Chemistry and Technology of Fuels and Oils, Vol. 49, No. 5, November, 2013 (Russian Original No.

5, September–October, 2013)

SEPARATION OF SULFUR COMPOUNDS BY ZSM-5 ZEOLITE MEMBRANE FILTRATION

Feng Xue, Shengui Ju, Weihong Xin, Bo Wang, and Tong Miao

We describe preparation of a ZSM-5 zeolite membrane, used for separation of benzothiophene

and 3-methylthiophene from their n-hexane solutions. We have established the effect of the feed flow
rate, the membrane operating time, filtration pressure, and concentration of sulfur compounds in the
feed on the membrane flux. As the membrane flux increases, the desulfurization ratio gradually decreases.
Filtration was carried out in two modes: cross-flow filtration and end-filtration. The separation factor
and the desulfurization ratio were higher in cross-flow filtration.
Key words: desulfurization, benzothiophene, ZSM-5 zeolite membrane, filtration, membrane flux,
separation factor.

Tougher environmental requirements for gasolines are the reason for the search for new desulfurization
technologies. The membrane method for desulfurization of petroleum products has many advantages, including
low energy consumption, no environmental pollution, high single-stage separation efficiency, etc. [1, 2]. High
desulfurization efficiency on ZSM-5 zeolite membranes has been noted in [3, 4]. The advantages of ZSM-5 zeolite
include uniform aperture, regular periodic arrangement of pore channels, large specific surface area, thermal stability,
acid resistance, carbon deposition resistance, etc. [5, 6].
In this work, we have studied membrane desulfurization of a model gasoline: solutions
of 3-methylthiophene (3-MT) and benzothiophene (BT) in n-hexane. A ZSM-5 zeolite membrane was prepared by
the second growth method [7-12]. Filtration was carried out in two modes: cross-flow filtration and
end-filtration [13-15].
In this work, we used analytical grade hydrochloric acid, n-hexane, benzothiophene, and 3-methylthiophene;
and also c.p. grade sodium hydroxide, tetrapropylammonium hydroxide (TPAOH), tetraethyl orthosilicate, and
sodium aluminate.

____________________________________________________________________________________________________
C o l l e g e o f C h e m i s t r y a n d C h e m i c a l E n g i n e e r i n g , N a n j i n g U n i v e r s i t y o f Te c h n o l o g y,
Nanjing, 210009, People’s Republic of China. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5,
pp. 30 – 33, September – October, 2013.

0009-3092/13/4905–0413 2013 Springer Science+Business Media New York 413

 Fig. 1 Schematic drawing of laboratory membrane desulfurization setup: 1) feed tank
(reservoir); 2) metering pump; 3) membrane tube; 4) membrane module; 5) flowmeter;
6) valve; 7) sample extraction tank.

The zeolite support was a hollow cylinder (inner diameter 8 mm) made from -Al2O 3. The pore diameter of
the support was 3-5 m. The cylinder was polished with emery paper and then placed in a 2 M HCl solution
for 24 hours, and in a 2 M NaOH solution for another 24 hours. Then the support was sonicated for 30 minutes.
Finally the support was washed with plenty of deionized water and dried in an oven at a temperature
of 175°C for 24 hours.
Preparation of the suspension: A 25:1:150:10:10000 mixture of Na 2 O, Al 2 O 3 , SiO 2 , TPAOH, and
water was heated for 30 minutes and kept in the dark for 48 hours. Then the following solution was
prepared: A 15:1:100:20:10000 mixture of Na 2O, Al 2O3, SiO 2, TPAOH, and water was heated for 30 minutes.
The prepared support was leached in the suspension and pulled upward by the Czochralski method several
times at room temperature for 30 minutes, and then dried at room temperature for 30 minutes. Then the support was
held at a temperature of 175°C for 24 hours; the membrane tube obtained was cooled with water down to room
temperature and washed with deionized water. Finally the membrane tube was calcined at a temperature
of 550°C for 3 hours under a nitrogen atmosphere.
A schematic drawing of the membrane desulfurization setup is shown in Fig. 1. The zeolite membranes are
placed in membrane modules, which are fed the model gasoline by a metering pump. Some of the product is
withdrawn for gas chromatography analysis of the sulfur compound content. The rest of the product is returned
to the feed tank.
The separation factor  and the desulfurization efficiency  were calculated from the formulas:

C1 p C 2i
 (1)
C2 p C1i

 Xp 
  1  100
 (2)
 XF 

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 Intensity

2  , degrees
Fig. 2 X-ray diffraction patterns: 1) zeolite ZSM-5; 2) support; 3) support with deposited
zeolite.

a b

c d

Fig. 3 Micrographs: a) surface of support; b) surface of support with deposited zeolite;

c) fracture surface of support; d) fracture surface of support with deposited zeolite.

where C 1p , C 2p are respectively the 3-MT and BT content in the product, mg/g; C 1i , C 2i are respectively
the 3-MT and BT content in the feed, mg/g; X P, X F are the total BT and 3-MT contents in respectively the product
and the feed, mg/g.

