FURFURAL AS A SELECTIVE SOLVENT IN

PETROLEUM REFINING
L. C.K E M P ,JR.,AND G . I3.HAMILTON
T H E T E X A S C O M P A N Y , NEW YORK. N. Y.

H. H . G R O S S
T E X A C O DEVELOPMENT CORPORATION, NEW YORK,N. Y.

The physical properties and availability of furfural point search for an ideal selective solvent and the best method to
to its use as a selective solvent in the separation of desir- apply such a solvent in the separation of these desirable and un-
able and undesirable components of petroleum derivatives. desirable components.
The use of furfural achieves superior quality in lubricat- The ideal solvent for extraction of lubricating oils should
ing oils compared to the quality formerly attained by re- possess the following properties:
liance on selected crude sources. This paper discusses the
1. High selectivity-that is, a large solubility differential be-
furfural refining process and describes the commercial ap- tween the undesirable and desirable components.
plication of the method to the solvent refining of lubricat- 2. Good solvent power for the undesirable components such
ing oil stocks and Diesel fuels. that the extraction can be made with a reasonably small amount
of solvent.
3. Easy recovery-that is, volatility characteristics should
permit easy separation from the products by some form of dis-
T HIS paper discusses the use of fuifural in the petroleum
field for the solvent extraction of lubricating oils. Furfural
has a high solvent power for those components of petroleum
tillation. The vapor pressure a t extraction temperature should
not be high, so that the use of pressure equipment can be avoided.
4. Lorn solubility of the solvent in the oil phase-that is, the
which are relatively unstable t o oxygen-as well as other un- undissolved phase.
5. Sufficient difference in density of the solvent or solvent
desirable materials including color bodies, resins, carbon-forming phase and the density of the oil phase to allow rapid separation.
bodies, etc.-and yet, a t the working temperatures, has a low 6. Low surface tension in order to permit rapid and complete
solvent power for the desirable components. The application of separation into two liquid phases.
furfural as a selective solvent in this respect is carried out by the 7. Reasonable cost and availability.
8. Reasonable temperature of application, preferably within
furfural refining process, which has enjoyed a n-ide application a temperature range in which all oils are relatively low in viscosity
both in the United States and abroad, and is one of the best and waxy oils are entirely liquid.
known selective extraction processes for the refining of lubricat-
10. Lovl;toxicitji.
-
9. BdaDtabilitv to a wide range of oils.
ing oils. The extent to n-hich this process is applied can be 11. Chemical stability under any conditions encountered in
visualized from the fact that there are today some twenty in- its use, recovery, or in storage.
stallations. Ten additional installations are in the process of 12. Lox freezing- point
_ to allow avoiding- complications
- in cold
being engineered and constructed. weather.
I n the past crudes often have been selected for the manufacture I n the early 1930’s The Texas Company was searching for the
of lubricating oils on the basis that these crudes contained high ideal selective solvent and found that furfural most closely met
proportions of “desirable” lubricating oil components. Generally these specifications. I n the commercial application of furfural
speaking, these desirable components are considered to be the during the past fifteen years it has been demonstrated that this
“paraffinic” type of materials having oiliness, low rate of viscosity solvent closely approaches the ideal solvent. The most impor-
change with change in temperature-that is, high viscositv tant physical properties of furfural are presented in Table I (9,11).
index-a high degree of oxidation stability. a low carbon-forming I n the treatment of lubricating oils furfural in general has high
tendency, good color, and high flash points. The name paraf- selectivity and good solvent power, and effects the desired im-
finic denotes the relative stability of these materials rather provement in a given quality of the raffinate-for example,
than chemical structure, since they are principally cyclic com- viscosity index-with the application of only moderate solvent
pounds with a wide variety of paraffinic side chains. dosages. I n addition to a high density and a low surface tension,
K i t h the increasing demands for high quality lubricating oils which permit rapid phase separation, furfural has sufficient vola-
to withstand the severe operating conditions of the modern tility to permit ready recovery from lubricating oils. I t is
gasoline and Diesel engines, it became apparent that the “select” available in large quantities a t relatively low cost. It does not
crudes were no longer sufficient in cither quantity or quality to react chemically with the oil components and under conditions of
supply the demand. Therefore, it was obvious that the petro- use has a high degree of stability. Finally, furfural is indus-
leum industry would have to resort to some means for separation trially nontoxic.
of the desirable and undesirable components of lubricating oil
stocks. Other than the heavy asphaltic materials and the nor-
mally solid paraffin waxes, which mag be removed by precipita-
I. PHYSICAL
TABLE PROPERTIES
OF FURFURAL
tion or by filtration a t reduced temperatures, the undesirable
Roilina noint. F. a t 760 mm. 323
components comprise those “aromatic” type hydrocarbons which F i i & i R g point, F. -34
possess low oiliness, low viscosity index, poor oxidation stability, Specific gravity a t 68’ F. 1.1622
Viscosity a t looo F., Saybolt Universalsee. 28.7
high carbon residue, and poor color. Specific heat (68’ t o 212” F.) 0.416
Heat of vaporization (29.9 in. Hg), B.t.u./lb. 193.5
Selective solvent refining has played an important role in the Vapor pressure a t 100‘ F., mm. 6.7
never-ceasing effort of the petroleum refiner t o improve the Flash point (Tag closed cup) O E’. 138
Solubility in water (96O F,),$6 by vol. 8.1
quality and quantity of lubricating oil products derived from Surface tension, dynedom. 49
petroleum. Much time and effoit have been devoted to the
220
February 1948 INDUSTRIAL AND ENGINEERING CHEMISTRY 221

