Separation and Purification Technology xxx (2015) xxxxxx

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Separation and Purification Technology

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Adsorption and separation properties of n-pentane/isopentane on ZIF-8

Lin Zhang, Gang Qian, Zongjian Liu, Qun Cui , Haiyan Wang, Huqing Yao
College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Adsorption equilibrium and kinetic data is essential for the design of an adsorption process. In this work,
Received 13 August 2015 the adsorption isotherms of n-pentane/isopentane on zeolitic imidazolate framework material (ZIF-8)
Received in revised form 7 October 2015 were measured at 308, 343 and 373 K over the pressure range from 0 to 9.7 kPa by a gravimetric system.
Accepted 15 October 2015
The equilibrium adsorption capacity at 303 K and 9.7 kPa is 0.2504 g g
1 for n-pentane and 0.1439 g g
1
Available online xxxx
for isopentane. Langmuir model was used to fit the adsorption isotherms. The adsorption kinetics of
n-pentane/isopentane was studied at 308 K in the pressure range from 0 to 69.9 kPa. The data was well
Keywords:
fitted with linear driving force model (LDF) model. The adsorption rate constant of n-pentane is from
ZIF-8
Light naphtha
0.0019 to 0.0326 s
1, which is higher than that of isopentane, represented 0.00070.0036 s
1. The
n-pentane adsorption selectivity of n-pentane/isopentane on ZIF-8 was contrast by the measurement of the binary
Isopentane breakthrough experiments at 343 K, 363 K and 393 K in the partial pressure of 7 kPa. When the
Adsorption separation adsorption temperature is 363 K, the adsorption selectivity of n-pentane/isopentane on ZIF-8 reaches
the maximum 55. Compared with 5A molecular sieve, the desorption temperature of n-pentane on
ZIF-8 was analyzed by temperature-programmed-desorption (TPD) method. The peak temperature of
n-pentane desorption on ZIF-8 is 361 K. However are 392 K and 443 K on a 5A molecular sieve. Thus,
ZIF-8 is more selective or preferential adsorption for n-pentane in comparison to isopentane molecules
at low temperature.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Light naphtha [1] is the petroleum fractions between 334 K and
318 K, wherein the contents of n-pentane and isopentane are 30
40%. Currently, light naphtha is primarily used for preparation
ethylene and gasoline, but the higher content of isoparaffin results
in a lower yield of ethylene production, and the presence of n-
paraffin affects gasoline octane number [24]. If light naphtha is
separated into the richer n-paraffin and the richer isoparaffin frac-
tions, the richer n-paraffin fraction will be used for ethylene pro-
duction and the richer isoparaffin fraction will be applied as a
component of gasoline. Light naphtha will be utilized more effec-
tively in the aspect of molecular management [5]. In recent years,
n/iso-paraffin adsorption separation has been deeply studied by
scholars. Among these researches, 5A molecular sieve, metalor-
ganic frameworks and other types of zeolite like MFI, SAPO, MCM
[68] were generally used as separation adsorbent. Simulated
moving bed was adopted by UOP [9] for the separation of n/iso-
paraffin heavier than C5 over 5A molecular sieve under liquid
phase. The desorbent was light normal alkanes (pentane),
Corresponding author.
E-mail address: cuiqun@njtech.edu.cn (Q. Cui).
adsorption temperature and pressure were 443 K and 2.3 MPa
respectively. The yield of normal alkanes could achieve 9599%.
Shen et al. [10] studied the adsorption separation of naphtha by
binder-less 5A molecular sieve at the temperature of 493573 K,
and the yield of normal alkanes was over 98%. Cui et al. [11] also
studied the desorption properties of n-hexane in light naphtha
on 5A molecular sieve. There were two desorption peaks of n-
hexane on the 5A molecular sieve, corresponding desorption acti-
vation energy was 39.35 and 67.48 kJ mol
1 respectively. The des-
orption temperature should reach 473 K for complete desorption
by using helium purge desorption. Overall these studies, it could
be found that over-high adsorptiondesorption temperature lead
to a very high energy consumption when 5A zeolite was used as
adsorbent for gas phase adsorption, so the development of a low
temperature adsorption technology is imminent.
Metalorganic framework (MOFs) materials [1214] with the
extraordinary chemical tunability of the pore geometry, surface
functionality and high surface areas, are used in the adsorption sep-
aration process. Patrick et al. [15] synthesized a three-dimensional
microporous metalorganic framework Zn(BDC)(Dabco)0.5, which
contents two types of intersecting pores about 7.5  7.5 and
3.8  4.7 , exhibiting a highly selective sorption with respect
to n-hexane, had been successfully implemented to the kinetic

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1383-5866/ 2015 Elsevier B.V. All rights reserved.

