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Adsorptive Desulfurization of Liquefied Petroleum Gas for Carbonyl Sulfide

Removal

Article · May 2014

DOI: 10.15764/OJCES.2014.01006

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Javad Alaei kadijani Elhameh Narimani

Research Institute of Petroleum Industry (RIPI) Université de Sherbrooke
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 OPEN JOURNAL OF CHEMICAL ENGINEERING AND SCIENCE
Volume 1, Number 1, MAY 2014

OPEN JOURNAL OF CHEMICAL ENGINEERING AND SCIENCE

Adsorptive Desulfurization of Liquefied

Petroleum Gas for Carbonyl Sulfide
Removal
Javad Alaei Kadijani, Elhameh Narimani*
Research Institute of Petroleum Industry (RIPI), Gas Department, West Boulevard of Azadi Stadium, P. O. Box 14665-1998, Tehran,
Iran.
*Corresponding author: inspirationj82@gmail.com

Abstract:
In order to reduce the sulfur content of Liquefied Petroleum Gas (LPG) to meet the universal
criteria the adsorption using two types of zeolite was carried out because the proportion of
sulfur even in the treated LPG especially as carbonyl sulfide exceeds the defined levels. This
study examined the proficiency of two different types of zeolite based on their dynamic sorption
capacity for carbonyl sulfide removal. To select the most efficient type of zeolite to treat LPG, a
laboratorial set-up of adsorption was used. Based on the tests result, the dynamics sorption
capacity of zeolite A with the greater special surface area was considerably higher than that of
zeolite B which had the smaller special surface area. Consequently, the zeolite A was applied to
treat LPG containing the significant amount of carbonyl sulfide as well as the small amount of
mercaptans in an industrial-scale. The experimental data elicited from one of Iranian refineries
revealed that zeolite A could significantly reduce the sulfur content of LPG, especially as carbonyl
sulfide.
Keywords:
Adsorption; Experimental Study; LPG treatment; Zeolite

1. INTRODUCTION

Currently, modern world markets have tightened the rules on the quality of LPG especially on its
sulphur content. Based on European standard EN 589, total sulphur content in the salable LPG must
be less than 50 ppm (50 mg/kg). To meet strict emission criteria, ultra-deep sulfur removal of fuel
has become extremely important for the petroleum refining industry. Although hydrodesulphurization
(HDS) is a conventional method to remove sulfur compounds, it is difficult to remove some heterocyclic
sulfur compounds such as dibenzothiophenes (DBT) and substituted DBTs in petroleum [1]. In order
to reduce the sulfur content of fuel, some new technologies are used- adsorption desulfurization [2–4],
biodesulfurization, desulfurization using extraction to name but a few [5].
Carbonyl sulfide (COS) is considered as a contaminant in materials, especially hydrocarbons due to
inclusion of sulphur which is a potential atmosphere pollutant. Furthermore, COS acts as a detrimental
contaminant in industrial processes in which it often poison the polymerization catalysts when existing in
petroleum-derived ploymerizable olefins like propylene. COS may be initially found at feedstocks or may
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result from molecular sieve-catalyzed reaction of carbon dioxide with hydrogen sulfide or other sulfur
compounds. Another negative effect of the existence of COS is related to the formation of hydrogen
sulfide during hydrocarbon storage, especially propane storage. The presence of moisture in storage tanks
promotes a reaction between carbonyl sulfide and water, which results in the production of hydrogen
sulfide. The corrosion of pipes is often considered as the most probable effect of hydrogen sulfide on
instrument. Therefore, based on the type of process and required purity of product, the COS level in
petroleum products must reach something around 10 to 1 ppm by weight [6]. The methods to remove
COS from hydrocarbons can be divided into three groups: distillation, hydrolysis and adsorption, that
each of which has some drawbacks.
At the first method that was invented by Khelghatian in US. Pat. No. 3315003 for removing COS from
a hydrocarbon, the hydrocarbon must be contacted with a liquid such as monoethanolaminc, which scrubs
hydrocarbon to remove acid gases such as H2 S and CO2 . Then, the hydrocarbon is distilled. After several
subsequent distillations, the liquid bottom product is treated with a soda lime to remove any remaining
COS. However, distillation processes in this case is considered economically insufficient due to the high
cost of energy to vaporize all of the liquid.
Another method described in U.S. Pat. No. 3265757, to remove COS from hydrocarbon uses the
catalytic hydrolysis which leads to the formation of H2 S. In this patent alumina was used as a catalyst.
The subsequent treatment is required to eliminate the hydrolysis products and water which is considered
as a serious disadvantage of removing COS. Petroleum refineries often treat propane to remove carbonyl
sulfide by its hydrolysis in an aqueous solution of sodium hydroxide or diethanolamine at a temperature
of 60-70◦ C. The equation (1) shows this reaction.

