IPTC-19783-MS

Hybrid System – An Emerging Solution to Sour Gas Treatment

Siddharth Parekh, Schlumberger

Copyright 2020, International Petroleum Technology Conference

This paper was prepared for presentation at the International Petroleum Technology Conference held in Dhahran, Saudi Arabia, 13 – 15 January 2020.

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Abstract
Shifting project economics into positive territory is a challenge for every project, but especially so for sour
to ultra-sour, unconventional, and remote natural gas reserves. The application of conventional technologies
incurs significant capital investment and operating expenses, and complexities of operations can make
projects economically inviable during the FEED stage. To improve the economics and potential of these
projects, shifting our approach to more innovative solutions is essential.
There are multiple methods to treat natural gas containing high amounts of acid gases. These can be
broadly categorized as absorption (chemical and physical solvents), adsorption, membranes, and cryogenic
distillation.
The traditional acid gas treatment approach utilizes amine solvent-based systems to meet desired acid
gas (CO2 and H2S) content in the treated gas. More than three decades ago, an alternative treatment method
using a membranes system became viable. Since then, membrane systems have become the preferred choice
for bulk acid gas removal. Combining membrane and amine solvent-based technologies and optimizing the
integrated system offers an economically attractive alternative for acid gas treatment. The combination of
acid gas removal technologies is termed hybrid acid gas treatment.
This paper will demonstrate a more cost-effective approach by using the combination of acid gas removal
membrane systems and conventional solvent-based technologies. With this combination, membrane systems
perform bulk separation of acid gases and reduce the acid gas load in the feed stream entering the amine
system. An amine system will further remove acid gas to meet the final product specifications.
A case study of the deployment of the hybrid system for an enhanced oil recovery project will be covered.
The comparative techno-commercial analysis for the hybrid and the amine solvent-based system will be
explained using an example for an acid gas treatment plant. Along with the salient features and configuration
of membrane systems, the advantages and disadvantages of membrane and amine solvent-based systems
will be presented to evaluate the hybrid system design.
Gas processors have adopted Industry 4.0 technologies such as devices using an industrial internet
of things (IIoT) and edge and cloud computing, improving the economics of the hybrid system. These
technologies enable near real-time computational analysis and insights derived from operational data, which
feeds into dynamic process simulators. Total network capacity – as limited by membrane throughput and
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bounded by the defined KPIs – is dynamically evaluated, allowing for adjustments in process design
configuration based on any change in operating parameters and required outlet KPIs like higher natural
gas liquid (NGL) recovery higher purity treated gas and higher acid gas recovery. The digital tools provide
insights to drive optimization of regular income from operations while protecting the integrity of the process.
In summary, the hybrid system has substantial economic advantages compared to the conventional amine
solvent-based approach alone. The system – if optimally designed, engineered, and operated – can leverage
the benefits of both technologies while minimizing their limitations. Advancements in complementary
digital solutions allow for subject matter expert insights and lessons learned from years of design and
operational experience to be seamlessly integrated into operations to ensure integrity, reliability, and
coherence of the process to new deployments.

Introduction
In order to meet the growing global demand of energy, in recent years, development of unconventional and
sour gas fields have become a sharper focus than ever before. As per EIA, 40% of the world reserves are
acid and sour gases, and the overall profile in Fig. 1 shows reserves with high acid gases – carbon dioxide
(CO2) and hydrogen sulfide (H2S).

Figure 1—Global Acid Gas Profile3

These reserves show significant fields yet to be produced, which have much higher concentrations of
CO2 and H2S. Most CO2-rich fields are in South America (Brazil), Far East Asia, Europe, Africa and USA.
H2S-rich fields are in the Middle East, Russia, Kazakhstan, and Europe. Cost-effective monetization of
such fields presents substantial economic challenges because of several factors such as higher production
of sulfur, which has poor demand in the global market due to its abundant supply, and overall life cycle cost
may not justify the revenue generated from product streams.
Removal of acid gases using conventional technologies often will not result in optimal and cost-effective
solutions to justify the investment. To improve the economics and potential of acid gas treatment projects,
we must shift our approach to more innovative solutions. A combination of acid removal technologies and
optimizing them as a combined system offers the most effective alternative to conventional technologies.
The combination of acid gas removal technologies is termed as hybrid acid gas treatment.
IPTC-19783-MS 3