Please cite this article in press as: L. Zhang et al., Adsorption and separation properties of n-pentane/isopentane on ZIF-8, Separ. Purif. Technol. (2015),
http://dx.doi.org/10.1016/j.seppur.2015.10.037
2 L. Zhang et al. / Separation and Purification Technology xxx (2015) xxxxxx
separation of hexane isomers by fixed-bed adsorption. Adsorption
capacity of n-hexane (n-HEX) on Zn(BDC)(Dabco)0.5 is
0.0202 g g
1, which was six times and nine times higher than that
of 3-methylpentane (3MP) and 2,2-dimethylbutane (22DMB) at
313 K. Peralta et al. [16] measured the breakthrough curves of
nHEX, 3MP, and 2,2DMB on ZIF-8, ZIF-76, and IM-22. The results
showed that ZIF-8 had many advantages than zeolite 5A because
it exhibited a sharp (kinetic) selectivity for the adsorption of linear
alkanes and at the same time a high adsorption uptake. Ferreira
et al. [17] studied the adsorption equilibrium isotherms and
differential heats of adsorption of hexane isomers on the ZIF-8 at
373 K. The results showed that the equilibrium absorption uptakes
of n-HEX and 2MP on ZIF-8 were 0.2356 g g
1 and 0.2064 g g
1
respectively, while 23DMB and 22DMB were only 0.1462 g g
1
and 0.0172 g g
1. It corroborated that ZIF-8 as a new adsorbent
can be employed in the improvement of the Total Isomerization
Process for the production of high octane number gasoline. A more
recent study [18] about single, binary and ternary breakthrough
experiments of hexane isomers (nHEX, 3MP, and 22DMB) were per-
formed on ZIF-8. They showed that a complete separation between
nHEX and the branched isomers in ternary breakthrough experi-
ments. In addition, Luebbers et al. [19] reported a complete separa-
tion between the linear n-pentane and the branched isopentane
with a molecular sieve effect by an inverse gas chromatography
(IGC) methodology at the zero-coverage limit and elevated
temperatures.
The above studies have reported complete adsorption equilib-
rium and properties of hexane isomers on ZIF-8, and the potential
application of ZIF-8 for separating pentane isomers also been mea-
sured by IGC methodology at elevated temperatures [19]. How-
ever, to apply this technology in industrial process, we must
further obtain the adsorption equilibrium, kinetics and desorption
performance of n-pentane/isopentane on ZIF-8. To do this, we syn-
thesized ZIF-8 by rapid crystallization for the separation of n-
pentane/isopentane. The phase, pore structure and thermo stabil-
ity of ZIF-8 were analyzed systematically with the aids of XRD,
N2 adsorptiondesorption and TG-DTA. Adsorption isotherms and
adsorption rate curves of n-pentane/isopentane on ZIF-8 were
measured by IGA-100. Breakthrough curves of n-pentane/
isopentane on ZIF-8 were measured with an adsorption column.
Compared with 5A molecular sieve, the desorption temperature
of n-pentane on ZIF-8 was analyzed by TPD method. This work
could be used for the future modeling of adsorption process for
the separation of light naphtha on ZIF-8.
2. Experimental
2.1. Materials and reagents
Chemicals including Zn(NO3)26H2O (AR, 99%), 2-
methylimidazole (AR, 98%), n-pentane (AR, 99%), and isopentane
(99%) were purchased from Aladdin Reagent (Shanghai) Ltd. Co.,
and methanol (AR, 99.5%) were obtained from Shanghai Ling Feng
Chemical Reagent Ltd. Co.
2.2. Synthesis and characterization of ZIF-8
A synthesis protocol reported was taken as reference by Zhu
et al. [20]. X-ray diffraction (XRD) of ZIF-8 was performed (a Rigaku
Smart Lab instrument) by scanning the 2h angle at 20 min
1
between 5 and 40 using Cu Ka radiation. N2-sorption were per-
formed on the samples using a BELSORP-max (BEL Japan, Inc.) with
a standard volumetric technique at 77 K. The sample was evacu-
ated at 523 K for 6 h in advance. BrunauerEmmettTeller (BET)
equation was used to calculate BET surface areas, t-plot method
