9

Crystallization in the Oil Industry:

Solvent Dewaxing

ll1if'1"-.1' IIfJmfwllrgf'r

9.1 Introduction
9.1.1 Purpose of Dewaxing
At the exit of the solvent extraction unit, the future lube oil base stock, called
"raffinate" at this stage of production, has been stripped of most of its aromatic
compounds. Its viscosity index or Vl has been adjusted to the required value.
The raffinate essentially consists of:
paraffinic compounds of varying lengths and branches;
naphthenic compounds.
The straight chain and slightly branched paraffinic compounds tend to
crystallize at ambient temperature. However, at low temperature - as low as
-20°C -the oil must remain fluid in the engine crankcase. It must not solidify
by crystallization on cooling, as this would keep it from flowing. Consequently,
it is indispensable to remove high crystallization point paraffinic compounds
from most base stocks. The dewaxing unit is designed to lower the cloud and
pour points of oil base stocks leaving the extraction unit by eliminating the
high crystallization point paraffinic compounds (cloud point and pour point
are defined in Vol. 1, Chapter 6). The method used is to crystallize the waxes
(solid phase) by cooling and then separate them from the oil (liquid phase) by
filtration.

9.1.2 Feed and Products

The feed to the dewaxing unit is the "raffinate" from aromatics extraction (see
Section 7.1). The products from the dewaxing operation are:
the dewaxed oil;
a waxy material called slack wax.
478 Chapter 9. CRYSTALLlZaTlON IN THE OIL INDUSTRY: SOLVENT DEWAXING

Slack wax can be sold as is for certain specific applications (production of

particle board for example), but its residual oil content is too high for most of
the other possible uses of waxy products. It will therefore have to undergo fur-
ther treatment to lower the residual oil content to under l%. This operation is
called “deoiling” and uses the same principle as dewaxing, i.e. crystallization
followed by separation of solid waxes by filtration. The difference between
dewaxing and deoiling is in the temperature prevailing during crystallization.
For dewaxing, the temperature will be approximately between -15 and -25°C
depending on the pour point required for the oil. Meanwhile, deoiling will take
place at a temperature ranging from +2 to +15”C.
The products from deoiling are:
waxes and paraffins;
a product between oil and paraffin called “foot’s oil”.
There are a great many applications for waxes and paraffins (see Vol. 1,
Chapter 6):
coatings for cardboard, boxes, containers;
thermal insulation;
candle manufacture;
waterproofing;
lamination;
polish manufacture.
The difference between a wax and a paraffin is as follows:
A paraffin is a hard, white, macrocrystalline (large crystals) solid that
melts at variable temperatures above 50°C depending on the grade.
A wax is a malleable, white to dark yellow, microcrystalline (small crys-
tals) solid that melts above 70°C.
Paraffins come from light cuts (viscosity lower than 20 mm2/s at 100°C),
while waxes are from heavy cuts (viscosity approximately 35 mm2/s at 100°C).
Figure 9.1 shows the cuts obtained from the dewaxing operation. The area
located above the bold dividing line represents the paraffin or wax composi-
tion, and the area below, the dewaxed oil composition.
Table 9.1 indicates the physical properties of base oil, paraffin and foot’s oil
from a North Sea crude light raffinate.
The dewaxed oil yield of the dewaxing operation and the paraffin yield of
the deoiling operation depend greatly on operating parameters and the type of
the feed processed, as we will discuss later on. The approximate percentages
of the raffinate volume (dewaxing unit feed) are as follows:
dewaxed oil 75%
paraffin 12%
foot’s oil 13%
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING 479

I I compounds
P a r a f f i n 2

1 Figure
Simplified diagram of the cuts obtained by solvent dewaxing. The area above
9.1
the separating straight line represents the wax (yield and composition>and the

Dewaxed Slack Foot’s

Characteristics oil Paraffin
WBX oil
~

Specific gravity (di5) 0.8607 0.8194 0.8091 0.8226

Refractive index (70°C) 1.4536 1.4362 1.4310 1.4365
Flash point (open cup) (“C) 224 226 230 244
Flash point (Penski Martens) (“C) 20 1 202 205 204
Viscosity at 100°C (mm2/s) 3.99 2.54 3.65 3.00
Viscosity at 40°C (mm2/s) 19.52
Pour point (“C) -18 34
Aniline point (“C) 103 109.2 111
Conradson carbon (% wt) 0 0 0
TAN (mgKOH/g) 0.045
Sulfur (% wt) 0.254 0.209 0.05 0.326
Color 0.5
VI 99
Oil content (%) (ASTM D 72 1) 19.1 0.05 36.7

Table
Physical properties o f products produced by dewaxing and deoiling a light,
North Sea crude raffinate.
480 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING

There are a large number of lubricant applications as shown in Table 9.2.

Engine uses (%I

Gasoline engines 25
Two stroke engines 2
Diesel engines 32
Aircraft engines 1

Subtotal 60

Industrial uses ("/.I

Hydraulic transmissions 12
Metalworking 6
Machine oils 4
Petroleum jelly 3
Insulating oils 2
Greases 2
Sump oil 2
Protection 2
Turbines 1
Stripping 1
Miscellaneous 5
Subtotal 40

Total 100
-
Table
9.2 Uses of lubricants. (France 1985).

9.2 Solvent Dewaxing

The most common oil/wax separation process is based on crystallization with
a solvent that modifies the conditions of thermodynamic equilibrium solely by
its presence in the liquid. The ideal solvent should dissolve the oil and pre-
cipitate all the wax. Additionally, in precipitating, the wax should form a crys-
tal lattice that is loose enough to allow the oil to filter through it.
The first operating variable in the dewaxing process is therefore the sol-
vent used. The properties of a good dewaxing solvent are:
solubility and selectivity: good solubility for the oil and good crystalliza-
tion selectivity for the wax;
 Chapter 9. CRYSJALLIZAJION IN THE OIL /NOUSTRY: SOLVENT DEWAXING 481

low boiling point: since the solvent will be eliminated from the oil and
from the wax by distillation, energy expenditure should be limited during
the operation;
low heat of vaporization and specific heat for the same reasons as men-
tioned above;
low congeal point: the solvent must remain liquid at filtration tempera-
tures;
no toxicity or corrosivity;
low price and wide availability.
Several solvents or mixtures of solvents meet the requirements listed
above to a greater or lesser degree:
mixture of methylethylketone and toluene;
methylisobutylketone;
dichloromethane;
trichloroethylene;
propane (process dating back to 1932, now phased out);
mixture of ethylene chloride and benzene (1930, currently phased out);
mixture of acetone and benzene (1927, now phased out).
Benzene (phased out because of its toxicity) and toluene are excellent oil
solvents, but they also display fairly good solvent power for wax and are there-
fore not very selective. If used by themselves, there would consequently be a
very high filtration differential, and the wax would crystallize in a very tight
lattice that would not permit filtration. The filtration differential is the differ-
ence between the temperature needed to crystallize the waxes and the pour
point required for the oil. The greater the solubility of a wax in the solvent, the
higher the filtration differential will be.
In contrast, acetone and the higher ketones (methylethylketone, methyl-
propylketone) do not dissolve oil particularly well but do precipitate the wax,
which crystallizes in a lattice that lends itself to filtration and retains very lit-
tle oil. These compounds are termed anti-solvents, since when mixed with sol-
vents like toluene they attenuate solvent properties. They exhibit poor solvent
power, but on the other hand their selectivity is good.
A mixture of these two types of solvent will yield something approaching
the ideal solvent. The most widespread is a mixture of toluene and
methylethylketone (or sometimes methylisobutylketone).
Methylethylketone is frequently abbreviated as MEK in the industry
(methyl ethyl ketone). Dewaxing operations using a mixture of MEK and
toluene account for 80%of the total, so we will confine our discussion to this
solvent in the rest of the chapter. It should be noted that methylisobutylketone
can be used alone. Its solvent power is greater than that of the MEK-toluene
mixture.
The characteristics of MEK and toluene are given in Table 9.3.
 Chapter 9. CRYSTALLIZATION IN THE OIL /NOUSTRY: SOLVENT DEWAXING 483

Before describing a dewaxing unit in detail, we will discuss the process

operating variables which are:
type of feed;
solvent composition;
final crystallization temperature (= filtration temperature);
cooling rate conditioning crystal nucleation and growth;
filtration methods;
principle and results of a double pass;
impact of using dewaxing aids.

