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IPA16-151-E

PROCEEDINGS, INDONESIAN PETROLEUM ASSOCIATION


Fortieth Annual Convention & Exhibition, May 2016

PERFORMANCE EVALUATION OF H2S ADSORBENT IN SINGA FIELD: CASE STUDY OF


ADSORBENT PIMIT-B1

Moh. Nurdin Ardianto*


Heru Wijaya Pamungkas*
Subagjo**

ABSTRACT INTRODUCTION

Medco E&P Lematang (MEPL) attempts to optimize Medco E&P Lematang (MEPL) operates Singa
operation performance and chemical expenses by Central Processing Plant (CPP) in Singa Field,
sourcing alternative H2S Adsorbent. PIMIT-B1 is Lematang block. CPP is located about 230 km
high local content H2S licensed under ITB & PIM southwest of Palembang, South Sumatra (Figure 1).
adsorbent. It is a new iron oxide based solid Singa CPP has sour gas treatment facility, configured
adsorbent for H2S removal. PIMIT-B1 was initially in two parallel acid gas removal systems. The acid
produced for the purpose of removal of H2S from gas removal consists of Amine Unit with Methyl Di-
natural gas feedstock in Ammonia Plants. Later, Ethanol Amine (MDEA) solvent and Membrane
PIMIT-B1 was proposed to be applied in oil and gas Unit.
upstream industries.
Two gas wells with High Temperature & High
This paper presents the results of performance Pressure (HTHP) characteristic were produced as
evaluation of PIMIT-B1 in its use as H2S Scavenger feed for CPP and to be processed into sales gas.
adsorbent in Singa Central Processing Plant (CPP). Singa CPP commenced production in April 2010,
PIMIT-B1 was placed in a tower that allows residue with 40 BBTUD sales gas delivered to gas buyer.
gas containing H2S from membrane unit to flow
SINGA CPP OVERVIEW
downward from the top section of the tower to its
bottom section. For evaluation its performance, the Acid gas removal unit in Singa CPP consists of two
sample gas was taken to measure H2S concentration systems, Amine unit and Membrane unit, were
in three sampling points along the tower, as well as designed to anticipate 38 percent mole CO2 and 350
inlet residue gas was taken on daily basis. These data ppm H2S in raw gas. To produce the sales gas with
are then processed to show the trends in which the specification of 4%vol CO2 and 4 ppmv H2S,
H2S from residue gas are being adsorbed. These Membrane unit will separate hydrocarbon gas from
trends will show the breakthrough point, shape of acid gas (CO2 & H2S) and moisture content.
breakthrough curve, and sulfur loading at any given Membrane output flow (residue gas) is not capable to
time that are used to evaluate the performance of achieve 4 ppm H2S due to design restriction (acid
PIMIT-B1. permeation). Thus, H2S Scavenger unit (2x50%)
containing adsorbent solid bed was installed
From the data gathered until day 180 of adsorbent downstream of Membrane unit to purify the gas
usage, with average flow of feed natural gas and stream from H2S.
average concentration of H2S 9.01MMscfd and
60.19ppmv respectively, the calculated breakthrough According to block diagram in Figure 3, the raw gas
point of the bottom of the adsorbent bed is at the day flows to CPP trough dedicated flowlines and collects
77. Prediction of the time when the bed becomes in one manifold. The process begins with a series of
saturated based on the trends is day 266-269 and steps to separate produced water (PW) from the raw
sulfur loading at the time is approximately 0.25. It gas while lowering its temperature. The PW is then
was concluded that PIMIT-B1 can be implemented flowed to H2S Stripper to remove H2S content and
for further operation and be more economical in further processing in Produced Water Treatment
Singa CPP. (PWT).