COS + 4NaOH → Na2 S + Na2 CO3 + 2H2 O (1)

According to the equation (1), the treatment of propane for COS requires the large quantity of caustic,
which results in the formation of the large amount of toxic sulfur-alkaline wastewater. Therefore, it was
highly preferable to remove sulfurous impurities namely, COS from hydrocarbons in the absence of water
using an adsorbent with high adsorption characteristics. One type of these adsorbents was shown in U.S.
Pat. No. 4835338 [6–9].
The adsorbent must be capable of regeneration, which means adsorbent can work efficiently for long
times, without losing a significant amount of its adsorption capacity. The drawback of this method is that
after some cycles, the adsorption capacity of adsorbent substantially decreases. As a result, the main issue
in the field of sulfur removal from hydrocarbons by adsorption is related to find an adsorbent with high
adsorption capacity, which keeps its adsorption capability high for a long time.
Zeolites are unique adsorbents, characterized by 20% to 50% void volumes and internal surface areas
of several hundred thousand square meters per kilogram. The adsorption can occur on the outer or inner
surface of the micro pores. Molecules with larger diameter than that of the pores cannot pass through the
windows and enter the canal system; therefore, zeolites are also known as molecular sieves [10].

2. METHODS AND MATERIALS

2.1 The laboratorial experiments

To study the sorption properties of two different brands of zeolite, a series of experiments were carried
out using a laboratory-scale sorption plant, which is shown in Figure 1 . According to Figure 1 , a
glass cylinder as an absorber was filled with zeolite and dreksel flasks 1, 2 and 3 were filled with 10%
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 Adsorptive Desulfurization of Liquefied Petroleum Gas for Carbonyl Sulfide Removal

Figure 1. The scheme of a laboratorial set-up to treat LPG for COS

Table 1. Characteristics of LPG

Composition Mass %
Methane <0.01
Ethane 0.37
Propane 51.22
N-butane 21.46
i-C4 11.18
ΣC5 12.1
ΣC6 and Higher 3.67
H2 S 0.0004
RSH 0.01
COS 0.0085

aqueous solution of cadmium chloride (to control the breakthrough of hydrogen sulfide formation during
carbonyl sulfide adsorption), 40% solution of caustic (to remove mercaptans) and 5% alcohol solution of
monoethanol amine (to remove carbonyl sulfide), respectively. In order to evaluate the rate of gas passing
through this set-up, wet gas meter, shown in Figure 1 was used.
The sulphur compounds sorption results in the generation of a yellow layer on zeolite bed. Based
on experimental procedure, tests had to be terminated when the generated yellow layer covered all the
surface of adsorbent bed. After the point in which this layer reached the highest level on the surface of
zeolite, H2 S appeared at the outlet.
The required amount of LPG as well as other chemicals involving zeolite A & B were provided by
RIPI authority. The chemical specification of LPG used in experiments and the process conditions are
indicated in Table 1 and Table 2 , respectively.
The adsorbent efficiency was determined based on its capacity for sorption of carbonyl sulfide. The
technical characteristics of two different types of zeolite were listed in Table 3 .

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Table 2. Process conditions for laboratorial tests

Process Conditions Numbers
Mass of Zeolite, Kg 0.04
Volume of zeolite, L 0.05
Temperature of adsorption, ◦ C 23
Pressure, MPa 0.1
Initial percentage of COS in feed, (mass)% 0.0185
Gas flow rate, L hr−1 6

Table 3. Technical Characteristics of two types of zeolite

Characteristics Numbers
Zeolite Type A B
Pellet Size, mm 3.35 3
Bulk density, Kg/cm3 760 750
Specific Surface Area, m2 /g 238 85
crushing strength, Kg 7.6 1.6
Dynamics capacity for water vapors, mg/cm3 215 111

2.2 The laboratorial tests results

The tests results for these brands of zeolite are tabulated in Table 4 in which propane was treated to
remove the sulfur content. Table 1 revealed that the large amount of sulfur content of propane was as
carbonyl sulfide. Regarding the test results from Table 4 , under the process conditions, the dynamics
sorption capacity of zeolite A was 1.8%. Compared to another type of zeolite, zeolite type A was the
better choice for sulphur sorption as its dynamic sorption capacity was 36 times more than that of zeolite
type B. This fact can be described using the characteristics of these brands in which the specific surface
area of zeolite A is significantly higher than that of zeolite B.
It must be taken into consideration that during carbonyl sulfide adsorption on zeolite, the small amount
of hydrogen sulfide was found at the outlet of this system, which can be justified by this fact that due to
the presence of moisture contained in the zeolite pores, carbonyl sulfide hydrolyzed with water, which
resulted in the generation of hydrogen sulfide as follows:

COS + H2 O ↔ H2 S + CO2 (2)

If you wish, you may write in the first person singular or plural and use the active voice (“I observed
that ...” or “We observed that ...” instead of “It was observed that ...”). Remember to check spelling. If
your native language is not English, please get a native English-speaking colleague to carefully proofread
your article.

