J.

of Supercritical Fluids 58 (2011) 352359

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Separation of alkanes and alcohols with supercritical uids. Part II. Inuence of
process parameters and size of operating range
C.E. Schwarz, G.J.K. Bonthuys, R.F. van Schalkwyk, D.L. Laubscher, A.J. Burger, J.H. Knoetze
Department of Process Engineering, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa

a r t i c l e

i n f o

Article history:
Received 3 March 2011
Received in revised form 5 July 2011
Accepted 5 July 2011
Keywords:
Pilot plant
Optimisation
1-Dodecanol
n-Tetradecane
Ethane
Carbon dioxide
Supercritical

a b s t r a c t
This paper is the continuation of a previous study on the investigation of the separation of detergent range
alkanes and alcohols with supercritical uids. Specically this paper presents results on the optimisation
of the process parameters for the separation of n-tetradecane and 1-dodecanol with supercritical carbon
dioxide and ethane. The optimum operating conditions were determined from the results of a study
of the inuence of the process parameters, as well as an investigation into the size of the operating
range. The results showed that the optimum temperature is a balance between good separation at lower
temperatures and better control at higher temperatures. The solvent-to-feed ratio should be kept low
(within the range of vapour-continuous operation) as lower solvent-to-feed ratios result in improved
separation, as well as lower energy requirements. The use of reux is necessary for good separation
when using carbon dioxide as solvent, but is not required with ethane as solvent. An analysis of the
operating range showed that a process using ethane is easier to control. Ethane as solvent is technically
superior to carbon dioxide yet, depending on the exact process and location, costs, safety and logistics
may favour the use of carbon dioxide.
2011 Elsevier B.V. All rights reserved.

1. Introduction
Long chain alcohols (C12C14), for use in the detergent and
cosmetic industries, are usually produced from their corresponding alkanes. However, complete conversion from alkane to alcohol
does not occur, necessitating the use of a post-production separation process. Due to low vapour pressures, cross-over melting
and boiling points, as well as problems associated with traditional
organic solvents, conventional separation processes such as distillation, crystallisation and liquidliquid extraction are costly and
difcult, if not impossible, to implement for the separation of these
alkanes and alcohols.
The aim of this series is to present results on the investigation
of the ability of supercritical uid extraction to separate detergent range alkanes and alcohols. Previous studies on the processing
of high molecular mass compounds (as liquids) with supercritical
uids include the following:

Removal of unreacted dodecanol from ethoxylated dodecanol [1].

Fractionation of polyethylene glycol [2,3].
Fractionation of parafn and synthetic wax [4].
Concentration of wax-like alcohol ethoxylates [5,6].

Corresponding author. Tel.: +27 21 808 4488; fax: +27 21 808 2059.
E-mail address: jhk@sun.ac.za (J.H. Knoetze).
0896-8446/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.supu.2011.07.005

A typical alkanealcohol mixture would consist of mainly

C12C14 compounds and from the phase behaviour [6] it follows that the most difcult separation would thus be between
n-tetradecane (nC14) and 1-dodecanol (1-C12-OH). The investigation is therefore conducted by considering the separation of nC14
from 1-C12-OH.
Part I [7] of this series presented results on the viability of
the separation of nC14 from 1-C12-OH with supercritical uids by
considering the phase equilibria, pilot plant testing and the estimation of the energy requirements for typical processes. Part I
concluded that both supercritical ethane and carbon dioxide are
able to separate the nC14 and 1-C12-OH with ethane showing superior selectivity. On the other hand, the process utilising carbon
dioxide is cheaper to run due to lower energy costs.
The aim of this paper is to present further results on this separation process. Part I proved that the process would be viable,
but further investigation into the optimisation of the process with
regard to the inuence of process parameters and the ability to
control the process was necessary. Although binary phase equilibria/solubility measurements have been conducted for the systems
concerned (see Part I), to date no thermodynamic model is able to
accurately predict the system [810] and thus one needs to rely on
experimental pilot plant data to optimise the process. Therefore,
the purpose of this paper is two-fold:
It highlights the inuence of a number of operating parameters
on the potential degree of separation. Specically, the focus is on

C.E. Schwarz et al. / J. of Supercritical Fluids 58 (2011) 352359

varied, a 5050 mass% mixture of nC14 and 1-C12-OH was used.

The 5050 mass% feed was selected to allow for a well balanced
column and easy analysis of the overheads and bottoms products.
The runs were operated so that the solvent ow rate, the solute ow
rate, the feed position and the temperature were selected. The pressure was then either manipulated so that an overhead to feed ratio
(based on extract to feed mass ow rates) of approximately 0.5 was
attained for the process parameter study or systematically varied
for the operating range study. Ideally the column would separate
the feed so that all the tetradecane reports to the overheads and all
the 1-decanol reports to the bottoms and, as a 5050 mass% feed
mixture was used, an ideal separation would result in an overheadsto-feed ratio of 0.5. The constant overheads-to-feed ratio approach
was selected so that one could determine how close to ideal the
separation is at the set operating conditions.
For the investigation of the size of the operating range the experiments were conducted in two parts. Firstly, an experiment was
conducted to determine the boundary conditions of the selected
parameter for the operating range, i.e. for a 0.9 and a 0.1 overheadsto-feed ratio. Secondly, the parameter under investigation was then
varied so that a minimum of 4 data points were available for the
particular series. Where possible, experimental runs were eliminated by the inclusion of data from Part I [7] and/or the process
optimisation study.
The samples were analysed on a Varian 3400 gas chromatograph
equipped with a 60 m Phenomenex Zebron ZB-5 column and an FID
detector. Results from duplicate samples showed an error of less
than 1.5% in the analyses.
Ethane and carbon dioxide were obtained from Afrox with a
purity of >99% and >99.5% respectively. 1-C12-OH and nC14 were
obtained from SigmaAldrich with catalogue numbers 126799 and
172456 and purities of >98% and >99% respectively. All compounds
were used without further purication.

