Session: Hydrocarbons and Other Fossil Fuels

CHEMCON – 05, New Delhi

Catalytic Dewaxing Of Vacuum Distillates For Lube Base Stock

Uttam Ray Chaudhuri, Shubhajit Dutta, Ritusree Paul, Pragati Giri,
Debashish Mukerjee and Biplab Guchait

Dept. of Chemical Technology, University of Calcutta, 92 A.P.C Road, Kolkata 700009

Email:urc@vsnl.net

Keywords: pour point,viscosity index,hydroisomerisation

ABSTRACT
Hydrotreated lube distillate from refinery was dewaxed catalytically in a batch reactor
with a zeolite catalyst in presence of hydrogen in the laboratory. Temperature and
pressure during study were kept at around 250-300oc and pressure 80-150 kg/cm2. A
good reduction in pour point has been observed with minor change in the viscosity and
viscosity index of the oil.

INTRODUCTION
Lube oil base stocks (LOBS) are obtained from vacuum distillation unit of refinery.
Traditional method employs a solvent extraction unit to dearomatise the distillate oil
selectively to adjust the viscosity index of oil followed by dewaxing to adjust pour point
and finally hydrotreated to finished lube base stock. The finished LOBS has to satisfy
desirable viscosity, viscosity index and pour point in addition to other properties. High
viscosity is contributed by the aromatic and naphthenic hydrocarbons in the oil with low
viscosity index. Whereas paraffinic hydrocarbons have high viscosity index but with low
viscosity. Therfore, viscosity and viscosity index are determined by the relative
proportions of the aromatic, naphthenic and paraffinic hydrocarbons in the oil. Presence
of paraffinic hydrocarbons in the oil is also responsible for formation of solid wax
amount of which varies with their proportion. However, aromatic and naphthenic
hydrocarbons of high molecular weight also give rise to the same problem of
solidification but at very low temperature. For the finished lube it is desirable that
solidification point ( or pour point) should be as low as possible to avoid congealing of
the lube oil in use. It is also observed that iso-paraffinic hydrocarbons (branched chain)
are less prone to solidification as compared to normal or straight chain paraffins in the oil.
Solvent treatment method involves use of solvents like furfural, methyle pyrrolodine,
phenol, propane, methyl-ethyl ketone etc for selective extraction of aromatic and
paraffin. Thus, a good amount of aromatic and paraffinic oil are extracted out as a non-
lube bye-products and as a result of which the yield of lube base stock is reduced. This
extraction process is a two stage process where aromatic extraction is done in the first
unit followed by removal of paraffinic hydrocarbons in the dewaxing unit. Both the steps
involve solvent recovery units. Dewaxing process involves propane or ammonia
refrigeration system with trains of precoolers and chillers.

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This extraction processes require large investment, operating cost, power consumption
and loss of yield. Catalytic process is the alternative solution for such a problem.
Catalytic hydrogenation of aromatics and isomerising the n-paraffins to I-praffins in
desirable extent can yield good quality lube base stock without using solvent extraction
and refrigeration processes.

EXPERIMENTAL METHOD:
In the present study reaction was carried out in a batch high pressure rocking type reactor
as shown in fig.1. Feed composition and properties are presented in Table-I. Catalyst used
in this experiment is made from zeolite. Composition and characteristics of the catalyst
are given in Table-II. Operating temperature was varied from 250 to 298oc and pressur
from 80 to 120 kg/cm2. Reaction time was varied from 48 minutes to less than 2 hrs.
Samples were analysed for pour point, viscosity, viscosity index, density and coke
formation.

