489

Preparation of High-Purity Normal Hexane from Reformate Raffinate by

Adsorption and Distillation Processes
Jichang Liu*, Tengya Ni, Juntao Liu and Benxian Shen State Key Laboratory of Chemical
Engineering, East China University of Science and Technology, Shanghai 200237, China.

(Received date: 23 November 2013; Accepted date: 26 May 2014)

ABSTRACT: In this study, a combination process of adsorption and distillation

was adopted to obtain high-purity normal hexane. In the adsorption separation
process, 5A zeolite was used as the adsorbent and the Shanghai Gaoqiao
Petrochemical Corporation reformate raffinate containing 24.24 wt% normal
hexane was separated into adsorption raffinate oil rich in non-normal paraffins
and desorption oil rich in normal paraffins. At pre-specified operation
conditions, concentration of n-hexane in the desorption oil reached higher than
96%. The concentrations of 3-methyl pentane and methyl cyclopentane, which
are the light- and heavy-key components in the distillation tower of normal
hexane, were reduced to 0.15% and 0.07%, respectively. According to the
simulation results obtained using the software Aspen Plus, when the distillation
tower has 15 stages, the n-hexane concentration can reach 99.02% with a
recovery rate of 72.89% at the reflux ratio of 7.5. The combination process
involving both adsorption and distillation has much higher efficiency than the
traditional distillation process for producing the high-purity normal hexane.

1. INTRODUCTION

As a non-polar solvent widely used in various industries, the high-purity normal hexane is
manufactured from the reformate raffinate on a large scale by the precise distillation process. The
production capacity of the reformate raffinate in China was more than 5 Mt/a (Wang 2005). With
the increase in the demand for aromatics compounds, more catalytic reforming plants will be put
into operation and the output of the reformate raffinate will increase rapidly. The concentration of
normal hexane in the reformate raffinate is 20–30%. However, the boiling points of 3-methyl
pentane (63.3 °C) and methyl cyclopentane (71.8 °C) in the reformate raffinate are close to that
of normal hexane (68.7 °C). The distillation tower needs a large number of plates to produce high-
purity n-hexane and in this case the energy consumption is huge. In Guangzhou Petrochemical
Corporation, the purity of normal hexane produced was less than 75% using two distillation
towers with 90 float valve plates (Wu and Ma 1998). In Shijiazhuang Refinery Corporation, the
separation of normal hexane was achieved through the combination of hydrogenation and precise
distillation using a packing tower with approximately 80 theoretical plates. The purity of normal
hexane achieved in this case was 86.23% (Zhang et al. 2006). A study by Hongik University
reported that the two columns used for producing 95.5 wt% normal hexane had 63 and 90 plates
and the reflux ratios were 106.6 and 22.8, respectively. Approximately 5.0 t of steam was required
for the production of 1 t n-hexane for the two reboilers even using the thermal integration method.
To reduce the production cost of the high-purity normal hexane, it is necessary to ensure a
distinctive difference between the volatilities of the light- and heavy-key components in the

*Author to whom all correspondence should be addressed. E-mail: liujc@ecust.edu.cn (J.C. Liu).
490 J.C. Liu et al./Adsorption Science & Technology Vol. 32 No. 6 2014

mixture. In this study, the reformate raffinate was used as a feedstock to prepare the high-purity
normal hexane (99% pure) by the adsorption–distillation process.
The 5A zeolite has been successfully used to separate n-paraffins from isoparaffins in light oil
with high selectivity (Liu et al. 2009). Some processes such as the Parex technology developed
by UOP have commercial plants in many countries (Foley and Sohn 2002; Daems et al. 2007).
Therefore, we used 5A zeolite to adsorb normal paraffins in reformate raffinate. After the
adsorption separation, the reformate raffinate is divided into two products, namely, the desorption
oil and the adsorption raffinate oil. The main components in the desorption oil (crude normal
hexane) are normal paraffins including n-pentane, n-hexane and n-heptane. The difference in the
boiling points between the two normal paraffins with the carbon numbers of N and N + 1 (N = 5, 6)
is approximately 30 °C. Further purification of the crude normal hexane, which involves the
separation of different normal paraffins by distillation, is much easier than the separation of 3-
methyl pentane, normal hexane and methyl cyclopentane.

2. EXPERIMENTAL ANALYSIS
2.1. Feeds and Reagents

The following are the reagents used in the experiments:

• The reformate raffinate was obtained from Shanghai Gaoqiao Petrochemical Corporation
(SGPC, Shanghai, China). Table 1 shows the hydrocarbon composition of the reformate
raffinate. The concentration of normal paraffins in SGPC reformate raffinate is 25.87%.
The concentrations of C6 paraffins are shown in Table 2. The main components are n-
hexane, 2-methyl pentane and 3-methyl pentane.
• Adsorbent: 5A zeolite (Shanghai UOP Company). Table 3 shows the physical
properties of the spherical molecular sieves. The adsorption isotherms and kinetics
of relevant hydrocarbons were previously reported (Silva and Rodrigues 1997a; Liu
et al. 2009).
• Desorbent: Nitrogen, 99% pure (Shanghai No. 5 Steel Works Company).

