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Energy Procedia 114 (2017) 6266 – 6271

13th International Conference on Greenhouse Gas Control Technologies, GHGT-13, 14-18

November 2016, Lausanne, Switzerland

CO2 Capture from Sulphur Recovery Unit Tail Gas by Shell Cansolv Technology

Farhang Abdollahia*; Ian GC Craigb; Mania Neisianic

a
Shell Cansolv, Montreal, Canada
b
Shell Cansolv, Montreal, Canada
c
Shell Cansolv, Montreal Canada

Abstract
A significant driver for the climate change effect is CO2 emission from the sources where fossil fuel is consumed to
generate energy. Capturing and sequestration of CO2 from these emission sources is a practical way to mitigate
GHG emission impact. However the cost of CCS projects has been a major obstacle to implementing these
technologies worldwide. Two main aspects which influence the cost of a CO 2 capture project are the CO2 utilization
pathway and the CO2 capture technology selection.
CO2-Enhanced Oil Recovery (EOR) can be a very good potential pathway to increase the revenue of the CCS
project. CO2-EOR also can be an attractive way of using CO 2 in areas such as Middle East where the oil and gas
reservoirs are mature. However one of the main constraints can be limited access to CO 2 especially where no power
plant is close to a potential oil reservoir.
For technology selection, the choice is typically between Pre- and Post-Combustion. Pre-combustion CO2 capture
technologies have been deployed in oil refineries & gas processing plants for decades, but the main source for CO2
emissions in these facilities is often off-gas (also known as acid gas) which is usually sent to the flare system or
incinerator. These off-gases are at low pressure, so a compression system is required to pressurize the gas before
sending it to the Pre-combustion CO2 capture unit. On the other hand, Post-combustion CO2 capture technology can
often require an additional desulfurization step to remove SO2 which can potentially result to higher operational and
capital cost as well as waste management and complexity of operation. This paper will discuss the deployment of

* Corresponding author. Tel.: +1-514-240-9406; fax: +1-514-382-5363

E-mail address: farhang.abdollahi@shell.com

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
doi:10.1016/j.egypro.2017.03.1765
 Farhang Abdollahi et al. / Energy Procedia 114 (2017) 6266 – 6271 6267

Shell Cansolv technology to capture CO2 from off-gas downstream of the Sulfur Recovery Unit (SRU) in a single
train, potentially as a new CCS application in the oil and gas sectors.
The off-gas from Tail Gas Treatment Unit (TGTU) downstream of the SRU will usually contain a higher amount of
CO2 compared to coal and gas power plants. The absorption affinity of Shell Cansolv solvent at low pressure off-gas
compared to other pre-combustion technologies allows the elimination of the primary compression system located
upstream of the CO2 capture unit. Since there is H2S slippage from the TGTU absorber overhead, the amine should
be characterized in terms of absorption affinity and stability in the reduced environment. The impact of H 2S on
amine performance in terms of degradation has been investigated in comparison to a post-combustion application
where H2S is incinerated and converted to SOx. SOx contaminates amine to form Heat Stable Salt (HSS), so it needs
to be removed prior to the post-combustion CO2 capture unit in a separate FGD unit (Flue Gas Desulfurization).
Shell Cansolv DC amine in pre-combustion lineup absorbs both H2S and CO2 in a single absorber so incinerator and
FGD unit is not required compared to post-combustion applications. Shell Cansolv DC amine has been tested to
remove up to 99% CO2 which is higher than the 90% typical capture rate for most post-combustion applications.
The other advantage of this application is the ability to operate at high temperature (~60 C). This is often a key
design parameter especially in the Middle East where most applications are considered hot climate applications. All
design parameters of the CO2 capture unit such as liquid per gas ratio (L/G), stripping factor at the regenerator side
and absorber packing height have been evaluated and optimized to reduce both capital and operational costs of the
project. Eventually, in a case study, an economic comparison was conducted and the result indicated potentially
more than 40% reduction in the cost of a CO 2 capture unit as well as same magnitude increase in Net Present Value
(NPV) compared to pre-combustion technology.

©Click
2017here and insert
The Authors. your abstract
Published text. Ltd. This is an open access article under the CC BY-NC-ND license
by Elsevier
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
© 2017 The Authors. Published by Elsevier Ltd.
Peer-review
Peer-review under responsibility
under of the
responsibility oforganizing committee
the organizing of GHGT-13.
committee of GHGT-13.

Keywords: CO2 Capture; TGTU off gas, Amine

1. Introduction

CANSOLV CO2 capture technology has traditionally been positioned as a post-combustion technology. For CO 2
capture, this has led to a reinforcing cycle of R&D and business development focused on power generation
applications, particularly coal-fired and combined cycle gas turbine (CCGT) applications. However, an emerging set
of projects in the Oil & Gas sector, such as CO2 capture from Tail Gas Treating Unit (TGTU) off gas downstream of
Sulphur Recovery Unit (SRU) for high-CO2 fields, indicate that the low operating pressure characteristics of
CANSOLV can lead to opportunities beyond power generation. CO2 injection for Enhanced Oil Recovery (EOR)
stands as the major utilization to monetize captured carbon in industrial scale at the moment. These projects are
emerging in the world especially in the Middle East, where they include CO 2-EOR as a pathway to improve the
economics of the CO2 capture project. However there are limited sources of CO 2 in these areas, in particular no
fossil-fuel-fired power generation near potential EOR reservoirs.
The proximity of the gas processing units as well as oil refineries to the reservoirs will justify capturing CO 2 from
these types of sources.