9.2.2 Influence of the ’Qpe of Feed

The type of feed is of critical importance for dewaxing results. The results of
the filtration step are directly related to the type of wax crystals formed, which
is in turn highly dependent on the chemical structure of the feed.
For instance, the more viscous the feed, the more microcrystalline (very
small size) the crystals, thereby making filtration more difficult. The heavy
cuts from vacuum distillation will therefore be more difficult to process than
the light ones and dewaxing unit feed flow rates will consequently be much
lower with viscous distillates.
Low viscosity distillates (drawn off the top of the vacuum distillation col-
umn) are called “light neutral” and higher viscosity distillates (drawn off at the
bottom of the vacuum distillation column) are termed “heavy neutral”. The
vacuum residue (with an added intermediate cut between the residue and the
heaviest distillate) is called “bright s t o c k or “BSS” (bright stock solvent).
Figure 9.3 illustrates the above with the filtration rate plotted versus feed
viscosity.
At equivalent viscosity, the nature of the feed can also be modified by
upstream treatment. For instance, an Arabian Light cut with a viscosity of
140 mm2/s at 40°C and a viscosity index of 96,will not behave in the same way
in a dewaxing unit as the cut of the same origin and the same viscosity at 40°C,
but which has a viscosity index of 98 (having been more severely treated in the
aromatics extraction unit).
Table 9.4 gives the chemical composition of these two feeds.
The 98 VI feed will have a slightly higher filtration rate than the 96 VI feed
due to the larger proportion of paraffins (thereby lowering the viscosity of the
feed going into the dewaxing unit). In contrast, the yield in dewaxed oil will be
quite a lot lower (-3%) because of the smaller proportion of naphthenics and
aromatics.
Note that overtreatment in the aromatics extraction unit will also cause
lower yield in the dewaxing unit, besides the lower extraction yield and the
extra processing cost as a result.
Average operating conditions for a dewaxing unit are indicated in Table 9.5.
484 Chapter 9. CRYSTALLlZATlON IN THE O I L INDUSTRY: SOLVENT DEWAXING

The properties of the dewaxed oil listed in Table 9.5 are realistic approxi-
mate figures, but obviously depend on the processing severity required
according to the final grade. The term "grade" is applied to the different base
stocks obtained, classed by viscosity.

200

r
h

N
E 150
v
5
-
*Q)
.-
.-C
2 100
s
-
C
.-0
=s 50
i
i

0
1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8
log,, (viscosity)
t
10 20 30 50 80 110 160 250 400 630
Viscosity (rnrn2/s)

Figure
9.3 Variation in filtration rate with feed viscosity.

% wt of components VI 96 VI 98
Paraffins 28.7 30.6
Mononaphthenics 18.3 18.5
Polynaphthenics 20.5 25.1
Aromatics 32.5 25.8
VI (after dewaxing) 96 98
Dewaxed oil yield
(% vol of the feed) 86 83
Table
9.4 Impact o f feed composition on dewaxed oil yield.
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING485

Light distillates Heavy distillates Bright Stock

Feed flow rate (m3/day) 1,000 850 600

Solvent ratio 3.3 3.9 5.5
Filtration temperature (“C) -20 -12 -16
% MEK 70 65 55
% toluene 29.5 34.5 44.7
% water 0.5 0.5 0.3

Viscosity at 100°C (mm2/s) 5.3 9.8 33

VI 101 100 95
Pour point (“C) -15 -6 -6

I I
9-5
Operating conditions used in dewaxing various cuts

9.2.3 Influence of Solvent Composition

Earlier we mentioned that:
MEK displays low solvent power for paraffinic compounds (and therefore
good selectivity).
Toluene has excellent solvent power for base stocks.
As a result, the proportions in the mixture of these two solvents can be
optimized. For example, Table 9.6 shows the main effects of dewaxing the
same base with different proportions of MEK and toluene.

I Cut with a Viscosity of 30 m 2 / sat 40°C

I
% volume MEK
% volume toluene
Final dewaxing temperature (“C)
40
60
-17
75
25
-12
1I
Filtration rate (liter/(m2.h)) 80 172
Oil content of wax (% wt) 6.1 9.0
Temperature differential (“C) 10 5
Pour point (“C) -7 -7
-
-
Table
9.6 Influence OF dewaxing solvent composition on process operating conditions.
486 Chapter 9. CRYSTALLIZATION IN THE O I L INDUSTRY: SOLVENT DEWAXING

This example illustrates the following key points:

An increase in the proportion of MEK in the mixture decreases the tem-
perature differential. This allows energy cost to be significantly reduced
during the crystallization phase.
An increase in the MEK ratio improves the filtration rate (the example
shows that the flow rate doubles when MEK goes from 40 to 75%). This
point is extremely important for rotary filters are extremely investment-
intensive (FF20 million for a 120 m2 filter, base 1992) and their mainte-
nance costs are also very high. There should be as few filters as possible.
An increase in MEK in the solvent mixture gives a higher residual oil con-
tent in the wax, which means that the dewaxed oil yield is lower.
However, this effect is only slight in the proportions generally used, i.e.
between 50 and 75% MEK.
As a result, it would seem advantageous for the solvent mixture to be very
rich in anti-solvent WEK), so that the temperature differential is small and fil-
tration is easy. However, the proportion of anti-solvent can not be raised indef-
initely, otherwise phase separation will occur. At an overly high anti-solvent
concentration an oil phase appears in addition to the existing oil/solvent and
wax/solvent phases. The new phase consists of molecules which are insoluble
at low temperature in the anti-solvent, even though they are not paraffins.
Phase separation results in:
a drop in oil yield;
a drop in viscosity index (W);
rapid clogging of filter cloths, since the precipitated oil phase plugs up
the mesh.
Phase separation also depends on the filtration temperature, the water
content of the solvent and the viscosity of the feed. When feed viscosity
increases, phase separation occurs with a lower MEK ratio in the solvent.
In order to determine the maximum anti-solvent concentration, a dewaxed
oil is mixed with the bisolvent containing different proportions of anti-solvent
and the mixture is cooled. The temperatures are noted at which a third phase
(precipitated oil) appears. The curve in Figure 9.4 is thus obtained for an oil
with a viscosity of 20 mm2/s at 100°C and a pour point of -6°C.
The diagram also shows a line labeled "filtration", which is used to deter-
mine the filtration temperature required to obtain a pour point of -6°C versus
the MEK ratio in the MEK-toluene solvent mixture. The curve labeled "phase
separation" delimits the domain where phase separation can be observed.
The diagram is utilized as follows:
For an MEK-toluene mixture having 40% MEK, filtration must be per-
formed at -19°C to get the desired pour point of -6°C (the temperature
differential is therefore 13°C). Phase separation occurs at -28°C for this
same solvent composition.
 Chapter 9. CRYSTALLIZATION IN THE OIL /NOUSTRY: SOLVENT DEWAXING 487

Filtration
100

75

8
v
Phase
separation /Y
Y
y 40

0
-30 -28 -20-19 -12-10 0
Temperature (“C)

Phase separation curve for an oil with: viscosity 20 mm2/s at 100°C and pour
point = -6°C.

The maximum possible MEK ratio without triggering phase separation is

75% (point where the filtration line intersects the phase separation
curve). At this ratio the filtration temperature is -12°C and the differen-
tial is 6°C.
However, the diagram was obtained with an anhydrous solvent and the
water content in the solvent has a considerable effect on phase separation.
Figure 9.5 shows the variation in phase separation temperature versus the
water content in the solvent. The water content has a very heavy impact on
the temperature at which phase separation occurs. It is therefore extremely
important for the solvent to be as anhydrous as possible. The higher the MEK
ratio in the solvent the more difficultthis objective will be, for water solubility
in the solvent increases as the MEK content rises.
Figure 9.6 shows water solubility in the solvent versus MEK content and
Figure 9.7 gives water-MEK miscibility versus temperature.
Note also that MEK and water form an azeotrope and consequently they
can not be separated by simple distillation. This point will be developed in
more detail in the process description section. Figure 9.8 shows the liquid-
vapor equilibrium for MEK and water.

9.2.4 Influence of Final Dewaxing Temperature

(Equal to Filtration Temperature)
All other conditions remaining equal (solvent composition, feed quality, etc.),
the lower the filtration temperature, the lower the pour point of the dewaxed
488 Chapter 9. CRYSTALLIZATION IN THE O I L INDUSTRY: SOLVENT DEWAXING

Phase
separation
I

Variation in phase separation temperature versus water content in the solvent

(40% MEK), for an oil with a viscosity o f 2 0 mmz/s at 100°C and a pour point
of -6°C.
LIVE GRAPH
Click here to view

0 10 20 30 40 50 60 70 80 90 100
Solvent composition (YOvol MEK)

Water solubility in the MEK-toluene mixture with varying proportions o f MEK,

at 60°C.
 ChaDter 9. CRYSTALLIZATION IN THE OIL /NOUSTRY: SOLVENT DEWAXING489

T (“C)
150
142.5
140

120

100

-
Water-MEK liquid-liquid
equilibrium diagram
(Source: Smensen
r

IL
Figure
9.7
1
I 80

60
et al.I.