TABLE 1. Hydrocarbon Composition of SGPC Reformate Raffinate

Hydrocarbons N-hydrocarbons Isohydrocarbons Olefins Cyclanes Aromatics

Concentration/% 25.87 65.79 0 8.31 0.03

TABLE 2. Concentration of C6 in SGPC Reformate Raffinate

Methyl 2,2-
N- 2-Methyl 3-Methyl cyclo Dimethyl Cyclo
Hydrocarbons Hexane pentane pentane pentane butane hexane Benzene
Concentration/% 24.24 18.36 15.69 3.73 2.84 0.25 0.02

TABLE 3. Physical Properties of Spherical Molecular Sieves from UOP

Typical particle Loss of ignition
diameter/mm Bulk density/(kg/m3) True density/(kg/m3) Crush strength/N (1000 °C)

3.5 820 2630 48 9%

Preparation of High-Purity Normal Hexane from Reformate Raffinate by Adsorption 491
and Distillation Processes

2.2. Adsorption–Desorption Process

The flow chart of the adsorption separation apparatus is shown in Figure 1. A fixed-bed adsorber
was used in the adsorption–desorption process. The 5A zeolite was used as the adsorbent and
nitrogen as the desorbent. The reformate raffinate is passed through the adsorption bed from the
top of the apparatus in gaseous phase. The normal paraffins are adsorbed by the zeolite.
The adsorption raffinate oil (mainly non-normal hydrocarbons) leaves the adsorption bed at the
bottom. When the zeolite reaches the adsorption equilibrium, the adsorption process is switched
to the desorption process. The adsorbed hydrocarbons (mainly normal hydrocarbons) are desorbed
by nitrogen flow by countercurrent exchange. In the first few minutes of the desorption process,
the retained feed in the bed is collected in the intermediate oil tank, following which the
desorption oil (mainly normal hydrocarbons) can be obtained.
The adsorber is a cylinder with a diameter and length of 50 and 1800 mm, respectively.
Approximately 2 kg of 5A zeolite was packed inside the cylinder. The adsorption cycle time is 30
minutes when the feed space velocity is 94 hour–1 with the nitrogen purge pressure of 0.2 MPa and
nitrogen space velocity of 100 hour–1.

Figure 1. Reformate raffinate adsorption-desorption flow chart.

492 J.C. Liu et al./Adsorption Science & Technology Vol. 32 No. 6 2014

2.3. Analytical Method

The compositions of SGPC reformate raffinate and the separation products are determined by a
gas chromatograph with a flame ionization detector (Shanghai Haixin Chromatographic
Instrument Co. Ltd.).

3. RESULTS AND DISCUSSION

3.1. Breakthrough Curves of Normal Paraffins Adsorbed on Zeolite at Different
Temperatures

The 5A zeolite with an approximate channel size of 4.9 Å offers excellent steric selectivity for the
separation of normal paraffins from isoparaffins and cyclic hydrocarbons. These adsorption
processes are run at temperatures high enough to prevent condensation of the hydrocarbons while
low enough to prevent chemical degradation. (Auerbach et al. 2003)
The operation temperatures have evident influences on the adsorption–desorption process. At low
temperatures, the equilibrium adsorption capacity of the zeolite is higher and the driving force for mass
transfer is larger. However, it is difficult to continue the desorption process due to low temperatures. In
addition, the molecules move slowly when the temperature is low, and therefore, the adsorption and
desorption processes are more likely to be confined by the diffusion process, especially by the internal
diffusion in zeolite (Silva and Rodrigues 1997b). Because the equilibrium adsorption capacity is lower
at higher temperatures, the working capacity for a single pass will be limited.
The breakthrough curves of total normal paraffins (n-pentane, n-hexane and n-heptane) on
5A zeolite with temperatures of 250–290 °C are shown in Figure 2. With the increase of the
adsorption temperature, the adsorption capacity is lower, and therefore, the breakthrough
point appears earlier. At the temperature of 290 °C and space velocity of 94 hour–1, the
breakthrough point of total n-paraffins is 30 minutes. The breakthrough curves of individual
normal paraffins at the temperature of 290 °C are shown in Figure 3. The n-pentane

30

25

20
Concentration /%

15

10

290 ∞C
5 270 ∞C
250 ∞C

0
0 20 40 60 80 100 120
Adsorption time/min

Space velocity: 94 hour-1

Figure 2. Adsorption breakthrough curves of total n-paraffins.

