Scientific & Technical Report FCASRCSENa

Separations Technologies to Improve

Amine System Reliability: A Case Study

Co-Authors:
Anabel Raymond, Marsulex Inc.
Francois Levesque, Pall Canada Ltd.
Hanif Lakhani, Pall Canada Ltd.

Paper originally presented at the Laurance Reid Gas Conditioning Conference, Norman, OK,
February 2008
Abstract

Today, many refineries are finding their amine where the amine is regenerated and returned
systems are struggling to handle the increased to the two refineries. As part of a 50%
acid gas loads resulting from low sulphur expansion project that was completed in 2006,
gasoline and diesel production. As initiatives Marsulex Montréal Inc. chose to install the
to increase amine and sulphur plant reliability latest separations technology to reach the
are undertaken, it is critical that suitable maximum design capacity by eliminating the
filtration and separation technology is par ticulate and hydrocarbon
employed to remove particulate and liquid ingression/contamination issues that were
contaminants from entering the amine circuits. previously reducing plant reliability due to
Marsulex Montréal Inc. operates a sulphur fouling. The deployment of rich-side filtration
handling facility located adjacent to two and high-performance liquid/liquid coalescers
refineries in Montréal. Hydrogen sulphide-rich mitigated expensive equipment replacement
amine is sent by pipeline to the Marsulex plant and saved a significant capital expense.

1
Introduction:

Today, many refineries are finding their amine is returned to the two refineries’ mix of
systems are struggling to handle the increased contactors. The sulphur is extracted and
acid gas loads resulting from low sulphur recovered by Marsulex. Marsulex’s sulphur
gasoline and diesel production. As initiatives processing facility in Montréal is one of the
to increase amine and sulphur plant reliability largest of its kind in the conventional crude
are undertaken, it is critical that suitable oil refining industry in Canada. This facility has
filtration and separation technology is provided sulphur removal and compliance
employed to remove particulate and liquid services to refineries in the area for more than
contaminants from entering the amine circuits. 40 years, and has never experienced an
Marsulex Montréal Inc. operates a sulphur unscheduled outage.
handling facility located adjacent to two As part of a 50% expansion project that was
refineries in Montréal. The hydrogen sulphide completed in 2006, Marsulex Montréal Inc.
laden (rich) amine solution from the various chose to install the latest technology avail-
refinery contactors is gathered and transported able to meet stringent requirements for
by pipeline to the Marsulex plant for plant reliability and performance.
regeneration. Once regenerated, the lean amine

Amine Contamination:

With expansions to existing refineries, the as possible.

shift in crude diets to heavier and more sour * Particulate matter found in amine solutions
“opportunity crudes” refinery amine circuits are, generally speaking, corrosion by-
and sulphur plants are under more stress than products. Solid contaminants are known to
ever before. With these increased sulphur stabilise foams when foaming occurs. A
loads, corrosion products, liquid hydrocarbons review of field test data from Pall’s databases
and organic acids are making their way into going back many years has shown a
the amine units. consistent trend – that the particle size
That amine cleanliness plays a crucial role in distribution (PSD) of suspended solids is
overall amine and sulphur plant performance generally finer than 20 µm, with the majority
and reliability is well known and documented. of par ticles being found in the
Contaminants must be reduced or eliminated sub-10 µm category. This observation has
to ensure reliable plant operation and been generally consistent even when total
environmental compliance. Refiners (and gas suspended solids have varied from site to
plants) have used different filtration and site.
separation methods to combat the most On the next page is a summary of amine
common contaminants found in amine circuits circuit filtration data compiled from Pall’s
with mixed results. What is generally accepted Scientific and Laboratory Services (SLS) field
as good practice is that total suspended solids tests. The data is a composite of results
in an amine circuit should be kept below 1 obtained in 10 countries, from 17 refineries
ppmw,1 and liquid hydrocarbons and organic owned by 10 oil companies.
acids must be reduced to levels as close to zero