Schlumberger supplies acid gas removal technologies for different onshore and offshore applications.
In addition to the provision of acid gas processing technologies, Schlumberger designed, engineered,
constructed, and now operates several acid gas treatment plants (one of which will be discussed under case
study) with a total capacity exceeding 1500 MMscf/d, which involves gas sweetening, enriching CO2 for
enhanced oil recovery, and production of NGL.
This paper will describe the different methods for acid gas removal with a focus on membrane and
solvent-based systems, explain the hybrid system using the case study, and discuss the example with techno-
commercial analysis, which signifies the features of the hybrid system. A later part of the paper will discuss
the suitable applications of hybrid systems.

Acid Gas Removal Technology Selection

Acid gas treatment can be achieved by different technologies, which can be broadly categorized by
absorption (chemical and physical solvents), adsorption, membranes, and cryogenic distillation. For
preliminary evaluation and high-level screening for selection of appropriate acid gas removal method, Fig.
2 can be used as a guide. For treatment of high acidic gases and large gas volumes, membrane and amine
system combination is the typical choice of technology.

Figure 2—Guide for selecting Acid Gas Removal method1

Due to economic uncertainty related to a wide range of unconventional natural gas reserves and recent
technological advancements on various technologies, generally, the selection made based on this graph
requires detailed analysis to ensure the selected technologies is indeed the best option.
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Membrane System
Membrane systems are differentiated by A. membrane materials (glassy and rubbery polymeric material), B.
membrane configuration (hollow fiber and flat sheet or spiral wound), C. membrane housing configuration
(horizontal and vertical).
Among several types of membrane polymers cellulose triacetate (CTA), or cellulose acetate (CA)-based
glassy polymers have proven to be the most effective for acid gas (CO2, H2S) removal. These membranes
operate on the principle of selective permeation and are optimized for acid gas (CO2 and H2S) service.
Schlumberger has successfully deployed CTA-based material in acid gas applications since the 1980s, and
it has proven to offer a long operational lifetime.

Membrane Separation Mechanism

The membrane fibers are constructed from a polymeric material that molecularly interacts with the gas
components to transport them through the membrane wall. When a pressure differential is applied, the
molecules diffuse into the pores of fibers and permeation occurs across the membrane. Refer to Fig. 3 for
the relative permeation rate for different components through CTA-based membranes. Components with the
higher permeation rates (i.e. CO2, H2S, H2) will permeate faster through the membrane than the components
with lower permeation rates (N2, and hydrocarbons). The rates that a component dissolves into the membrane
and diffuses through the membrane determine the efficiency of the separation.

Figure 3—Relative Permeation Rate thru Membrane

Inside the CTA-based hollow fiber membrane element depicted in Fig. 4, CO2 and H2S molecules along
with the light components such as hydrogen and helium permeate through the wall of the fiber to form a
low-pressure permeate gas stream. The hydrocarbon-rich molecules pass around the wall of the membrane
with minimal pressure drop to form the high pressure "non-permeate" or product gas stream.

Figure 4—Hollow Fiber Separation Mechanism

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The pressure difference between the feed gas (higher pressure) and the permeate (low pressure) provides
the driving force for the membrane separation. Therefore, the pressure difference between the feed gas and
the permeate gas, as well as the concentration of the permeating component, determines the product purity
and the amount of membrane surface area required.

Membrane Housing and Flow Configuration

Membrane elements are constructed of thousands of individual asymmetric, hollow membrane fibers that
selectively separate gases. Hollow fibers offer much greater surface area than spiral wound membranes for
the same equipment footprint. Pressurized feed gas flows into the membrane housing shown in Fig. 5, where
it is introduced to the membrane element. The gas flows radially across the fiber bundle while the fast gases
permeate the membrane to the bore side of the fiber and are collected at both tube sheet ends at low pressure.
The permeate exits at both ends of the membrane element, which produces a short flow path and reduces
permeate pressure drop. The non-permeate gas flows across the fiber bundle into the perforated core and
leaves the membrane with minimal pressure drop.

