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1 Walid Nabgan, Tuan Amran Tuan Abdullah*, Bahador Nabgan, Adnan Ripin, 1
Kamarizan Bin Kidam, Ibrahim Saeh and Kamal Moghadamian
5
A Simulation of Claus Process Via Aspen Hysys 5
for Sulfur Recovery
DOI 10.1515/cppm-2016-0019 Keywords: simulation, Claus process, aspen hysys, sulfur
10 Received March 16, 2016; revised May 5, 2016; accepted March 5, Recovery 10
2016
needs high temperature. This actual process exhaust high as H2S, NH3, CO2, CS2, COS, C6H6 and C8H10, as well as
amount of SO2 from the incinerator stack to the environ- unwanted unburnable chemicals, such as N2 [1–3]. The
ment. The Claus process is the best method to recover petroleum fractions which contains sulfur molecules
sulfur from acid gases that contain hydrogen sulfide. The must be reduced due to environmental pollution [4].
20
particular reaction for sulfur removal from sour gas is Sulfur removing has become a serious issue in the che- 20
hydrogen sulfide (H2S) sulfur dioxide (SO2) reformation mical processing industry because of the lower limits of
(2H2S + O2 = S2 + 2H2O). The aim of this study is to get a sulfur content in gasoline, diesel and jet fuels that is
simulation that is suitable for the characterization of sulfur being promulgated by regulatory agencies [1]. It is
recovery units. The experimental design for this study was known that H2S in the environment causes health threats,
25
collected from a petroleum refinery located in Iran. This such as, irritation in the breathing system, skin and eyes. 25
experimental relation supports us to gather with definite H2S is the source of generating a numerous hazardous
consistency that is normally not available online for such chemical compounds such as SO2, H2SO3 and H2SO4,
process. Aspen HYSYS v8.8 software was used to simulate therefore H2S removal is environmentally beneficial and
the Claus process by reactors and component splitters. The plays an important roles in the air pollution. Raw natural
30
result shows the complete conversion of sour gas to pro- gas is one of the main sources of H2S. Furthermore of the 30
duct. The simulation protects the environmental impact by main impurities that cause acid rain is SO2 [4].
SO2 emission. This behavior can be reproduced by this Most of the refineries are using Claus unit for sulfur
HYSYS design very well. It was found that the BURNAIR recovery, particularly for refineries which produce sulfur
feed composition and molar flow is the only factors which more than 10 tons a day [5, 6]. In refineries, the com-
35
can affect the hydrogen sulfide conversion. The sulfur pound of sulfur converts to H2S in hydrogenation pro- 35
mole fraction increased only in the range of 0.94 to 0.98 cess. After that, H2S goes to sulfur recovery unit and in
by increasing N2 from 0.7 to 0.9. this step commercial sulfur will produce. Claus process is
a widely used technology for recovering sulfur and
*Corresponding author: Tuan Amran Tuan Abdullah, Centre of energy from acid gases. It is conventionally divided into
40 Hydrogen Energy, Institute of Future Energy, Universiti Teknologi thermal and catalytic stages in order to achieve very high 40
Malaysia, 81310 Skudai, Johor, Malaysia, conversion of acid gas [1].
E-mail: tamran@cheme.utm.my Lurgi company in 1993 [7] mentioned that the Claus
Walid Nabgan, Bahador Nabgan, Adnan Ripin, Centre of Hydrogen
process system with the capacity of 10 tons a day has
Energy, Institute of Future Energy, Universiti Teknologi Malaysia,
81310 Skudai, Johor, Malaysia 99.8 % efficiency. According to previous research done by
45 Kamarizan Bin Kidam, Department of Chemical Engineering, Faculty Khazini et al. [7], in Iranian petroleum and petrochemical 45
of Chemical and Energy Engineering, Universiti Teknologi Malaysia, companies, incinerator is still in used which exhaust SO2
81310 Skudai, Johor, Malaysia to the atmosphere for sulfur recovery units (see Figure 1).
Ibrahim Saeh, Department of Electrical Power Engineering, Faculty
Those refineries exhaust thousands of ppm pollution
of Electrical Engineering, Universiti Teknologi Malaysia, 81310
Skudai, Johor, Malaysia
every day due to conversion of sulfur compound to SO2.
