 2 per cent of the
total amount of wax charged.
Since a fairly close cut wax was desired and since at about
125' F. (51.7' C.) melting point the melting points of the 0
loo VISCOSITY SAYBOLT IW'F
cuts were closer to each other than a t the very beginning
or a t the end of the distillation, a selection of cuts was made
from the second fractionation and these were distilled in a
5-liter vacuum still. From these cuts a n amount of quite PLATE VI1
pure 12.5' F. (51.7' C.) melting point wax was prepared. SOLUBILI'W OF
A sample of 111' F. (43.9' C.) melting point wax was made IZS'F 151.7%) M.I
by a recrystallization of twice-distilled low melting point
PARAFFINE WAY
cuts from ethylmethyl ketone. A sample of 145' F. (62.8' 2
C . ) melting point wax was selected from the higher melting
I \ I
SAYBOLT 100 F VISCOSITY
fractions of the second fractionation. OF OIL SOLVENTS
The boiling point range of these fractionated waxes was
5' C. a t 5 mm. pressure. Their cooling curves are compared
in Plate XI1 with the cooling curve for the sample of 125' F.
(51.7' C.) melting point commercial wax whose solubility
was also determined.
Solvents
To study the solubilities of these various waxes it was
necessary to obtain oils that were practically free from paraf-
fin wax. It was also desirable to use as solvents oils in
which the wax occurs in the plant. The best source for such
oils seemed to be a wax-free pressed distillate. Since the
ordinary pressed distillate with a chill of 20' F. (-6.67' C). a t 100' F. (38" C.) and could not be improved in color by
contains an appreciable amount of wax, a quantity of it was claying. It was accordingly redistilled to a small bottom
repressed to a cold test of -20' F. (-28.89' C.). Ten and an oil of good color and 333 viscosity obtained.
liters of this oil were charged to the still and distilled at The following solvents were used:
5 mm. pressure, taking 10 per cent cuts. It was from these (1) Petroleum ether (b. p., 21.0" to 82.0' C.).
cuts that the fractionated oils used in the solubility deter- (2) 34-viscosity oil obtained as a bottom in rerunning
minations were obtained. These fractions were clear and heavy naphtha.
fluid at 0" F. (-17.78' C.) and hence were considered to (3) 36-viscosity oil from fractional distillation of a wax-
be wax-free. A blend corresponding to a 15 per cent bottom free pressed distillate.
from this distillation had a viscositv
" of 420
~~- Savbolt
. I. . ~seconds
..._..... (4) 75-viscosity oil from the same source.
 1044 INDUSTRIAL A N D ENGINEERING CHEMISTRY Vol. 19, No. 9

\
4
PLATE IX
SOLVBlLlTY
2
*D
MELTING PMNT MKTING mim
or FFU\CTIWTED
I
W FPKTKNATD
W\RAFFINE WPX

MaTlNG POINT
378 433 4888 c 544 690 656

1 1 I
100 I10 EQ 'F 130 140 150
MEUING mitn
378 433 489 'C 54.4 WLI 656

( 5 ) 191-viscosity oil from the same source,
(6) 71-viscosity wax-free pressed distillate, not frac-
tionated.
(7) 45 per cent bottom from pressed distillate diluted
to 46 viscosity with 34-viscosity heavy naphtha bottoms.
(8) 65 per cent bottom from pressed distillate diluted
with 15 parts of heavy naphtha bottoms; viscosity 71.
(9) 333-viscosity oil obtained by redistillation of a 20
per cent bottom from the fractional distillation of a wax-
free pressed distillate.
Solubility Determinations
Since the majority of the waxes used in this work were
closely cut fractions-that is, contained relatively few chem-
ical individuals-it was decided that the cloud temperature
would indicate the point at which the wax in question satu-
rated the solvent.
The apparatus used consisted of a 1 by 6-inch (2.5 by 15-
cm.) test tube fitted with a chill-test thermometer and a
stirrer made of thin glass with a ring at the end. Stirring
was effected by a Cenco electric motor geared t o produce
an up-and-down motion of the glass rod. The wax solution
was cooled by immersing the test tube in a beaker of water
for cloud points a t higher temperatures and by immersing
in an ice and salt bath, protecting the glass tube by a metal
jacket for cloud points a t lower temperatures. For some of
the very low cloud points brine a t -25" F. (-31.67' C.)
was used as the cooling medium.
Twenty-five cubic centimeters of the oil were measured
out into the test tubes and the required amount of wax was
weighed out into them. The oil was then warmed and
stirred until all of the wax was dissolved. The tube was then
put into the cooling bath and stirred until the first sign of
cloudiness appeared. At this point the temperature was
read. I n general, the results could be duplicated within less
than 1" F. (0.56" C.). The cloud point was more difficult
to determine a t the lower temperatures, particularly in the
case of viscous oils, in the sense that it was not so definite.
Since the primary purpose of the work was to investigate
solubilities over a range of pressing temperatures, the cloud
points of the maximum concentrations of the solution used
were in general below 75" F. (23.89' C.),
Solubility Curves
The curves shown in Plate I were constructed from the
data obtained from determinations of the cloud points of
various concentrations of 111" F. (43.9' C.) melting point
wax in the solvents listed. Plates 11, 111, and I V show
similar curves for two fractionated waxes of higher melting
points and a commercial paraffin wax. Most of these curves
were based on solubility determinations a t eight different
September, 1927 I N D U S T R I A L A N D ENGINEERING CHEMISTRY 1045