Preparation of High-Purity Normal Hexane from Reformate Raffinate by Adsorption 493
and Distillation Processes

30

25

20
Concentration/%

15

10
N-pentane
N-hexane
5 N-heptane

0
0 20 40 60 80 100 120
Adsorption time/min

Adsorption temperature: 290 ∞C

Figure 3. Adsorption breakthrough curves of n-paraffins.

penetrates the adsorption bed earlier than the normal hydrocarbons with longer carbon chains.
However, the normal pentane molecules occupying the micro-channels of 5A zeolite can be
partly displaced by normal hexane. The roll-up phenomenon, which is caused by the
displacement of a weaker adsorbate by a strong one (Yang 1987), can be observed in the
adsorption breakthrough curves of the n-pentane. In this study, to obtain high n-hexane yield
in the desorption oil, the n-hexane concentration in the adsorption raffinate should be as low
as possible. The adsorption process is switched to the desorption process when the n-pentane
penetrates the zeolite bed in each adsorption–desorption cycle.

3.2. Influences of Temperature on Desorption Products

The concentrations of n-hexane and total n-paraffins in the desorption oils at the purge nitrogen
space velocity of 100 hour–1 and with operation temperatures of 230–290 °C are shown in Figure 4.
Because the desorption process is endothermic, the increase of temperature benefits the desorption
process. As the desorption temperature rises from 230 to 290 °C, the content of n-hexane
increased from 93.99% to 95.23% as more normal paraffins are desorbed from the zeolite channel.
The suggested operation temperature is 270–290 °C.

3.3. Influence of Intermediate Oil on n-Hexane Concentration in Desorption Oil

After the adsorption process, a certain amount of the feed fills the void volume around and inside
the zeolite particles in the adsorption bed. In order to improve the concentration of n-hexane in the
desorption product, the operation step for cutting the intermediate oil was performed before the
desorption process. At the operation temperature of 280 °C, the influences of the intermediate oil
fraction on the concentration of n-hexane in the desorption product are shown in Figure 5. When
the intermediate oil fraction is less than 13% of the total desorption product, the n-hexane
concentration improves obviously with the increase of the intermediate oil proportion. When the
494 J.C. Liu et al./Adsorption Science & Technology Vol. 32 No. 6 2014

98

97

Concentration/%
96

95

N-hexane
94 N-paraffins

230 240 250 260 270 280 290

Desorption temperature/ ∞C
Figure 4. Concentration of N-paraffins in desorption oil at different desorption temperatures.

100
99
98
97
96
Concentration/%

95
94
93
92
91
90 N-hexane
89 N-paraffins

88
0 10 20 30 40 46
Intermediate oil cutting/%
Figure 5. Concentration of N-paraffins in desorption oil with different intermediate oil proportions.

intermediate oil reaches 13% of the total desorption product, most of the feed has been purged out
of the zeolite bed, and therefore, the n-hexane concentration in the desorption oil increases from
88.45% to 96.04% and the concentration of total n-paraffins increases to 99.11%.
After the adsorption separation process, SGPC reformate raffinate is divided into adsorption
raffinate oil and desorption oil. The composition of the desorption oil is shown in Table 4. The
concentrations of 3-methyl pentane and methyl cyclopentane are 0.15% and 0.07%, respectively.
The composition of the adsorption raffinate oil is listed in Table 5. The concentration of normal
hexane in the adsorption raffinate oil is only 0.59%, which indicates that the yield of normal
hexane in the desorption oil is high.
Preparation of High-Purity Normal Hexane from Reformate Raffinate by Adsorption 495
and Distillation Processes

TABLE 4. Main Components in Desorption Oil

N- N- N- 2-Methyl 3-Methyl Methyl 2-Methyl 3-Methyl
Hydrocarbons pentane hexane heptane pentane pentane cyclopentane hexane hexane
Concentration/% 2.22 96.04 0.85 0.20 0.15 0.07 0.16 0.13

TABLE 5. Composition of Adsorption Raffinate Oil

Hydrocarbons N-pentane N-hexane N-heptane Isoparaffins Cyclanes Aromatics
Concentration/% 0.25 0.59 0.002 89.23 9.91 0.02

TABLE 6. Normal Hexane Concentrations in Products in the Top Layers

Distillation rate/% 8.6 21 57.4
Experiment 86.2 97.1 99.1
N-hexane concentration/%
Simulation by Aspen Plusa 85.1 97.0 99.2
a
Property method: RKS-BM.