Please cite this article in press as: L. Zhang et al., Adsorption and separation properties of n-pentane/isopentane on ZIF-8, Separ. Purif. Technol. (2015),
http://dx.doi.org/10.1016/j.seppur.2015.10.037
used to count microporous volume according to the adsorption iso-
therm. The thermal stability of the ZIF-8 sample was measured on
WCT-1 differential thermal balance (TG-DTA, Beijing Optical
Instrument Factory).
2.3. Adsorption isotherms and adsorption kinetic curves
Adsorption isotherms and adsorption rate curves of n-pentane/
isopentane on ZIF-8 were measured by Intelligent Gravimetric
Analyzer (IGA-100). The system consists of a fully computer con-
trolled microbalance with both pressure and temperature regula-
tion systems. The microbalance had a long-term stability of 1 mg
with a weighing resolution of 0.2 mg. Prior to the adsorption, the
sample was activated in the sample basket by heating from ambi-
ent temperature to the activation temperature (523 K), under vac-
uum (lower than 0.01 kPa), until the weight of ZIF-8 remained
constant, which took approximately 6 h at 523 K. The pressure
was then increased gradually to the desired pressure, over a period
of 60 s, in order to prevent disruption of the balance. The equilib-
rium was considered when the values of pressure, temperature
and mass persisted constant for at least 10 min. Once the equilib-
rium was reached, adsorbate was fed again to obtain the next
adsorption equilibrium point. This procedure was repeated for
each point of the isotherm until the desired maximum pressure
was attained.
2.4. Experimental set-up for breakthrough experiments
The breakthrough experiments of n-pentane/isopentane on ZIF-
8 were measured by the apparatus showed in Fig. 1 consisting of
two main sections. The adsorption section consists in a 3.9 mm
i.d. stainless steel column with 280 mm in length containing the
adsorbent. The adsorbent was introduced into the column in the
form of pellets with diameters from 250 to 425 lm. For making
the pellets, dried ZIF powder was humidified with ethanol. Then,
the resulting paste was pressed into a circular mold (diameter of
3 cm) with a mechanical force of 3 MPa. The temperature of col-
umn was maintained by heat band (controlled by temperature
controller), utilizing diphenyl oxide as the heating medium. The
preparation section includes a trace injection pump used to intro-
duce the adsorbable species in the carrier gas. The carrier gas used
in this work is nitrogen and is introduced in the system through a
mass flow controller (MFC). At the outlet of adsorption section the
analysis of adsorbable species was executed by a chromatographic
column and a flame ionization detector (FID), using a SE30 capil-
lary column.
The experimental procedure follows: Firstly, the column was
activated for at least 3 h at 523 K under a nitrogen flow. A adsor-
bent bed was operated in the adsorption process by introducing
the feed containing the adsorbable species diluted in nitrogen at
a fixed partial pressure. The experiment consisted of measuring
continuously the concentration profile at the outlet of the column
at a certain temperature. The equilibrium loading was obtained by
integrating the concentration profiles of the breakthrough. Before
each run, the mixed adsorbable species and nitrogen would be con-
stantly leading to the emptying for 10 min, to ensure that the
adsorbing species are adequately mixed in the carrier gas.
2.5. TPD curves of n-pentane on ZIF-8 and 5A molecular sieve
The TPD curves of n-pentane on ZIF-8 and 5A molecular sieve
were measured on micro reactor LW5. Firstly, 10 mg ZIF-8 (5A
molecular sieve) was put into the reactor, and activated by hydro-
gen (99.999%) for 3 h. Secondly, n-pentane was pushed in the reac-
tor by hydrogen for adsorption about 0.5 h after the temperature
dropped. Thirdly, hydrogen was pushed after adsorption for 0.5 h,
 L. Zhang et al. / Separation and Purification Technology xxx (2015) xxxxxx 3