The range of conditions of application permissible with fur- I n lubricating oil processing, solvent refining is normally
fural makes it simple to select the most advantageous dosage applied t o specific fractions obtained by distillation from crude
(or solvent quantity) and temperature, for production of the petroleum. In general, crude oils as obtained from the earth,
highest yields of refined product of the desired quality as gen- after stabilization t o remove low boiling components, are dis-
erally measured by viscosity index, oxidation stability, etc. tilled into fractions approximating the following:

Approximate Boiling Range, a F. Product

(Atm. Pressure)
95-375 Gasoline and special naphthas
375-500 Kerosene and burning oils
500-600 Diesel fuels,.gas oils, solvents, and
burning oils
600-850 Light lubricating oil!
8504- Heavy lubricating oils and residua

The residua from such distillation may be used in the produc-

tion of asphalt or lubricating oil.
The boiling point of furfural falls well below the boiling ranges
of the lubricating oil and gas oil fractions. Therefore, in its
application t o such oils, the recovery of the furfural is relatively
simple. Furfural is used t o refine or extract gas oils and kero-
RAFFINATE YIELD% BY VOLUME
senes as well as lubricating oils, t o increase stability, t o remove
Figure 1. Relation of yields t o
sulfur, or to produce high quality Diesel fuel oils and burning
temperature and solvent ratio oils. However, in application of furfural t o the extraction of
low boiling point gas oils and kerosenes, the recovery of furfural,
Furfural refining, by countercurrent opera-
tion, of medium viscosity distillate from because of the small difference or even overlapping of the boiling
mid-continent crude points, is less simple, and a form of azeotropic distillation may be
employed.
Since the selectivity or ability of furfural to effect a sharp
separation between the desirable and undesirable components
TEMPERATURE~EBOTTOM OF TOWER
of the oil is not materially lowered-when the temperature of
extraction is raised, it is possible t o apply furfural to highly
viscous stocks a t temperatures which permit easy handling or t o
waxy stocks a t temperatures well above their pour point. Thus,
2 100
Li
in the case of waxy stocks, dewaxing, which generally involves
higher unit capital and operating expense, may follow furfural 2 90
extraction in the refining sequence with resultant lower over-all
e
X
processing cost. ::80
Furthermore, this versatile organic compound is readily avail- 5
>
able, and its availability is being increased as its demand in- 5 70
creases. If the demand should become greater, there ai-e nu- sG
merous raw materials, such as agricultural wastes, from which it
80
can readily be produced. Although the process of manufacture 50 60 70 80 90 100
of furfural is relatively simple, it involves special equipment and R AF FI NAT E YIELD %BY VOLUME

is further complicated by the problem of accumulating and Figure 2. Relation of yields t o