40

20

0
0 10 20 30 40 50 60 70 80 90100
Water MEK(%wt) MEK

oil. Lowering the pour point has a direct impact on the viscosity index of the
dewaxed oil and on the yield of the dewaxing operation. These effects can be
more or less significant depending on the viscosity of the feed as shown in
Table 9.7.
This fact can be readily understood by examining Figure 9.9. The dewaxed
oil obtained with a pour point of -13°C has fewer paraffinic molecules (whose
VI is high). The target pour point for the oil base stock must therefore be taken
into account when the aromatics extraction unit is adjusted in order to
achieve the required VI in the end product. Table 9.7 also shows the effect of
the pour point specification on the dewaxed oil yield.
Filtration temperature is determined by the target pour point, but also by
what is called the “temperature differential”. As mentioned earlier, the tem-
perature differential is the difference between the temperature to which the
dewaxing unit feed must be cooled down and the pour point of the oil obtained
after dewaxing.
490 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY.’ SOLVENT DEWAXING

90

Figure
9.8 MEK/water liquid-
vapor equilibrium
diagram (Source:
Gmehling et a1.J
80 ‘9.6

70
10 20 30 40 50 60 70 80 90100
Water MEK (“AM) MEK

Base Light distillate Bright Stock

Reduction in pour point (“C) 3 3

Lost VI 1 0.5
Lost yield (% vol) 1 1

1 9.7 Relationship between pour point, VI and yield For two types of Feed.
 ChaDfer 9. CRYSTALLIZATION IN THE OIL INDUSTRY.' SOLVENT DEWAXING 491

Paraffinics Paraffinics

. Pour point = -1 0°C Pour point = -1 3°C

Influence of pour point on the composition of the wax and the dewaxed oil.
The area above the straight line represents the wax (yield and composition)
and the area below it stands for the dewaxed oil (yield and composition).
This representation is illustrative as in Figure 9.1.

The many attempts made to reduce the temperature differential have

shown that it unfortunately does not depend only on the solvent composition
and conditions of use. It also depends on the desired pour point of the
dewaxed oil and on the nature of the oil. The differential increases as the pour
point of the dewaxed oil decreases.
The higher the viscosity index of the dewaxing unit feed oil, the greater the
differential. This is because the wax oil contains mainly paraffinic and naph-
thenic hydrocarbons with paraffinic side chains, which are not good solvents
for high pour point waxes. Low viscosity index oils contain more aromatic and
naphthenic hydrocarbons which dissolve waxes better and consequently
delay their crystallization. The solvent ratio does not have much influence on
the temperature differential.

9.2.5 Influence of Solvent Ratio and Dilution

Distribution Mode
The aim is to determine:
the degree of dilution (solvent ratio);
the distribution of dilution.
492 Chapter 9. CRYSTALLIZATION IN THE O I L INDUSTRY: SOLVENT DEWAXING

The solvent ratio is generally expressed in volume flow rate of solvent over
volume flow rate of feed. Dilutions are called "primary, secondary, tertiary,
etc." in keeping with the fluid flow direction. Accordingly, primary dilution will
be injected at the very beginning of the process. Dilution is also often
expressed in volume flow rate of solvent versus volume flow rate of feed.
Points to be remembered are:
Solvent injection at the beginning of the feed circuit promotes crystal
growth, which takes place in a fluid medium and thus gives big crystals.
It makes filtration easier but tends to increase oil retention in the crystals
(which means a loss in dewaxed oil yield).
Injection at the end of crystallization gives the opposite effect, i.e. little
oil retention in the crystals but more difficult filtration.
It is obvious that the way dilutions are divided up and sequenced will have
to be optimized constantly depending on the type of processed feed and the
desired objectives.

9.2.5.1 Effect of Solvent Ratio on Filtration Rate

In general filtration rate is the flow rate of filtered dewaxed oil per unit of fil-
tering area, so it is measured in liters/(m2.h). An increase in the solvent ratio
first of all causes a very clear cut improvement in the filtration rate (because
crystal growth is promoted by the solvent and mainly due to lower viscosity of
the feed entering the filter). Then the effect becomes asymptotic until an opti-
mum is reached, after which the filtration rate decreases very slightly. When
the volume of solvent increases, the proportion of oil contained in the solvent
decreases (the curve shows the flow rate of filtered dewaxed oil, excluding sol-
vent) and this effect overrides the viscosity lowering effect. The curve illus-
trates the equation given in 9.2.7.3 Figure 9.10 illustrates this discussion.

9.2.5.2 Effect of Solvent Ratio on Dewaxed Oil Yield

and on Oil Content in the Wa x
An increase in solvent ratio, as shown in Figure 9.10, causes an increase in
dewaxed oil yield. It can be seen that the last points of improved yield are
"expensive" to achieve, since the extra solvent will first of all have to be cooled
to the filtration temperature then removed from the dewaxed oil by distilla-
tion.
The increase in dewaxed oil yield with a low solvent ratio is directly related
to promotion of crystal growth caused by increasing the solvent ratio. The
desired yield will be the result of an optimization between criteria such as:
availability and price of the dewaxing unit feed;
cooling and distillation capacity of the dewaxing unit;
energy costs.
At the same time as the yield in dewaxed oil rises, the residual oil content
in the wax decreases (see Fig. 9.10).
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING 493

200 40

180 35
160
30
140
25
120

100 20

80 15
60
10
40
5
20

0 0
1.5 2 2.5 3 3.5 4
Solvent ratio

-
Figure
9.10 EFFect of solvent ratio on Filtration rate, on dewaxed oil yield versus Feed
(in % 001) and on oil content in the wax (% wt), with all other conditions

9.2.5.3 Effect of Dilution Distribution Mode

The filtration rate, oil yield and oil content in the wax do not depend only on
the total volume of solvent introduced in the unit, but also on how the solvent
is distributed at each injection point during the dewaxing operation. The dif-
ferent solvent injections are usually called "dilutions" and are expressed in vol-
ume flow rate versus the volume flow rate of feed, like the solvent ratio.
There are four types of dilution:
primary dilution injected before cooling begins;
secondary dilution injected during cooling;
tertiary dilution possibly injected at the end of cooling;
washing dilution injected on the filter cloths to eliminate the oil retained
in the wax crystals.
As mentioned earlier, these different dilutions do not have the same effects,
so their distribution will be the result of optimization according to the objec-
tives sought. For example, maximum throughput in the dewaxing unit will give
494 Chapter 9 CRYSTALLlZATlON IN THE OIL INDUSTRY: SOLVENT DEWAXING

pride of place to primary dilution over tertiary dilution. Moreover, dilution dis-
tribution will have to be modified depending on feed composition. Clearly, a
viscous feed with microcrystalline wax crystals will need more primary dilu-
tion (to promote the formation of big enough crystals to achieve easy filtra-
tion) than a low viscosity feed with macrocrystals.
Filter washing dilution has quite a significant effect on the residual oil con-
tent in the wax, particularly for viscous feeds.
Figure 9.1 1 represents the oil content in the wax versus the wash dilution
rate, all other conditions remaining the same.
LIVE GRAPH
Click here to view

60
50

40
30
20
10

0
0 0.5 1 1.5 2
Wash dilution rate

-
Figure
9.1 1 Effectof wash dilution rate on oil content in the wax. Feed: Arabian Light with
a viscosity of 140 mmz/s at 40°C.

Secondary or tertiary dilutions can be partially replaced by filtrate (see

Fig. 9.12), which is the mixture of oil plus solvent exiting the filtration stage.
The oil content in the filtrate varies between 5 and 20% depending on the fil-
tration method used. Given its oil content, the filtrate should be used carefully,
since dilution with filtrate will not be as effective as fresh solvent in terms of
filtration rate and dewaxed oil yield. The advantage of using filtrate in dilution
is the saving on redistillation energy, since it is recirculated.