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 b
a

Membrane flux, L/(m 2·h)

Membrane flux, L/(m 2·h)

Feed flow rate, v·10 -3, m/s Membrane operating time, minutes
c
d

Filtration pressure, MPa Sulfur compound content, mg/g

Fig. 4 Membrane flux vs. feed flow rate (a), membrane operating time (b), filtration
pressure (c), and sulfur compound content in the feed (d).

X-ray diffraction (XRD) analysis of the membranes was carried out on a D8 Advance (Bruker) diffractometer
using CuK radiation with a nickel filter, 40 kV, 20 mA, with scanning speed 0.02°/0.2 s, in the range 5°–40°/2 . The
morphology and microstructure of the membranes were studied using a Quanta electron microscope
with 200FEI detector (Netherlands).
Figure 2 shows x-ray diffraction patterns of the zeolite, the support, and the support with deposited
zeolite. The change in the intensity of the peaks for the support after deposition of the zeolite is evidence that
the ZSM-5 phase formed on its surface.
Micrographs of the support and the support with deposited zeolite are shown in Fig. 3. In
comparing Fig. 3a and Fig. 3b, we see that after deposition of the zeolite, crystalline particles were formed on the
surface of the membrane which were distributed uniformly over the surface. Comparing Fig. 3c and Fig. 3d shows
that the crystalline layer extends beyond the support, i.e., the ZSM-5 zeolite filled the entire support.
The first series of experiments involved the cross-flow filtration mode at a temperature
of 25°C. Figs. 4a-d show the membrane flux vs. respectively the feed flow rate, the membrane operating time, the
filtration pressure, and the sulfur compound content in the feed. Obviously as the feed flow rate increases, the
membrane flux increases. The higher the feed flow rate, the greater the shear force it exerts. In turn, a significant
shear force decreases the thickness of the membrane filter cake by sweeping away deposited particles. As a result,
the flow resistance is reduced and the amount of permeate increases. However, a high feed flow rate has its own
disadvantages. So in this work, we maintained the feed flow rate at 9·10 -3 m/s.

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 Desulfurization ratio, %
Membrane flux, L/(m 2·h)
Fig. 5 Effect of membrane flux on desulfurization ratio.

a
Separation
factor
Desulfurization

b
ratio, %

Membrane operating time, minutes

Fig. 6 Dependence of separation factor (a) and desulfurization ratio (b) on filtering
mode: 1) end-filtration; 2) cross-flow filtration.

From Fig. 4b we see that the membrane flux is significantly reduced during the first 80 minutes of filtration,
and then it remains constant at 300 L/(m 2·h) The thickness of the filter cake increases at the beginning of filtration,
and then at some point in time it reaches a constant value and the membrane flux no longer changes.
Since the pressure is the driving force for the separation, the membrane flux increases rapidly with filtration
pressure (see Fig. 4c). However, at a pressure above 0.018 MPa, the membrane flux increases but not as fast. With
an increase in membrane flux, the thickness of the membrane filter cake increases gradually, and as a result a
polarization layer is formed on its surface.
In order to study the effect of sulfur compound content in the feed on the membrane flux, we prepared
model solutions of a mixture of (BT + 3-MT) in n-hexane with concentrations 500, 750, 1000, 1250, and 1500 mg/g.
From Fig. 4d, we see that the membrane flux is reduced with an increase in sulfur compound content in the feed.
Obviously when filtering a feed with a higher sulfur content, the amount of sulfur compounds on the membrane
and the thickness of the filter cake rapidly increase and then the effect of the polarization layer becomes obvious,
leading to a decrease in membrane flux.
The effect of membrane flux on the desulfurization ratio is shown in Fig. 5. The initial content of
the (BT + 3-MT) mixture in n-hexane was 1000 mg/g. Obviously as the membrane flux increases, a decrease in the
desulfurization ratio is observed. On the one hand, an increase in membrane flux leads to a shorter residence time

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of the fluid in the membrane tube. Under these conditions, some of the sulfur compounds are not retained by the
membrane and are transferred to the permeate. On the other hand, for significant membrane flux, the amount of
sulfur compounds on its surface increases and a polarization layer is rapidly formed, which also reduces the
membrane separation efficiency.
Figure 6a shows the dependence of the separation factor on the filtering mode. As we see, the separation
factor under cross-flow filtration conditions is higher than for end-filtration. When fluid flows through the
membrane, as the membrane operating time increases polarization phenomena occur, the thickness of the membrane
filter cake increases, and the zeolite pores are blocked. When the feed flows parallel to the membrane surface in
cross-flow filtration, if all other conditions are the same, the membrane filter cake is thinner than in the
end-filtration mode and the effect of polarization phenomena is weaker.
Figure 6b shows the dependence of the desulfurization ratio on the filtering mode. In the initial stage of
the process, filtration resistance is low, the diffusion rate through the membrane is high, and therefore efficient
desulfurization of the feed results. When the membrane operating time increases, the thickness of the filter cake
on the surface of the membrane increases and the zeolite pores are blocked. In this case, the filtration resistance
increases and the desulfurization ratio gradually declines. As already noted, in cross-flow filtration mode, a
thinner filter cake is formed than in end-filtration, and so the desulfurization ratio is higher in cross-flow filtration.
Based on the above discussion, cross-flow filtration is more efficient than end-filtration.

This work was conducted with the support of the National Natural Science Foundation of China (project
No. 21176118).

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