* Medco E&P Indonesia


** Institute of Technology Bandung
Once passed through the gas filter, sour gas is then Government of Indonesia by Permen ESDM No. 15
processed further in the AGRU, which consists of / 2013.
Amine System and Membrane System. A major
quantity of gas is processed in Amine Unit while the OBJECTIVE
remaining is processed in the Membrane Unit. These
processes produce sweet gas and residue gas at a A field trial was conducted in full scale basis with 15
lower CO2 and H2S content. Moisture content in the tons PIMIT-B1 adsorbent in one vessel, with
sweet gas from Amine system is removed in the minimum 180 days trial operation to conclude the
dehydration system, meanwhile the residue gas from performance. The objective of this study is to publish
Membrane system which contains H2S to be purified the performance data of PIMIT-B1, including
in H2S Scavenger Unit process data (pressure drop, H2S content etc), sulfur
removed per adsorbent weight (lbs/lbs) and
Membrane Unit which depends on physical breakthrough time (days). Thus the field trial result
permeation separates hydrocarbon from acid gas and to be compared with adsorbent design data
moisture content in the feed gas to produce residue
gas. As per design, membrane output is 18 ppmv HYDROGEN SULPHIDE REMOVAL
where will not achieve H2S as per sales gas SYSTEM
specification (4 ppmv). Therefore, a H2S Scavenger
unit 2 x 50% containing H2S adsorbent solid bed was H2S Scavengers are used to remove small quantities
installed at downstream Membrane Unit (Figure 2). of sulfur compound. It has relatively high operating
This unit is designed to remove H2S in residue gas up cost per weight of sulfur removed and is suitable for
to 4 ppm. treatment of low H2S. H2S Scavenger processes are
typically batch operations. The reactive material is
As the feed gas passes through the membrane tubes, brought into contact with sour gas stream until the
the gas is separated into a high-pressure methane- sweet gas sales requirements can no longer be met.
rich gas (residue), and a low pressure gas stream Then reactive material must be replaced and
concentrated in carbon dioxide (permeate). Because removed as waste and disposed of in an
H2S content at residue gas outlet of membrane unit environmentally acceptable procedure.
was still too high, two parallel of H2S Scavengers
were installed to reduce H2S content. Numerous commercial scavenger units are available
on the market. They can generally be categorized
BACKGROUND into two different groups as follows:
The consumption of chemical H2S adsorbent used in
Dry Sorption Processes
Singa CPP is up to 60 metric ton per year. This was
significant for operations costs. During initial
The reactants in this process are solid without free
operation, MEPL attempted to optimize the
water and thus are called dry. Some of the
requirements for chemical consumption and to obtain
compounds may require a hydrate form of the basic
more efficient chemicals for gas processing.
reactant in order to precipitate in the treating
reaction. In addition there must be some water
MEPL attempted to optimize operation performance
available either with gas feed or moisture on the dry
and chemical expenses by sourcing alternative H2S
solid to initiate the reaction. Once started, the
Adsorbent. Institut Teknologi Bandung (ITB)
reaction will produce of mole of water with each
promoted PIMIT-B1, a new iron-oxide based H2S
mole of H2S removed. Several processes in the dry
adsorbent, jointly researched and produced with PT
sorption are classified based on metal type such as
Pupuk Iskandar Muda (PIM) Aceh. PIMIT-B1
Iron Oxide base, Zinc Oxide base and Alkaline base.
adsorbent is high local content and licensed under
ITB & PIM. PIMIT received its patent from
Direktorat Jenderal HKI RI in 2009. Liquid Absorption Processes

After several technical discussions and considering The reactants in this process are liquid in form of
plant availability and configuration, MEPL decided either aqueous or slurry. Gas-Liquid Contactors are
to conduct the field trial in full scale basis to observe used to increase contact surface and maximize gas
the PIMIT-B1 adsorbent performance. This activity contact time (Wang, 2011). Several process
also will promote the utilization of material with high technologies are available and classified as slurry
local content (TKDN) where regulated by process, zinc oxide slurry, oxidizing solution, etc.
Table 1 lists the process technology available for H2S ρb = bulk mass-density of adsorbent, kg/m3
Scavenger.
CONFIGURATION OF H2S SCAVENGER
Considering the amount of H2S present in residue gas
is less than 1% v/v, MEPL chose dry sorption process H2S Scavenger Unit installed in Singa CPP has two
using solid scavenger. parallel vertical vessels 35-MBA-187 A/B size 1525
mm OD x 8895 mm S/S. It was designed for 1315
MONITORING OF H2S REMOVAL psig at 150F and capable of handling 25 MMscfd
PERFORMANCE residue gas arising from gas-gas exchanger. It has
bed height of 8.050 m.
Wang (2008) explained the breakthrough curve
which gives an indication of an adsorbate (H2S) is The H2S Scavenger vessel was designed with criteria
distributed within a fixed bed when a gaseous stream max H2S concentration at outlet flow 4 ppm,
containing a percentage of the adsorbate passes allowable pressure drop max 2 psi, dry gas moisture
through a fixed until the adsorbate emerges in the content and 0.2 lb/lb adsorbent sulfur loading.
exit stream. Figure 4 shows a typical breakthrough
curve and Figure 5 shows the concentration of There are three nozzles spread evenly above all the
adsorbate in the gas phase at any given point packing with the distance between the nozzle and the
(location) in the bed as a function of time. top and base of packing more than 2 m. The top
nozzle is Nozzle 9, as far as 2.001 m from the top of
The adsorbent quickly becomes saturated at the inlet the packing, followed by Nozzle 10 as far as 2.099 m
of the bed and the adsorbate concentration falls off below it, and the Nozzle 11 as far as 2.000 m from
rapidly along the bed forming a concentration profile the Nozzle 10 and 1.950m from the bottom of the
along the bed which is called the transition zone. packing adsorbent.