9.2.6 Influence of Cooling Rate

The cooling rate affects crystal shape and size as well as oil occlusion. As the
temperature becomes lower the forces of interaction between wax molecules
get stronger, thereby triggering the crystallization process by nucleation. The
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING495

Feed
Crystallization -:
Ii Wax + solvent
to distillation
Filtrate
Primary dilution

-.
Figure
9.12 Principle o f dilution using filtrate.

seeds formed grow when the cohesion energy between the crystals formed
and the free molecules increases. When the product is cooled to lower than
the crystallization temperature, crystal size increases dramatically, modifying
the rheological properties. The crystals then cluster together, which signifi-
cantly affects the value of the congeal point (see Sections 8.4 and 8.7). The fol-
lowing points should be remembered:
A slow cooling rate usually promotes the growth of crystals with a “mul-
tilayer spiral” type of morphology, exhibiting oil occlusions.
A fast cooling rate will promote the formation of smaller crystals, but
with a tendency to form along an axis giving “needle” type crystals liable
to clog filter cloths rapidly and consequently reduce filtration rate.
The optimum gradient ranges between 3 and 5°C per minute depending on
the type of feed.
It is also important not to create thermal shocks during the crystallization
operation. We have seen that dilutions are injected at different points during
the crystallization phase. Their temperature should be as close as possible to
the temperature at the injection point. A dilution injected at a different tem-
perature from that of the injection point causes a thermal shock, disturbing
crystal formation and the subsequent filtration operation. A difference of 10°C
can reduce filtration rate by 30%. It should be emphasized that the feed mix-
ture should be perfectly homogeneous before cooling. This means the raffinate
(dewaxing unit feed) and the solvent need to be heated during mixing, care-
fully stirred and monitored. In particular, all the wax crystals must be thor-
oughly melted into the mixture by using a temperature higher than the melting
point of the heaviest waxes. Otherwise they would act as seeds during cooling
with the solvent and might orient crystallization toward an unwanted shape.
496 Chapter 9. CRYSTALLIZATION IN THE O I L INDUSTRY: SOLVENT DEWAXING

9.2.7 Filtration Method

Before going into the theoretical principles of filtration and the effects of filter
control parameters, we will describe the mechanical device used for the oper-
ation.

9.2.7.1 Purpose of Filtration

The cooling section allowed a transition from a liquid feed + solvent phase to
a liquid-solid mixture (called a slurry) which is made up of:
a homogeneous liquid phase rich in dewaxed oil:
a crystalline solid phase rich in wax.
The filtration section will separate the two phases so that they can be
treated later on in two distinct solvent recovery sections.

9.2.7.2 Principle of Filtration

A cloth stretched on a support (press or drum) holds back passing suspended

matter with a diameter greater than the diameter of its mesh. The material
passing through the cloth is called “filtrate” while the material retained on the
cloth is called “cake”.
Two types of filter are used:
Filter presses which run discontinuously. The first dewaxing units
worked with filter presses, which entailed isolating the filters periodically
in order to recover the wax which had accumulated on the cloths, grad-
ually hindering filtrate passage. These filters required a large number of
parallel elements to handle the flow rate, as well as constant supervision
and servicing.
Rotary filters which run continuously and are now widely used in dewax-
ing units. The main advantage is that they operate continuously.
Figure 9.13 gives a cutaway view of a rotary filter with the terms for its
component parts. Figure 9.21 shows an industrial filter.

9.2.7.3 Filtration Theory

By definition, resistance to filtration is:

R = APjq
where AP is the differential pressure available across the filter and V, is the
flow rate of filtrate going through the filter per unit of area of filter cloth.
This resistance is the sum of three resistances:
R,: cake resistance, which always predominates. It depends on crystal
consistency and cake thickness.
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING497

Filter cloth support

Separation of segments
\

Figure
9.13 Cutaway view of a rotary filter (Source: Padovait, reworked by ENSPM-FI).

R,: cloth resistance, which will increase as the cloth gets clogged, but will
return to its initial value after periodic hot washing.
R,: resistance of the cloth support and of the distribution lines of the filter
segments, which is constant.
In actual practice, the total resistance is assumed equal to R,, cake resis-
tance, and the throughput of a filter (VJ can be expressed by the following for-
mula:
V, = K x D x LVNx s M PIR,
with:
N rotation speed of the drum in rpm
S angle corresponding to the submerged part of the drum expressed in
radians (close to 71 radian)
D diameter of the drum (m)
L length of the drum (m)
K constant depending on the filter and the cloth
R, cake resistance
498 Chapter 9. CRYSTALLIZATION IN THE OIL /NDUSTRv: SOLVENT DEWAXING

This equation shows that the flow rate across the filter is proportional to
the square root of the filter's rotation speed and to the square root of the avail-
able pressure differential.
Since the geometry of the filter and the grade of the filter cloth (material
and texture) are fixed, the operating variables of a rotary filter are:
rotation speed;
vacuum applied:
- in the submerged zone,
- in the washing zone;
submergence (filter surface area immersed in the feed);
thickness of the wax cake;
frequency of hot washing.
The rotation speed can not be accelerated too significantly without running
the risk of uneven cake distribution on the filter cloth, with the cake becoming
partially unstuck and the filter cloth getting excessively clogged. A drop in oil
yield is also observed, since more oil is locked up in the wax crystals.
On the contrary, it is always advantageous to operate with the greatest pos-
sible pressure differential in the washing zone. The pressure differential in the
submerged zone will be adjusted according to the objectives sought (maxi-
mum unit throughput or maximum oil yield). Figure 9.14 shows the effect of fil-
ter rotation speed on the unit filtration rate, all other conditions remaining
identical. The graph shows that the faster the filter rotates, the higher the unit
flow rate and the thinner the cake.
It is always advisable to have a relatively thin cake, to make draining easier
during the washing phase as shown in Figure 9.15.

9.2.8 Principle of Dual Pass

(or Repulping) and Results
It may be advantageous to have the wax pass through a filter a second time
once it has already gone through one filtration stage for the following two main
reasons:
to get very low oil content in the waxes;
to improve dewaxed oil yield.
The operation can proceed as follows: at the exit of the first filtration stage,
the cake, which is at filtration temperature, is injected with another dilution.
This is called second pass dilution and aims to make the mixture easier to han-
dle. Then the mixture goes through another filter at the same filtration tem-
perature as indicated above. The oil yield is enhanced by 3 to 5% volume
depending on the processed feed and the oil content in the associated wax is
lower.
 LIVE GRAPH
Click here to view

Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING 499

500

400 \

E
300 E
v
v)
In
a
c
Y
0
.-
s
200 \ 10
(u

%
0

100 3

0 +
0 i minirev

10 1 0.5 0.33 0.25 0.20 rPm

Effectof Filter rotation speed on cake thickness and unit Filtration rate, all other
conditions remaining equal.

-
Figure
9.15 Oil content in the wax Venus cake thickness. LIVE GRAPH
Click here to view
500 ChaDter 9. CRYSTALLIZATION IN THE O I L INDUSTRY: SOLVENT DEWAXING

9.2.9 Dewaxing Aids

There are products on the market to promote crystal growth, thereby improv-
ing dewaxing operation performance. The results are:
an increase in dewaxed oil yield;
a higher unit filtration rate.
As these products can be found in "food grade" waxes, they are required to
pass acceptance testing as laid down by the Food and Drug Administration
(FDA). As they are often costly, a thorough economic study should be made
before using them, even more so because their performance is closely related
to the quality of the processed feed.

9.3 Description of a Dewaxing Unit Using

the MEKaToluene Solvent Mixture

9.3.1 General Flow Diagram

a . Basic Simplified Flow Diagram without in Line Deoiling
This diagram is presented in Figure 9.16.

6. Flow Diagram of a Dewaxing Unit with in Line Deoiling

A dewaxing unit produces dewaxed oil and a wax with a relatively high oil con-
tent (10 to 25%) called slack wax or petrolatum wax (when the cut is Bright
Stock or BSS). Slack wax is inappropriate for the most common uses of paraf-
fins and waxes (see Section 9.1.2) and consequently has to undergo further
processing to reduce the oil content to values of approximately 0.5 to 2% vol.
This objective is achieved by running the slack wax through the dewaxing unit
again as described in the preceding sections, but at a different filtration tem-
perature. The operation is called "deoiling" and the resulting products are
waxes and paraffins with a very low oil content and a product which is neither
wax nor oil, called "foot's oil".
Table 9.8 gives typical values of a deoiling operation and also shows the
effect of the variation in filtration temperature on the yield and quality of the
wax produced.
The higher the filtration temperature, the higher the waxes' melting point,
and consequently the lower the wax yield from the operation.
It is economically advantageous to perform the deoiling operation directly
on the cake exiting the dewaxing filters (still containing carried over solvent),
rather than process it in the distillation section to eliminate the solvent and
then store it before reprocessing in the dewaxing unit. The direct process is
called in line deoiling (Fig. 9.17).
 Chapter 9. CRYSTALLIZATION IN THE o / L INDUSTRY: SOLVENT DEWAXING501

L
I
Filtrate

--
Cake
oil
Solvent
system
‘ Solvent

=
Figure
9.16 Simplified flow diagram of a solvent dewaxing unit without in line deoiling.

I
~

Deoiling of a slack wax from an oil with a viscosity of 140 mm2/s at 40°C
Filtration temperature (“C) 6 9

Wax yield (% vol) 42.9 39.3

Needle penetration:
at 25°C 21 19
at 42°C 63 50
Oil content (x wt) 1.1 0.9 0.9
Dropping point (“C) 69.2 69.7
Viscosity at 100°C (mmz/s) 7.8 7.8 7.8
-
9.8 Properties of waxes according to deoiling operating conditions.
502 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWRYING

Solvent
Solvent

a 1
system
~

Cake +_solvent
T

Foot's
A
T

distillation
r
L

De-oiling feed /
circuit -l-Kc ;gt
4
-
&+l
De-oiling
NH3
1
Solvent

crystallization
I b
Wax
distillation

w
Figure
Simplified flow diagram of a dewaxing unit with in line deoiling.