Figure 5—Membrane casing and housing arrangement and flow configuration

NGL Recovery and Hydrocarbon Liquid Using Membrane

CTA-based membrane systems are fairly resistant to intermediate hydrocarbons, making them a worthy
choice for hydrocarbon-rich gas streams. Unique vertical membrane housings enable hydrocarbon-rich
condensate to form on the exterior of the membrane fibers and to drain into a liquid recovery line. CTA
polymer material and membrane packaging allow condensing hydrocarbons on its surface while removing
acid gas. In many applications, hydrocarbons are condensed on the membranes, providing a valuable liquid
hydrocarbon product.
The pressure drop from the feed gas side to the low pressure permeate side of the membrane fiber causes
Joule-Thomson cooling of the permeate gas. Due to the heat transfer between the permeate and the non-
permeate gas, non-permeate gas cools, and the heavier hydrocarbons in the non-permeate are condensed.
Additionally, as the CO2 and some lighter components permeate, the dew point of the remaining non-
permeate stream changes, causing further condensation.
As CTA based membranes allow condensing hydrocarbons and are not damaged by liquid hydrocarbons,
it is not necessary to superheat the gas to prevent condensation or add nitrogen purge gas during membrane
depressurization.
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Membrane Design Scheme

Membrane systems can be configured in a single-stage or a two-stage system (Fig.6). Hydrocarbon losses
can be significantly reduced by using a two-stage system. Two-stage systems will require an additional
recycle compression system.

Figure 6—Membrane System Flow Diagram

Amine System
The most common acid gas treatment process is gas absorption using amines. As shown in Fig. 7, the acid
gas is contacted by aqueous alkanolamines counter-currently in the absorber and removed from the gas
based on its solubility. Sometimes, a physical solvent or additive is blended to enhance the performance
of the amine in special situations to increase the solubility of acid gas or treat the gas containing RSH
(mercaptans). The treated gas leaves from the top of the tower, and the rich solvent leaving the tower bottom
is sent for regeneration. The regeneration is achieved by the application of heat and a reduction in pressure
in the regenerator. Lean solvent returns to the absorber and acid gas is sent for further treatment.

Figure 7—Typical Chemical Solvent-Based Amine System Flow Diagram2

IPTC-19783-MS 7

Membrane system advantages over amine system

• Smaller footprint and lower weight: This feature is especially valuable for offshore installation.

• Lower life cycle cost: Typically applicable for more than 15% acid gas in the feed.

• Operating cost (OPEX): Lower for a single-stage and moderate to high for a two-stage membrane
system.
• Unmanned operation (for single stage membrane system): Suitable for a remote location, as no
moving parts are involved.
• Total installed cost: Low CAPEX for high content of acid gas (more than 15%).

• Flexibility in design: higher turndown capability by adjusting the membrane element counts.

• No foaming or corrosion issues

• Permeate gas as a fuel: Depending upon utility system design, selection, and emission
requirements, permeate can be used as a fuel and is typically applicable for less than 15% acid
gas in the feed.
• Permeate gas injection: Permeate gas (with a high amount of CO2) can be reinjected back into the
field for EOR or carbon capture.

Amine System Advantages Over Membrane System

• Lower hydrocarbon loss: This would be a significant factor if the acid gas content in the feed is
8%-10% or less and deep removal is required (<2% CO2 in the treated gas).
• Remove CO2 and/or H2S to PPM levels: This is very crucial for many applications like CO2
spec of 50 ppm in LNG and cryogenics applications. H2S of 4 ppm or less meet typical pipeline
specifications for most markets.
• Selective removal: A wide range of solvent options are available depending upon the acid gas
removal need.

Hybrid System
Hybrid system (Fig.8) consists of the membrane system followed by the amine system. The membrane
system acts as a bulk acid gas removal step and reduces the feed acid gas concentration entering amine
system, which treats the gas to meet the final product specifications. The selection of this system is
dependent upon the optimization of the combined technologies and required outlet specifications. The
hybrid system will be discussed further in the case study.