Connect to Pressure
Vacuum pump gage

Connect to
Soap film
flowmeter
Sampling tap

Trace injection pump

N2 Emptying

Fig. 1. Scheme of the breakthrough experimental set-up.

and the desorption process was conducted at 10 K min
1 under 600

hydrogen atmosphere. The signal was detected by chromato-
graphic with TCD detector. The curves of TPD were calculated by 500
these signals.

-1
Va, cm (STP) g
400
3. Results and discussion
Adsorption
300 Desorption

3
3.1. Characterization of the materials

3.1.1. Phase analysis of ZIF-8 200

The XRD pattern of the synthetic ZIF-8 is shown in Fig. 2. XRD
characteristic peaks of synthesized ZIF-8 in this work is the same 100
as the peaks simulated by Yaghi group [21] reported, and no other
miscellaneous crystal peaks are observed. The synthetic product is
0
pure phase ZIF-8 crystal material. 0.0 0.2 0.4 0.6 0.8 1.0
P/P0

3.1.2. Pore structure analysis of ZIF-8 Fig. 3. Adsorption/desorption equilibrium isotherms of N2 on ZIF-8 at 77 K.
The nitrogen adsorption/desorption isotherms of ZIF-8 at 77 K
are shown in Fig. 3. The nitrogen adsorption isotherm is consistent
with type I adsorption isotherm defined by IUPAC, corresponding 400
microporous adsorption (from Fig. 3). Further inspection of the
low pressure region of the adsorption isotherm (Fig. 4) shows that
ZIF-8 exhibits type VI behavior. It could be attributed to the gas
induced structural flexibility of the ZIF frameworks. Yaghi [21], 300
Va/cm3(STP) g-1

Fairen-Jimenez [22], and Webley [23] also have reported this inter-
esting phenomenon.
Furthermore, the adsorption isotherm coincides with desorp- 200
tion, and no hysteresis loop is observed. The microporous volume
is 0.7538 cm3 g
1 calculated by t-plot method. The synthesized
sample is a microporous material with a BET specific surface area
100
with 1971 m2 g
1 (calculated relative pressure from 0.005 to
0.029 [23]). This value is slightly higher than that of the reference
[23] in which using the same calculated relative pressure
(1871 m2 g
1). In addition, the adsorption uptake of nitrogen on 0
1E-5 1E-4 1E-3 0.01
P/P0

Fig. 4. Adsorption equilibrium isotherms of N2 on ZIF-8 under low pressure region.

ZIF-8 is about 480 cm3 (STP) g
1 in this work, while approximately
420 cm3 (STP) g
1 in the reference [23]. This could be ascribed to
As-synthesized the difference of activation temperature. We improved the activa-
Intensity, a.u.

tion temperature by 130 K, which is similar to the work reported

by Ferreira et al. [17].

3.1.3. Thermal stability of ZIF-8

Fig. 5 shows the TG-DTA curves of ZIF-8 measured on WCT-1
Simulated differential thermal balance at air atmosphere.
As shown in Fig. 5, the weight loss of ZIF-8 is only 0.84% from
room temperature to 523 K. It should be attributed to the desorp-
tion of methanol in the channel and 2-methylimidazole on the sur-
10 20 30 40
2 (degree) face. When the temperature increases from 523 K to 773 K, the
corresponding weight loss is 65.10% due to the decomposition of
Fig. 2. XRD patterns of the synthesized and the fitted ZIF-8. 2-methylimidazole ligand in ZIF-8.There are two exothermic peaks

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4 L. Zhang et al. / Separation and Purification Technology xxx (2015) xxxxxx

wt%= -0.84% 0.15

-1
Adsorption capacity, g g
wt%= -45.04%
0.10
wt%= -20.06%

TG

0.05
Tm=705 K 308 K
Tm=730 K
343 K
373 K
DTA
0.00
0 2 4 6 8 10
300 400 500 600 700 800 900 Pressure, kPa
Temperature, K
Fig. 7. Adsorption isotherms of isopentane on ZIF-8 at different temperature. The
lines are fitted results using corresponding model.
Fig. 5. TG-DTA curves of ZIF-8 at air atmosphere.