1 Verma, Narendra; Verma, Anil; 2009, “Amine System Problems Arising from Heat Stable Salts and Solutions to
Improve
Performance,” Fuel Processing Technology, Vol. 90, Issue 4.
Brown, Jr, Robert L., Hashemi, Reza; 1993, “Predicting Contamination Levels of Upset Conditions in Amine

2
Figure 1:
Composite of TSS
Results for Various Amine Contamination
Amines

120

100
Ucarsol
80 MEA
TSS
(ppmw) 60 MDEA
Flexsorb
40
Selexol
20
DEA
0

Figure 1 above shows DEA as the most sampled expert literature.

amine, and exhibiting the widest band of In the figures below, we see the PSD for several
contamination – ranging from a few ppmw to samplings of DEA and MDEA (Figures 2 & 3)
nearly 120 ppmw. What is telling is that in showing that the majority of particles are
nearly all cases, the TSS levels exceed the sub-20 µm in size.
recommended best practice of no more than
1 ppmw suspended solids as advised in the

Figure 2 (left):
PSD for DEA DEA Contamination - PSD MDEA Contamination - PSD
Samples 100 Percentage (number) 100
Percentage (number)

80 80
Figure 3 (right):
PSD for MDEA 60 60
Samples 40 40

20 20

0 0
0 20 40 60 80 100 0 20 40 60 80 100
Particles Size (micron) Particles Size (micron)

In complex refineries, ingressing liquid be felt in the rich/lean heat exchangers,

hydrocarbons can come from amine/LPG regenerator, re-boiler tubes, and tower trays
contactors or as condensibles in the refinery and packing, if left untreated. The consequences
fuel gas. Typically, poor liquid/liquid contactor can range from heat exchanger fouling,
outlet disengagement between LPG and amine hydrocarbon ingression in the sour-water reflux
or inadequate inlet separation of free liquids discharge, increased corrosion, high amine
in refinery fuel gas entering vapour/liquid losses due to foaming in contactors, formation
contactors is the root cause. In complex of amine degradation products, and/or
refineries where there are multiple contactors, generation of heat stable salts.
and when it is difficult to pin-point culprit The efficiency of the sulphur recovery unit
streams, the best option is to deploy central and the converter catalyst life are also affected
filtration and separation as a means to by carried-over hydrocarbons in the acid gas.
eliminate free liquid hydrocarbons from the In the event of a serious hydrocarbon carry-
amine. High-performance liquid/liquid over episode, the consequences can be much
coalescers (Pall’s PhaseSep® technology) can more severe, including soot deposition in the
break the stable, rich-amine/hydrocarbon converters, runaway hydrocarbon combustion
emulsion that can have adverse effects on the in the Claus unit, and high SO2 emissions
amine unit and sulphur plant operations, which resulting in regulatory penalties and possibly
can in turn impact overall refinery SO 2 expensive capacity reductions. In the worst
emissions. cases, there might be the necessity to switch
Within the amine circuit itself, the impact would to sweeter crude slates as a mitigating strategy.
3
Rich-Side PhaseSep Liquid/Liquid Coalescer to Separate Hydrocarbons:

In the rich-amine side of the process, the

proposed system will perform a dual role as The PhaseSep coalescer is a multiple-stage
follows: system starting with pre-filtration (see Figure
• 100% Rich-Side Filtration - remove solid 4 below) that will remove particulate matter,
particles - mainly FeS corrosion products provide protection, and pre-condition the feed
• Eliminate the free-hydrocarbon ingression to the coalescer. The coalescence stage that
to the downstream process to near solubility follows breaks the emulsion and allows the
levels capture of dispersed hydrocarbon phase
droplets, resulting in the separation of the two
dissimilar streams. PhaseSep Liquid/Liquid
Figure 4: coalescers operate over a wide range of
Full-Flow Rich-Side
Filter and conditions, including where:
Py-gas
Liquid/Liquid Sump
Coalescer System Pre-conditioning • The emulsion has an IFT as low, or lower
Filters
than 5 dyne/cm (PhaseSep coalescers have
been applied in applications with an IFT as
Outlet low as 0.5 dyne/cm)
Heavy Oil
Coalescers Sump
• The dispersed phase fluid is hydrocarbon,
Inlet