Table 4. Comparing test results for zeolite A & B

Zeolite type Time of adsorption before “break-through” of COS or H2 S, hr Dynamics sorption capacity , %(mass)
A 340 1.8
B 10 0.05

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 Adsorptive Desulfurization of Liquefied Petroleum Gas for Carbonyl Sulfide Removal

Figure 2. The PFD of LPG treatment unit using adsorbent A

2.3 The Pilot-Commercial tests of zeolite A

In the second part of this study, the pilot-commercial tests were conducted to study the treatment of
LPG using zeolite A due to its high sorption capacity, which was proved during laboratorial tests. The
pilot-commercial tests were conducted in kharg Refinery’s plant of LPG demercaptanization. The aim of
this plant was production of a desulfurized LPG product, which meets the requirements of international
standards, i.e. total sulfur content in the treated product should not exceed 10 ppm. A simple Process
Flow Diagram (PFD)of LPG treatment unit for sulfur compound using the pilot-commercial tests is
shown in Figure 2 .The treatment process was carried out based on a four-adsorber scheme in which two
adsorbers were used to treat LPG and the third one had to be on the regeneration mode and cooling stage.
Furthermore, another adsorber was required to be in reserve. In addition to carbonyl sulfide, LPG contains
some amount of moisture and mercaptans; therefore, to decrease a load on the main adsorbent, which was
zeolite type A, a system of two-layer zeolite loading was used to treat LPG. One of the layers was loaded
with NaX zeolite and another layer contained zeolite A in which the proportion of NaX at adsorbent bed
can be varied from 12% to 40% of total mass. Regarding a research conducted by M.W.B. Mangnus, NaX
is widely used to remove hydrogen sulfide and mercaptans from natural gas and LPG [11].
Based on experiments procedure, LPG had to be passed through NaX bed and through the section of
zeolite A, respectively. Adsorber tanks had to be loaded with 21790 kg of zeolite type A for upper layer
and 2900 kg of NaX for lower zone in which the ratio of NaX to zeolite A was 12% to 88%. To reduce
the dynamic effect of gas flow and to create a uniform distribution inside adsorbers, they were also loaded
with a distributive packing consisting of inert porcelain balls. Figure 3 shows a scheme of adsorber used
at this study.
The first step was an injection of regeneration gas at temperature of 150◦ C that lasted for two hours.
The second step included an increase in temperature of regeneration gas to 250◦ C during two hours (the
determined temperature had to be set in the gas inlet).
Finally, the third step involved an increase in temperature to 300◦ C; over the period of four hours (the
determined temperature had to be set in the gas inlet).After initial regeneration of zeolites in adsorber
(AD-3), it was put into operation while the adsorber (AD-4) had to be kept reserve. The LPG flow at a

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Figure 3. A scheme of the adsorber used in the commercial-pilot tests, 1- Porcelain balls 2- NaX, 3- A, I-LPG to
treatment, II-LPG after treatment, III-regeneration and cooling gas, IV- gas after regeneration and cooling