can be seen from the DTA line between 523 K and 773 K. It also
shows that there are two steps for the decomposition of
2-methylimidazole ligand, the weight loss of the first step is
45.04% and the peak temperature is 705 K, and there are 20.06%
and the 730 K in the second step. In addition, the sample is quite
stable as temperature is below 523 K, so 523 K is considered as
the activation temperature in the adsorption experiment.
3.2. Adsorption equilibrium performance of n-pentane/isopentane on
ZIF-8
3.2.1. Adsorption isotherms of n-pentane/isopentane on ZIF-8
The adsorption isotherms of n-pentane/isopentane on ZIF-8
were measured at 308, 343, and 373 K in the pressure range of
09.7 kPa. The results are shown in Figs. 6 and 7. As shown in
Figs. 6 and 7, the adsorption isotherms of n-pentane/isopentane
on ZIF-8 indicate that its adsorption is highly favorable at low tem-
perature. When the adsorption temperature is increased, the
inflection of the adsorption isotherm changes. Similar phe-
nomenon about the adsorption isotherms of alkanes on ZIF-8 also
appeared in the literature reported by Fairen-Jimenez et al. [24]. It
is attributed to the flexible structure of ZIF-8 [25]. The adsorption
capacity of n-pentane on ZIF-8 is 0.2504 g g
1 at 308 K when the
partial pressure is 9.7 kPa, and 0.1439 g g
1 at 373 K. While the
loading of isopentane is 0.1410 g g
1 at 308 K at the same pressure,
and 0.0673 g g
1 at 373 K. The adsorption capacity of isopentane
decreased by 52.27% at the same temperature range, larger than
that of n-pentane 42.53%. It indicates a stronger impact of the tem-
perature on the adsorption of isopentane than that of n-pentane on
ZIF-8.
In addition, it can be observed from Fig. 6 a considerable loading
capacity of n-pentane on ZIF-8, reaching 0.2504 g g
1 at 308 K at a
partial pressure equal to 9.7 kPa. For comparison, the maximum
loading capacity of n-pentane on 5A molecular sieve is around
0.1325 g g
1 at the same temperature and pressure. This value
was measured in our laboratory apparatus which was described
in the publication [26]. It means that the capacity of n-pentane
on ZIF-8 is almost twice higher than that of 5A molecular sieve.
This is due to that ZIF-8 exhibits approximately 2 times higher
accessible pore volume to accommodate linear alkanes than 5A
molecular sieve [18].
According to the literature [17,18], the adsorption isotherms of
n-pentane/isopentane on ZIF-8 could be fitted by Langmuir model.
The formula of Langmuir model is,
bp
q qm 1
1bp

where p is the adsorption equilibrium pressure of adsorbate, kPa; q

0.25
is the equilibrium adsorption capacity, g g
1; qm is the maximum
adsorption capacity, g g
1; b is the adsorption equilibrium constant,
kPa
1. To give thermodynamic consistency the parameter qm is sup-
-1

posed to be a constant independent of temperature.

Adsorption capacity, g g

0.20
The solid lines in Figs. 6 and 7 correspond to the fitting of the
Langmuir model. The fitting parameters is given in Table 1. A good
0.15 agreement between the experimental and simulated adsorption
equilibrium data of n-pentane/isopentane on ZIF-8 is observed in
0.10
Table 1
308 K Fitting parameters for n-pentane and isopentane on ZIF-8.
0.05 343 K
Adsorbate Adsorption temperature, K qm, g g
1 b, kPa
1 R2, %
373 K
n-pentane 308 0.25 2.60 0.07 99.44
0.00 343 0.38 0.01 99.26
0 2 4 6 8 10
373 0.13 0.00 99.60
Pressure, kPa
Isopentane 308 0.16 0.78 0.04 98.63
343 0.18 0.01 99.53
Fig. 6. Adsorption isotherms of n-pentane on ZIF-8 at different temperature. The
373 0.08 0.00 99.86
lines are fitted results using corresponding model.

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 L. Zhang et al. / Separation and Purification Technology xxx (2015) xxxxxx 5

Figs. 5 and 6. We assume a maximum loading capacity qm of n- 3.5 1

pentane/isopentane on ZIF-8 equal to 0.25 g g
1 and 0.16 g g
1 adsorption pressure
respectively. From the Langmuir model parameters, the affinity 0
3.0

Adsorption pressure, kPa

constant b for n-pentane is found to range from 2.60 to 0.13 kPa
1 ln (1-Mt /Me )
between 303 and 373 K, while the affinity constant b for isopen- -1
tane is from 0.78 to 0.08 kPa
1.

ln (1-M t /Me )
2.5
-2
3.2.2. Isosteric heats of adsorption of n-pentane/isopentane on ZIF-8 2.0
The isosteric heat of adsorption is a measure of the interaction -3
between the adsorbate and adsorbent at different coverages
[23,2728]. The isosteric heats of adsorption of a single component 1.5
-4
can be calculated by ClausiusClapeyron equation [29], based on
the fitting result of the adsorption isotherms of n-pentane/ 1.0 -5
isopentane on ZIF-8. The results are shown in Fig. 8. The calculation
formula of isosteric heats is as follows: 0 50 100 150 200 250 300
Time, s
Q
ln p
C 2
RT Fig. 9. Adsorption pressure and ln(1
Mt/Me) curve of n-pentane on ZIF-8 versus
time at 308 K (13 kPa).