handling a bulk. of material from which to obtain a relatively temperature and solvent dosage
small volumetric yield of furfural. However, construction of a Furfural refining, by countercurrent opera-
tion, of medium viscosity distillate from
unit for production of furfural a t the point a t which it is to be mixed mid-continent crude
used would not be out of the question; such an installation has
been made in connection with an extraction unit.
Furfural also is applied as a selective solvent
in the extractive distillation for the separation and
purification of C4 hydrocarbons in connection with
TABLE
11. EFFECTOF COOLINGEXTRACTOUTLETZONEIN FURFURAL butadiene production and has proved efficient in
REFININGOF MEDIUMVISCOSITY DISTILLATE
MID-CONTINENT this application. During the recent war several
Amt. furfural applied, 200 198
70by vol. larger producers of butadiene employed furfural in
Temp., F. connection with the synthetic rubber industry. De-
Raffinate outlet zone" 230 230
Extract outlet aoneb 200 140 tails of this process have been covered adequately
Yield raffinate, %
' by vol. 70.9 81.0
in the recent literature (1, S), and this applica-
Charge Raffinate Raffinate tion of furfural will not be discussed in this paper.
De- De- Ex- De- Ex-
Waxy waxed Waxy waxed tract Waxy waxed traot As previously pointed out, furfural possesses
Physical character- the property of removing the undesirable con-
istics stituents from the lubricating oil fraction by
Gravity "A.P.I. 25.9 23.9 31.5 29.7 13.7 30.6 28.6 8.5
Viscosit; a t 100"F., .. 507 .. 318 .. .. 342 .. selective solvent action while the high quality oil
s.5.u.c
Viscosityat210°F., 53.3 58.3 49.3 52.9 .. 50.4 53.3 .. remains undissolved. Two liquid phases are
S.S.U.
Viscosity index
Pour point, ' F.
.. 65.5
0
.. 93.5
0
.... .. 85.7
0
.... formed when unrefined lubricating oil and furfural
are mixed a t a temperature below the point of
Viscosity-gravity
const.
01841 0.851 0:SOS 0.812 .. 0:812 0.821 .. complete miscibility. The miscibility point de-
a Top of tower. pends on the composition of the petroleum frac-
b Bottom of tower.
c Ssybolt seconds, Universal. tion and the quantity of solvent. To indicate the
order of magnitude of temperature: For an
222 INDUSTRIAL AND ENGINEERING CHEMISTRY Vel. 40, No. 2
I
 February 1948 INDUSTRIAL AND ENGINEERING CHEMISTRY 223
average viscosity and composition and using an average quantity
of furfural, say twice the volume of oil, the miscibility TABLE111. EFFECTOF DECREASINGAMOUNTOF FURFURAL
point is 290' F. or slightly above. At or below this tem- APPLIED WITH CONSTANTEXTRACTION TEMPERATURE ON
FURFURAL REFININGOF MEDIUMVISCOSITYMID-CONTINENT
perature, in this particular example, two liquid phases will DISTILLATB
exist. The temperature of extraction, in the application of Amt. furfural applied, 200 148
furfural t o the refining of a petroleum fraction, is adjusted t o %
' by vol. ~~

Temp., O F.
give the maximum yield of refined oil of the desired quality and Raffinate outlet zone 230 230
is generally considerably below the miscibility temperature. The Extract outlet zone 200 200
Yield raffinate, % by vol. 70.9 72.7
separation of the phases is readily effected because of the high
Raffinate Raffinate
specific gravity of the furfural as compared y i t h that of oil. De- Ex- De- Ex-
The oil phase is commonly called the raffinate phase or mix Waxy waxed tract Waxy waxed tract
and consists of approximately 90% r e h e d oil and 10% furfural, Physical characteristics
Gravity, A.P.I. 31.5 29.7 1 3 . 7 31.2 28.7 13.3
with furfural dissolved in the oil. The solvent phase, or extract Vis_oosi!y a t 100" F., ,, 318 .. .. 350 ..
S.S.U.
solution, consists conversely of about 90% furfural and about Viscosity a t 210' F., 49.3 52.9 .. 49.7 54.3
10% of undesirable oil components dissolved in the furfural. S.S.U.
Viscosity index 93.5 .. .. 90.5
.. ..
I .