In Figure 5, t1 shows the initial formation of the Residue gas enters at the top section of the vessel via
concentration profile, t2 shows one at some a pipe distributor and flows downwards through
intermediate time, and tb shows another just before distributor plate and top section ceramic ball,
breakthrough. The point at which the adsorbate H2S adsorbent bed, bottom section ceramic ball then
is first detected at the exit stream. After exiting from bottom of vessel. As the residue gas
breakthrough, the adsorbate concentration in the passes down the adsorbent bed.
effluent stream rises steeply up to the value of the
inlet concentration during the time interval between ADSORBENT PIMIT-B1
tb and tc as shown in Figure 4.
PIMIT is used for absorption to remove the sulfur
Break through time is the time where the break (H2S) contained in natural gas and other gaseous
through point occurs. While sulfur loading is the hydrocarbons. PIMIT has operating temperature in
amount of sulfur sequestered by the adsorbent at a range 20-60°C. This product has been licensed under
certain time. Equation (3) is modified equation for ITB & PIM, Patent Certificate No. P00200200732
calculating sulfur loading by Wang (2008) on the from Direktorat Jenderal HKI RI.
breakthrough time.
Based on local content calculation, the local content
, of this adsorbent is up to 40 percent. Therefore,
PIMIT-B1 has the highest local content of H2S
(1) Adsorbent ever used in MEPL. PIMIT-B1 also has
been used in PT Pertagas Sumbagut for trial H2S
Where adsorption (5 ton) and delivered the expected result.

VH2S = feed molar velocity, kmol/h PIMIT-B1 is an ironoxide based H2S Scavenger to
tb = breakthrough time, h react with adsorbed H2S. The reaction of sulfur
CA,in = H2S Concentration, ppmv removal using iron oxide adsorption (Wang, 2008)
MWs = Weight Molecule of Sulfur = 34 kg/kmol is:
Wfb = bed weight, kg = A x Z x ρb
A = adsorbent-bed surface area, m2 H2S (g) + Fe2O3  Fe2S3(s) + H2O (l)
Z = height of adsorbent-bed, m ∆H = -22 kJ (25 °C and 1 atm)
The reaction is exothermic, which means the C0= H2S inlet (scfd)
adsorption of H2S may increase the temperature of Cn= H2S at nozzle n (scfd), n= 9, 10, 11
internal vessel and require special attention. The
reaction is best performed at room temperature. From the data that has been collected, break through
Therefore, the gas temperature should be monitored time to point at Nozzle 9, 10, and 11 can be seen
and maintained to prevent overheating. clearly. To estimate the break through time on the
basis of packing we used approach through piles of
PIMIT-B1 is produced in pellet shape with dark red sulfur loading PIMIT. From the break through time
color, detail specifications are listed in Table 2. and the break through curve tendency to reach a point
where no further adsorption can occur, the lifetime
TRIAL AND EVALUATION METHOD of the adsorbent PIMIT can be estimated. Further, the
calculated lifetime and sulfur loading were compared
To perform the field trial in full scale, the operating with PIMIT-B1 specification.
procedure for catalyst change out has been developed
to ensure the adsorbent was safely loaded into the TRIAL RESULT AND EVALUATION
vessel. The new adsorbent PIMIT-B1 with weight
H2S Concentration
32,000 lbs is loaded into the vessel H2S Scavenger,
which includes the ceramic balls and support
The Figure 8 chart represents daily residue gas
equipment. After removing the oxygen in the vessel,
flowrate from gas/gas exchanger to H2S Scavenger
the gas is introduced from the outlet of Membrane
Vessel and residue gas flowrate which was bypassed.
into the inlet H2S scavenger vessel.
During this observation period (12 Des 2013 – 12
Oct 2014), average residue gas flowrate entering H2S
To evaluate its performance, H2S concentration was
Scavenger is 9.01 MMscfd.
sampled on daily basis at three points along the tower
as well as inlet residue gas. These data are then It is noted that residue gas flowrate to H2S Scavenger
processed to show the trends in which the H2S from tended to decrease over time, since CO2 content of
residue gas are being adsorbed. The trends will residue gas from Membrane tended to increase over
shows the breakthrough point, shape of breakthrough time. Therefore residue gas must be decreased in
curve, and sulfur loading at any given time that are flowrate prior to mixing with sweet gas from amine
used to evaluate the performance of PIMIT-B. The unit, so that the mixed gas meets sales gas
other data such as inlet gas flowrate, bypass flowrate specification. Refer to the profile of H2S content
and the vessel pressure drop to be recorded and Figure 8, residue gas for 180 days observation
monitored closely. contains 60.19 ppmv H2S average.