1
Q is the isosteric heat of adsorption, kJ mol ; C is the equation
parameter.
Fig. 8 presents isosteric heats of adsorption for n-pentane/
isopentane on ZIF-8 as a function of adsorption capacity. The isos- adsorption pressure
teric adsorption heat of n-pentane/isopentane on ZIF-8 almost 3.0 0
have no change with the increase of adsorption capacity. This fea-
Adsorption pressure, kPa
ln (1-Mt /Me )
ture is consistent with the process of monolayer adsorption. The
2.5
isosteric adsorption heat of n-pentane is about 39 kJ mol
1, higher

ln (1-M t /M e )
-1
than that of isopentane about 32 kJ mol
1. It shows that the
adsorption force between n-pentane and ZIF-8 is stronger than that 2.0
of isopentane. Luebbers et al. [19] reported that the heat of adsorp-
tion of n-pentane on ZIF-8 is 32.74 kJ mol
1, slightly differs from -2
1.5
the value in this work (39 kJ mol
1). While the heat of adsorption
of n-pentane on 5A is 47.72 kJ mol
1 reported by Vavlitis et al.
[30]. It shows that the adsorption force between n-pentane and 1.0 -3
5A molecular sieve is stronger than ZIF-8.
0 200 400 600 800 1000 1200 1400 1600
3.3. Adsorption kinetics performance of n-pentane/isopentane on ZIF-8 Time, s

Fig. 10. Adsorption pressure and ln(1
Mt/Me) curve of isopentane on ZIF-8 versus
The adsorption kinetics of n-pentane/isopentane on ZIF-8 were time at 308 K (13 kPa).
measured at 308 K in the pressure range of 069.9 kPa. LDF model
[3133] was used to calculate the adsorption rate constant k of n-
pentane/isopentane. The calculation formula of LDF is shown as Table 2
follows: Adsorption rate constant and adsorption capacity of n-pentane/isopentane on ZIF-8
with different pressure at 308 K.
Mt
1
e
kt 3 Adsorption Adsorption Adsorption Adsorption Adsorption
Me pressure, rate constant capacity of rate constant capacity of
kPa of n-pentane, n-pentane, of isopentane, isopentane,
10
3 s
1 g g
1 10
3 s
1 g g
1
01.0 16.4 0.1646 1.1 0.0084
100 1.03.0 18.4 0.2046 1.5 0.0221
3.05.0 16.2 0.2167 1.3 0.0358
5.07.0 17.2 0.2242 1.4 0.0501
-1

n-pentane 7.09.0 14.6 0.2297 1.4 0.0651

Heat of adsorption, kJ mol

80
isopentane 9.011.9 17.6 0.2370 1.6 0.0859
11.914.9 32.6 0.2416 2.2 0.0999
14.919.9 21.4 0.2475 3.6 0.1130
60 19.929.9 20.6 0.2556 2.2 0.1288
29.939.9 5.2 0.2611 1.4 0.1382
39.950.0 2.5 0.2650 1.4 0.1432
40 50.060.0 1.9 0.2667 0.7 0.1463
60.069.9 2.8 0.2668 0.9 0.1468

20
t is the adsorption time, s; k is the adsorption rate constant, s
1; Mt
is the adsorption capacity when the time is t, g g
1; Me is the equi-
0 librium absorption capacity at certain pressure, g g
1.
0.00 0.03 0.06 0.09 0.12 0.15
Adsorption pressure and ln(1
Mt/Me) curves of n-pentane/
q, g g -1
isopentane on ZIF-8 versus time calculated by the adsorption
Fig. 8. Isosteric heats of adsorption of n-pentane/isopentane with a function of kinetics data under 13 kPa, are shown in Figs. 9 and 10. It is
adsorption capacity. apparent that the graphs are close to linearity over typically

