SPE-177784-MS

A New Approach to NGL Recovery From Off-Gases

Kevin L. Currence, David M. Rapavi, and Michael J. Clifford, Black & Veatch

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition and Conference held in Abu Dhabi, UAE, 9 12 November 2015.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Off-gas from refining and petrochemical facilities often contains significant quantities of valuable natural
gas liquids (NGL) and olefins. The composition and pressure of these off-gas streams is commonly much
different than conventional natural gases and presents unique challenges.
While many gas processing technologies exist, most were developed for high-pressure natural gas
applications. High hydrogen content often found in off-gases can reduce the effectiveness of these
traditional processes. Further, certain trace components can require other considerations that are not
common in natural gas processing facilities. Nitrogen oxides (NOx) that are often contained in off-gas
streams can solidify and accumulate within the cryogenic plant. NOx, especially nitrogen trioxide (N2O3),
are considered hazardous; limiting the minimum operating temperature of the plant can reduce the risk of
accumulation. For conventional technologies, this temperature limitation can significantly reduce the
recovery of valuable NGL.
Single mixed refrigerant (SMR) processes have been used for liquefied natural gas (LNG) liquefaction
in numerous facilities dating back to the 1970s. A new process configuration was recently developed for
an off-gas processing plant that incorporates an SMR system. The patent-pending process provides several
advantages for NGL recovery from refinery or petrochemical off-gas compared to conventional processes,
including the flexibility to accommodate a wide range of feed gas compositions and fluctuations in feed
rate that are common in off-gas applications.
In addition to a detailed description of the process configuration, this paper presents the features of the
SMR-based process and compares its performance to conventional technologies for off-gas processing. A
case study is provided that illustrates the advantages of SMR over conventional processes.

Introduction
Off-gas is generated by a number of refining and petrochemical processing units. For example, cracking
processes are commonly used to increase the yield of gasoline or diesel from heavy crudes or to reduce
the viscosity of bitumen from oil sands production. The off-gas created as a byproduct during these
processes often contains significant quantities of ethane, propane, butane, and other valuable natural gas
liquids (NGL).
Some operators choose to blend the off-gas into the facility fuel gas system, forgoing the potential
revenue from NGL sales even though these components often have a higher value as a separate NGL

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product than when they are burned as fuel. These valuable NGL can be recovered from the off-gas
and integrated into the existing refinery processing units by, for example, blending them into existing
refinery liquefied petroleum gas (LPG) fractionation systems where they can be separated and sold
as finished products, used as feedstock to other refinery units (alkylation, dimerization, isomerisation
units, etc.), or blended into the gasoline pool. While this use is a simple method for disposing of the
off-gas, the presence of these heavier components in the fuel stream results in higher carbon dioxide
emissions than those for methane used as fuel. In addition, certain fuel consumers can suffer reduced
life and operational problems from high levels of these heavier components or high variability in the
heating value of the fuel.
Many gas processing technologies are available to the industry, but most were developed
specifically for natural gas applications. Since refining and petrochemical processes normally operate
at relatively low pressures, the off-gas is available at pressures well below the typical feed pressures
for natural gas processing plants. In addition, many refining processes operate in a cyclic or
non-steady state, resulting in fluctuations in the flow rate and composition of the combined off-gas
from its multiple sources. Coker bed switches, outages of process units, and changing crude slates are
a few examples of operations that can contribute to the high variability of off-gas compared to natural
gas production.
Further, the severe processing conditions encountered in the cracking unit also result in production of
hydrogen and nitrogen oxides (NOx), as well as valuable olefinic compounds (ethylene, propylene, etc.)
that are not typically found in natural gas. High hydrogen content can reduce the effectiveness of some
traditional natural gas processing techniques because hydrogen is noncondensable.
Other components require special considerations even when present in trace quantities. For
example, NOx that may be present in off-gas are considered hazardous. NOx can undergo further
reaction with other components in the cold sections of the plant to form NOx gums, NOx salts, and
nitrogen trioxide (N2O3), often referred to as blue oil. These compounds can undergo explosive
decomposition when the plant is warmed during maintenance activities, potentially damaging
equipment and posing a safety hazard to personnel. Since NOx and blue oil can solidify and
accumulate in piping and equipment at cryogenic temperatures, the likelihood of occurrence can be
reduced by operating at warmer temperatures.
Given the significant differences outlined above, it should be no surprise that a traditional natural gas
plant configuration may not be the best solution for off-gas processing. A new process configuration has
recently been developed that incorporates a single mixed refrigerant (SMR) system. This patent-pending
process, detailed in the following sections, offers several advantages over conventional processes for NGL
recovery from off-gases.