Nomenclature
1-C12-OH
nC14
S
xnC14,O
xnC14,B

353

1-dodecanol
n-tetradecane
selectivity
n-tetradecane composition of the overheads
product
n-tetradecane composition of the bottoms
product

the effect of temperature, the use of reux, solvent-to-feed ratio

and feed composition.
It identies the operating range with respect to temperature,
pressure and the combined effect of solvent-to-feed ratio and
solute ow rate.
The presented experimental pilot plant results provide an indication of the optimum operating conditions as well as which
solvent is better suited to the process.
2. Experimental set-up and methods
A previously constructed experimental set-up was used to conduct the pilot plant tests. The core of the pilot plant is a 28 mm
diameter column equipped with a 4.32 m total packed height of
Sulzer DX packing capable of operating at a maximum temperature and pressure of 150 C and 30 MPa respectively. The solute is
fed at either the top or the middle of the column and the solvent
at the bottom of the column. The loaded solvent exits the top of
the column where the solvent and the overheads/extract are separated with a pressure reduction and a temperature increase and
the non-extracted fraction exits at the bottom of the column (bottoms). A schematic representation of the experimental set-up, a
summary of the operating procedure and the accuracy of the measurements and results are given in Part I [7] of this series with a
detailed description of the setup provided elsewhere [4,11,12].
Pilot plant experiments are expensive to run and rather time
consuming. The number of experiments should thus be kept to a
minimum while at the same time extracting the maximum possible
information. In order to obtain the maximum information from the
minimum number of experimental runs, 37 carefully planned additional experimental runs were conducted. This data complements
results presented in Part I of this series and is used in conjunction
therewith for the process parameter and operating range studies.
Importantly, it should be noted how the experiments were conducted: in most cases, except where the feed composition was

3. Results and discussion

The experimental results for the pilot plant runs are given in
Tables 1 and 2 for carbon dioxide and in Table 3 for ethane. Data
for runs 114 are presented in Part I [7] and the reader is referred
thereto for details. The results are evaluated by considering the
overheads-to-feed ratio (where applicable) and the selectivity. For
the 5050 mass% feed used in this work, the overheads-to-feed
ratio should ideally be 0.5. As explained in the experimental procedure above, for the investigation of the inuence of the process
parameters, the pressure was varied to obtain an overheads-to-feed
ratio of approximately 0.5 while for the investigation of the size of
the operating range pressure is regarded as an output of the study.
The selectivity is a measure of the ability of the process, under the

Table 1
Pilot plant results for carbon dioxide as solvent (part 1).
Run

15

16

17

18

19

20

21

22

23

24

25

26

Feed position
Reux
Reux ratio
Pressure (MPa)
Temperature ( C)
Solvent ow rate (kg/h)
Feed ow rate (kg/h)
Solvent/feed ratio
Overheads/feed ratio
% tetradecane in feed
% tetradecane in overheads
% tetradecane in bottoms
Selectivity
% maximum capacity

Top
No

14.80
80.6
17.1
0.48
36
0.56
50
66
36
1.8
47

Top
Yes
8.8
13.20
80.7
16.0
0.28
57
0.50
50
68
29
2.3
68

Top
No

14.40
81.0
16.0
0.48
33
0.48
50
68
35
1.9
44

Mid
No

14.91
81.3
13.1
0.46
28
0.52
50
68
36
1.9
38

Mid
Yes
6.6
15.00
81.1
13.1
0.46
28
0.41
50
67
40
1.7
55

Top
No

8.68
40.4
18.0
0.17
106
0.53
50
72
24
3.0
36

Top
No
0
11.65
70.1
17.0
0.48
35
0.16
50
71
43
1.7
45

Top
No
0
11.65
70.1
17.0
0.48
35
0.19
56
73
53
1.4
45

Top
No

9.05
40.1
16.3
0.30
55
0.55
50
77
3.1
25
42

Top
No

9.03
40.8
16.9
0.34
50
0.23
50
77
47
1.7
42

Top
No

9.03
41.9
16.8
0.35
48
0.17
50
78
41
1.9
41

Top
No

9.04
42.6
16.8
0.33
51
0.12
50
77
48
1.6
40

354

C.E. Schwarz et al. / J. of Supercritical Fluids 58 (2011) 352359

Table 2
Pilot plant results for carbon dioxide as solvent (part 2).
Run

27

28

29

30

31

32

33

34

35

36

37

38

39

Feed position
Reux
Reux ratio
Pressure (MPa)
Temperature ( C)
Solvent ow rate (kg/h)
Feed ow rate (kg/h)
Solvent/feed ratio
Overheads/feed ratio
% tetradecane in feed
% tetradecane in overheads
% tetradecane in bottoms
Selectivity
% maximum capacity