* I n the refining operation the raw lubricating oil fraction to be Pour point, F. 0 0
Viscosity-gravity 0:808 0.812 0:809 0.820
processed is introduced into a packed, vertical extraction tower const.
wherein countercurrent flow with furfural takes place, by virtue
of the fact that furfural has a much higher specific gravity than
pr
oil a t the temperature of operation. The furfural is introduced
near the top of the tower and the raw charge oil near the bottom The raffinate and extract solutions or phases pass from the top
or some intermediate point in the tower. During the counter- and bottom of the tower, respectively, to separate systems for
flowing contact of furfural and oil, the undesirable components of recovery of the furfural.
the raw charge stock are selectively dissolved from the desirable From a theoretical standpoint, liquid-liquid extraction is
components by transfer from the oil phase to the furfural phase. closely analogous to distillation. This analogy is covered ade-
The necessary intimate contact of the counterflowing phases is quately in the literature (6, I $ ) , and no attempt will be made to
achieved by packing the tower with ceramic or carbon Raschig recite it a t this time. However, some of the factors that affect
rings arranged in nests, with interspersed devices to separate solvent refining results are considered and examples given illus-
the phases and redistribute them into the next adjoining packing trating the influence of these factors in the refining of a medium
nest; in effect this provides mixing and settling within the tower. viscosity mid-continent distillate with furfural.
With a given extraction column the important
factors are solvent-oil charge ratio and tempera-
tures in the extraction column. Assuming a con-
L stant solvent dosage and constant top and bottom
151
'
tower temperatures (which means that the cooling
7 S O L V E N T ENTRY
a t the bottom of the tower must be constant),
there must be a constant yield of raffinate of con-
stant quality. If the amount of bottom tower
cooling is increased without the other variables
being changed, the bottom tower temperature
decreases and the yield of raffinate increases, but
the quality of the raffinate-as measured, for
example, by viscosity index-is lowered as a re.
sult of less undesirable material being stripped
-OIL ENTRY
from the charge oil. This effect of bottom tower
cooling is illustrated by the data of Table 11,
which also shows the pertinent physical charac-
teristics of the unrefined distillate and a dewaxed
portion of the distillate to indicate the relative
quality of charge oil and refined product without
the influknce of wax, although extraction was
actually conducted on the waxy oil. The viscosity
7 R E C Y C L E ENTU index of the dewaxed, unrefined distillate is deter-
mined since it is used as a reference point in the
yield-viscosity index relation, as will be shown
later for another unrefined distillatc.
If the solvent dosage is decreased instead of the
temperature changed, the yield of raffinate in-
io01
creases and the quality of the refined oil decreases,
VISCOSITY INDEX FOR 0-F P W R POINT T
~ EXTRACT
PHASE OUTLET
since less material is extracted. Here again, the
stripping action of the solvent on the oil rising in
PHYSICAL CHARACTERISTICS OF CHARGE AND END PRODUCTS the tower is less, and the yield-viscosity index
WAXY CHARGE WAXY RAFFINATE DEWAXEO RAFFINATE T - E relation is not so favorable (Table 111).
GRAVITY~A~I. 27.0 . 32.7 3a5 9.3 On the other hand, by increasing the solvent
VIS IOO°F, S 5 U 155 9 130 1727
VIS 13210°F,SSU 4286 4192 44 21 dosage and'increasing the amount of bottom tower
WUR~F 0
VISCOSITY INDEX 81 111 96 cooling simultaneously, it is possible t o maintain
the raffinate yield at a fixed value and t o improve
Figure 4. Relation of tower height t o degree of furfural refining of
low viscosity mid-continent distillate its quality. An example of this is shown by the data
 224 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 40, No. 2

TABLEIV. EFFECT O F IXCREASING AXIOUXTO F FURFURAL

APPLIEDAND COOLINGO F EXTRACT OUTLET Z O X E SIYULTBNE-
OUSLY, I N FURFURAL
REFININGO F l $ E D I U M VISCOSITY ?\IID-
COSTINEKT
DISTILLATE
Amt. furfural applied, 100 152
yo by Vol.
Temp., F.
Raffinate outlet zone 230 230
Extract outlet zone 171 140
Yield raffinate, %
' by vol. 83.7 83.7
g '.,
\
Raffinate Raffinate l5'\.

..%.
W
De- Ex- De- Ex- 0
.
'

Physical characteristics
Gravity, A.P.I.
F'is_co_sj!y a t looo F.,
Waxy

29.5
..
waxed

27.9
356
tract

9.7
..
Waxy

30.1
..
waxed

28 4
349
tract

7.3
..
2
W

-
3
1.0. .--.-- .
------_
s.s.lJ.
Viscosity a t 210' F., 60.6 53.8 , , 50.4 64.0 .. 05
S.S.U.
Viscosity index .. 84.0 .. .. 88.8 .. 1
Pour point, F. 0 .. 0 4
Viscosity-gravity
const.
O:b19 0.826 ,. 0:SlS 0.822 :. " 0

in Table IV. This is similar to increasing the reboiling and

reflux in a distillation colunin to obtain improved fractionation.
Decreasing the top tower temperature tends to decrease both
the stripping efficiency of the solvent and the solubility of the
more aromatic-tyFe materials in the solvent; the result is a
extraction tower. The introduction of this reflux fractionates or
higher yield of a poorer quality raffinate (Table V).
throws out of solution the least soluble material contained in the
Additional data illustrating that quality of the raffinate
downcoming furfural phase. This material in turn again rises
(as measured by viscosity index) may be controlled by changing
in the tower t o be combined with the oil phase for re-extracting;
solvent dosage and/or temperatures are presented in Table
thus the possible yield of raffinate of given quality is improved.
VI.
Data illustrating the effect of the use of extract reflux recycle are
These variables of amount of furfural applied and terminal
presented in Table VI1 for a variety of stocks from different
temperatures of the extraction column are thus seen to be inter-
crude sources.
related, and the same quality raffinate can be produced with
A number of theoretical methods have been advanced for the
. either high solvent dosage and a low temperature or a low solvent
analysis of solvent extraction processes-for example, the mathe-
dosage and a high temperature. However, the maximum yield
matical method presented by Varteressian and Fenske ( I 4 ) , and
of a given quality raffinate is produced when a high solvent
the graphical methods presented by Othmer (IO), Saal and
dosage and a low temperature are employed. This relation can
van Dyck ( l a ) , Varteressian and Fenske (14), Thiele (IS), and
best be illustrated graphically by plotting yield of waxy raffinate
Kurtz (8). Additional graphical methods developed by Evans
against viscosity index of dewaxed raffinates. Such graphs,
which are presented in Figures 1 and 2, illustrate results that may
be expected by varying the solvent dosage and/or temperature of
-
--_-CARBON RESIDUE OF RAFFINATE
CARBON RESIDUE OF RAFFINATE
DEWAXED
extraction in the refining of medium viscosity distillates, having
the same viscosity, from two different mid-continent crude
sources with varying composition. These relations are presented
for the purpose of illustration and do not necessarily apply to
stocks of the same viscosity from other crude sources, which
may differ in composition. This type of relation is developed
for residual stocks also. In plant operation it is found desirable
t o determine this relation for each charge stock to be processed.
Although the degree of fractionation between the undesirable
and desirable components of the charg? oil can be controlled by