Figures 9.16 and 9.17 show that a dewaxing unit consists of four main sec-
tions:
A crystallization section, to cool the raffinate and the solvent, thereby
crystallizing the waxes.
A filtration section to separate the dewaxed oil from the wax cake.
 ChaDter 9. CRYSTALLIZATION IN THE OIL /NDUSTRY: SOLVENT DEWAXING 503

A distillation section, with two distillation operations for a dewaxing unit

without in line deoiling and three with in line deoiling, to separate the sol-
vent from the dewaxed oil, the wax and the foot’s oil.
A solvent system recovering the solvent exiting the distillation opera-
tions and redistributing it in the form of dilutions.
A section producing the required refrigeration for cooling the feed and for
crystallization should be added to these four sections.
When the diagrams with and without in line deoiling are compared, the eco-
nomic advantage of in line deoiling is clear. In a unit without in line deoiling,
the slack wax is processed in the corresponding distillation step to eliminate
the solvent it contains. When deoiling is performed, solvent is introduced once
again in the feed train for crystallization to take place, but it must be distilled
once again. It is as if there were a total of four distillation operations. In a unit
equipped with in line deoiling, there are only three distillation operations (oil,
wax and foot’s oil), as shown in the corresponding figure.

9.3.2 Detailed Description of the Process

We are now going to describe how each of the five sections listed above works
in detail, for a unit equipped with in line deoiling. A sixth section will be
devoted to ancillaries.

9.3.2.1 Crystallization Section

a. Dewaxing Crystallization Section

The flow scheme can be seen in Figure 9.18.
Injection of Primary Dilution
After adding the primary dilution solvent, the dewaxing unit feed is heated in
exchanger E, by low pressure steam condensation depending on the melting
point of the waxes in the feed cut. The mixed feed is then cooled by exchange
with the mixed slack wax coming from the filtration stage (which is therefore
at the filtration temperature) in exchanger E30. The mixed feed is then sent to
exchanger E, where it is cooled to a temperature between 20 and 30°C
(depending on the viscosity of the feed) by giving up its heat to the process
water.
At this point in the process, crystallization begins and cooling can no
longer be carried out in conventional exchangers which can not handle a mix-
ture of solid and liquid.
Double Pipe and Chiller Circuit on the Mixed Feed Side
Double pipes and chillers are the key components of the crystallization sec-
tion. Before describing the rest of the process we are going to describe the
design and operation of a chiller.
 Primary
dilution
A
ED112A P p
ED112B
tn
0
P

Feed 3l 11-15
(raffinate)

Mixed slack wax

To oil distillation
Solvent
d
T -’
k
7
u u u u
EDlllC ED1llB EDlllA
T I

“Rich”DW filtrate c- To dewaxing

“Poor”DW filtrate I filters

<
Tertiarv
dilution

I
E3NB
Cooling of dry solvent for
tertiary and wash dilutions

I-
Figure
9.18 Dewaxing crystallization circuit.
 Chapter 9. CRYSTALLIZATION IN THE OIL \NDUSTRY: SOLVENT DEWAXING505

Description of a Double Pipe and a Chiller

Chillers and double pipes are tubular exchangers that cool the mixture of
feed + solvent by heat exchange with a cold fluid. They have 10 to 12 elements
made up of coaxial pipes mounted in rows of two pipes wide and five or six
pipes high. Each of these elements consists of 6" and 8" pipes 15 m long, and
in each one there is a wax scraping system. The total exchange area of a chiller
(or a double pipe) is approximately 80 m2.
The scrapers are spring loaded metal blades attached to a drive shaft.
There are several variations on scraper technology (attached to the shaft by
springs: Worthington system, or by metal sheets with a specified flexibility:
Vogt system), but the basic principles remain the same. The scrapers provide
the agitation that is favorable to crystal growth. They are also used to prevent
wax from accumulating on chiller walls, which would be detrimental to the
exchange coefficient, or even clog the unit completely in extreme cases. As
such, it is extremely important to make sure the scrapers are working prop-
erly, and their degree of wear should be checked periodically. The 10 or
12 scraper drive shafts are connected by a chain and driven by an electric
motor. At this stage in the description, a chiller and a double pipe are identi-
cal. The difference between them is the heat transfer fluid.
A double pipe takes its negative calories from the filtrate (oil + solvent)
exiting the filters which is at the filtration temperature (i.e. between -10 and
-28°C depending on the type of feed and the composition of the solvent used
in the unit). A chiller takes its negative calories from liquid ammonia which
vaporizes. A chiller can therefore be distinguished by the fact that it is sur-
mounted by an ammonia tank. The tank is supplied with ammonia at a tem-
perature of some -40°C from the dewaxing unit's refrigerating system. Level
control regulates the supply and ammonia degassing is controlled by the tem-
perature of the mixed feed coming from the chiller. Figure 9.19 shows a chiller.
Operation of Double Pipes and Chillers
After cooling in E,, the mixed feed is cooled in double pipe EDlllc by exchange
with the dewaxed filtrate. Secondary dilution is added at the outlet of the dou-
ble pipe. Crystallization continues in double pipes ED,,,, and (countercur-
rent exchange with the dewaxed filtrate) then in chiller ED,,,, and finally in
chiller ED112B. When it exits ED,,,, it has reached the final filtration tempera-
ture. Tertiary dilution can be injected at the outlet of ED112A, or at the inlet,
middle or exit of ED11,B. The potential injection points for dewaxed filtrate dilu-
tion are identical.
The slurry (liquid-solid mixture of feed and solvent) is then sent to drum B,
and goes down to the filters by gravity individually controlled by filter drum
level.

b. Deoiling Crystallization Section

The diagram of the deoiling feed circuit is given in Figure 9.20
The mixed slack wax coming from the dewaxing filters is heated in E30 (by
the dewaxer feed) then in E,, before it is sent to surge drum B130 when in line
506 Chapfer 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING

r NH3 gas

Vogt system

Figure
9.19 Simplified flow diagram of a chiller and two types of scrapers.

deoiling is in service. When the in line deoiling unit is shut down, the mixed
slack wax is sent to drum B14 which is the surge drum for the wax distillation
feed. Some slack wax is recirculated from B130 when the deoiling unit is work-
ing (from B14 when it is shut down) to the dewaxing filter chutes t o make sure
the temperature is high enough on the discharge side of the slack wax pumps
for these filters.
Drum B130 storing the mixed slack wax from dewaxing has a large enough
capacity to allow for operating flexibility between dewaxing and deoiling.
The mixed slack wax stored in B130 still contains 4 to 6 times its volume of
pure solvent, corresponding to the volume required for primary dilution. It is
therefore unnecessary in most cases t o inject primary dilution in the deoiling
feed circuit and this partly explains the economic advantage of in line deoiling.
The operating principle for the deoiling feed circuit is identical t o that of
dewaxing. The mixed slack wax is heated in ElO1by low pressure steam, then
cooled in EIo2 by foot's oil filtrate (from B104/B105). Secondary dilution is
injected at the exit of El,,. The mixed slack wax is then crystallized in chillers
ED,,,* and ED,,,,. At the exit of ED,,, the product is at the filtration tempera-
ture (from 10 to 20°C) and is sent t o BJBwhich is the feed drum for the deoil-
ing filters.
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING 507

De-oiling filtrate

c
m
B3B

To filter chutes

De-oiling primary
-----------------'
dilution (if any)
De-oiling secondary
dilution
oil distillation
L
To de-oiling

filters

De-oiling tertiary L
r
dilution

Figure
9.20 Deoiling crystallization circuit.