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>95% of the capacity change in the specific pressure range incre- the adsorption of guest molecules (n-pentane/isopentane)
ment. The adsorption rate constant and adsorption capacity of each [22,25], while the molecular dynamics diameter of n-pentane is
adsorption pressure section are shown in Table 2. The adsorption closer to the pore size, so the adsorption resistance is smaller. It
rate constant curve versus adsorption pressure is shown in Fig. 11. could be adsorbed faster than isopentane on ZIF-8.
As shown in Fig. 11, the adsorption rate constant of n-pentane/
isopentane increases firstly, and decreases with the adsorption 3.4. Breakthrough curves of n-pentane/isopentane on ZIF-8
pressure. This should be attributed to that ligand and guest mole-
cules need to rotate [22,25] at adsorption process when the A set of breakthrough experiments with equimolar binary mix-
adsorption pressure is lower than 10 kPa. The greater adsorption tures of n-pentane/isopentane were performed to evaluate the
resistance leads to slower adsorption rate. When adsorption pres- adsorption dynamics behavior on the apparatus showed in Fig. 1.
sure is between 10 kPa and 30 kPa, due to the pore door [18] has Figs. 1214 disclose the breakthrough curves for equimolar mix-
been turned away, the adsorption resistance become smaller, so tures (n-pentane/isopentane) at the partial pressure around 7 kPa
the adsorption rate is the fastest in this section. When the adsorp- as a function of the temperature.
tion pressure reaches 50 kPa, adsorption process becomes satu- The adsorbed capacity of each compound is calculated by the
rated. The slowest adsorption rate occurs for a very small part of following relation (4). In the case of an equimolar mixture, the
the adsorption process. selectivity S is given by the quotient between the capacities
In addition, as presented in Table 2, the adsorption rate constant adsorbed of the two species as follows:
of n-pentane is from 0.0019 to 0.0326 s
1, which is 10 times Z  
M  c0 tb
c
greater than that of isopentane (0.00070.0015 s
1). The difference qb 1
dt 4
of adsorption rate constant between n-pentane and isopentane is
m 0 c0
due to the distinction of molecular kinetic diameters. The molecu-
q1
lar kinetic diameters of linear and mono-branched alkanes are s 5
q2
0.43 nm and 0.50 nm respectively, and the pore size of ZIF-8 was
0.34 nm [17]. The rotation of ligand in the pore is necessary for

0.035
2.0
0.030 n-pentane
i-pentane
0.025 1.5

0.020
-1
k, s

C/C0

1.0
0.015

0.010
0.5
0.005 n-pentane
0.000
isopentane
0.0
0 10 20 30 40 50 60 70 0 1000 2000 3000 4000 5000
Adsorption pressure, kPa Time, s

Fig. 11. Adsorption rate constant of n-pentane/isopentane on ZIF-8 versus pressure Fig. 13. Experimental breakthrough curves for adsorption of n-pentane/isopentane
at 308 K. on ZIF-8 performed at 363 K.

2.0
2.0

1.5
1.5
C/C0

C/C0

1.0
1.0

0.5 0.5
n-pentane n-pentane
isopentane isopentane
0.0 0.0
0 1000 2000 3000 4000 5000 6000 0 1000 2000 3000 4000
Time, s Time, s

Fig. 12. Experimental breakthrough curves for adsorption of n-pentane/isopentane Fig. 14. Experimental breakthrough curves for adsorption of n-pentane/isopentane
on ZIF-8 performed at 343 K. on ZIF-8 performed at 393 K.

Please cite this article in press as: L. Zhang et al., Adsorption and separation properties of n-pentane/isopentane on ZIF-8, Separ. Purif. Technol. (2015),
http://dx.doi.org/10.1016/j.seppur.2015.10.037
 L. Zhang et al. / Separation and Purification Technology xxx (2015) xxxxxx 7

Table 3
Experimental conditions for binary breakthrough runs, adsorption capacity and selectivity.

Adsorption Adsorption pressure Adsorption pressure Breakthrough Breakthrough Adsorption capacity Adsorption capacity Adsorption
temperature, of n-pentane, kPa of isopentane, kPa time of n-pentane, time of of n-pentane, g g
1 of isopentane, g g
1 selectivity
K s isopentane, s
343 1 6.85 6.85 4242 84 0.1632 0.0032 51
363 1 7.78 7.79 3648 66 0.1488 0.0027 55
393 1 6.99 6.99 2196 54 0.0862 0.0021 41

the separation process of n-pentane/isopentane should be exe-

1.0
cuted at 363 K in that the highest selectivity at this temperature.
Experiment curve
0.8 Fitting curve
3.5. TPD curves analysis of n-pentane on ZIF-8 and 5A molecular sieve

