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Mercury Removal Processes
Mercury Removal Processes
A careful evaluation of the options for removing mercury from natural gas plant
feed and product streams is a prudent exercise
Neil Eckersley and David Radtke UOP, a Honeywell Company
Leon Rogers and Shawn Brennan Enterprise Products
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Gas 2013 1
Trace suspended
Condensate
Trace ionic
Some organic
Some suspended
Elemental
Prevalent
Some ionic
Trace organic
Trace suspended
Crude oil
Figure 1 Forms of mercury in common process plant hydrocarbon streams
1-500g/Nm3
North Africa
1-130g/Nm3
Asia-Pacific
200-2000g/Nm3
The Americas
1-100g/Nm3
Gulf
Off-shore
Australia
50-200g/Nm3
Figure 2 Mercury levels reported in natural gas reservoirs in various geographic locations
2 Gas 2013
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compromising of these valuable pieces of equipment. In the early 1970s, trace levels of mercury
accumulating in the cryogenic recovery section
of an LNG production plant at Skikda, Algeria,1
caused catastrophic failure of a heat exchanger.
It was found that a combination of mercury and
water at temperatures around 0C caused corrosion in aluminium tubes constructed from
aluminium alloy 6061. Subsequent studies
revealed far more data on the mechanistic
details of how mercury reacts with aluminium,
with aluminium diffusing into the mercury droplet followed by conversion to Al2O3 by reaction
with air and water.
The consequence is that mercury bores into
aluminium and significantly compromises
aluminium-containing equipment. Specifically,
LME has been responsible for a number of failures in the 40 years since the Skikda incident.
LME can cause crack initiation and propagation,
particularly in the proximity of a weld.2 In order
to safeguard against the catastrophic failure of
cryogenic equipment, typical maximum levels of
mercury are now required in and around these
valuable cold boxes within gas processing trains.
One level that has found prominence is that the
gas entering cryogenic equipment contains no
more than 10 ngHg/Nm3 gas.
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tend to be less effective at posiImpact of liquids on mercury removal using activated carbon
tions upstream of molecular
in the gas phase
sieve drying systems or glycol
injection due to the risk of capilBed
Total volatiles Total S, wt% Total Hg, wt% Hg/S on
Hg/S on a
% Sulphur
lary
condensation
in
the
position (200C), wt% (dry basis)
(dry basis)
w/w basis molar basis, % utilisation
micropores
of
the
carbon
Layer 1
21.1
7.02
1.89
0.27
0.0429
4.29
sub-structure. The pore size
Layer 2
21.0
6.57
1.71
0.26
0.0414
4.14
Layer 3
26.8
8.32
2.12
0.25
0.0406
4.06
distribution of carbon products is
Layer 4
24.4
7.97
0.29
0.04
0.0057
0.57
such that this has been problematic in the past, particularly
where MRU locations have been Table 1
in the up-front position, where
raw gas is often at or close to its dew point and percentage of utilised sulphur was also measured
entrained liquids are common. This is where on a molar basis. The percentage of sulphur
fixed-bed, metallic-based MRU products find utilised in the equilibrium section of the vessel
greatest success in their ability to treat wet gas (layers 1, 2 and 3) was measured at ~4 wt%. By
comparison, on a dry natural gas without the
streams in up-front positions.
Non-regenerative metal sulphides can success- attendant issues of liquid entrainment, this
fully remove mercury from raw gas, upstream of percentage utilisation would be expected to be
the amine unit and the dehydration vessels. >>10 wt%. The data confirm that sulphur-imUtilising larger MRU vessels, this approach pregnated activated carbon is prone to sulphur
protects the brazed aluminium heat exchanger dissolution and micropore blocking when treating
and ensures significantly less mercury contami- wet gas.
The data also strongly suggest that the carbon
nation in and around the process plant. This
option has become increasingly popular, since it has co-adsorbed a significant quantity of liquid
minimises the total mercury present before there (20-30%) from the raw natural gas. This contribis any opportunity for mercury to migrate to uted to its shortened service life.
various locations within a gas processing plant
and avoids the risk of subsequent partitioning Reclaiming mercury from spent adsorbents
into processed natural gas and condensate Activated carbon
streams.4 It also avoids subsequent adsorption After the carbon is discharged from an MRU, it
onto any pipeline asset or piece of equipment is usually sent to a specialised plant, where
mercury is reclaimed via vacuum distillation.
downstream.
There is no useful purpose for the remaining
carbon and it undergoes high-temperature
Liquids carry-over onto sulphur-impregnated
incineration.
activated carbon
The degree of liquid adsorbed onto carbon during
the life of a sulphur-impregnated carbon-based Metal sulphides
MRU is shown in Table 1. The MRU can be Specialised processes are used for mercury
shown in terms of total wt% volatiles (200C). reclaiming from metal sulphides. For both
Layer 1 represents carbon recovered from the carbon-based and metal sulphide-based adsorinlet portion of the bed, and layers 2, 3 and 4 bents, controls are in place to ship material
represent subsequent layers. Each layer was internationally from source (gas processing
bagged upon discharge, following a lifetime meas- plant) to destination (reclaim facility). The
paperwork and experience required to accomured in months rather than years, as per design.
The total wt% of active sulphur was measured plish such transportation is complex and
on each layer of discharged carbon. While sulphur requires very careful consideration.
levels on newly installed activated carbon are
typically 10-18 wt%, the levels on the spent mate- Molecular sieve-based adsorbents
rial were measured at 6-9 wt%. In order to As the mercury is passed to the regeneration
measure the mercury removal efficiency of gas in properly regenerated beds, the spent
sulphur-impregnated activated carbon, the adsorbent contains no mercury, and therefore
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Gas 2013 5
Inlet filter
Inlet
scrubber
Trim heater
Raw
natural
gas
Mercury
guard bed
Inlet
dehydrators
Cryo
feed
Dust filter
Booster
Gas/gas Reflux
exchanger exchanger
Compressor
Expander
Residue gas
compressor
Demethaniser
TIC
Cryo feed
Bottom-side
reboiler
Top-side
reboiler
Cold
separator
Case studies
The following case studies represent real examples of the use of various forms of mercury
removal media outlined above and offer examples of the types of circumstances different
facilities may be required to deal with to address
mercury contamination.
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NGLs
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Approach temperature, F
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13
12
20
5/
20
6/
18
/1
0/
12
20
1/
4/
01
14
/9
/2
01
26
/2
/2
01
/2
/8
10
22
/1
/2
01
09
08
20
7/
20
6/
08
2/
20
18
/1
07
6/
1/
20
1/
/1
14
28
/4
/2
00
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Natural gas
530 MMscfd
48 kg/cm2
18C
50-200 g/Nm3
<0.01 g/Nm3
Table 3
8 Gas 2013
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Mercury concentration,
g/Nm3
Conclusion
There are various treatment options available for
mercury removal from natural gas plant feed
and product streams. A careful evaluation of
pros and cons of these options is a prudent exercise. A favourable Capex solution may not
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References
1 Oil & Gas Journal, 15 Sept 1975, 192.
2 Willhelm M S, Risk analysis for operation of, AIChE, April 2008,
New Orleans.
3 Jt. UOP/Equistar paper, Hg removal from cracked, 2004
Ethylene Producers Conference.
4 Edmonds B, Moorwood R A S, Szcepanski R, Mercury
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