9.3.2.2 Filtration Section

a. Dewaxing Filtration Section
Rotary Filters
The main equipment in the filtration section is the rotary filter (see Fig. 9.21).
The most common size for a rotary filter is from 65 to 100 m2of filtering sur-
face area. To get an industrially acceptable through flow rate, several filters
are used in parallel.
A drum covered with an outer filter cloth rotates constantly around a hor-
izontal axis at an adjustable speed of 0.1 to 1 rpm. The drum is enclosed in a
metal cylinder which is under inert gas protection and has ports so that the
operation inside can be monitored. The mixture to be filtered is let into the
lower part of this cylinder up to a specified adjustable level (from 40 to 50% of
the drum height). The drum is divided up into some thirty segments, each one
connected by flow lines to two of the openings in the rotating valve located at
one end of the drum. Through the openings in the rotating valve, the segments
are connected alternately to filtrate flow lines then to gas blowing lines during
508 Chapter 9. CRYSTALLlZaTlON IN THE OIL INDUSTRY: SOLVENT DEWAXING

Rotary filter for dewaxing base oils (Source: Mobil). (Sarofot Photographie,
I I , rue Berthelot, 76600 Le Havre, France).

rotation. One particular segment goes through the following phases during a
360 degree rotation (see Fig. 9.22 for the description below):
Filtration Phase
The segment rotates first of all submerged in the feedsolvent mixture. It is
connected by the flow lines and the rotating valve to the filtrate holding drum
which is kept under a vacuum (approximately 0.250 bar abs.). Since the out-
side of the filter drum is at a pressure slightly higher than atmospheric, the fil-
trate is sucked into its holding drum while the cake is laid down on the cloth.
Note that the cake is formed by accumulation of wax crystals which leave
voids, or pores, full of liquid between them. The liquid has the same composi-
tion as the filtrate and therefore contains oil. The ratio between liquid and
solid volumes in the cake varies from 4 to 7 depending on the processed cut
(4 for light distillates, 7 for Bright Stock).
Washing Phase
When the segment comes out of the liquid-solid filter feed mixture, the cake
still contains oil that needs to be recovered. As such, an input of cold solvent
at the top part of the filter (washing dilution) is sprayed onto the cake surface
while the vacuum is maintained. The filtrate contained in the cake is displaced
by the solvent and is thus recovered. At the end of the washing phase, solvent
injection is stopped so as to allow the cake to dry out.
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING 509

FILTRATION WASHING

Filtration

BLOWING WAX CAKE RECOVERY

Blowing
of wax
cake

-
Figure
Filtration
- Filtration
cake

9.22 Diagram showing the operation o f a rotary filter (Source: Mobil).

The importance of washing dilution has been demonstrated in

Section 9.2.5.3. To achieve good efficiency for this dilution, the solvent must be
evenly distributed. This is the purpose of the injection nozzles and the spray
systems mounted on the filter's solvent ramps.
It some cases it may be advantageous to use a relatively low vacuum for
suction in the submerged part of the filter, whereas it is always advisable to
have a very high vacuum in the washing zone. This is why the filtrate is recov-
ered by means of three separate lines of pipe equipped with valves that also
allow the filtrates to be segregated according to where they come from: the fil-
tration segment in the submerged zone, the one in the drainage zone or the
one in the drying zone.
Another asset of this technique is that the filtrate recovered in the drying
zone can be used in dilution for it contains around 95%volume of solvent. This
is why the filtrate holding drum is generally made up of two compartments
("rich" filtrate and "poor" filtrate).
Purging Phase
During this phase the internal lines are purged of their filtrate.
510 Chapter 9. CRYSTALLlZPiTlON IN THE OIL INDUSTRY: SOLVENT DEWAXING

Blowing Phase
Pressurized gas is sent into the segment's flow lines, goes through the filter
cloth making it bulge slightly, thereby loosening the cake. It then goes through
the cake, breaks it and removes it completely. The cake then slides into a
worm conveyor which discharges it to a storage drum. A metal plate called a
scraper is placed a few millimeters from the filter cloth to keep the wax cake
from falling back into the mixture and being recycled, as this would reduce fil-
ter capacity.
Even though the operation of a rotary filter is continuous, each segment
works in a discontinuous way during a filtration cycle.
The materials used for the filter cloth are diverse (cottons, nylons, etc.)
and laboratory testing (porosity, filtration rate, etc.) must be done before the
cloth is used industrially. The mesh size of the cloth also needs to be chosen
according to the type of feed processed (micro- or macrocrystalline).
Periodic Washing of Filter Cloth
During continuous operation the filter cloth gradually gets clogged by wax
crystals. As a result, filtration resistance increases significantly and a more or
less rapid drop in filtrate flow rate is observed. The filter must then be isolated
from the production process to be washed with hot solvent in order to dis-
solve the crystals plugging the cloth. Washing frequency (every 6 hours to
every few days) depends on the feed grade and the texture of the crystals
passing through the filters. The more viscous the feed, the more often the fil-
ter needs to be washed.
The filtrate (oil + solvent) is separated from the mixed slack wax on filters
FD,, to 15. It is collected in drums B4/B5 that are kept under a vacuum (see
Fig. 9.27). The mixed slack wax is collected in accumulator drums specific to
each filter and each one is equipped with a condensate pump. The filters are
equipped with dedicated drums so that they can be moved around in the pro-
cess and used for example in dewaxing or in deoiling. If interchangeable filters
are not needed, one single mixed slack wax drum is sufficient for all the filters.

Dewaxing Filtrate Circuit (see Fig. 9.18)

The dewaxing filtrate or DW filtrate from drum B4 is sent to double pipes
ED,,,m,c. The filtrate therefore circulates countercurrently with the mixed
feed in order to optimize the exchange between the two products. Part of the
filtrate that has cooled the mixed feed is used to cool the secondary dilution
in E,. The DW filtrate from drum B, that is not sent to the double pipes goes to
exchanger E34/B where it cools the dry solvent for tertiary and washing dilu-
tions. It is allocated to cooling the mixed feed and cooling tertiary and wash-
ing dilutions according to the operational optimization of chillers ED, and ,*
solvent coolers E4. The DW filtrate from E, and E, is then sent to oil distillation
to separate the dewaxed oil from the solvent. The DW filtrate from drum B,
(called "poor" filtrate, see Section 9.2.7: Filtration method) is sent to filtrate
dilution.
 Chapter9. CRYSTALLIZATION IN THE OIL INDUSTRY.' SOLVENT DEWMING 511

b. Deoiling Filtration Section

Except for the filtration temperature, the deoiling filtration section works
according to the same principle as dewaxing filtration. The products from fil-
tration are:
a solid product, wax with a low oil content along with 4 to 6 times its vol-
ume of solvent;
a liquid product, the foot's oil filtrate, whose structure is between oil and
wax, diluted in 90% of solvent.
On exiting the filters, the wax is collected in intermediate drums (specific
to each filter) before being pumped to wax distillation. Recirculated hot mixed
wax (about 70°C) is injected on the discharge side of the pumps to guarantee
proper handling.
The foot's oil filtrate is recovered in drums B104/B105, which are under vac-
uum conditions, then pumped to foot's oil distillation (see Fig. 9.20).

9.3.2.2 Distillation Sections

a. Distillation of the Solvent Contained in the Dewaxed Oil
The oil distillation flow scheme is given in Figure 9.23. The solvent contained
in the DW filtrate is vaporized at four levels:
at 0.2 bar gauge and 90°C in C2A (low pressure and low temperature level):
at 1.2 bar gauge and 120°C in CZc (medium pressure level):
at 2.2 bar gauge and 160°C in CZB(high pressure level);
at 0.2 bar gauge and 180°C in C,, (low pressure and high temperature
level).
As a result, the solvent is recovered at three pressure and temperature lev-
els:
+140-100°C (subcooled) HP condensation;
+115-95"C (subcooled) MP condensation;
+90-75"C LP condensation.
The bottom of C3Ais evacuated by pressure to the steam stripping tower
C, which serves to eliminate the last traces of solvent. Since the oil exiting
the unit has to be free of any trace of water (added during steam stripping) so
that it is clear and light, the final treatment is drying in tower C4 under vacuum
conditions (the vacuum in C, is produced by a liquid ring pump).
Some units use furnaces instead of steam exchangers.
Solvent recovery is broken down as follows:
First stage (CzJ 27% wt
Second stage (C23 31% wt
Third stage (Czd 35% wt
Fourth stage (C3J 6% wt
512 Chapter 9. CRYSTALLIZATION IN THE O I L INDUSTRY: SOLVENT DEWAXING
(
r
 Chaorer 9 CRYSTALLiZATlON IN THE OIL /NDUSTRy: SOLVENT DEWAXING 513

b. Distillation of the Solvent Contained in the Wax and in the Foot's oil
The wax and foot's oil distillations are similar to the oil distillation and so will
not be described in detail.