Top
No

9.02
40.0
21.4
0.34
63
0.64
50
74
1.2
61
37

Top
No

9.03
43.3
16.8
0.31
54
0.16
50
78
45
1.7
39

Top
No

8.20
40.1
17.1
0.31
55
0.06
50
79
47
1.7
39

Top
No

8.41
40.1
17.1
0.31
55
0.10
50
79
49
1.6
39

Top
No

8.57
40.1
16.5
0.30
55
0.14
50
72
46
1.6
39

Top
No

8.81
40.0
16.6
0.30
55
0.27
50
76
39
2.0
38

Top
No

9.09
40.3
16.9
0.30
56
0.77
50
74
0.0

40

Top
No

9.99
69.6
17.0
0.48
35
0.06
56
76
55
1.4
43

Top
No

12.88
70.6
17.0
0.48
35
0.36
56
71
46
1.6
45

Top
No

14.11
70.0
17.1
0.48
36
0.77
56
72
11
6.4
46

Top
No

9.03
39.9
8.0
0.30
27
0.22
50
76
43
1.8
49

Top
No

89.9
40.0
13.0
0.35
37
0.29
50
76
44
1.7
37

Top
No

90.3
39.2
16.9
0.35
48
0.62
50
76
2.6
29
38

particular operating conditions, to separate the feed and is dened

as the nC14 mass fraction in the overheads (xnC14,O ) divided by that
in the bottoms (xnC14,B ):
S=

xnc14,O
xnc14,B

in temperature leads to a decrease in the percentage nC14 in the

overheads, an increase in the percentage nC14 in the bottoms and
a decrease in the selectivity. The selectivity thus decreases as temperature increases at constant overheads-to-feed ratio. In the runs
compared there is a certain amount of variation in the feed ow
rate. Although the feed ow rate both increases and decreases
as temperature increases, the trends with regard to the effect of
temperature on the separation remain the same and the conclusions drawn are thus valid. The observed trends can be explained
by the fact that as temperature increases, the solubility difference
between nC14 and 1-C12-OH decreases. A sharper separation is
thus achieved at lower operating temperatures and lower operating
temperature should be favoured.

(1)

In addition to evaluating the selectivity, the compositions of

the overheads and bottoms streams will also be considered and
the hydrodynamic capacity (100% equals onset of ooding) of the
packing estimated. As the loading increases, the efciency of the
packing increases slightly up to a maximum at approximately 80%
of capacity, above which ooding is approached and the efciency
decreases drastically. The optimum loading for operation is thus
approximately 80% of ooding where the ow rates are such that
mass transfer is enhanced, yet at the same time ooding is avoided.
The hydrodynamic capacity is calculated with Sulcol 2.0.9 [13] and
details pertaining to the calculations are given in Part I.

3.1.2. Inuence of the use of reux

As in other extraction type processes, reux can be used to
improve the separation efciency of a process. Crause [11] showed
that, when applied to the fractionation of alkane mixtures, the use
of reux can enhance the separation and the effect is most dominant on the high molecular fraction of the overheads product.
Schwarz et al. [5] showed that reux can be used to manipulate the
product quality for the fractionation of wax-like alcohol ethoxylates and, as in the case of Crause [11], showed that the addition
of reux signicantly inuences the overheads product quality. For
the work reported here the inuence of reux was investigated
by keeping the remaining conditions (temperature, solvent and
feed ow rate and feed position) constant and merely introducing reux by switching on the reux pump. However, the pressure
was manipulated to obtain an overheads-to-feed ratio of approximately 0.5. The solvent ow rate thus remained the same while
liquid loading in the column increased.
For carbon dioxide as solvent, the effect of reux is seen when
run 6 is compared to run 4 and run 18 to run 19. In the rst case,

3.1. Inuence of the process parameters

3.1.1. Inuence of temperature
A number of studies have already investigated the inuence of
temperature on the separation ability of a supercritical process.
Schwarz et al. [5] found that, for the fractionation of alcohol ethoxylates with supercritical propane, an increase in temperature, at
constant overheads-to-feed ratio, leads to a decrease in selectivity.
Although different systems and solvents are used here, the phase
behaviour trends are not very different and it is expected that the
results will be similar.
The inuence of temperature on the selectivity is evident when
the temperature is increased (compare runs 6 and 15, runs 4 and
16 as well as runs 7 to 17 for carbon dioxide as solvent and compare runs 14 and 41 for ethane as solvent). In all cases, an increase
Table 3
Pilot plant results for ethane as solvent.
Run

40

41

42

43

44

45

46

47

48

49

50

51

Feed position
Reux
Reux ratio
Pressure (MPa)
Temperature ( C)
Solvent ow rate (kg/h)
Feed ow rate (kg/h)
Solvent/feed ratio
Overheads/feed ratio
% tetradecane in feed
% tetradecane in overheads
% tetradecane in bottoms
Selectivity
% maximum capacity