concentrations of wax in the respective solvent-between colorized with clay, was also made. The results of these
0.25 approximately and 3.5 per cent, with as high as 6 per cent proved to be almost identical with those obtained on the
in a few cases; a few are based on the results of only four or pressed distillate before claying and are therefore not in-
five determinations. The numbers designating the curves cluded.
correspond to the num-
I50 65 I) Conclusions
I 1 I bers assigned t o t h e
4 solvents yn the list of 1-The solubility of paraffin waxes increases as the melting
solvents already. given. point of the wax decreases.
I -
2-The solubility of paraffin Taxes in petroleum oils decreases
I40
~0 From these curves, with increasing viscosity of solvent.
another set of curves 3-Differences in solubility due t o differences in the melting
has been constructed point of the wax or t o variations in the viscosity of the solvent
.r,30 ,14y showing the effect of decrease with decreasing temperature.
52 v i s c o s i t y upon solu- Attempts to develop a useful mathematical expression of
Y
$ bility a t various tem- the rate of change of solubility with changes in the melting
4 ~ 29 peratures, for t h r e e
‘L
5 120\ point of the wax or the viscosity of the solvent have not been
fractionated waxes and successful. The rate of change of solubility with tem-
a commercial wax. perature is also so variable that any attempt to express
A third set of ‘curves it approximately leads to erroneous conclusions.
PLATE XI1 43’ ( P l a t e s V I 1 1 to XI) The curves should be of value in making calculations
u t i l i z e s t h e results dealing with the freezing of wax-bearing oils. It is possible
shown in Plates I to that the wax content of a n oil whose viscosity and cloud
I I
looo
K) 20
TIME M I M E S
’378 IV to compare the effect point are known could be predicted from such curves, but
~

of the melting point of the accuracy of such an application remains to be determined.

the wax upon its solubility in the various solvents, at differ-
e n t temperatures.
A series of solubility determinations, using as solvent some
of the 71-viscosity pressed distillate which had been de-
Note-The use of a similar curve for this purpose has been described
by Bjerregard, THISJOURNAL, 14, 215 (1922). No one curve will give
acceptable results for distillates from different crudes and made under
different conditions of fractionation.

Role of Lead Sulfide in the Sweetening of Petro-

leum Distillates and chemistry of the
Mercaptans’
By J. C. Morrell a n d W. F. F a r a g h e r

UXIVERSAL
OIL PRODUCTS
COMPANY, ILL.
CHICAGO,

012 yews refiners have known that lead sulfide facili- easily wetted by oil, it adsorbs sulfur compounds, especially

F tates the sweetening of petroleum distillates. “Spent

doctor” or plumbite sludges containing lead sulfide
and sodium hydroxide have been regenerated by blowing
with air. and although this operation has not been under-
stood, i;.s value in the reactivation of plumbite sludges has
been appreciated. More recently it has been observed that
air and lead sulfide are beneficial in the sweetening of re-
fractory distillates. Although the practice -of agitating
lead sulfide sludges with air in the batch agitator is old,
the refiner now introduces specially prepared lead sulfide
into the sweetening mixture.
The react ion of sweetening is as follows :
R-S
PRSH -+ NazPbOn + S+ 1 + 2NaOH f PbS
R-S
The action of lead sulfide in the sweetening of petroleum
distillahes has been generally characterized as catalytic,
i n the absence of an experimental basis of explanation.
P e n d t and Diggs2 :$signed to lead sulfide a catalytic action,
h t offered the explanation that, since the lead sulfide is
1 Presented under ,:he title “Role of Lead Sulfide in the Sweetening of
Pmtroleum Dis .iIlates’’ ltefore the Division of Petroleum Chemistry a t the
73d Meetiag o f the .4merican Chemical Society, Richmond, Va., April 1 1
t o 1 6 , 1927.
2 T H I . JOURNAL , 1114 (1924).
16,
the mercaptans, thereby promoting their reaction with the
constituents of the sodium plumbite solution. The present
writers do not agree with this purely physical explanation,
and present the following experiments that prove the func-
tion of lead sulfide in sweetening.
Materials
The materials used were pure mercaptans-ethyl, n-
butyl, isoamyl, heptyl, and benzyl-dissolved in a sulfur-
free naphtha made from Pennsylvania crude oil, and a
gasoline from Panhandle (Amarillo, Texas) crude oil. The
gasoline contained 0.05 per cent of mercaptans and was
difficult to sweeten.
The nitrogen and oxygen were taken from standard com-
mercial cylinders. Ozonized air was prepared by passing
air through a laboratory ozonizer. The nitrogen contained
4 per cent of oxygen, and when necessary was purified by
bubbling through alkaline pyrogallol.
The lead sulfide was obtained from several different
sources. I n the preparation of lead sulfide great care must
be taken to avoid contact with air as it is readily oxidized
to lead sulfate. Two samples dried in air showed an average
of 22 per cent of lead sulfate. Hence the precipitated and
washed lead sulfide was not dried except for special experi-
ments.