50 Kamal Moghadamian, Islamic Azad University of Mahshahr, The effectiveness of every Claus unit is determined by 50
Mahshahr, Iran the Claus unit’s reactor stages. For example the two reactor
Q1 2 W. Nabgan et al.: Simulation
1 1
5 5
10 10
stage has an efficiency of 90 %–96 %, or the three reactor byproduct gases originating from physical and chemical
stage has an efficiency of 95 %–98 % (2005). Thus the gas and oil treatment units in refineries, natural gas
Claus process unit is unable to recover the total entered processing, and gasification plants. It consists of a ther-
sulfur. Since the complete sulfur is not possible to remove mal reaction furnace, a waste heat boiler, and a series of
15 from sour gas, it is clear that sour gas must be treated by catalytic (Claus) reactors and condensers (see Figure 2). 15
additional process. Therefore the purpose of this study is The overall reaction characterizing the process is shown
to design and analyze the Claus process through Aspen in (reaction 1) [12, 13] but there are few more mechanism
Hysys®. ASPEN uses mathematical models for prediction might take place in the Claus process (reactions 2, 3
of the process performance by an appropriate selection of and 4) [14]. The oxidizing reaction (2) is exothermic and
20 thermodynamic models and Assumed a design of a pro- without any thermodynamic restriction which molecule 20
cess. This information can then be used in an iterative of hydrogen sulfide reacts with oxygen and produces
fashion to optimize the design. sulfur dioxide and water. The remainder of the hydrogen
sulfide then reacts with the produced sulfur dioxide from
reaction (2) to produce elemental sulfur.
25
2 Process description 2H2 S + O2 ! S2 + 2H2 O (1)
25
H2 S + 32 O2 ! SO2 + H2 O (2)
2.1 General description of the Claus
2H2 S + SO2 ! 32 S2 + 2H2 O (3)
processes
30 2H2 S + SO2 ! 83 S8 + 2H2 O (4) 30
Aspen Hysys v8.8 was used to design the process flow
sheet. This software offers a powerful thermodynamic The most important indicators of the process perfor-
mance is the molar ratio H2S/SO2 at the sour gas that
package called the “Amine package” which is a special
package designed for simulation of amine sweetening should be as close as possible to the value of 2 to get the
maximum conversion in sulfur [14, 2]. This index is a 35
35 units. The gas absorption process with a chemical reac-
controlled variable measured by means of an online ana-
tion using amine is recognized as the most cost effective
lyzer and included in a feedback control where the inlet
and has the best proven operability record [8]. This pack-
air feed flow rate is the manipulated variable to close the
age includes experimental solubility and reaction kinetics
loop. This measure is particularly sensitive to several
data over wide range of conditions [9]. Aspen Hysys has
process perturbations.
40 its own amine property package which uses both equili- 40
brium and kinetic models, has the additional capability
of employing the so-called “Electrolyte Insert” thermody-
namic package which considers only the equilibrium 2.2 Description of the sour gas treatment
model for predicting the process performance [10, 11]. for sulfur recovery
45 Incorporating this package in the simulation, generally, 45
reduce errors arising from using general thermodynamic The sour gas cleaning section is aimed at the removal of
equations of state or activity models. It provides can the sulfur components from sour gases which is mainly
provide summarized and highly detailed estimated infor- contains hydrogen sulfide and sulfur dioxide. The pro-
mation depending on the user’s requirements. duced sulfur then can be used in military as well as
50 The task of Claus processes is to recover elemental medical purposes [15, 16]. The process flow diagram of 50
sulfur from hydrogen sulfide and, more generally, from this section is reported in Figure 2. A first treatment for
W. Nabgan et al.: Simulation 3
1 1
5 5
10 10
15 15
20 the reduction of sulfur component in the sour gas is The gaseous product from BurnVap stream flows to the 20
performed in the conversion reactor. The conversion reac- E1 cooler. In the E1 cooler, the gaseous cooled just below its
tor normally used to support one particular reaction type. boiling point under 266.8 kPa pressure to make the X1
For sulfur recovery unit, a conversion reactor will only splitter feed to vapor and liquid. The objective of the item
function properly with conversion reactions attached. As splitter is to separate the sulfur ingredients from sour gas.