Top
No

9.23
70.8
10.2
0.48
21
0.73
50
64
3
23
32

Mid
No

8.93
70.5
9.5
0.57
17
0.55
50
78
19
4.1
33

Top
Yes
9.2
8.30
70.6
9.5
0.32
30
0.42
50
81
30
2.7
52

Top
No

6.26
42.0
10.4
0.57
18
0.60
50
81
1.0
81
34

Mid
Yes
4.5
8.93
70.5
9.5
0.56
17
0.48
50
80
26
3.1
33

Mid
No

8.00
69.9
9.5
0.25
38
0.46
50
79
28
2.8
27

Top
No

8.60
57.7
9.9
0.48
21
0.80
50
62
3
19
31

Top
No

8.60
61.2
10.0
0.48
21
0.71
50
71
3
25
32

Top
No

8.55
81.4
10.0
0.48
21
0.27
50
72
38
1.9
34

Top
No

8.64
69.8
9.6
0.48
20
0.55
50
68
31
2.2
37

Top
No

8.34
70.6
10.1
0.48
21
0.38
50
77
29
2.6
33

Top
No

7.79
70.0
10.2
0.48
21
0.22
50
80
42
1.9
34

C.E. Schwarz et al. / J. of Supercritical Fluids 58 (2011) 352359

where, in run 4, reux was added to the conditions of run 6, the

reux resulted in a larger quantity of nC14 in the overheads, a
smaller quantity of nC14 in the bottoms and thus a higher selectivity. Importantly, the overheads-to-feed ratio remained the same
and thus the same amount of product was withdrawn but with a
superior quality. Run 19 had the same conditions as run 18, with the
exception of the addition of reux and a decrease in the overheadsto-feed ratio. The fraction of nC14 in the overheads was the same,
yet for the run using reux it was slightly higher in the bottoms
stream resulting in a marginal decrease in selectivity. The separation is thus not as sharp and is further away from the desired 5050
split. From this second comparison it can be concluded that for carbon dioxide as solvent reux may improve separation but needs to
be applied correctly, usually with a slightly increased pressure, to
improve the separation.
For ethane as solvent the addition of reux has no real effect, or
rather results in effects that counter-balance one another or are
within the accuracy of the analysis technique. This can be seen
if runs 12 and 42, runs 43 and 11 as well as runs 41 and 44 are
compared. Specically one notices that neither the overheads nor
bottoms compositions change much with the addition of reux.
An important aspect that has not been taken into account in the
above analysis is the effect of the additional liquid created by the
reux on the hydrodynamic behaviour of the column and the efciency of the packing within the column. To date very little work
has been conducted on the hydrodynamic and efciency behaviour
of high pressure/supercritical columns and this work is limited to a
few systems [14]. The ow rates and efciency of supercritical uid
extraction processes are usually based on previous results and pilot
plant measurements. In the case of low pressure measurements the
efciency of the separation per unit packed height usually increases
as the liquid and vapour ow rates increase up to a point, after
which it starts to decrease as the ooding point is approached. This
decrease is associated with the ooding of the column. From the
Sulcol simulation results it is seen that the additional reux denitively increases the percentage of operating capacity. However, in
all cases operation is in the acceptable region, i.e. sufciently far
from the ooding point. With respect to the experimental conditions applied in this work, reux should not negatively affect the
separation, and if anything, improve the separation. With respect
to carbon dioxide, the hydrodynamic changes due to the addition of
reux may thus contribute to the improved separation. On the other
hand, for ethane, any possible enhancement in the hydrodynamics
due to the addition of reux is counteracted by other changes in
the column.
3.1.3. Inuence of solvent-to-feed ratio
The solvent-to-feed ratio was varied by keeping the solvent ow
rate constant and varying the solute feed rate. By varying only the
solute ow rate the loading in the column was not signicantly
affected (maximum 10% change in capacity) as the solvent ow rate
is much higher than the solute ow rate. Changes in the hydrodynamics of the column and the efciency of the packing should
thus be minimal. Previously, Schwarz et al. [6] studied the effect
of solvent-to-feed ratio but they did not keep the overheads-tofeed ratio constant and rather worked at constant pressure. They
found that at the same pressure an increase in solvent-to-feed
ratio resulted in a higher overheads-to-feed ratio and, should their
results regarding composition be applied to the system being investigated here, it would result in a higher concentration of nC14 in
the overheads and a lower concentration in the bottoms. However,
it should be remembered that in this work the overheads-to-feed
ratio was kept approximately constant by manipulation of the pressure.
Consider carbon dioxide as supercritical solvent. If run 20 is
compared to both run 6 and run 7 (both with much lower solvent-

355

Table 4
Energy requirement for SCF processing of alkanealcohol mixture for optimised
experimental conditions.
Solvent

CO2

Ethane

Reux ratio
Operating temperature
Operating pressure
Tetradecane overheads
(solvent free)
Overheads-to-feed ratio
(solvent free)
Solvent-to-feed ratio
Separator pressure
Without energy integration
Pump duties (kJ/kg feed)

C
MPa
g/g

10
55
11.0
0.80

0
55
7.5
0.80

g/g

0.5

0.5

g/g
MPa

20
5.7

20
3.8

P1
P2
P3

14
111
37

9
179

Heating duties (kJ/kg feed)

HX1
HX5
HX6

82
3585
1974

82
4659
3180

Cooling duties (kJ/kg feed)

HX2
HX3
HX4

830
3941
800

1445
5392
1122

11,374

16,068

1146
2333
2439

1408
3585
3251

6496

9566

43%

40%

Total energy requirement

(kJ/kg feed)
With energy integration
Heating duties (kJ/kg feed)
Cooling duties (kJ/kg feed)
Integrated heat exchangers
Total energy requirement
(kJ/kg feed)
Reduction in energy
requirement after energy
integration