Pre-combustion CO2 capture technologies have been deployed in Oil & Gas applications, but the typical source for
CO2 emissions in these applications is off-gas (acid gas) which is usually sent to the flare system or incinerator.
These off-gases are at low pressure so a compression system is required to pressurize the gas before sending it to a
typical CO2 capture unit such activated Methyl diethanolamine (MDEA) technologies.

In order to apply activated MDEA, for this application a primary compressor is needed to pressurize the feed gas to
a certain pressure. At the evaluation stage, different absorption pressures have been evaluated at 2, 11, 22 and 44
bar; eventually 11 bara has been selected as optimal pressure to absorb CO 2 in the absorber. For comparison, a
parallel work has been conducted to evaluate the potential CANSOLV DC-103 advantage as a solvent with higher
absorption ability which can strongly absorb CO 2 at atmospheric pressures. The preliminary results implied that
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there would be a significant value proposition compared to activated MDEA or other pre-combustion applicable
solvents. CANSOLV DC-103 is stronger amine than activated MDEA allowing for deep CO 2 removal at low
pressure conditions. Figure 1 indicates process flow chart for both options:

Treated Gas

H2O/H2S
Treated Gas

Feed gas containing CO2/H2S at 10 bar

Amine (train 1)
CO2
Feed
SRU/TGTU Compressor CO2 Compressor Mol Sieve

Amine (train 2)

Treated Gas
H2O/H2S

Feed gas containing CO2/H2S at atmospheric

CO2

SRU/TGTU CANSOLV CO2 Compression Mol Sieve

Figure 1. Process flow chart for: top: activated MDEA , bottom: Shell Cansolv

2. Result and Discussion

CANSOLV DC-103 has been successfully deployed for CO2 capture from the post-combustion flue gas with
different design and operating window [1,2]. Now, the technology design window has been successfully extended
for new application lineup. The highlights for the extended design window are:

x higher capture rate of CO2 – up to 99% †(correlated to low partial pressure of CO2 at top of absorber);

x Presence of reduced sulphur species mainly H2S in feed gas and maybe other contaminants such as COS
and CS2;

x CO2 capture at a high inlet CO2 concentration;

x High operating temperature for absorber, feed gas and lean amine up to 60 ºC
 Farhang Abdollahi et al. / Energy Procedia 114 (2017) 6266 – 6271 6269

2.1. Reduced Species

For the new application, the feed gas from TGTU absorber is sent to CANSOLV unit before the incinerator.
Consequently, this feed gas contains H2S, H2 and depending on the upstream unit’s performance such as the SCOT
hydrogenation reactor or TGTU, maybe traces of other sulphur compounds such as COS and CS 2. If captured by the
solvent, COS will be hydrolyzed to H2S and CO2, and will be presence in CO2 product at negligible levels. CS2 has
low solubility with the amine and is expected to exit the unit through absorber in the treated gas to the incineration
unit. In conclusion, the impact of these contaminants on the capture system is negligible. Hydrogen (H2) is not
absorbed in CANSOLV DC-103 and exit the capture unit with treated gas from the absorber. The impact of H2S
would be studied from two points of view:

a. Absorption affinity of CANSOLV DC-103 for H2S

Depending on H2S concentration in the feed gas, H2S is absorbed due to the fact that it has similar pKa as CO 2 and a
better solubility in water than CO2. Therefore, similar absorption and desorption affinities are expected for H 2S and
CO2 in CANSOLV DC-103. For TGTU off gas a typical 200 ppm H 2S is expected which will be concentrated in the
CO2 product by up to 800-1000 ppm. In the applications where a purified CO2 stream is required, H2S removal by
Mol Sieve adsorption in dehydration stage could be considered.

b. Degradation of solvent in the presence of H2S

Two tests have been done with conditions summarized in Table 1. The objective of these tests is to determine
relative change in degradation rate of the DC-103 in presence and absence of H 2S. The baseline test was run for 408
hours and the test with H2S lasted 456 hours. Several samples were taken at different run hours.

Table 1. Degradation test conditions

Parameters Unit Base Case (No H2S containing

H2S) case
Total Pressure Bara 2.1 2.1
N2 Concentration %Vol 10 10
CO2 Concentration %Vol 90 90
H2S Concentration ppmV --- 1000
Temperature ◦C 120-121 120-121

Following analysis have been performed on each sample:

x PTR-MS analyses for measuring/ identification of degradation products with wide range of MW spectra
x Karl Fisher (KF) water titration for measuring the water concentration of the samples
x pH of all samples
x CO2 concentration samples by acid disclosure of CO2 with GC
x H2S concentration samples by AgNO3 titration
x Complexing power and Iron solubility test on end samples (measure of corrosiveness)
x LC-MS on start and end samples for degradation products
x IC analysis for organic acids and heat stable salts
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From both series of PTR-MS and LC-MS analyses it was proved that there is no significant decrease of the main
amine concentration. Also H2S presence in the gas does not have impact on the solvent degradation.
Based on analysis of the condensate traps it can be seen that no light degradation products were detected from PTR-
MS analysis which is aligned with the expectation from DC-103 and its molecular structure.