25 is presented in Figure 2 and data in Table 1, the main The pressure in the splitter is lower than the pressure 25
stream of acid gas (98 % H2S) goes to conversion reactor BurnVap stream which is 165.5 kPa, so when the feed inters
at 21 °C, 273 kPa and 105 kgmole/h. The acid gas flow the splitter, it starts to boil. With a component splitter, a
controls the temperature and the flow rate of burner material feed stream is separated into two component
stream, which receive the necessary amount of O2 and streams based on the parameters and split fractions that
30 N2 to burn the H2S as well as hydrocarbons in the con- come from the conversion reactor. The lighter components 30
version reactor. Majority of sulfur (95 % wt.) converted in the feed, rise on the splitter and goes to X1Vap stream.
and goes to the Burnliq stream by the absorption in an The remaining liquid which consists primarily of the hea-
amine based solvent of Methyl diethanolamine (MDEA) vier item in the feed moves down and goes the bottom
[17, 18]. The BurnVap stream still contains sulfur compo- stream (sulfur component only). The X1 item splitter sepa-
35 nents as H2S and SO2 which must be recovered. rates the sulfur (S) only at 0.159 kmole/h flow. Table 1 35
Components BURNAIR HS FEED BurnLiq BurnVap XVap XLiq ClausVap XLiq XVap ClausVap XLiq XVap
40 H S . . . . . . . . 40
O .
SO . . . . . . . .
HO . . . . . . . . .
S . . . .
N . . . . . . . . .
45 45
S . .
S . .
S . .
S . . .
S . . . .
S . . . .
50 50
S . . . .
4 W. Nabgan et al.: Simulation
.
.
.
.
.
.
,.
.
,.
Sulfur
1 1
nents which must be decrease to the standard value.
The X1Vap stream reaches equilibrium at constant pres-
XLiq
.
.
.
.
.
.
,.
.
,.
sure and temperature. In general, every system seeks to
5 achieve a minimum of free energy. Therefore a Gibbs reac- 5
.
.
.
.
,.
.
−,.
−.
−,,.
XVap
tor is used for X1Vap feed. The mixed of X1Vap stream
which contain mixtures of gaseous components (H2S, SO2,
H2O and N2) transported into the RGibbs reactor (CLAUS 1)
reactor with steam and the chemical equilibrium calcula-
.
.
.
.
,.
.
−,.
.
−,,.
ClausVap
10 tion was performed in RGibbs reactor by an equilibrium 10
approach based on the Gibbs free energy minimization
method. More than 96 % of water is separated and flow to
.
.
.
.
.
.
−,.
−.
.
Clausdum
Calus1dum stream. This water contains less than 4 wt%
H2S, SO2 and N2 components which go to sour water treat-
.
.
.
.
,.
.
−,.
.
−,,.
EOut
15 ment plant. The rest of gases which contain small sulfur 15
molecules (S5, S6, S7 and S8) go to the Claus 1Vap stream
and inter the second splitter (X2).
.
.
.
.
.
.
,.
.
,.
XLiq
As same as X1 splitter, in the X2 stripper the heavy
items which are S2 to S8 molecules separated and go to
20 the X2Liq stream and then feed to the mixer (MIX-100). The 20
.
.
.
.
,.
.
−,.
.
−,,.
rest of the ingredients (N2, H2O, H2S and SO2) feed to the XVap
.
.
,.
.
−,.
.
−,,.
ClausVap
.
.
.
.
−,.
−.
.
Clausdum
H2S, SO2, S6, S7, and S8 were mixed with the N2 and H2O.
Therefore the third stripper (X3) was employed to produce
XLiq
.
.
.
.
.
.
,.
.
,.
the small sulfur molecules. The X3Liq stream contains S2 to
30 S8 molecules go to the MIX-100 mixer and mix with X1Liq 30
and X2Liq streams.
.
.
.
.
,.
.
−,.
.
−,,.
XVap
.
.
.
.
,.
.
−,.
.
−,,.
35 35
Operating data of the sour gas treatment process for
sulfur recovery is reported in Table 2. The ideal equation
.
.
.
.
,.
.
−,.
.
−,,.
BurnVap
.
.
.
.
,.
.
,,.
BurnLiq
.
.
,.
.
−,.
.
−,,.
HSFEED
.
.
,.
.
−.
−.
−,.
BURNAIR
Molar entropy
Temperature
[kg/h]
Pressure
[kPa]
flow
Vapour
[C]
Molar
Mass
100 100 1. Ibrahim S, Gupta AK, Al Shoaibi A. Xylene and H2S destruction
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