HX5b
HX3b
HXI

to-feed ratios) it is seen that the composition of the overheads is

approximately the same for all three runs with run 20 containing
marginally less nC14. At the same time, run 20 has a slightly higher
nC14 content in the bottoms. The selectivity of run 20 is thus lower
than that of runs 6 or 7. Run 20 is at a lower pressure than runs 6 and
7 and thus at the lower pressures carbon dioxide may be less selective than at the higher pressures (Schwarz et al. [6] noted the same
effect with respect to pressure). Although this may seem contrary
to common trends, it should be remembered that the pressure had
to be manipulated to maintain a constant overheads-to-feed ratio
as the solvent-to-feed ratio changed. A change in the solvent to feed
ratio may also result in a change in the hydrodynamic loading of
the column but, as shown in Tables 24 and mentioned above, all
runs were well within the hydrodynamic capacity of the unit.
Consider ethane as supercritical solvent. Comparing run 41 with
that of 45, which is at a higher solvent-to-feed ratio, it follows
that for ethane similar results are obtained, yet the overheads-tofeed ratios differ (0.55 for run 41 vs. 0.46 for run 45). The higher
overheads-to-feed ratio in run 41 may result in the lower nC14
content in the bottoms, yet the difference in composition is large
(28% in run 45 vs. 19% in run 41 in the bottoms). It is thus suspected that the improved separation in run 41 compared to run 45
may be a combination of the slightly higher overheads-to-feed ratio
together with the lower solvent-to-feed ratio. Further verication,
which is beyond the scope of this project, is required to determine
the exact cause of the increase in overheads-to-feed ratio.
Lower solvent-to-feed ratios thus seem to provide a better separation (at slightly higher pressures) and, in combination with
the fact that the energy costs per unit feed are dominated by the
solvent-to-feed ratio, as shown in Part I [7], lower solvent-to-feed
ratios should be favoured.

C.E. Schwarz et al. / J. of Supercritical Fluids 58 (2011) 352359

3.2. Size of the operating range

During experimental measurements used to prove the viability of the process [7], as well as those investigating the effect of
the various process parameters, it was observed that the operating range is quite small. Small changes in temperature, pressure
and/or solvent-to-feed ratio resulted in reasonably large changes in
the overheads-to-feed ratio. These observations raise the question
as to the size of the operating range and hence the controllability of the process. In this section an investigation into the size of
the region in which separation can be achieved and the variation
of the separation quality within this region is presented. To facilitate this investigation the operating range is dened as the group
of process parameters that result in an overheads-to-feed ratio of
between 0.1 and 0.9. It is vital that the size of the operating range be
investigated: specic values of one parameter may result in a better
separation but if the product quality is very sensitive to changes in
this parameter it may be advantageous to operate the process at a
higher or lower value of this parameter where the operating range
is larger and hence the process easier to control. For all experiments
the feed was introduced at the top of the column and reux was
not used.
Firstly, consider the size of the operating range with variations
in temperature, as illustrated in Fig. 1, where part (a) illustrates the
effect of temperature with carbon dioxide as solvent and part (b)
the effect of temperature with ethane as solvent. By extrapolating
the overheads-to-feed ratio trends, it can be seen that, for the said
pressure, carbon dioxide can be operated between approximately
37 and 44 C while ethane can be operated between 54 and 88 C.
Although the investigated temperature ranges do not overlap, a
process using ethane is considerably less sensitive to changes in
temperature and thus easier to control. With respect to temperature, a process using ethane would thus be easier to control. This
observation can be explained in terms of the phase behaviour, as
presented in Part I of this series. For ethane as solvent, the increase
in the phase transition pressure, at constant composition for a set
temperature increase, is not as large as for carbon dioxide. For
carbon dioxide as supercritical solvent the phase transition pressure of nC14 is thus a much stronger function of temperature at
constant pressure than for ethane as solvent. A small change in
temperature will result in a much larger change in solubility for carbon dioxide as solvent and therefore also a much larger change in
overheads-to-feed ratio, hence a smaller operating range. However,
at higher pressure, the system may be less temperature dependent

Overheads/Feed

Overheads to Feed Rao

nC14 content

3.1.4. Variation in feed

The effect of the variation in the feed composition was investigated by comparing a feed with 50% nC14 (run 21) with that of
56% nC14 (run 22) at the same temperature, pressure, feed ow
rate and solvent ow rate, all with carbon dioxide as supercritical solvent. The results showed that for the higher nC14 feed both
the overheads and the bottoms nC14 content is higher: the overheads composition increases from 71 to 73% while the bottoms
composition increases from 43 to 53%. The overheads-to-feed ratio
also increases from 0.16 to 0.19. The results can be interpreted by
considering the equilibria at the top of the column where the feed
enters. At the top of the column the feed is theoretically in equilibrium with the overheads stream. This equilibrium is a function of
the feed composition and thus the higher the nC14 content in the
feed, the higher the nC14 content in the overheads. The solubility of
nC14 relative to 1-C12-OH in the solvent, carbon dioxide, is higher,
hence a higher nC14 feed content would result in a higher nC14
content in the overheads product stream. The nC14 in the bottoms
will be determined from a mass balance and, at constant solventto-feed ratio, should also increase with an increase in nC14 in the
feed.