0.6 TPD curves of n-pentane on ZIF-8 and 5A molecular sieve are

Voltage, mV

shown in Figs. 15 and 16. The desorption temperature of n-

0.4 pentane on ZIF-8 is between 298 and 393 K, and the desorption
peak temperature is 361 K. While the desorption temperature of
n-pentane on 5A molecular sieve is between 298 and 523 K, and
0.2
there are two desorption peaks of 392 K and 443 K. It is obvious
that the desorption peak temperature on ZIF-8 are 31 K and 82 K
0.0 lower than that of 5A molecular sieve. In general, the separation
of n-pentane/isopentane could be produced on ZIF-8 at lower oper-
-0.2 ation temperature, and the energy consumption could be cut. It
275 300 325 350 375 400 425 450 will also accelerate the industrialized application of light naphtha
Temperatrue, K adsorption separation.

Fig. 15. TPD curves of n-pentane on ZIF-8 (experimental and fitting line).
4. Conclusions

c0 is the content in the raw material, wt%; tb is the breakthrough
time (c/c0 = 0.05), s; M is the feed flowrate, g s
1; m is the amount
of adsorbent, g; qb is the adsorption capacity, g g
1; S is the selectiv-
ity of the two species.
Figs. 1214 show that the breakthrough time of n-pentane is
longer than isopentane at 343393 K. This also illustrates that n-
pentane adsorbs stronger than isopentane on ZIF-8. Table 3 shows
that, the adsorption capacity of n-pentane reduces quickly with the
increase of adsorption temperature. The adsorption capacity of n-
pentane at 393 K reaches about 52.8 wt% at 343 K. While the
adsorption capacity y of isopentane reduce slightly compared to
n-pentane. The selectivity S calculated by relation (5) shows that
2.5
Experiment curve
Fitting curve
2.0
Voltage, mV
In the present study, ZIF-8 was synthesized and investigated for
the separation performance of n-pentane/isopentane. The ZIF-8
sample shows the same XRD characteristic peaks as the literature,
with a good thermal stability. The BET specific surface area and
microporous volume of ZIF-8 is 1971 m2 g
1 and 0.7538 cm3 g
1
respectively.
The equilibrium of adsorption for n-pentane/isopentane on ZIF-
8 was investigated at 308, 343, and 373 K in the pressure range
from 0 to 9.7 kPa. N-pentane is more adsorbed than isopentane
in all the conditions studied. Note however that the n-pentane
adsorption on ZIF-8 is more favorable at low temperature. The isos-
teric heats of adsorption of n-pentane/isopentane on ZIF-8 is 39
and 32 kJ mol
1 respectively.
Adsorption kinetics of n-pentane/isopentane was studied at
308 K in the pressure range from 0 to 69.9 kPa. The data was well
fitted with LDF model. The adsorption rate constant of n-pentane is
0.00190.0326 s
1, it is greater than that of isopentane, repre-
sented 0.00070.0036 s
1.
The binary breakthrough experiments based on n-pentane/
isopentane show a complete separation of linear n-pentane from
the branched isopentane at 343 K, 363 K and 393 K in the partial
pressure of 7 kPa. When the adsorption temperature is 363 K, the

1.5 adsorption selectivity of n-pentane/isopentane on ZIF-8 reaches

the maximum of 55.
1.0 The desorption peak temperature of n-pentane on ZIF-8 is
361 K, however it was 392 K and 443 K on 5A molecular sieve.
The data reported in this work can be used for the modeling and
0.5 design of adsorption separation process between n-pentane and
isopentane in the light naphtha.
0.0
Acknowledgements
300 400 500 600 700
Temperatrue, K
We acknowledge the financial support for this work by the
Fig. 16. TPD curves of n-pentane on 5A molecular sieve (experimental and fitting National Science Foundation of China (No. 51476074), the Research
line). and Innovation Project for College Graduates of Jiangsu Province

Please cite this article in press as: L. Zhang et al., Adsorption and separation properties of n-pentane/isopentane on ZIF-8, Separ. Purif. Technol. (2015),
http://dx.doi.org/10.1016/j.seppur.2015.10.037
8 L. Zhang et al. / Separation and Purification Technology xxx (2015) xxxxxx
(No. KYLX0765) and the Priority Academic Program Development
of Jiangsu Higher Education Institutions (PAPD).
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