There are three essential steps to achieving an efficient liquid/liquid separation:

Stage 1: Pre-filtration Stage 3: Separation

A rich-side full-flow pre-filter is essential to The coalesced dispersed phase separates in the
protect and provide maximum operating life settling zone of the coalescer housing. Due to
to the liquid/liquid (L/L) coalescer. At the same the density difference on the two phases, these
time, and more importantly, 100% rich-side separated liquids exit through separate drain
filtration prevents the passage of suspended and outlet connections at the back end of the
solids that may deposit in downstream L/L coalescer housing.
equipment such as rich/lean heat exchangers,
column packing or trays, and re-boilers.

Stage 2: Coalescence
The two-phase liquid emulsion enters the
coalescing element and flows inside-to-outside.
This is where small, suspended droplets of
the dissimilar fluid come together, or coalesce,
as the emulsion moves through the proprietary,
specially formulated coalescer medium.

4
The Marsulex Experience:

Up until 2004, the Marsulex amine unit was residence time in the flash-drum. The
relatively reliable. Although the unit never operational residence time would be reduced
had to be shut down for unplanned to 13 minutes (at operating liquid level) or 9
maintenance, its efficiency and maintenance minutes (at 50% liquid level). This was
costs were affected by amine contamination. considered insufficient to adequately separate
The residence time of the flash-drum was 22 liquid hydrocarbon from the amine, raising
minutes on average, with a design residence serious concerns about the reliability of the
time of 19 minutes. This was sufficient to plant under the new operating regime.
handle most hydrocarbon carr y-over In preparation, Marsulex invited Pall to perform
conditions. A simple particle filter assembly an on-site demonstration of rich-side full-flow
was installed on a 15 - 20% kidney loop on pre-filtration and L/L coalescence. Testing
the lean amine side. It offered partial filtration performed during the fall of 2004 helped better
of the lean amine prior to the refiners’ define the level of contamination at the outlet
contactors, but no protection for the Marsulex of the existing flash-drum. The site trials also
amine unit and sulphur plant. validated the effectiveness of rich-side filtration,
Following the planned 2006 expansion project, and confirmed the efficiency of the
the maximum amine recirculation flow capacity liquid/liquid coalescer technology at separating
would increase, and therefore, reduce the hydrocarbons from rich-amine.

During on-site testing, the following observations were made:

1. Even with adequate flash-drum residence suspended solids to concentrations near or

time, hydrocarbon/amine emulsion remained below 1 ppmw.
stable, as evidenced by rich-amine samples 3. Hydrocarbon (C5 to C60) levels found
remaining hazy for longer than three weeks upstream of the L/L coalescer pilot unit
(see Figure 5-B). Pall’s high-efficiency ranged from 86 to 193 ppmw, and included
PhaseSep liquid/liquid coalescer was capable low levels of benzene, toluene, ethyl-
of breaking and separating this emulsion in benzene, and xylene. Pall’s PhaseSep L/L
a single pass. coalescer reduced overall hydrocarbon levels
2. Rich-amine particulate concentrations vary to near solubility in amine, based on a total
substantially depending on the refinery’s extractable hydrocarbon analysis, utilizing
operating conditions at a given point in a Horuba Oil Content Analyzer (extractive
time. Using a 10µm absolute-rated filter IR analyzer).
(Beta10 µm = 5000) helped reduce 4. The average solids loading at the outlet of
the flash tank (inlet of the rich-side filter)
Figure 5:
Test Samples was
5 ppmw, with the lowest data point being
Rich Amine (DEA 25%): 2 ppmw and the highest being 10 ppmw.
Filtration and Liquid/Liquid Coalescer September 2004 The average solids loading at the outlet of
INLET OUTLET OUTLET A: Rich-amine sample at the outlet of the flash
(10 µm absolute) (10 µm absolute) (PhaseSep) tank. Note the solution color, indicative of
finely divided corrosion particles – FeS.
B: Rich-amine sample following 10 µm (Beta
5000) filtration. Note the haze – indicative of
a stable emulsion. This sample remained hazy
and unchanged for three weeks.
A B C C: L/L coalescer outlet sample – clear and bright
after a single pass through the PhaseSep L/L
coalescer. Emulsion was broken and liquid
hydrocarbons separated.