Overheads nC14

Booms nC14

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
36

37

38

39

40

41

42

43

44

45

(a) Temperature ( oC)

Overheads/Feed

Overheads to Feed Rao

nC14 content

356

Overheads nC14

Booms nC14

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
50

55

60

65

70

75

80

85

90

(b) Temperature ( oC)

Fig. 1. Plot of the overheads-to-feed ratio, overheads nC14 mass fraction and bottoms nC14 mass fraction as a function of temperature for (a) carbon dioxide at
9.0 MPa, solvent ow rate 17 kg/h and solute ow rate 0.33 kg/h (see runs 2326,
28 for details) and (b) for ethane at 8.6 MPa, solvent ow rate 10 kg/h and solute
ow rate 0.48 kg/h (see runs 4649 for details).

but most probably still more temperature dependent than ethane

due to the higher temperature dependency of the phase transition
pressure/solubility.
If one considers the composition of the overheads and bottoms streams it follows that for both ethane and carbon dioxide
the overheads has a reasonably constant composition. This can be
attributed to the fact that the loaded solvent exiting the column is
in equilibrium with the feed stream. As the feed stream composition remains constant, the loaded solvent composition should also
remain constant. However, the composition of bottoms product for
the process with carbon dioxide is much more sensitive to changes
in temperature, especially near the desired 0.5 overheads-to-feed
ratio. The observed increase in sensitivity is due to the smaller
operating range and that, within the temperature range, the mass
balances need to be adhered to. A process using carbon dioxide
would thus require very good temperature control to maintain a
constant bottoms composition. The composition trends observed
in Fig. 1 reinforce the above observation that a process with ethane
is less sensitive to temperature changes.
The effect of pressure on the operating range is shown in Fig. 2.
Parts (a) and (b) consider carbon dioxide as solvent at 40 and
70 C respectively while part (c) considers that of ethane at 70 C.
For the conditions in Fig. 2(a) the operating range is between
approximately 8.4 and 9.1 MPa while at the higher temperatures
of Fig. 2(b) the operating range is between approximately 10.5
and 14.3 MPa. The process is thus easier to control at higher temperatures. However, these two plots provide interesting trends:
consider, for carbon dioxide, the pressure where the overheads-tofeed ratio is 0.5: pressures of 9.0 and 13.3 MPa are required at 40 and
70 C respectively. The ideal overheads-to-feed ratio is thus much

C.E. Schwarz et al. / J. of Supercritical Fluids 58 (2011) 352359

Overheads nC14

Overheads/Feed

Booms nC14

Overheads to Feed Rao

nC14 content

Overheads to Feed Rao

nC14 content

Overheads/Feed

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
8.0

8.2

8.4

8.6

8.8

9.0

9.2

357

Overheads nC14

Booms nC14

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
10

20

30

40

50

60

70

80

Solvent to Feed Rao

(a) Pressure (MPa)

Overheads to Feed Rao

nC14 content

Overheads/Feed

Overheads nC14

Booms nC14

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
9

10

11

12

13

14

15

(b) Pressure (MPa)

Overheads to Feed Rao

nC14 content

Overheads/Feed

Overheads nC14

Booms nC14

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
7.0

7.5

8.0

8.5

9.0

9.5

10.0

(c) Pressure (MPa)

Fig. 2. Plot of the overheads-to-feed ratio, overheads nC14 mass fraction and bottoms nC14 mass fraction as a function of pressure (a) carbon dioxide at 40 C,
solvent ow rate 17 kg/h and solute ow rate 0.30 kg/h (see runs 23, 2933 for
details); (b) carbon dioxide at 70 C, solvent ow rate 17.0 kg/h and solute ow
rate 0.48 kg/h (see runs 22, 3436 for details) and (c) ethane at 70 C, solvent ow
rate 10 kg/h and solute ow rate 0.48 kg/h (see runs 4851 for details).

closer to the upper limit than the lower limit of the operating range
and in the case of the lower temperature (40 C) is within 1 bar. This
observation is due to the increasing gradient of the overheads-tofeed ratio line as pressure increases and may have its origin in the
phase behaviour. For carbon dioxide an increase in temperature
at constant composition results in an increase in pressure at an
increasing rate [15].
With respect to the composition, it is once again noted that
the overheads composition is not very dependent on the pressure, while the bottoms initially remains reasonably constant with
increasing pressure, but then increases in gradient as pressure
increases. It should be noted that the runs used to compile Fig. 2(b)
were conducted with a 56% nC14 feed. This difference in feed is
not expected to change the results signicantly except for a slight

Fig. 3. Plot of the overheads-to-feed ratio, overheads nC14 mass fraction and bottoms nC14 mass fraction as a function of solvent-to-feed ratio for carbon dioxide
at 9.0 MPa, 40 C and solute ow rate 0.32 kg/h (see runs 23, 27, 37 and 38 for
details).