9.3.2.4 Solvent System

a. Solvent Recovery/Distribution
Solvent distilled at the top of distillation towers is collected in one of two ves-
sels B, and B,,. The solvent coming from oil distillation is recovered in B, and
that coming from wax and foot's oil distillations in B,,. The purpose of segre-
gation is to have only solvent free of traces of oil in B,,, so that no oil is rein-
troduced in the wax by means of the solvent used as deoiling dilutions. We will
see later on how the balance between these two drums is carried out.
Drum B, is divided into two compartments, B,, and BgWThe subscripts "S"
and "H" are for "dry" and "wet". Any solvent that may contain water (first dis-
tillation stage and solvent from water/solvent settlers) is sent to BgH and the
water free solvent to Bgs. This is done to avoid fouling or even clogging of sol-
vent coolers.
Primary and secondary dilutions in the dewaxing section are drawn from
BgH, while tertiary and washing dewaxing dilutions are taken from Bgs. Deoiling
dilutions are withdrawn from Bll. All these dilutions must be at the same tem-
perature as the injection point. This will be achieved in conventional exchang-
ers for all dilutions (by exchange with other process products to optimize
energy recovery), except for tertiary and washing dewaxing dilutions (which
must be at the filtration temperature), which are cooled by ammonia vapor-
ization in "kettle" type exchangers.
b. Dehydrating the Solvent. Ketone Tower
The simplified flow diagram is shown in Figure 9.24.The oil, wax and foot's oil
are stripped with medium pressure steam at the end of the distillation opera-
tion in order to remove the last traces of solvent. This results in an added
amount of water, around 2 t/h, that has to be eliminated. The steam and sol-
vent vapors coming from the stripping towers are condensed and then sent to
the settling drum B13. Due to the composition of the solvent in B13 (90%
toluene), settling is easy and the solvent phase exiting BI3 contains approxi-
mately 0.2% vol water. Since this value is satisfactory, many plants do not
include any further treatment and the solvent from settling is directly sent to
the main solvent drum (B, in this case). We have, however, seen previously
that it is necessary to maximize the MEK content in the solvent and that max-
imum MEK content depends on the water content (see Section 9.2.3).
Consequently, it may be advantageous to continue dehydrating the solvent
and some plants have more complex systems than the one described here.
The water phase from B13 is sent to tower C, called the "ketone tower".
Water and MEK form an azeotrope (see Fig. 9.8) and therefore the
azeotropic composition (85% MEK and 15%water) will be found at the top of
C,, while solvent free water will be at the bottom from where it will be dis-
charged to the sewer.
514 Chapter 9. cRYSTALLlZaTl0N IN THE OIL /NDUSTRY: SOLVENT DEWAXING

From top
of strippers y
Water

Solvent-rich

v
phase

To solvent

Water-rich
phase
' system

ky I
L
1

A
Solvent settling system
and water discharge.

Tower C1works at approximately 97°C and at atmospheric pressure. The

energy required to vaporize the azeotrope is provided by the heat recovered
from the tower bottom effluents and from the stripping steam. The tower is
equipped with 1" stainless steel rings.
The azeotrope at the top of C, is returned to the settling drum Blp The sol-
vent phase from drum B13 containing around 90%toluene is sent back t o the
solvent system.
c. Recovery o f Filter Wash
To keep filters from getting clogged up and maintain a proper filtration rate,
they are washed with hot solvent at intervals from every few hours to every
few days depending on the type of processed feed. The filter wash effluents are
recovered in a surge drum and then pumped either directly into the feed train
at the primary dilution point or into drum B13.

9.3.2.5 Refrigeration Section

a. Objectives and Principle o f the Refrigeration Circuit
The purpose of the section is t o provide the negative calories required to cool
down the feed and solvent as well as crystallize the slack wax and/or wax. This
 Chapter 9. CRYSTALLIZATION IN THE OIL /NDUSTRK' SOLVENT DEWAXING 515

can be achieved by a refrigeration system operating on the basis of compres-

sion or absorption. Compression systems account for the great majority of
industrial refrigeration units.
In a compression refrigeration system, a product called a coolant circulates
in a cycle that converts it alternatively from the gaseous to the liquid state.
Most coolants are pure substances and the most commonly used in the dewax-
ing process are propane and ammonia. In most cases the coolant used in the
compression cycle (ammonia or propane) exchanges its negative calories
directly with the dewaxing unit feed and the solvent, but it may be more advan-
tageous to have a system with two coolants. It is possible to use freon R2,
(CHCIFJ for example as a coolant in the compression cycle transferring its
negative calories to ammonia, which in turn will transfer them to process flu-
ids. The advantages of the dual loop system are as listed below:
Safety: the ammonia circulating in the unit will be at a much lower pres-
sure (2 to 3 bar gauge instead of 10 bar).
Refrigeration system stability: the dual loop of coolant helps attenuate
process disturbances on the compression cycle.
No fouling: chillers are not fouled by entrained compressor lube oil.
In the rest of the discussion we will describe a system with two coolants,
freon R,, and ammonia.

b. Description o f the Refrigeration Cycle

The simplified flow diagram is given in Figure 9.25 and the thermodynamic
principle in Figure 9.26. The stream numbers on the two diagrams allow the
two diagrams to be compared.
The main piece of equipment in the cycle is the centrifugal compressor
Kzool, with three compression stages. The gaseous freon exiting K2001 is at a
pressure of 11 bar abs. and a temperature of 120°C. It is condensed by
exchange with water in condensers E,,,,. The freon exiting E,,,, is in a state of
liquid-vapor equilibrium and at a temperature of 26°C. Its temperature is first
lowered by isenthalpic expansion in the C2004 level control valve. The vapor
fraction at the top of C2004is sent to the HP stage inlet of compressor K,,,,,
which allows the inlet temperature of the third stage to be lower and reduces
energy consumption. The liquid freon in the bottom of C2004 is sent to econo-
mizer C2005 through the drum's level control valve. Isenthalpic expansion in the
valve lowers freon temperature to -16°C. The C2005 vapors are sent to the inlet
of the second compressor stage. The liquid freon exiting C,, undergoes a
final expansion in the level control valve of E,, (NH, c~ndensers/R,~ evapo-
rators). In E2006,
the (gaseous) ammonia coming from the chillers and solvent
coolers is condensed by transferring its heat to the freon which vaporizes
before it undergoes another compression cycle. The ammonia exiting E,, is
at -42°C and at its bubble point pressure. It is pumped up to the chillers and
solvent coolers.
Notu bene: Compression is neither isothermal nor isenthalpic, but almost
isentropic.
516 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING

NH3+
from
chillers

NH, to
chillers

-
Figure
9.25 Refrigeration.

9.3.2.6 Ancillary Equipment

Having described the five sections, we will now go into ancillaries.
a . Vacuum Pumps
In order to generate the vacuum required to separate the dewaxed oil from the
wax in the filters, a dewaxing unit is equipped with vacuum pumps. The vac-
uum pump is supplied from filtrate drums B, (for the dewaxing section) and
BIo5 (for the deoiling section). An intermediate trap drum is incorporated
between vacuum pump suction and the filtrate drum to prevent any liquid
carry-over that would be detrimental to the pump. The discharge of the vac-
uum pump (approximately 200 mbar gauge) goes to the blowing segments of
the filters to help detach the paraffin cake. The inert gas from pump discharge
is cooled to a temperature close to 0°C to prevent the temperature from rising
in the filter blowing sector. A system of pressure control valves is used to
adjust the blowing pressure value to its optimum and make sure that the
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING 517

I
b
H (kJlkg)

-
Figure
9.26 Freon 22 cycle.

vacuum pump runs properly under any and all conditions. The simplified flow
diagram is given in Figure 9.27.
6. Inert Gas Circuit [Fig. 9.27)
For safety reasons, all the vessels in the unit containing solvent and all filter
hoods are kept at a slight overpressure (around 30 mbar gauge) with inert gas.
Any negative pressure occurring in the vessels (caused for example by a drop
in liquid level) will be offset by an inflow of inert gas. A gasometer is installed
to attenuate the system's pressure variations. The inert gas is produced by
stoichiometric combustion of propane, or if nitrogen is used it is produced on
site by membrane separation.

9.4 Operating a Solvent Dewaxing Unit

The main aim of a dewaxing unit is to make sure that the pour point of base
stock meets specifications. The pour point will therefore be monitored as the
first priority, either by frequent laboratory analyses or by a continuous pour
point analyzer installed at the exit of the unit.
Besides this specification, the points that need to be routinely monitored
during operation of a solvent dewaxing unit are as follows:
feed train operation;
518 Chapter9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING

lnerting of filter hood

'
I
Cake blowing

lnerting of solvent
I
I
(*) Filters

I
I Filtrate
storage tanks
!
D DPCV

L&
4
Vacuum pump

LJ LCVb

Drain

Figure
9.27 Inert gas circuit.

filter operation;
solvent quality;
temperatures and pressures of the solvent recovery system;
refrigeration unit performance;
operation of the azeotropic system and solvent dehydration section;
solvent consumption.
Distribution of dilutions will have to be optimized constantly versus speci-
fied objectives (getting maximum capacity from the unit or maximum dewaxed
oil yield) and constraints observed on the unit.
The particular feature of a dewaxing unit is also that it does not really run
continuously in the same way as a topping unit does. In fact, several grades of
oil or base stock are handled in the same unit, so that it will work batch-wise.
For instance it will process a light cut for three days and then a heavy cut. Each
time the grade changes, called stock change, all the settings must be com-
pletely readjusted, thereby causing significant modifications in the working of
the unit (change in filtration temperature to meet the pour point specification
for the new grade, appearance of new constraints, variation in the MEK-
toluene ratio in some cases, etc.).
 Chapter 9. CRYSTALLIZATION IN THE OIL /NDUSTRY: SOLVENT DEWAXING 519

9.4.1 Feed Train Operation

It is indispensable for the feed train to run efficiently,as this guarantees proper
crystallization, which in turn directly influences the performance of the filtra-
tion section as well as giving satisfactory throughput and dewaxed oil yields.
The parameters that serve to monitor feed train performance are the fol-
lowing:
The temperature profile from the discharge of the unit feed pump to the
filter feed drum. The profile, also called crystallization curve, is estab-
lished according to the basic principles of crystallization and on the
experience gained in the industry. The fundamental rule to remember is
to avoid thermal shocks either from performance differences between
one chiller and another or from dilutions at temperatures that are too dif-
ferent from those measured at the injection point.
The total pressure drop in the feed train and the pressure drop per
double pipe or chiller. An increase in pressure drop means a chiller or
double pipe is fouled. Fouling affects their heat transfer coefficient sig-
nificantly and causes difficulties in getting the required crystallization
curve and even in getting the required filtration temperature.
The temperature of the filter feed drum, which must be the same as the
desired filtration temperature in order to achieve the dewaxed oil pour
point.
It is also recommended to set up a regular material balance of the feed train
to make sure that the dilution rates actually injected comply with the specified
values.