Figure 8—Hybrid System

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Case Study – Gas Plant in West Texas, USA

The CTA hollow fiber membrane technology was first applied commercially for bulk CO2 separation by
Schlumberger in December 1983. During the 36+ years of continuous operation at Gas Plant in West Texas,
it is proven that membrane technology is a reliable and economically attractive technology for separating
bulk acid gas from produced gas streams.
Inlet gas volume is more than 1 Bscf/d at approximately 90% CO2, with membrane outlet of
approximately 10% CO2. This gas feeds the amine unit to achieve <2% CO2 in the final treated gas. This
facility produces more than 20,000 bbls/day of liquid hydrocarbons in the membrane and chiller packages.
The operating availability for the total facilities installed has been 99.4% since the date of the start-
up in 1983. Four major membrane system expansions occurred since the first installation. Today's plant
process flow diagram is shown in Fig. 9 below, and operating time lost due to shutdowns is included in
the calculation of availability.

Figure 9—Gas Plant Process Flow Diagram

The unit operates successfully in this condensing hydrocarbon environment. With the implementation of
the CTA membrane technology, this plant maximized and monetized every component of the feed stream
by producing NGL and enhancing the efficiency of the CO2 flood.
This case study signifies the proven combination of technologies in operation for very high CO2 and EOR
applications. Suitabality of hybrid system for moderate acidic gas will be discussed in detail in next example.

Example – Acid Gas Treatement

This example reflects high flow and moderately high CO2 application for onshore installation and it will
help understand the characteristics of the hybrid system.
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Feed gas with flowrate of 325 MMscf/d and 33% CO2, 1.0% H2S enters the gas plant. The treated gas
specifications are <50 ppm CO2 and <4 ppm H2S. To achieve the final product specifications, Amine and
hybrid system will be evaluated and compared to select suitable method for gas treatment. The system will
be designed with amine and hybrid system as explained below.
Amine Only System (Base Case): The system is configured with Amine system as showin in Fig. 10.
The gas is treated thru liquid recovery system (dew point control and condensate stabilizer) to knock the
heavy hydrocarbons down, followed by amine system. To meet the desired specs. Four (4) trains of Amine
system are required.

Figure 10—Example-Acid Gas Removal using Amine System

Hybrid System: In this system membrane system is placed prior to amine system for bulk acid gas
removal and Guard Bed is placed downstream of dew point control system to capture any glycol vapors
before entering membrane system. Hybrid system (membrane + amine) (Fig. 11) is configured such that the
membrane system reduces CO2 from 33% to 18% and H2S from 1% to 0.5%. And the amine system treat
the gas further to meet the final CO2 and H2S product spec.

Figure 11—Example-Acid Gas Removal using Hybrid System

Based on the conceptual level techno-commercial analysis for technology selection, the comparison of
the hybrid system with reference to amine only system is prepared as shown in Table 1 below.
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Table 1—Comparative Analysis

Based on above analysis of different cost factors, the hybrid system stands out as the cost-effective
alternative in comparison to the amine-only system. Based on the client's end goals, hybrid system scheme
can be reconfigured further by leveraging the combination of membrane and amine system. Determining
the most suitable hybrid configuration depends upon many factors like location, site utility infrastructure,
ongoing gas pricing, permeate or acid gas destination etc…

Cost Minimization Through Optimization

To identify the optimal hybrid system, detailed design optimization of entire gas system including all the
associated gas treatment units is required. To explore this aspect, alternative choices of hybrid system will
be analyzed for the same application as discussed in example above.
The earlier example has a chiller upstream of membrane system and then treated gas from the membrane
system feeds to the amine system. In alternative schemes, different design schemes will be evaluated as
explained below.
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Alternative-A (Fig.12): This flow scheme consists of the solid desiccant-based dehydration system
followed by the two-stage membrane system, dew point control, stabilizer, and amine unit.

Figure 12—Example - Hybrid System Alternative A (Higher NGL Recovery)

The membrane system is configured in two stages to reduce HC loss but this adds the cost of compression
system. The membrane system reduces CO2 from 33% to 9%, which significantly reduces the acid gas load
to amine system and hence reduces amine size significantly.
This scheme added to the cost of an additional membrane system, dehydration system, and recycle
compressors but also gained the cost savings because of the smaller sizes of the dew point control system,
stabilizer system, and amine. Based on preliminary analysis, overall cost savings outweighes the capital
cost incurred due to addition of several other units. Estimated cost savings are listed below.

• Amine System: The size of the amine system was reduced by almost 75% (1 train instead of 4).