Table-I: Feed properties

Type Hydrotreated Raffinate
APIo 24-27
Specific gravity at 15oc 0.89-0.91
Viscosity in cst at 100oc 28-30
Flash point oc 240-290
Pour point oc 60-67
Sulfur, wt% 1.5-2

2
 Table-II: Catalyst composition
Bulk volume 1.25 gm/cc
Silica/ Alumina ratio 2.43
Porosity 0.48
Pore diameter 7.4 Ao

350

300

250
kg/sq.cm, deg c

200

150

100

temp press
50

0
1

11

13

15

17

19

21

23

25

27

29

31

33

35
time, minutes

Fig.2 Time temperature and -pressure variation in the reactor

RESULTS & DISCUSSIONS

Results are presented in the Table-III at various operating temperatures and pressures.
Variation of temperature and pressure in the reactor for a typical run is presented in the
fig.2. There are three distinct zones of variations in both the variables namely heating,
reaction and cooling zones. Average temperature and pressure in the reaction zone at the
viccinity of 250-300oc have only been taken in to consideration.Attempts were made to
reduce heating and cooling times. Variation of pour points of the liquid products for
typical runs at different operating reaction times, temperatures and pressures are
presented in fig. 3, 4 and 5 respectively. Approximate correlations for pour point of the
product are obtained as,

Y=0.0131 θ2 -3.049 θ + 157.97 ……..(1)

Y=0.009 T2 -5.7204 T + 889.87 …….(2)
Y=0.0039 P2 -1.8431 P +174.36 …….(3)

CONCLUSIONS
Variation of pour points of the products with residence time in the reactor showed a
tendency towards reduction of pour points as observed in fig.3. Reaction temperature
also played a vital role in reducing the pour point as seen in fig.4. However increase of
temperature above 350oc attracted cracking reactions and coke formation. Hence
temperature had to be maintained below 350oc and sufficient hydrogen pressure had to be

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maintained to avoid coking. With the increase in total pressure pour point further fell
mainly because of hydrocracking. Correlations determined in the reaction study indicate
that pour points of the products drop as the reaction time, temperature and pressure
increases.

80

60

40

po
ur 20
po
int
,
de 0
g 0 20 40 60 80 100 120 140 160 180

-20

-40

-60
time, minutes

Fig.3 variation of pour point with reaction time

Table-III
operating conditions and pour points of feed and products from batch reactor runs
Run Nos Reaction Temperature Pressure, Feed pour Product,
o
time c Kg/cm2 point oc pour point,
o
mins c
1 48 262 88 60 45
2 40 255 87 60 50
3 86 299 149 62 31
4 81 298 129 60 -20
5 114 289 149 60 -38
6 102 309 156 60 -26
7 108 260 111 66 18
8 154 243 117 60 6
9 103 264 146 61 -32
10 119 289 119 67 -43

These may be helpful for determining the desired degree of pour point reduction of the oil
in an industrial reactor. In fact in the refineries catalytic dewaxing is carried out in packed
beds where hydro-isomerisation reaction takes place. Normal paraffins are converted to
iso-paraffins and thus pour point is lowered as iso-paraffins has lower point as compared
to normal paraffins. However, generation of gases and light ends cannot be avoided due
to hydrocracking as sufficient pressure has to be maintained in the reactor to avoid
coking.

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In addition to these, hydrodynamics and mass transfer kinetics in a packed bed must be
taken in to consideration foe determining the desired conversion.

60

40

20
pour point in c

0
0 50 100 150 200 250 300 350

-2 0

-4 0

-6 0
te m p e r a tu re ,c

F ig .4 . v a r ia tio n o f p o u r p o in t w ith r e a c tio n te m p e r a tu r e

60

40

20
pour point in C

0
0 20 40 60 80 100 120 140 160 180

-20

-40

-60
pressure in kg/sq.cm
Fig.5 variation of pour point with reactor pressure

NOMENCLATURE
P: pressure in the reactor, kg/cm2
T:temperaure in the reactor, oc
Y: pour point of the product, oc
θ: residence time in the reactor, minutes.

REFERENCES
Hargrove J.D, 1983, Dewaxing Catalytic, Encyclopedia of Chemical Processing and
Design, Vol 15, Marcel Dekker, New York, pp 346-352.
Zakarian J.A and Zimmer J.N, 1988, Catalytic Dehazing Of Heavy Lube Oils; A case
History, Energy Progress, 8(2):109-111.
Smith K .W, 1980, New Process Dewaxes Lube Base Stocks, Oil & Gas J, 78(21):75-85.

Rodes R.K, 1989, Worldwide Catalyst Report, Oil & Gas J., 87(4):49-76.