9.4.2 Filter Operation

The parameters below should be carefully attended to:
Achieving a proper vacuum for the filtrate withdrawal valves.
Wash solvent distribution, i.e. regular distribution of the solvent sprayed
on the whole filter, no unused solvent (i.e. not absorbed by the wax cake
and falling directly into the chute or into the filter drum for example).
Insufficient wash solvent causes the wax cake to dry out and crack open.
The inert gas and wash solvent will pass through the cracks, thereby
reducing the vacuum of the filtrate withdrawal valves.
The thickness of the wax cake, which will be adjusted by modifying the
rotation speed of the filter.
The load level in the filter drum. It must be high enough to allow the wax
cake to form regularly, but not so high that the feed might overflow into
the wax recovery chute (the consequences of an overflow are a signifi-
cant loss in dewaxed oil yield and a serious increase in oil content in the
Wax).
The condition of the filter cloth: with the naked eye, the operator checks
that there are no tears in the cloth. A tear would allow wax crystals to
520 Chapter 9. CRYSTALLIZATION IN THE O I L /NOUSTRY: SOLVENT DEWAXING

pass through into the oil, thereby affecting the pour point, cloud point
and general aspect of the dewaxed oil.

9.4.3 Solvent Quality

Solvent quality should be checked very frequently. The following analyses are
performed:
Gas chromatography to determine the MEK, toluene and water contents.
MEK content must comply with the value specified according to the type
of processed feed as indicated in Section 9.2.3. Water content must not
exceed the maximum values set according to the process of water elimi-
nation used in the unit and the safety margin chosen for MEK content
before phase separation appears.
Determination of pollutants such as oil and wax (coming from carry-over
in the solvent recovery towers). An overly high oil content will cause
severe difficulties, and may even make it impossible to produce waxes
with a low oil content. An overly high wax content will cause rapid foul-
ing of solvent coolers.

9.4.4 Temperatures and Pressures of the Solvent

Recovery System
One of the oil and wax specifications is the flash point. It is obvious that any
residual solvent traces in these products immediately affect their flash point.
As an example, 200 to 300 ppm of MEK in the oil are enough to make it fail to
pass its flash point specification. Consequently, it is crucial for distillation
units to work perfectly and they will be monitored by checking that tempera-
tures and pressures comply with the values calculated at every stage, includ-
ing the drying tower (to guarantee the bright, clear aspect of the oil). This type
of supervision is also warranted economically as explained in the section
devoted to oil distillation operation.

9.4.5 Refrigeration Unit Performance

The critical point to monitor is the temperature of the cooling medium s u p
plied to the solvent coolers and chillers. In order to guarantee proper heat
exchange, the temperature must be much lower than the filtration tempera-
ture. For example, if the filtration temperature is around -2O"C, it is recom-
mended to have a coolant temperature of about -40°C.

9.4.6 Operation of the Azeotropic System

and Solvent Dehydration Section
It is indispensable to monitor the settling quality in settler drum Blp Poor
settling causes the solvent phase to contain too much water and can make
 Chapter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING 521

dehydration tower ClO7malfunction. This means more water in the dilution sol-
vent, with the consequences mentioned previously. A water phase that is
overly rich in solvent will not allow ketone tower C1 to run properly, and will
usually cause MEK pollution of the discharge streams from this tower. The reli-
ability of interface level B,, is crucial and should be checked frequently.

9.4.7 Solvent Consumption. Environmental Protection

Since the solvent used in the process is recovered by distillation and then
recycled, there is theoretically no solvent consumption. In actual fact, solvent
unfortunately is consumed due mainly to leakage from equipment (pump
seals, rotating valve seals in filters, etc.).
It is important to minimize leakage for three main reasons:
MEK and toluene are dangerous water pollutants. A few ppm of MEK in
water are sufficient to increase the COD (chemical oxygen demand) sig-
nificantly.
MEK also comes in the category of volatile organic compounds (VOC).
MEK is a relatively expensive solvent. A kilogram of MEK cost around FF 4
in 1992.
As a result, a solvent dewaxing unit is equipped with a system to collect
solvent leakage called a “drain”. The system is of the gravity type, i.e. solvent
collected by catchers installed where there are risks of leakage will flow by
gravity into an underground catch drum.
However, the major risk of solvent loss to the sewer is a malfunction in
ketone tower C,. Here it is possible to lose several m3/h of solvent, particularly
when the interface level of the settling drum BI3 is wrong and the pure solvent
phase is fed to C, instead of the water phase.

9.4.8 Optimizing Dilutions

Distribution of dilutions must be constantly optimized as mentioned earlier.
Depending on the type of feed, the filtration section can become the bottle-
neck of the unit, and if maximum capacity is desired, primary dilution will have
to be increased (larger sized crystals) at the expense of tertiary dilution. In
other cases, the oil distillation section will be limiting and this will be seen by
an increase in filtrate dilution (which is a recirculation) at the expense of ter-
tiary dilution, so as to reduce the total amount of solvent to be redistilled.

9.5 Economics
9.5.1 Energy Consumption
Energy consumption per m3 of dewaxed oil produced is broken down as
follows:
522 Chapter 9 CRYSJALLIZAJION IN THE OIL /NDUSJRY: SOLVENT DEWAXING

Refrigeration unit (60 kWh) 13.3 toe

Solvent distillation 185.1 10” toe
Transfer and utilities 14.5 10” toe
Total 212.9 10-3 toe
Nota bene: toe = ton of oil equivalent = 4 500 kWh.
The specific energy consumption of a dewaxing unit is huge, around
10 times higher than for a crude oil topping unit. Distillation’s share in con-
sumption is overriding (high solvent latent heat of vaporization). This explains
why so many efforts are being made to minimize the energy consumption in
distillation (multistage vaporization, optimized energy recovery, etc.). As an
example, a two-stage vaporization set up consumes 20% more energy than a
threestage system.

9.5.2 Operating Costs

Operating costs for a dewaxing unit are mainly due to energy consumption. If
the unit is not saturated, an economic balance should be established between
the added energy consumption with an increase in the total solvent ratio and
the resulting added yield in dewaxed oil.
As an indication, for a dewaxing unit using an MEK-toluene solvent mixture
with a capacity of 1,000 m3/day, operating costs will be approximately:
Standing expenses FF 120/ton of dewaxed oil
Variable costs FF 7O/ton of dewaxed oil
These figures can be extremely variable as they depend greatly on the
degree of sophistication of energy recovery.

9.5.3 Cost of Major Equipment (1992 Figures)

A rotary filter with a filtering surface area of 120 m2 cost around FF 20 million
and a chiller with an exchange surface area of 80 m2 cost some FF 5 million
in 1992.

9.6 Process Developments

9.6.1 Applications of Computerized Process Control
We have seen that a solvent dewaxing unit often has its operating parameters
readjusted, and so it is particularly advantageous to control them with com-
plex advanced process control loops. The most typical application is in getting
an optimum crystallization curve according to chiller performance (calcula-
tion of transfer coefficients and temperature set points at the exit of each
chiller or double pipe exchanger). The most profitable section to computerize
 ChaDter 9. CRYSTALLIZATION IN THE OIL INDUSTRY: SOLVENT DEWAXING 523

is filtration, but this objective is very difficult to attain, due to the large num-
ber of experimental aspects which still remain in the area of filtration.

9.6.2 Other Techniques: Dilchil Process

The Dilchil process (patented by Esso) can not be explained in detail because
of its proprietary nature. It differs from a conventional unit in the crystalliza-
tion section, where chillers are replaced by crystallization columns using
multi-staged solvent injections. The improved process performance is appre-
ciable, since it is possible to obtain slack wax with less than 3% residual oil
content.