Conventional Technology
Cryogenic processes are widely used and provide efficient NGL recovery from a wide variety of feed gas
streams. Many of these facilities use a configuration that derives a substantial portion of the required
cooling from an expansion-based process via the Joule-Thomson (JT) effect. Expansion across a control
valve or turboexpander is used to provide the necessary refrigeration to liquefy the NGL components from
the feed gas.
As the NGL content of a feed gas increases, additional refrigeration duty is required to condense the
desired components. This refrigeration can be provided by supplemental mechanical refrigeration (commonly propane) or by increasing the expansion ratio. An example turboexpander process (TXP) for
recovery of ethylene and heavier (C2) components from an off-gas is shown in Fig. 1.

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Figure 1Conventional Turboexpander Process (TXP).

Off-gas is typically available at low pressure and must be compressed to provide the necessary
expansion for cooling. Depending on the required feed pressure to achieve the desired recovery level,
multiple compression stages and intercooling may be required, including the expander-driven booster
compressor. Following compression, pretreatment of the feed gas may be required to remove certain
contaminants. As a minimum, dehydration is typical to remove water that would freeze in the downstream
process.
Treated feed gas is cooled and partially condensed by cross-exchange with the product streams and
tower liquids. For feed gases containing higher quantities of NGL, a supplemental propane refrigeration
system is also incorporated. The vapor and liquid phases are separated, and the vapor is then expanded
into the absorber tower. The liquids are split, and a portion is fed to the top tray of the demethanizer. The
remaining liquid is sent to the top of the absorber tower as supplemental reflux.
Heat is supplied from the feed gas to the demethanizer to drive out the lighter components and produce
a specification C2 product. The demethanizer overhead vapor is cooled using the absorber overhead
vapor and then routed to the top of the absorber as reflux.
Reflux liquids pass downward through the absorber, contacting the vapors that are travelling upward.
In the process, this reflux helps extract the desired components from the feed gas. The absorber bottoms
liquids are then pumped to a middle feed location on the demethanizer tower.
If the ethane is not desired as a liquid, the process can also operate in ethane rejection mode. In that
case, the demethanizer acts as a deethanizer, with a C3 product. The unit can convert to C3 product
by a change in operating conditions, with minimal hardware and valve position changes.

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Single Mixed Refrigerant Technology

SMR processes have been used in numerous facilities for decades and have proven to be safe, efficient,
and robust. The refrigerant fluid is a mixture of light hydrocarbons from methane to pentane, which can
be adjusted to match the requirements of each application.
Mixed refrigerants can operate at much lower temperatures than propane or propylene refrigerant
systems. This makes it possible to achieve low processing temperatures without the need for large
expansion pressure drops of the process gas.
Fig. 2 shows a new patent-pending SMR process for NGL recovery. As with conventional technology,
off-gas is typically available at low pressure and may be compressed prior to processing. However, by use
of the mixed refrigerant, the processing pressure will be much lower than it is for a TXP plant. Following
compression, pre-treatment of the feed gas similar to the conventional technology may be required to
remove certain contaminants, including dehydration to remove water.

Figure 2Single Mixed Refrigerant (SMR) Process.