H2S Scavenger performance data have been The Figure 9 chart represents the H2S concentration
collected. It represents various operating conditions (Ca) in Nozzle 9, 10 and 11 at H2S Scavenger Vessel.
of H2S Scavenger from December 2013 till October The H2S concentration at these nozzle tended to
2014. The processed data were taken daily from the increase due to adsorbent saturation.
first day usage up to 180 days using H2S detector.
Breakthrough Curve
Data from the initial concentration of H2S in natural
Figure 10 represents the comparison of H2S content
gas into the vessel and daily H2S concentration data
at the outlet and the inlet during the trial days.
were observed at each position of the nozzle,
According to the chart at Figure 10, in the early days
calculated percent H2S adsorbed and the ratio
of usage PIMIT adsorbent, the gas passing through
between the concentrations of H2S in a certain
the Nozzle 9, 10 and 11 have been completely
position with the inclusion concentration. Both data
cleaned and no longer contain H2S. On the 23th day
sets are presented in graphical form to illustrate the
break through times of the Nozzle 9 and 10 began to
trend of decrease in the amount of H2S that can be
register slight H2S. As it passes through the gas is
adsorbed by the adsorbent PIMIT.
cleaned in the packing that exists between the Nozzle
10 and 11. On the 41st day, a breakthrough time
The equation to calculate percentage H2S adsorbed is
occurred for Nozzle 11.
as follows:

% 100% (2) From the graph it can be seen that the break through
curve formed at Nozzle 10 and 11 show similarities,
Where: but deviation occurs at breakthrough curve formed
by Nozzle 9. Based on this deviation, the data on the  The breakthrough curve with comparison of H2S
position of the Nozzle 9 will no longer be used for content predicted 58 days breakthrough time at
the next observation. Correlations for position of bottom vessel.
Nozzle 10 and 11 were obtained with a value of R
0.7625 and 0.787 respectively. Correlation for the  The lifetime of adsorbent PIMIT-B1 in H2S
position of Nozzle 11 was selected to determine a Scavenger vessel in Singa CPP with flowrate and
time when the H2S inlet rate equaled the H2S outlet, concentration of H2S in the first 6 months of use
which means that at that time, adsorbent packing is 302-305 days.
above Nozzle 11 is no longer able to adsorb H2S.
 Sulfur loading PIMIT in H2S Scavenger
Correlation of Nozzle 11 gives R value that is closer
adsorbent vessel Singa CPP at complete
to1and apposition that is closer to the bottom of the
saturation point is 0.25 gram H2S/gram
packing. Smaller interval data provides a better
adsorbent
alignment with what is happening on the basis of
packing. According to this correlation, adsorbent has
no longer time to adsorb H2S at day 269, or 228 days Based on the conclusions, MEPL should continue the
from breakthrough time until complete saturation collection of data for monitoring and comparing with
point. other adsorbents. Meanwhile, the operator should
monitor the H2S content at outlet vessel closely after
Table 3 summarizes the breakthrough time and the passing the breakthrough time at bottom vessel.
calculated sulfur loading based on the position of PIMIT-B1 also can be used for further operations for
sampling point. Equation (1) is used to calculate the H2S removal system in Singa CPP.
sulfur loading.
At the position of Nozzle 11, the sulfur loading is REFERENCES
0.18grams/gram of adsorbent. By assuming that in
the event of a breakthrough at the bottom of the Lili Dj., Subagjo, Susanto T.P., Edy H.P., 2012,
packing, distribution H2S adsorbed is same with a Adsorben Sulfur PIMIT-B1 Sebuah Pengembangan
breakthrough on the position of the Nozzle 11, the Produk Hasil Kerjasama antara Industri dan
sulfur loading that occurs also can be assumed to Perguruan Tinggi, Seminar Nasional Teknik Kimia
have a value equal or close. The break through time Soebardjo Brotohardjono IX, page C.5-1 – C.5-4
for the bottom of the packing is on the 77th day. So
that the life time of the adsorbent packing PIMIT Subagjo, 2015, Restorasi Semangat Membuat Baju
obtained is 302-305 days or approximately 10.1 dari Batu: Peranan ITB dalam Pembuatan Katalis
months. Nasional, Pidato Ilmiah pada Peringatan Dies
Sulfur loading calculated at the time of complete Nataliske 56, Institut Teknologi Bandung, page 5-8
saturation is reached at 0.25 gram H2S/gram – 5-12
adsorbent. Sulfur loading slightly exceeds the ability
of sulfur loading of 0.24 gram H2S/gram adsorbent Wang, H., Wang D.M., and Chuang K.T., 2011, A
provided by the manufacturer due to the different Sulfur Removal and Disposal Process through H2S
residue gas flow rate used. With smaller gas flow, Adsorption and Regeneration: Breakthrough
ability of adsorbent to adsorb H2S could rise further Behavior Investigation, Process Safety and
as the contact time increases and provide more Environment Protection
opportunities for equilibrium between the adsorbate
in the gas and in the adsorbent. Wang D.M, 2008, Breakthrough Behavior of H2S
CONCLUSION AND RECOMMENDATION Removal with an Iron Oxide Based CG-4 Adsorbent
in a Fixed-Bed Reactor, Department of Chemical
Based on full scale field trial, it can be concluded: Engineering University of Saskatchewan
TABLE 1

H2S SCAVENGER PROCESS TECHNOLOGY

Iron Sponge Process


Iron Oxide Basis Process
Sulfa Treat Process

Sorption
Zinc Oxide Basis Process ICI Low Temp Zinc Process
Dry
Alkaline Solid Softnolime RG Process
H2S Scavenging Process Technology

Slurry Process Iron Oxide Process


Zinc Oxide Slurry ChemSweet ; Slurry Process
Permanganate / Dichromate
Oxidizing Solution
Processes
Oxidizing Chlorine Based
Liquid Absorption

Diklor Processes
Solution
Sulfa Check Processes
Oxidizing Nitric Solution
Hondo HS-100 Process
Aldehyde Based Processed
Polyamine Based Process Sulfa Srub
Sulfa Guard
Alkylamine Gas Treat 114 Process
Process Sulfa Check
Caustic Scrubbing NaSH Process

TABLE 2

SPECIFICATION OF PIMIT-B1 ADSORBENT

Specification Unit Description


Color - Dark red
Size mm 5x8
Shape - Pellets
pH - 8–9
Fe2O3 (dry basis) % 78,08
Moisture % 3 -4
Crushing Strength Kgf 4-9
Bulk Density Kg/l 0.90 – 1.051
Surface Area m2/gr 83 - 101
Absorption Capacity Kg/kg 0.24

TABLE 3

BREAKTHROUGH TIME AND SULFUR LOADING

Position Breakthrough Time Sulfur Loading


Nozzle 10 24 days 0.10
Nozzle 11 41 days 0.18
Bottom of Vessel 58 days 0.25
Figure 1 – Location of Singa CPP in Lematang Block

Figure 2 - Membrane unit in Singa CPP


Figure 3 - Block diagram of Singa CPP

Figure 4 - Breakthrough curve from the breakthrough point, tb, to the complete saturation point, tc.

Figure 5 - Development and progression of a transition zone along the bed: transition zones at different time
t1, t2 and breakthrough time tb
Figure 6 - H2S Scavenger vessel 35-MBA-187 A/B

Figure 7 – PIMIT-B1 in pellet shape


Figure 8 - Gas flow rate and H2S concentration in inlet of H2S scavenger vessel during PIMIT trial

Figure 9 - H2S concentration in nozzle 9, 10 and 11 of H2S scavenger vessel during PIMIT trial
Figure 10 - Breakthrough curve comparison from each nozzle