upward movement in the composition plots and possibly a slightly

lower operating pressure.
When considering the behaviour of ethane, as shown in Fig. 2(c),
it follows that the operating range is between pressures of 7.4
and 9.6 MPa at 70 C. The absolute pressure range for ethane is
smaller (2.2 MPa) than that for carbon dioxide (3.8 MPa) at similar temperatures yet the percentages of the full scale are similar
(23% for ethane, 27% for carbon dioxide). Additionally, the shape
of the curves for ethane is different to that of carbon dioxide.
The ethane overheads-to-feed ratio curve is close to linear with
the ideal overheads-to-feed ratio approximately in the centre of
the operating range. The overheads and bottoms composition also
decrease with increasing pressure with a less steep gradient than
for carbon dioxide as solvent. The approximately linear increase in
overheads-to-feed ratio as well as approximately linear decrease
in composition may be attributed to a generally linear relationship
between the phase transition pressure and temperature at constant
composition [16]. With respect to pressure, indications are thus
that the process utilising ethane will be easier to control.
Finally, the combined effect of the solvent-to-feed ratio and the
solvent ow rate was investigated. The solute feed ow rate was
kept constant while the solvent ow rate was increased, resulting in a simultaneous increase in the solvent-to-feed ratio and
solvent ow rate. As the solvent ow rate increased the hydrodynamic capacity decreased from 49 to 37%. However, in this range
the hydrodynamic capacity should not have a signicant effect
on the efciency of the packing and the effect of changes in the
hydrodynamic capacity on the efciency of the packing should be
smaller than that of the overheads-to-feed ratio and solvent ow
rate. The size of the operating range is shown in Fig. 3 for carbon
dioxide. From the analysis it is seen that, by extrapolation of the
experimental results, at constant temperature and pressure, the
operating range includes solvent-to-feed ratios between 12 and
78, with the optimum being at approximately 52. In addition it is
seen that the trend is generally linear and that small changes in the
solvent-to-feed ratio would thus not adversely affect the product
quality. Similar trends are noted for the composition. This observation, together with the fact that it is relatively easy to control the
ow rate of the solvent or solute within 10% of the set point, indicate
that, although the solvent ow rate should be controlled, the solvent ow rate and solvent-to-feed ratio are not the most important
parameters to control during operation and a control philosophy
should rather focus on the temperature and pressure. Additionally, the selection of the solvent ow rate and solvent-to-feed ratio
should rather be based on hydrodynamics and energy principles
than controllability. The effect of the solvent-to-feed ratio and the
solvent ow rate was only investigated for carbon dioxide but simi-

358

C.E. Schwarz et al. / J. of Supercritical Fluids 58 (2011) 352359

lar results are expected for ethane as solvent. Considering the effect
of solvent-to-feed ratio, as presented above, it can be seen that
similar trends are observed for both carbon dioxide and ethane. In
both cases the change in solvent ow rate, and as a result solventto-feed ratio, were extreme (one solvent-to-feed ratio double the
other). However, for both solvents, although changes in the selectivity were noted, these were not very large and of the same order
of magnitude. Therefore the results of the operating range analysis
as presented for carbon dioxide are in all likelihood also applicable
to ethane as supercritical solvent.
As was the case for the investigation of the inuence of the
process parameters, the changes in process parameters were not
adjusted to ensure constant hydrodynamic capacity. Typically, during operation, the column geometry of a separation column is xed
and hence the approach used here is justied: a process parameter will change without changing the geometry of the column.
However, during design the hydrodynamics of the column and the
efciency of the packing needs to be taken into account.
Taking the results of the operating range into account it seems
like ethane may be the superior solvent. With regard to temperature and pressure the results show that a process using ethane is
easier to control than a process using carbon dioxide while indications are that the solvent-to-feed ratio has a much smaller effect
on the operating range than what temperature and pressure have.
3.3. Optimum operating conditions
Based on the experimental results, both supercritical ethane and
carbon dioxide are able to achieve the desired separation and there
are no technical problems associated with either of these solvents
that can eliminate one of them. However, with respect to technical viability, ethane is superior. Ethane is able to achieve a sharper
separation, does not necessitate the use of reux if the correct operating conditions are selected, requires a lower operating pressure
and seems to be easier to control due to a larger operating range and
a more regular relationship between the input parameters and the
product quality. On the other hand, a process run with carbon dioxide will have lower operating costs as the energy requirements, as
calculated in Part I [7], are less and the cost of the make-up solvent
will be lower. In terms of capital costs, a detailed costing needs to
be conducted. Ethane requires lower operating pressures and does
not require the additional equipment associated with reux, yet
due to its ammability, equipment such as pumps may be more
expensive. Both ethane and carbon dioxide processes can be operated safely, but the ammability of ethane must undoubtedly be
taken into consideration during the design of the process and during operation. The exact location of the process may also contribute
to the decision as to whether ethane or carbon dioxide should be
used: should such a plant be located within a larger petrochemical complex, where other ammable liquids and gasses are being
processed, the use of ethane should not be a problem, since general safety precautions and procedures for working with ammable
components (such as ethane) should already be in place.
The experimental results show that for both solvents, an
increase in temperature leads to a decrease in selectivity (as dened
above) and thus, based on selectivity alone, the temperature should
be as low as possible. However, a number of other aspects favour
higher operating temperatures. From the analysis of the size of the
operating range it is seen that a process is easier to control at higher
operating temperatures. Additionally, at higher operating temperatures, the operating pressure is higher and hence there is a larger
difference in the pressure between the process and the separation
vessel resulting in better separation and, for ethane, less process
problems due to product entrainment into the recycle section. For
both solvents, at higher temperatures, the energy requirements are
lower once energy integration has been applied (see Part I [7]). Tak-