Before entering the absorber tower, feed gas is cooled and partially condensed using tower liquids,
residue gas, and mixed refrigerant in the main exchanger. In the absorber, the feed gas is contacted with
reflux liquid to remove NGL, which exit the bottom of the tower. The majority of the liquids are pumped
to the stripper tower, and a slipstream is returned as reflux to the top of the absorber.
The stripper tower is used to remove the lighter components from the NGL to produce a specification
product. The stripper overhead is equipped with a reflux system to reduce losses of the desired NGL in

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the overhead vapor. The reflux condenser is cooled using a portion of the mixed refrigerant, and the
condensed liquid is returned to the stripper as reflux. The stripper overhead vapor stream is combined with
the absorber reflux liquid and fed to the top of the absorber.
The absorber overhead stream is the residue gas that can be used to meet facility fuel requirements. In
many cases, the fuel system operates at a lower pressure than the NGL recovery system. To increase
process efficiency, a turboexpander can be used for this expansion and to provide a portion of the feed
gas compression. If the additional capital investment for the turboexpander cannot be justified for a
particular application, a control valve may be used.
The configuration of the mixed refrigerant package, shown in Fig. 3, is a simple closed-loop cycle,
similar to a conventional propane refrigeration system. The low-pressure mixed refrigerant is compressed
in two stages. At the interstage, the refrigerant is cooled to remove the heat of compression. Any
condensed liquid is separated and pumped to the second-stage discharge piping.

Figure 3Mixed refrigerant system.

The high-pressure refrigerant compressor discharge is cooled and sent to the refrigerant separator.
Using air or water cooling, the refrigerant is not yet totally condensed. To ensure adequate distribution,
vapor and liquid are fed separately to the main exchanger, where final condensation occurs as the
refrigerant flows downward. Condensed high-pressure refrigerant is flashed across a control valve to low
pressure to produce cold refrigerant. The cold refrigerant is vaporized as it flows upward through the
exchanger, cooling the process streams and condensing the high-pressure refrigerant.
As with conventional technology, if the ethane is not desired as a liquid, the SMR process can also
operate in ethane rejection mode. In that case, operating conditions are modified to produce a C3

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product in the stripper tower. Conversion to ethane rejection involves minimal hardware and valve
position changes, similar to TXP.

Case Study
Black & Veatch recently completed a direct comparison of the TXP and SMR processes for an off-gas
application. This comparison illustrates the features and benefits of the SMR process.
The design basis for the project is shown in Table 1. Feed gas was generated by a coking process and
contained significant quantities of hydrogen as well as paraffinic and olefinic NGL components. Three gas
compositions (design, high molecular weight [MW], and low MW) were evaluated because of known
variations in upstream processing units. The feed gas flow rate also exhibited characteristic fluctuations
caused by regular coker bed switching cycles; every 8 hours, the feed flow would drop to 66% of the
normal flow for approximately 30 minutes.

Table 1Case study design basis.

Since the feed gas could contain NOx compounds, the client limited the minimum operating temperature of the NGL plant to 84.4C (120F). This temperature was selected to provide a safety margin
from the freezing point of blue oil to minimize the possibility of accumulation within the NGL recovery
plant.
Process simulations were prepared for both technologies using similar parameters, such as 80%
polytropic compressor efficiency, 82% adiabatic expander efficiency, and 2.8C minimum exchanger
approach temperatures. Summaries of the results of these simulations are provided in Table 2.

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Table 2Case study results.