5
Marsulex Solution:

Based on the field trial results, Marsulex made filtration package followed by a full-flow high-
the decision to install a full-flow, duplex performance PhaseSep liquid/liquid coalescer
Figure 6:
Marsulex Amine Cooling Water
Unit Flow
Schematic
E-230

Lean Amine
Tank
E-210

Light Foul Amine

H/C Return

Liquid
Foul Amine H/C Amine
Flash Tank Regen.
Tower

E-211 E-212 E-213 E-214 E-215

E-221
E-222
E-223
E-224
Duplex Pre-filters
Steam
PhaseSep Coalescer

Figure 7 (left):
Duplex Ultipleat®
High Flow
Rich-Amine Filters

Figure 8 (right):
PhaseSep L/L
Coalescer Unit

Marsulex Operating Data:

The rich-side filter and coalescer units were improvement has been in the consistently low
installed early in 2006 and started up in June concentration of suspended solids. Prior to
of that year. Prior to start-up of the equipment, the rich-side filtration coming on-line, the total
the rich-amine was hazy and had a green/gray suspended solids in the circuit would reach 30
color at the outlet of the flash tank. Since the ppmw. Today, the solids are found to be in the
unit has been in operation, amine samples at 1 ppmw range on average, downstream of the
the outlet of the filtration and coalescing system rich-side filter. With the L/L coalescer in place,
are clear and bright, exhibiting the the continuous low-level hydrocarbon
characteristic light straw color of a clean amine, ingression is being removed everyday. More
just as was seen in Figure 5-C. critically, when episodic hydrocarbon spikes
It was observed both in amine analysis and occur, the L/L coalescer responds immediately
overall process stability that the amine quality by separating the liquid hydrocarbon slugs,
has improved. The most significant preventing circuit contamination and

6
Upset:

Since start-up of the rich-side filters and L/L took three days and eight filter replacements
coalescers, there has only been one major to clean the particles and hydrocarbon out of
hydrocarbon carry-over to the Sulphur the amine loop and restore stability.
Recovery Unit (SRU) and one major foaming The second incident was most likely due to
incident at the refinery contactors. hydrocarbon contamination of the amine
On the first occasion, an upset occurred at during a coalescer shutdown. However, given
the time when the filters and L/L coalescer the system is a closed loop, it cleaned up and
were by-passed for filter element change-out. recovered once the coalescer was returned to
This was during a period of very high solids, service. Employing the best practice of rich-
and filter life was short. The event should side filtration and hydrocarbon coalescence
have been a warning for the larger hydrocarbon proved the system can, and will, recover
spike that followed. Following the five-hour quickly. The alternative is unchecked
shutdown to replace the filter elements, it contamination of the circuit that conventional
separations techniques are inadequate at

Figure 9 (left):
Coalescer Hydrocarbon Extracted by the Coalescer F-212 (US gal) Total 2008 Hydrocarbon Extracted from F-212 (US gal)
Performance, 2007 300 800
5 hours Coalescer
280 shutdown Total H/C extracted for JAN-JUN’07: 1449 US gal
260 Total H/C extracted for DEC’07: 1583 US gal 700
Figure 10 (right):
240
Coalescer 220 600
Performance, 2008 200
500
180
160
400
140
120 300
100 81 hours
Coalescer
80 shutdown 200
60
40 100
20
0 0
20-Nov-07 27-Nov-07 04-Dec-07 11-Dec-07 18-Dec-07 25-Dec-07 JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC

Since December 2007, the system has been To date, the amine heat exchanger train, re-
operating without any required coalescer boilers, and regenerator tower have been
shutdown. In February 2009, there was another performing without any need for shutdown.
major hydrocarbon carry-over from one of the Unfortunately, we cannot compare performance
refineries. This time the coalescer extracted 840 before and after the installation of the rich-side
US gallons (20 bbl) of hydrocarbon liquid over equipment because the entire circuit was
a two-day period. High solids did not significantly modified during the 2006 project.
accompany this event, and the filter did not However, directionally, Marsulex can confirm
plug prematurely. With the separation train the general fouling tendency is greatly reduced
remaining on-line, there was no impact on vs. prior to the filtration unit start-up.
the amine loop and the situation returned to Today, Marsulex is projecting a three-year or
normal as soon as the hydrocarbon better turn-around schedule for the entire heat
contamination source was located and exchanger train. The re-boiler cleaning
addressed. schedule will be based on the trends revealed
from Marsulex’s monitoring program.

7
Process Benefits:

The most important benefit that the system is expected to save a minimum of $100,000 on
provides is an increase in overall reliability of maintenance costs. This is in addition to the
the amine system and sulphur plant. While energy savings realized with reduced steam
the system’s ability to allow for quick recovery consumption in the regenerator re-boiler (not
after a particulate and/or hydrocarbon calculated here).
contamination event – which keeps the system The liquid/liquid coalescer allowed greater
performing at capacity – is the primary benefit, liquid hydrocarbon recovery when compared
the operating costs are also greatly improved to the flash-drum alone. On average, the
due to longer time between cleaning, and amount of liquid hydrocarbon recovered is
better hydrocarbon recovery. increased by 25%. For example, in 2008, this
The lean/rich exchangers cleaning frequency resulted in the recovery of an additional 4,830
has returned to a PM (preventative US gallons
maintenance) schedule, five in three years vs. (115 bbl) of liquid hydrocarbon. This offsets
a required eight in three years due to fuel costs since the recovered oil is now being
significant fouling of the heat exchanger train. fed to a boiler. Most importantly, the removal
Over time, Marsulex will re-assess the schedule of this volume of hydrocarbon ensures amine
based on inspections. The frequency reduction circuit stability, and protection of the

Conclusion:

Rich-amine filtration and liquid/liquid The filtration and separation train provides
coalescence is crucial for the removal of protection of the lean/rich heat exchangers,
particulate matter such as corrosion products regenerator tower, and reboilers and lean
and liquid hydrocarbons circulating in the amine coolers. The benefits are: reduction in
amine loop immediately downstream of the overall energy consumption, acid gas mass
flash-drum. As demonstrated at Marsulex, the transfer maximisation, prevention of foaming
best practice targets of ~1 ppmw (avg.) episodes and loss of amine, maintaining the
suspended solids, and free liquid hydrocarbon re-boiler tubes in good condition, which
levels at near solubility, are achievable. prevents fouling and formation of local ‘hot-
High performance liquid/liquid coalescers spots’ responsible for amine degradation, and
provide a more efficient and economical means the initiation of the problematic corrosion
for the removal of liquid hydrocarbons from cycles.
an amine stream when compared to carbon Refineries have to assure amine and sulphur
beds or centrifugal devices. Liquid/liquid plant performance and reliability in parallel
coalescers are also a highly efficient means to with production of low sulphur gasoline and
control incoming hydrocarbon slugs and diesel. The Marsulex case study emphasizes
maintain amine loop stability after an event. that there exists a robust and reliable means
to control particulate and liquid hydrocarbon
contamination.

8
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FCASRCSENa Printed in the USA July 2011