ing these aspects into account, an operating temperature between

50 and 60 C is recommended for both solvents.
The experimental results indicate that, for both carbon dioxide and ethane, a lower solvent-to-feed ratio should be favoured
despite the fact that slightly higher pressures are required. However, the solvent-to-feed ratios investigated in this work were
reasonably high and as such solvent loading (amount of solute in
the loaded solvent exiting the column) did not limit the process
and was not really taken into account. Typically, a solvent loading
of 0.23.5% was used in this work and ideally one would like to work
below but close to 2.5% (above this value a signicant amount of
1-C12-OH may be present in the extract, below this value the process becomes too expensive). A solvent-to-feed ratio of 20 results
in a solvent loading of 2.4% for an overheads-to-feed ratio of 0.5
and thus seems like an ideal balance of a good separation and the
correct solvent loading.
The use of reux depends on the solvent used: for carbon dioxide
the use of reux is required for good selectivity yet for ethane sufciently high selectivity can be achieved without the use of reux
at the hydrodynamic conditions investigated.
Taking the above, based on the experimental results, into consideration the following optimum conditions can thus be specied:
for ethane as solvent the process temperature should be between
50 and 60 C, the solvent-to-feed ratio should be around 20 and
no reux is required. For carbon dioxide, the temperature and
the solvent-to-feed ratio should be similar yet reux is required.
In both cases, the pressure can then be manipulated to obtain
an overheads-to-feed ratio of 0.5. The energy requirements for
the optimum process can be calculated using the same method
as presented in Part I using the same assumptions and operating
conditions, except those different due to the use of the optimum
operating conditions. The energy calculations were conducted at a
temperature of 55 C and pressures of 11.0 and 7.5 MPa were used
for carbon dioxide and ethane respectively. The calculated energy
values are shown in Table 4 (see Fig. 6 in Part I for schematic representation of the process) and are comparable to those of other
supercritical uid extraction processes [6]. The energy requirements are lower than any of those calculated in Part I [7] for the
same solvent mainly due to the lower solvent-to-feed ratio in combination with energy integration.

4. Conclusions and further work

This paper presents results on the investigation of the inuence of the process parameters and the size of the operating
range for the separation of nC14 and 1-C12-OH with supercritical carbon dioxide and ethane. The results have shown that the
optimum temperature is a balance between low temperatures
(40 C), which improves separation efciency, and higher values
(7080 C), which improves controllability. Lower solvent-to-feed
ratios (<25) should be favoured as the solvent-to-feed ratio does
not signicantly inuence the separation efciency, while lower
solvent-to-feed ratios result in lower energy costs. The use of reux
depends on the solvent used: for carbon dioxide reux is necessary
to ensure good separation, while for ethane good separation can
be achieved without the use of reux. Energy integration is important and, for the optimum operating conditions, results in energy
savings of approximately 40% with the energy requirements of an
energy integrated system being comparable to other supercritical
uid extraction processes.
With regard to the question as to which solvent is more suitable,
Table 5 shows a comparison of the two solvents. Ethane seems to
be technically superior. For the same packed height, a better separation is achieved with ethane while at the same time the process
is easier to control and reux is not required, thus allowing for a

C.E. Schwarz et al. / J. of Supercritical Fluids 58 (2011) 352359

359

Table 5
Comparison of ethane and carbon dioxide as supercritical solvent for the separation of detergent range alkanes and alcohols.

Separation efciency

Temperature
Temperature control
Pressure
Pressure control

Reux
Energy costs
Safety

Solvent costs

Ethane

Carbon dioxide

Overall excellent separation at various

conditions
Excellent for 1-C12-OH in bottoms,
good for nC14 in overheads
4080 C
Not very sensitive: operating range
larger than 30 C
610 MPa
Not very sensitive: operating range
approximately 20 MPa

Overall good with excellent separation

at selected conditions
Excellent for 1-C12-OH in bottoms,
good for nC14 in overheads
4080 C
Very sensitive: range less than 10 C

Not required
Acceptable
Flammable
Non-toxic
Lower pressures
High

simpler process. In addition, lower pressures are required. However, carbon dioxide does hold some advantages: it requires less
energy, the solvent costs are lower and it is safer to operate. The
nal decision on a solvent would, however, have to take all these
aspects, in conjunction with a detailed costing, into account.
To date the study has shown that it is technically possible to separate nC14 and 1-C12-OH with reasonable energy requirements.
However, the study of detergent range alkanes and alcohols is far
from complete and future work includes, but is not limited to, the
following:
Investigation of a feed containing a range of alkanes and alcohols,
as well as the presence of non-primary alcohols with between 12
and 14 carbon atoms.
Investigating the effect of side branching of both alkanes and
alcohols on the separation.
Modelling of the process with a process simulator, such as
AspenPlus , including the incorporation of more advanced thermodynamic models.
Detailed economic analysis including estimation of the capital
costs.
Acknowledgements
The nancial assistance of Sasol Technology (Pty) Ltd. and the
Department of Trade and Industry (DTI) of South Africa through the
Technology and Human Resources for Industry Programme (THRIP)
towards this research is hereby acknowledged. Opinions expressed
and conclusions arrived at are those of the authors and are not
necessarily to be attributed to the sponsors.
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values: optimum within 0.5 MPa of
upper limit
Required
Good (33% lower than ethane)
Non-ammable
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Higher pressures
Low

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