Because of its dependence on expansion to provide process refrigeration, TXP operates at a much
higher inlet pressure and devotes a greater proportion of the total power to compression of the feed gas
than the SMR process. As shown in Table 2, approximately 88% of the total power for TXP is used for
feed gas compression, with the remaining 12% used for refrigeration. The fractionation towers are
operated at low pressure to provide the necessary expansion ratio. Therefore, the coldest operating
temperatures of the plant occur in the low-pressure portions of the process.
In contrast, the SMR process operates at a lower inlet pressure, with the fractionation towers operating
at similar pressure. A greater proportion (approximately 40%) of the total compression power is reserved
for refrigeration, significantly reducing the dependence on expansion cooling. For the SMR process, the
absorber tower operates near the minimum operating temperature but at a much higher pressure than for
TXP. This allows a greater quantity of the NGL to be condensed from the feed gas, resulting in improved
product recovery levels.
On the basis of product prices of USD 98/m3 for ethane/ethylene, USD 709/m3 for propylene, and USD
200/m3 for propane, the additional NGL recovery for SMR yields incremental revenue of over USD 4
million per year for the design case. In addition, removal of these components from the feed gas
significantly reduces the MW of the residue gas stream. In the high MW feed case, the feed gas has an
MW of 21.7; whereas, the residue gas has a MW of approximately 12.5. For facilities that consume the
residue gas as fuel, this lower MW results in lower carbon dioxide emissions since fewer heavy
hydrocarbons are burned. For example, propane generates approximately 20% more carbon dioxide than
methane to produce the same amount of heat.
The two processes were also compared across a range of compositions that would be typical of refinery
off-gas. As shown in Table 2, the liquids recoveries achieved by the SMR process are consistent across
the range of compositions. The recoveries for TXP improve for higher MW gas, but it still has 6.3
percentage points lower ethylene recovery and 3.6 percentage points lower ethane recovery than the SMR
process. The comparison assumes design-level equipment performance for each case. This assumption is
optimistic because the efficiency of a turboexpander decreases dramatically below its design point. The
flow rate to the expander in the higher MW cases is approximately 15 to 20% lower than for the design
case, so in reality, process performance would be lower as a result of reduced expander efficiency.
An important consideration for this application was the ability of the process technology to adjust to
recurring flow rate changes. The capability of the process to maintain consistent product recovery and
avoid temperature excursions below the stated minimum operating temperature was critical. The performance in Table 2 is based on steady-state operation and does not reflect the fact that TXP is sensitive to

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changes in flow rate and composition. With SMR, a single refrigerant control valve can regulate the
process cooling independent of the feed gas rate. The turboexpander in the SMR is located on the residue
gas, so the NGL process and fractionation equipment operate at a constant pressure level. It is not
necessary for the operator to adjust tower pressures to compensate for reduced turboexpander efficiency
or to avoid exceeding the minimum temperature constraint. Therefore, SMR would be expected to
maintain a higher level of productivity through the fluctuations in flow and composition inherent in most
off-gas applications.
As a result of its reduced dependence on expansion, the SMR technology also experiences less impact
in the event of a turboexpander shutdown. Loss of the turboexpander-driven booster compressor reduces
the NGL plant feed pressure for both technologies. However, the larger reliance on refrigeration and the
colder temperatures of the mixed refrigerant as compared to propane refrigerant allow the SMR process
to achieve much higher NGL recoveries than TXP during a turboexpander shutdown.
With expansion across a control valve rather than the turboexpander, TXP propylene recovery drops
from 97% to 72% for the design case. In comparison, the SMR process experiences a propylene recovery
reduction from 98% to 86%. In total, the NGL revenue for the SMR technology is more than USD 60,000
per day greater than TXP when operating without the turboexpander.

Conclusions
Many unique characteristics often associated with off-gas applications can reduce the effectiveness of
conventional gas processing technologies. These characteristics include low feed gas pressure, high
hydrogen content, minimum operating temperature restrictions, and highly variable feed flow rate and
composition.
Mixed refrigerant systems have been used in the oil and gas industry for decades and have proven to
be reliable and efficient. While as simple to operate as other refrigerant systems, SMR systems also offer
the flexibility to modify the refrigerant recipe as needed to match the process demands, which is not
possible with traditional propane systems.
The SMR technology differs from conventional methods by making greater use of refrigerant for the
required cooling, which decreases dependence on expansion pressure drop. The SMR process configuration allows enhanced NGL recovery by virtue of the higher operating pressure in the coldest portions
of the plant. This is in contrast to the turboexpander plant, where the coldest portions of the plant operate
at a lower pressure because of its reliance on pressure drop for cooling. For the design composition of the
case study, SMR achieved greater than 10 percentage points higher ethylene recovery and 6 percentage
points higher ethane recovery than conventional TXP. The liquids recoveries achieved by the SMR
process are consistent across the range of composition, and the SMR process would be expected to
maintain a higher level of productivity through the flow fluctuations inherent in off-gas.
The patent-pending SMR technology has been specifically developed for NGL recovery from offgases. In addition to improving the quality of a facility fuel supply and reducing carbon dioxide emissions,
enhanced recovery of NGL can represent significant additional revenue. The SMR technology has
advantages over conventional technology from economic, reliability, operability, and environmental
perspectives.