• Dew point control system: Chiller duty and chiller compression duty were reduced by 65%. The
overall size of the chiller system was reduced by 30%, as the feed flow to dew point control unit
was much lower. The proposed scheme required carbon steel as material of construction, while the
flow scheme (Fig.10) required stainless steel as the gas is wet and acidic. As the gas feeding to dew
point control system being dry, hydrate formation will not be an issue.and hence MEG regeneration
unit will not be required for this scheme.
• Stabilizer system: Inlet flow rate and reboiler duty were reduced by 20% and 35%, respectively.
And off gas compression duty was reduced by 85%.
• Net sales gas production: The proposed scheme provided almost 5% higher gas production with
similar calculation as considered in the above example.
Alternative B (Fig.13) : This flow scheme is similar to that of Alternative-A (Fig.12), except this case
doesn't have a dew point control system. This option offers an additional capital cost savings by removing
dew point control system but produces less condensate. So, there is a tradeoff between capital cost savings
(by removing the chiller/refrigeration unit) and loss in revenue (lower condensate production). The cost
savings for other items remain same as that discussed for Alternative A.
12 IPTC-19783-MS

Figure 13—Example - Hybrid System Alternative B (No Chiller)

The techno-commercial analysis similar to what developed for example above (Fig. 10 and 11), can be
developed for Alternative-A and Alternative-B to evaluate their suitability as well as to identify the best
suitable hybrid choice. A profitability analysis over complete project lifecycle is required to be performed
to select an appropriate alternative.

Suitable Hybrid System Applications

The viability of the hybrid system widely differs from one application to the other. As discussed above, the
detailed techno-commercial comparative analysis and optimization are required to evaluate the suitability
of the hybrid system and to select the technology which would be the right fit for the application. Typical
applications where the hybrid system can be favorable are:
a. Very high gas flow − 500 MMscf/d or higher (with >15 % CO2): Typically, large scale Gas plant or
LNG application with high CO2 content is a suitable choice.
b. A combination of high CO2 and H2S in feed and ppm level of product specification requirements like
<50 ppm CO2 and <4 ppm H2S.
c. Offshore installation with moderate to high acidic gas. The hybrid system offers a real advantage
where footprint and weight are key factors. The membrane system at offshore followed by the amine
system at onshore can be an attractive combination, especially for cases a and b above.
d. Feed Gas with high CO2 and presence of H2S with other sulfur compounds like mercaptans, COS in
gas; and the product specification requires ppm level of total sulfur.
e. Existing plant retrofitting. Where amine system exists and more bulk removal is required upfront
(using membrane system) if the feed gas is getting enriched in acid gas like EOR application OR where
membrane exists and more removal is required to achieve ppm level specs (using Amine system) if
the treated gas specifications or feed flow conditions change.
f. Enhanced oil recovery or carbon capture and storage: The plant referenced and discussed in the case
study above is a good example of this.
Selection of the suitable technology is driven by various other factors like delivery time, location of
the system, client's preference and familiarity, design specifications, nature of the project (greenfield or
brownfield), and end-use of the final products.

Digital suite
The system equipped with digital solutions can facilitate the reliability of the process technology and
enhance the plant performance, plant operation through predictive monitoring, and analysis. Digitized plant
operation will enable operators to anticipate performance upset by applying predictive monitoring and active
IPTC-19783-MS 13

machine learning using continuous monitoring of facility operations. The proprietary performance modeling
integrates technology manufacturer expertise with empirical data analytics from an extensive database of
operating facilities.

Conclusion
Schlumberger has 36+ years of experience in designing, operating and supplying membrane system; it is a
proven and mature technology. The combination of the membrane with amine technology is an emerging
alternative, as it can potentially leverage the benefits of both technologies while minimizing their limitations.
With new technological development and mature membrane technologies, innovative alternatives with
hybrid system often replace conventional technologies and offer significant overall economic benefits. To
determine the suitability of hybrid system and identify the optimal design scheme, the detailed techno-
commercial comparative analysis and careful plant optimization study are required to be performed as
discussed in the example.

References
1. Oil Field Processing of Petroleum, Vol.1 Natural Gas by Francis Manning and Richard
Thompson
2. GPSA Engineering Manual
3. The Oil & Gas Year Abu Dhabi 2015