3.4. Purification Experiments of Normal Hexane from Desorption Oil

The desorption oil was distilled in a batch distillation tower with eight plates. First, the normal
pentane was collected from the top layer, followed by the normal hexane. A large amount of
heptane and other heavy components are settled at the bottom. The high-purity normal hexane
could be obtained by cutting the fractions properly. At the reflux ratio of 3, the normal hexane
concentrations in the products on the top layer with different distillation rates are shown in Table 6.
The normal hexane concentration reached 99.1% as the distillation rate was 57.4%.

3.5. Distillation Simulation of Reformate Raffinate and Desorption Oil Using Aspen Plus

To obtain the high-purity normal hexane with reduced production cost, it is necessary to
ensure a distinctive difference between the volatilities of the light- and heavy-key
components in the mixture, which are 3-methyl pentane and methyl cyclopentane,
respectively. Both of these compounds have volatilities similar to that of the normal hexane.
By contrast, for the distillation of the desorption oil, the light- and heavy-key components are
normal pentane and normal heptane, which can be easily separated from normal hexane. In
order to compare the distillation processes of reformate raffinate and desorption oil, we used
the software Aspen Plus to simulate the distillation towers. In order to verify the distillation
model, we compared the simulation results of the eight-plate batch distillation tower with
experimental data. From Table 6, it can be seen that the simulation results with Aspen Plus
are consistent with the experimental data.
The simulation conditions for the distillation towers of reformate raffinate and desorption oil
are listed in Table 7. The concentration distributions in the distillation towers of reformate
raffinate and desorption oil are shown in Figures 6 and 7, respectively.
496 J.C. Liu et al./Adsorption Science & Technology Vol. 32 No. 6 2014

TABLE 7. Simulation Conditions of Distillation Towers for Reformate Raffinate and Desorption Oil
Reformate raffinate Desorption oil

Property method RKS-BM RKS-BM

Feed flow rates 1000 kg/h 1000 kg/h
Feed temperature/°C 50 50
Number of stages 85 15
Feed stage 75 11
N-hexane stage 60 8
Reflux ratio 15 7.5
Purity of n-hexane/% 80.72 99.02
Yield of n-hexane/% 59.94 72.89

80

70
N-pentane
60 Cyclopentane
Concentration/%

2, 2-Dimethyl butane
50 2-Methyl pentane
3-Methyl pentane
N-hexane
40
Methyl cyclopentane
2-Methyl hexane
30 3-Methyl hexane
N-heptane
20

10

0
0 20 40 60 80
Distillation stage
Figure 6. Composition profiles in the distillation tower of reformate raffinate.

100

80
Concentration/%

60

40

N-pentane
N-hexane
20 N-heptane

0
5 10 15
Distillation stage
Figure 7. Composition profiles in the distillation tower of desorption oil.
Preparation of High-Purity Normal Hexane from Reformate Raffinate by Adsorption 497
and Distillation Processes

For the separation of reformate raffinate, the maximum concentration of normal hexane is
80.72% with the recovery rate of 59.94% at the reflux ratio of 15 in a distillation tower with 85
stages; however, the 3-methyl pentane and methyl cyclopentane cannot be separated distinctly
from normal hexane at this reflux ratio. For the desorption oil, when the distillation tower has 15
stages, the concentration of normal hexane can reach up to 99.02% at the reflux ratio of 7.5 with
the recovery rate of 72.89%. Based on the normal hexane concentration in the products and the
distillation conditions of the distillation towers for reformate raffinate and desorption oil, it can be
concluded that the combination process of adsorption and distillation has much higher efficiency
than the single distillation process to produce the high-purity normal hexane.

4. CONCLUSIONS

The combination process of adsorption and distillation is used to obtain high-purity normal
hexane. Using the adsorption separation process with 5A zeolite as the adsorbent, the SGPC
reformate raffinate is separated into the adsorption raffinate oil and the desorption oil. At the
suggested temperature of 280 °C, the concentration of n-hexane in the desorption oil reaches
higher than 96% if 13% of the desorption product is cut as intermediate oil. The concentrations of
3-methyl pentane and methyl cyclopentane, which are the light- and heavy-key components in the
distillation tower of normal hexane, reduce to 0.15% and 0.07%, respectively.
The distillation tower for separating desorption oil is used to obtain high-purity normal hexane.
According to the simulation results using Aspen Plus, when the distillation tower has 15 stages,
the concentration of normal hexane can reach 99.02% at the reflux ratio of 7.5 with the recovery
rate of 72.89%. By contrast, for the separation of reformate raffinate, the maximum concentration
of normal hexane is 80.72% at the reflux ratio of 15 in a distillation tower with 85 stages. Thus,
our results suggest that the combination process of adsorption and distillation has much higher
efficiency than the single distillation process to produce the high-purity normal hexane.

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