PERCENT EXTRACT REMOVED

TABLEV. EFFECTOF COOLINGRAFFISATEOGTLETZONEIN Figure 6. Relation of carbon res-

FURFURALREFININGOF MEDIUMVISCOSITYMID-CONTINENT idue t o percentage of extract re-
DISTILLATE moved
Amt. furfural auplied,
.. 197 196 Furfural refining of deasphalted mid-conti-
% by$:: nent crude
Temp
Raffinate outlet zone 262 200
Extract outlet zone
Yield raffinate, 7% by vol.
170
76.7
169
79.8
(a),Hunter and Kash (4, 6, 7) and Saal and van Dyck ( l a ) pro-
vide calculation methods for countercurrent furfural extraction
Raffinate Raffinate
De- Ex- De- Ex- with a temperature gradient, reflux, etc., and are based on use of
Waxy waxed tract Waxy waxed traat an additive property of the oils such as viscosity-gravity constant
P h sical characteristics for characterizing the equilibrium relations of the oil-solvent
dravity, 0 A.P.I. 31.4 29.3 10.9 30.4 28.7 10.1
Visaosity a t 100" F., .. 335 .. . . 352 .. on a trilinear phase diagram. These last computation methods
S.S.P.
Viscoslty at 210° F., 49.3 53.1 , .. 49.7 53.9 .. employing trilinear diagrams allow direct plotting of data and
S.S.U. minimize the additional calculations required. I t can be shown
Viscosity index .. 91.5 .. .. 89.3 ..
Pour point, a F.
Viscosity-gravity 0:808
0
0.817
.. ,. 0:i15
0
0.819
..
.. that calculated yields, viscosity-gravity constants, and solvent
const. contents of various streams correspond closely to the results
obtained in actual operations.
 February 1948 INDUSTRIAL AND ENGINEERING CHEMISTRY 225

TABLEVI. EFFECTOF AMOUNTOF FURFURALAPPLIEDAND TEMPERATURE

OF APPLICATION
IN FURFURAL
REFINING
OF MEDIUM
VISCOSITY MID-CONTINENT
DISTILLATE
Physical Characteristics
Refining Conditions Raffinate, waxy
Amt. Temp., ' F. Yield of Vis- Raffinate, dewaxed
furfural Raffi- raffi- cosity Vis- Vis-
applied, nate Extract nate, at 210° cosity- Viscosity, S.S.U. pour vis- cosity- Extract
% outlet outlet % Gravity, F., gravity Gravit 100" 210° point, cosity gravity gravity.
b y vol. cone zone by vol. OA.P.1. S.S.U. const. OA.P.? F. F. O F. index const. OA.P.1
' 198 170 139 82.8 30.4 49.9 0.814 28.7 334 53 1 0 87.8 0.820 7.3
196 200 169 79.8 30.4 49.7 0.815 28.7 352 53.9 0 89 3 0.819 10.1
100 231 200 76.2 30.6 50.5 0.812 28.2 365 54.2 0 86.0 0.822 12.5
148 230 200 72.7 31.2 49.7 0.809 28.7 350 54.3 0 90.5 0.820 13.3
200 230 200 70.9 31.5 49.3 0.808 29.7 318 52.9 0 93.5 0.812 13.7
300 220 190 64.0 32.9 49.2 0.790 30.6 295 52 5 0 100.5 0.804 14.7