The following conclusion is achieved for other contaminants in the feed gas:

x COS: will hydrolyze in the water and convert to H2S and CO2, therefore same interaction with DC-103 will
apply to COS.
x CS2 is expected at very low levels in the feed gas and it is not captured by the DC-103 solvent so will leave
the absorber with the treated gas
x CO, N2 and Ar act as inert and will not react with DC-103.

2.2. High CO2 Capture Rate

In most of post-combustion applications 90% of CO2 has been evaluated as an optimum capture rate, while in this
evaluation where the main driver for the project is CO 2-EOR application, maximum capture rate (99%) has been
considered which the following issues need to be addressed:

x Sufficient packing height and optimal L/G to achieve 99% CO 2 capture and reasonable approach to
equilibrium;

x Adequate amine leanness to provide sufficient driving force at the top of the absorber where CO2 has
relatively low partial pressure;

2.3. Absorption Temperature and CO2 Concentration

CO2 concentration in the feed gas can be up to 25% Vol. Achieving 99% capture results in releasing significant
amount of heat of absorption in the absorber and consequently a high bulge temperature. Acceptable prediction of
the absorber temperature profile is critical to achieve 99% CO2 capture rate at hot climate conditions (~60 °) due to
the following reasons:

1. Accurate prediction of temperature bulge: as a results of 99% CO 2 capture and hot temperature conditions
(~60 °C), the temperature bulge is expected to be in 85-90 °C range
2. Accurate prediction of temperature bulge location: it is important to avoid having the temperature bulge at
very top sections of the column (polishing sections), to achieve high CO2 capture rate.
3. Intercooler location: in order to mitigate item 1 and 2 mentioned above, it is important to have an optimized
intercooler location.

Moreover, the solvent leanness, L/G and height of packing have been adjusted to compensate the impact of high
temperature on the process performance.
 Farhang Abdollahi et al. / Energy Procedia 114 (2017) 6266 – 6271 6271

3. Economic Evaluation

A case study has been conducted to evaluate economic and technical differentiators for capturing CO 2 from a typical
natural gas plant TGTU off gas downstream of SRU with a capacity of 240 tonnes of suldur per day. The results
confirmed both technical and economic benefits of CANSOLV DC-103 compared to the activated MDEA line up.
As shown in Figure 1, the primary compressor is eliminated resulting in simplified line-up, smaller plot space, ease
of operation and significant cost reduction. Moreover, due to high volumetric flow rate for a typical natural gas plant
and the limitation of the size of the absorber (high pressure vessels), two trains were considered for activated
MDEA, whereas the atmospheric absorption in CANSOLV DC-103 enabled the capture unit to be offered as a
single train.
Preliminary estimates indicate a net CAPEX reduction potentially more than 40% for CANSOLV, this can be
predicted for any other competitor solvent for high pressure applications. Table 3 shows the CAPEX comparison in
Total Installed Cost (TIC) between CANSOLV DC-103 and activated MDEA line-ups in mentioned case study. The
evaluation has been done based on preliminary cost estimation carried out with the Shell internal cost estimation
tool (CCET):

Table 3: Relative CAPEX and OPEX comparison for activated MDEA and CANSOLV DC-103

Activated
Solvent MDEA
CANSOLV DC-103

CO2 Recovery 99% 99%

Relative CAPEX 100% 58%
Relative OPEX 100% 62%
Relative $/ ton CO2 100% 59%

4. Conclusion

CANSOLV DC-103 has been tested to capture CO2 from TGTU off gas and showed very promising cost reduction
as well as simplicity in the lineup compared to other conventional pre-combustion amine such as activated MDEA.
This is a cost effective CCS technology for this type of feed gas or other source of CO2 with similar characteristics
as TGTU off gas, especially for locations where midstream O&G installations are the only source of CO 2 for EOR
application. Also it would significantly increase the NPV of the project by reducing $ per ton of CO2 to 41% of
activated MDEA. That being said, all CCS applications are very case-specific and depends on many other factors
such as products requirements, environmental constrain, project scale, etc. Therefore, the precise economical
suitability needs to be confirmed on a case-by-case basis.

Acknowledgements

The authors would like to acknowledge Shell Gas Processing and other colleagues for their continuing support.

References

[1] Stéphenne K. Start-Up of World’s First Commercial Post-Combustion Coal Fired CCS Project: Contribution of Shell Cansolv to SaskPower
Boundary Dam ICCS Project. Energy Procedia (2013)
[2] Singh A, Stéphenne K.. Shell Cansolv CO2 capture technology: Achievement from First Commercial Plant. Energy Procedia 63:1678-1685 .