temperature of 38◦ C and a pressure of 1.8 MPa was fed into the bottom of adsorbers (AD-1) and (AD-3).
On the adsorber (AD-3), the treatment for mercaptans and carbonyl sulfide was conducted on NaX and
zeolite A layers, respectively. The rate of LPG had to be no more than 57ton/hr. The adsorption period in
the absorbers, was 24 hours and then, the adsorber was cooled and regenerated.
In order to regenerate the zeolite particles of adsorber (AD-3), LPG had to be emptied and sent to
the Loading-Unloading vessel (E-1) at a pressure of 2.1 bMPa. Afterwards, the moisture droplets were
purged using purging gas. Subsequently, the purging gas was discharged to a separator (C-2) and then to a
purging gas line. The condensed droplet of hydrocarbon and moisture were separated using demister pad
in separator (C-2) and flowed into drain. The next step involved regeneration using regenerator gas. In
fact, the regenerator gas consisted of a mixture of HP (High Pressure) methane enriched with nitrogen at
a temperature of 320◦ C and a pressure of 4MPa was sent into an adsorber. During the regeneration step, a
temperature-changing rate had to be no more than 50◦ C per hour in which any increase in temperature
from 0◦ C to 300◦ C was performed by mixing hot and cold gas flows. Passing through the absorber from
top to bottom, the regenerator gas heated the adsorbent and desorbed the adsorbed components, which
made it rich in sulfur components, hydrocarbon and water vapor. The air cooler (AC-1) reduced the
temperature of regenerator gas stream to 45◦ C. The cooled spent regenerator gas was sent to the separator
(C-1), where the condensed hydrocarbon and moisture were removed from gas. The liquid phase from
separator (C-1) was discharged to a drain and then combined with the liquid phase from the drainage of
separator (C-2) and collected in the drainage vessel (E-2), while the separated regeneration gas was sent
to regenerator gas line.
Consequently, the cooling step was required, in which the temperature of adsorber has to be lowered.
The coolant was a mixture of HP (High Pressure) methane enriched with nitrogen. Passing through the
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 Adsorptive Desulfurization of Liquefied Petroleum Gas for Carbonyl Sulfide Removal

Table 5. Results of LPG sample analyses during pilot-commercial tests of zeolite A

Time of sampling, Hour Sampling points
LPG to treatment LPG after treatmentOutlet from A-2(3) LPG after treatmentOutlet from A-1
Sulfur compound content, S ppm
H2 S RSH COS H2 S RSH COS H2 S RSH COS
4 0.4 22.5 12
10 0.7 116.4 24.4
16 0.7 131.9 16.6 (0) (1.2) (0.1) 0 0.5 0.2
22 0 31 7.5 (0) (1.1) (3.4) 0.3 7.4 6.5
16 0 28.5 17.2 (0) (0.4) (0.3) 0 1 9.1
4 1.2 67 21.20 0(0) 0.5(1.7) 8.7(0.8)

adsorber column, from top to bottom, a cooling gas cooled the adsorber down to 45◦ C. This sharp fall in
temperature led to a significant decrease in the pressure of adsorber when it was 2.1 MPa and the absorber
was fed by LPG again to start the new process of desulfurization.

2.4 The commercial-pilot tests results

In order to run pilot-commercial test and reach a required degree of desulfurization, the loading ratio of
NaX to zeolite A was assumed 40:60 (mass %). The results of analyses for this process are tabulated in
Table 5 . According to Table 5 , adsorber AD-1 was working in pair of adsorber AD-2 or AD-3. The
sampling was conducted over the period of 24 hours. The results revealed that the percent of carbonyl
sulfide in treated LPG flow reached just less than 10 ppm, which was the main aim of this study.

3. CONCLUSION

This study compared two types of zeolite used in petroleum industry to remove sulfur content of LPG
especially as carbonyl sulfide. The laboratorial tests of zeolite A and B types revealed that the dynamic
sorption capacity of zeolite A was remarkably higher than that of the zeolite B due to its larger specific
surface area, which was 36 times greater than that of type B. Therefore, to reduce the sulfur content, as
carbonyl sulfide in LPG the zeolite type A should be used. The pilot-commercial tests results of zeolite A
in a process of LPG treatment for carbonyl sulfide suggested that sulfur content at all the sampling points
reached lower than 10 ppm, which was the main aim of this study.

4. ACKNOWLEDGEMENT

The financial support for this project provided by the Research Institute of Petroleum Industry (RIPI)
of Iran is gratefully acknowledged.

References

[1] K. G. Knudsen, B. H. Cooper, and H. Topsøe, “Catalyst and process technologies for ultra low sulfur
diesel,” Applied Catalysis A: General, vol. 189, no. 2, pp. 205–215, 1999.

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[2] S. Velu, X. Ma, and C. Song, “Selective adsorption for removing sulfur from jet fuel over zeolite-
based adsorbents,” Industrial & engineering chemistry research, vol. 42, no. 21, pp. 5293–5304,
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[3] R. T. Yang, A. J. Hernandez-Maldonado, and F. H. Yang, “Desulfurization of transportation fuels
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[7] H. M. Khelghatian, “Process for removing carbonyl sulfide from normally gaseous hydrocarbons,”
Apr. 18 1967. US Patent 3,315,003.
[8] L. K. Frevel, “Catalytic hydrolysis of carbonyl sulfide,” Aug. 9 1966. US Patent 3,265,757.
[9] P. K. Liu, “Process for removal of carbonyl sulfide from organic liquid by adsorption using alumina
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