VII. EFFECTOF USE OF EXTRACT

TABLE RECYCLE
IN FURFURAL
REFININGOF DISTILLATE
AND RESIDUAL
STOCKS
Crude source Mid-Continent Mid-Continent Mid-Continent Venezuela So. Texas Pennsylvania Pennsylvania
Grade Deasphalted
bright stock S.AE 20 Nonwaxy Light Cylinder
SAE 20 SAE 40 residuum distillate distillate distillate , stock
Amt. furfural applied, % by vol. 353 352 352 349 524 534 352 353 350 352 300 305 200 199
T omn
_-.1.=.,
ow
Raffinatk'outlet zone 265 265 275 275 290 296 285 285 260 260
250 255 280 279
Extract outlet zone 190 190 200 200 218 225 210 200 185 186
170 175 190 191
Extract recycle ratio (basis, charge oil) 0.00 0.67 0.00 0.68 0.00 0.65 0.00 0.28 0.00 0.00
0.56 0.41 0.00 0.35
Raffinate yield, Yo by vol. 57.8. 63.9 56.0 62.0 71.2 75.4 58.9 63.9 59.1 63.0
80.4 84.0 86.5 90.0
Raffinate gravity, OA.P.1. 32.2 32.5 30.2 30.4 28.1 28.0 32.9 32.8 26.5 26.3
33.2 33.4 27.5 27.5
Raffinate viscosity-gravity const. 0.795 0.793 0.800 0.798 0.799 0.798 0.785 0.786 0.791 0.791 0.801 0.801
Dewaxed raffinate viscosity index 102,5 102.5 92.5 92.5 98 97.5 106.5 106.0 6915 70:O 110.0 110.5 103.5 103.5
Dewaxed raffinate viscosity-gravity const. 0.800 0,800 0.806 0.805 0.801 0.800 0.795 0.796 0.825 0.826 0.793 0.792 0,802 0.803

TABLE
VIII. FURFURAL
REFINING.
OF LUBRICATING.
OIL STOCKSFROM VARIOUSCRUDESOURCES
Crude source East East Oklahoma Oklahoma Gulf Penn-
Texas Texas Illinois City City Coast California sylvania Arabia Arabia Venezuela
Grade Deas- Deas-
phalted Inter- Medium Light phalted
Light bright Medium Light mediate viscosity neutral Light Deas- bright
neutral stock viscosity neutral viscosity distillate distillate Cylinder neutral phjdted stock
distillate residuum distillate distillate distillate (nonwaxy) (nonwaxy) stock distillate residuum residuum
sical characteristics
p%harge oil
Gravity OA.P.1. 28.3 23.1 24.7 27.6 25.4 20.8 20.1 25.4 25.0 20.1 23.3
Viscositi at 210' F.. 41.0 132.6 53.3 45.7 69.3 53.3 40.7 165.6 42.4 128.9 175.0
S.S.U.
Viscosity index 26.5 -25
Carbon residue, % i:io i:9s
Pour point, F.
0:07
... ... ...
o:i4 0:04
... ...
0:52 0.17
-25
0.05
~ 2 5 ... 0:09
..*
2:27
... i:o2
...
Raffinate
Gravity OA.P.1. 32.5 29.6 31.5 33.3 30.9 24.7 27.5 27.6 30.6 26.6 26.7
Viscositb a t 210° F., 40.4 102.3 47.9 43.5 58.4 53.0 40.9 149.5 41.4 109.2 147.4
S.S.U.
Viscosity index
Carbon residue, %
... ... ... .*. 61.0 49.0
0.01 .
... ...
Pour point, F.
0.01
... ...
0.20 0:Ol
... ...
0:Ol 0.03
... 0.07
-25 -25 ...
0.97 0:62
... ...
0:+4 0.28
e..
Dewaxed raffinate
Gravity OA.P.1.
Viscosit; at 210° F.,
29.8
43.0
27.2
140.6
31.2
49.9
31.5
45.4
29.7
63.2
...
... ...
... 27.1
161.0
28.4
43.4
25.5
122.4
25.9
174.7
S.S.U.
Viscosity index
Pour point, O F.
96.0
20
94.1
0
102.0
0
96.5
0
96.0
0
...
... ...
... 103.5
10
96.5
-5
98.8
10
95.8
10
Extract gravity, "A.P.I. 8.0 13.9 13.2 8.8 9.5 6.8 9.5 7.9 5.6 95 9.6
Refining conditions
Amount furfural applied,
% by:; 124 507 349 263 264 174 223 247 101 445 360
Temp.,
Raffinate outlet zone 200 290 264 224 265 165 159 271 183 250 260
Extract outlet zone 140 233 180 149 190 101 101 191 119 175 195
Raffinate yield, Yoby vol. 85.0 60.9 64.2 82.4 76.9 80.2 61.6 90.1 80.4 65.7 81.6

Although the graphical methods provide interesting theoreti- The commercial application of solvent refining of lubricating
cal approaches to refining of petroleum fractions with furfural, oils with furfural is illustrated by the flow diagram shown in
they are rarely used in establishing the merits of operations on a Figure 3, which shows a typical flow for a furfural refining unit.
given refinery stock. The practical aspects of refinery opera- This unit comprises principally a countercurrent flow extraction
tions almost always require control data on the nonadditive or treating tower, a section for recovery of the furfural from the
aspects of quality, such as viscosity index, color, sulfur, carbon raffinate solution, a section for the recovery of the furfural from
residue, and oxidation stability, which are often determined the extract solution, and a section for recovery of furfur4 from
after such further processing as dewaxing and clay treatment. the condensate water stream, since steam stripping is employed
For this reason it is standard practice t o utilize laboratory or for removal of the last traces of furfural from the products.
pilot scale operations in preference to mathematical or graphical The extracfion tower is so designed as to assure thorough
analyses in evaluating stocks for extraction operations such as contact of the oil and furfural and seDaration of intermediate.. and
*
the furfural refining piocess. final phases; this allows efficient ;emoval of the undesirable
226 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 40, No. 2

taken a t a number of point,s in the vertical of the tower show that

TABLEIX. FURFURAL
REFIXING Gds OIL
OF UNCRACICED the undesirable components of the charge are rapidly removed
Crude source K e s t Texas Venezuela in the refining or stripping section (section above the point of
Amount furfural applied, 70 123 oil feed entry) and that, in the redfying or enriching section
7"by roi.
Temp., F.
O
(section below point of oil feed entry), there is a sharp fractiona-
Raffinateo uoutlet
Extract zone
t l e t zone 139
100 156
95 tion \Thich removes the desirable components from the down-
Yield raffinate, % by vol. 82.0 66.6 flowing extract phase. This is shown in Figure 4, which in-
Ex- Ex- dicates the fract,ionation obtained with respect. to viscosity
Charge Raffinate tract Charge Raffinate tram index in one of the modern extraction towers \Then charging a'
Physical character-
istics mid-continent distillate lubricating oil. With a given extraction
Gravity, O -kP.I* 3 3 . 9
Sulfur, % 1.12
37.8
0.49
41.8 24,2
0.80
30.8
0.37 ., , tower the solvent dosage and temperatures, particularly the
,..
. I .

Cetane h o . calcd. 53.2 62.9 34.4 49.6 ,., temperature gradient, may be adjusted t o ac-
complish sharp fractionation as previously
TABLE x. FURFERAL REFIXKGO F C.AT.kLYTIC CR.4CKED C Y C L E GAS OIL described; and a study of the tower action as
illustrated in Figure 4 is useful in the selection
Crude source Mid-Continent California Arabia
of the most advantageous conditions for the stock
Sniount furfural applied, 24 53 57
yo by 701. being refined.
Temp.,
Raffinate
O F. outlet zone 78 131 132 Table F'III presents data obtained from typi-
Extract outlet zone
Yield raffinate. % by vol.
75
70
104
73
102
79
cal operations in furfural refining of a few of the
lubricating stocks from various crude sources
Raffi- Ex- Raffi- Ex- Raffi- Ex- charged t o furfural refining process units. Fur-
Charge natc tract Charge nate tract cilarge nate tract
Physical character- fural is effective and is widcly applied in refining
Gravity,
istics OA.P.1. 24.0 30.7 14.5 2S.6 35.4 11.2 3 2 . 0 4 0 . 5 1 3 . 3 both distillate and residual stocks from a wide
Sulfur 72 0.53 0.51 . . 0 . 5 3 0.33 , . 1.39 0.39 . . variety of crude sources.
&tank KO,calcd. 30.7 42.4 , . 38 53.2 , , 45.0 62.5 .,
The raffinates produced in the furfural re-
fining- of Pennsylvania cylinder stock residua
have a substant'ially lower carbon residue than
the charge stock, as shown in Figure 5 . Typical results
-CARBON RESIDUE OF RAFFINATE
EAST T E X A S DISTILLATE 6 4 5 SU/210°FVlS obtained in furfural refining of deasphalted mid-continent type
CARBON RESIDUE OF RAFFINATE of residual stock are shown in Figure 6. In the case of dis-
OKLAHOMA DISTILLATE 63 S S U /210°F: VIS
----CARBON RESIDUE OF RAFFINATE: tillate stocks low carbon residues are obtained on the prod-
OKLAHOMA DISTILL. DEWAXED 725511 /210°f VIS uct raffinates when refining t o viscosity indices in the range of
90 to 95. Results are shown in Figure 7 for typical xnid-conti-
I
nent and East Texas distillates.
The removal of materials highly susceptiblc t o oxidation is
reflected by lower deposits of sludge and other deposits in auto-
motive and Iliescl engines. Solvent refining also enhances the
response of the product oil t o so-called additives, which are in-
corporated for further quality improvement to permit satis-
factory lubrication under extremely severe operating conditions.

0 50 10.0 150 200 250

P E R C E N T EXTRACT REMOVED

Figure 7. Relation of carbon residue

t o percentage of extract removed
Furfural refining of mid-continent medium
viscosity distillates

components of the untreated oil. The untreated oil is intro-

duced into tlic continuous countercurrent tower a t approximately
its mid-point, and a temperature gradient is maintained between
the top and bottom of the toner t o improve fractionation be-
tween relatively insoluble desirable compone!its and the more
soluble undesirable components. Temperature control of RAFFINATE YIELD % BY VOLUME
the incoming iurfural and charge oil streams, as i ~ e l as
l indirect
Figure 8. Relation of raffinate
water coolers, are provided to regulate the terminal and inter- yield t o cetane number
mediate tower temperatures at the desired l~vcls.
Furfural refining of California catalytic
The extraction tower is operated with oil as the continuous cycle gas oil
phase and furfural as the discontinuous or dispersed phase,
the latter passing downward through the oil to extract the un-
desirable components. The concentration of these components The degree of sulfur removal is dependent upon the type of
in the furfural phase increases toward the bottom of the tower, stock and thc type of sulfur compounds present. Kormally, a
from which the extract solution is withdraa n continuously. sulfur reduction of 60 t o 70% is obtained when refining t o 90 to
Conversely, thc oil quality improves toward the top of the tower, 96 viscosity index. Substantial removal of color bodies also is
from which the raEnate or refined oil solution overflows. obtained in the refining of distillate stocks and deasphalted
A knowledge of the fractionation being effected is of assistance residua.
in the operation of an extraction tower. Analyses of samples As pointed out earlier in this paper, furfural also is used in the
February 1948 INDUSTRIAL AND ENGINEERING CHEMISTRY 221
refining of gas oils, The flow in this operation is similar t o that the result of the combined efforts of members of The Texas
for lubricating oils. The data presented in Table IX illustrate Company and the Texaco Development Corporation. Special
the increase in cetane’number and reduction in sulfur content credit is due W. P. Gee of Texaco Development Corporation for
the application of this process. The authors wish to thank The
Texas Company for permission to present this paper.

LITERATURE CITED

Buell and Boatright, IND. ENG.CHEM.,39, 695 (1947).

Evans, Ibid., 26, 860 (1934).
Happel et al., Trans. Am. Inst. Chern. Engrs., 42, 189 (1946).
Hunter and Nash, IND.ENQ.CHEM.,27, 836 (1935); J . Inst.,
Petroleum Tech., 22, 49 (1936).
Hunter and Nash, J . SOC.Chem.Ind., 53,95T (1934).
Ibid., 53, 285T (1932).
Hunter and Nash, Proc. World Petroleum Congr., 11, 340 (1933).
Kurtz, IND. ENG.CHEM.,27, 845 (1935).
Miner Labs., “Furfural and Its Derivatives,” Bull. 2 (June,
1928).
Othmer, Chem. & Met. Eng., 43, 325 (1936).
Quaker Oats Co., Tech. Div., “Furfural as a Selective Solvent,
Figure 9. Relation of furfural/oil ratio (1940).
t o cetane number of raffinate Saal and van Dyck, Proc. WorZdPetroZeum Congr., 11, 352 (1933).
Furfural refining of California catalytic cycle gas oil Thiele, IND.ENG.CHEY.,27,392 (1935).
Varteressian and Fenske, Ibid., 28, 1353 (1936).

obtained in the furfural refining of two uncracked gas oils boiling RECEIVED
October 8, 1947.
within Diesel fuel range.
With the advent of catalytic cracking the
availability of intermediate distillates has in-
creased in the form of catalytic cycle gas
oil. However, these cycle gas oils are not
entirely satisfactory without additional proc-
essing for use as burning oils or as Diesel
fuels, principally because of their relatively
low paraffinicity. Furthermore, their sulfur
content is quite high when produced from
stocks derived from high sulfur crudes. Here
again, furfural refining can be applied t o pro-
duce raffinates of relatively high paraffinicity
and low sulfur content. Typical results ob-
tained in the extraction of catalytic cycle
gas oils boiling within Diesel fuel range from
three different crude sources are shown in
Table X. Figures 8 and 9 also show the
yield-cetane number relation and the furfural-
oil ratio required for the refining of a California
cycle gas oil. Excellent yields of high cetane
number and low sulfur content fuels can be
produced from both uncracked and cracked
gas oils with very low furfural-oil ratios.
The extent t o which it is possible suc-
cessfully to apply the principles of solvent
refining to commercial operations with fur-
fural is illustrated by the fact that a t this
time units ranging in capacity from 60 t o
6000 barrels per day, totaling over 41,000
barrels of charge oil per day, are installed t o
process oils of a wide range of viscosities and
from a wide selection of crudes. There is a
constant demand for the furfural refining
process, and the charge oil capacity just
given will be increased by approximately
19,000barrels by the end of 1948 by additional
units now under contract for construction.

ACKNOWLEDGMENT

The development and successful applica-

tion of the furfural refining process for ex- Furfural refining u n i t for petroleum lubricants i n
traction of lubricating oils and gas oils is G u l f Coast areas