MERCURY, THE VOLATILE SURPRISE IN GAS PROCESSING

Cornelis J. Smit

Henk Meijer

Eric M. Hendriks
Shell Global Solutions International B.V.
Amsterdam, The Netherlands

ABSTRACT

The concentration of mercury in natural gas varies widely from 450 - 5000 µg/Nm3 in some fields
in North Germany to 180 µg/Nm3 for Groningen in The Netherlands to less than 0.01 µg/Nm3 in some
parts of the US and Africa. Mercury can be present in many forms in hydrocarbons, such as elemental,
organic, metal organic or inorganic, however, in gas processing plants conditions are such that elemental
mercury is the prevailing species.
By making use of Shell’s Modified and Improved Redlich Kwong equation of state, to calculate
the distribution of elemental mercury between gas, condensate and aqueous streams and combining this
with a HYSYS simulation of a gas processing plant, the distribution of mercury over the various process
streams can be predicted. Using the model a case was generated in which the mercury content of the export
gas was set at 30 µg/Nm3, mimicking the current situation in an operating plant. Using the mercury inlet
concentrations that generate a mercury concentration in the export gas of 30 µg/Nm3, mercury levels for
the produced LPG and condensate that are close to the levels actually measured were predicted, thereby
validating the current model.
Consequently, we now have the tools to calculate the distribution of mercury in various types of
gas processing equipment such as gas-liquid separators, condensate stabilizers and debutanizers. By
implementing the results for the individual process units into a HYSYS model of the whole gas processing
plant we are capable to predict mercury concentrations in the most important process and product streams
by measuring the mercury contents of two gas streams.
In the example given in this paper 80 % of the mercury present in the feed gas would report to the
export gas, whereas this would be 49 % of the mercury present in the feed condensate. Liquid mercury
deposition would first occur in the LTS unit, the unit with the lowest operating temperature in the process
flow scheme.
 MERCURY, THE VOLATILE SURPRISE IN GAS PROCESSING

INTRODUCTION

The concentration of mercury in natural gas varies widely from 450 - 5000 µg/Nm3 in some fields
in North Germany to 180 µg/Nm3 for Groningen in The Netherlands to less than 0.01 µg/Nm3 in some
parts of the US and Africa [1]. No general rule can be given for the mercury content of natural gas for new
fields that are brought into production and therefore an assessment must be made of the presence of
mercury for any new development. Mercury can be present in many forms [2] such as:
1. Free elemental mercury (Hg0).
2. Organic mercury (R1HgR2) one example being dimethylmercury (CH3)2Hg.
3. Metalorganic mercury (RHg+) one example being methylmercury chloride CH3HgCl.
4. Inorganic mercury (Hg2+), examples being mercuric chloride HgCl2, mercuric sulfide HgS
and mercuric oxide HgO.
5. Inorganic mercurous compounds (Hg22+) generally involving a mercury-mercury bond such
as Hg2Cl2.
In gas processing generally the first operation is the separation of gas and reservoir fluids such as
condensate and water. Ionic species RHgCl and HgCl2 are soluble in water and will report for a major part
to the production water. Mercuric sulfide and mercuric oxide when present are insoluble in water or
hydrocarbons and have negligible vapor pressure and as a result they will end up in the sludge upon
production. Mercurous compounds tend to be unstable and are rare in nature [3]. As a result both free
mercury metal and organic mercury species need to be considered. Under reservoir conditions organic
mercury species tend to be unstable and to date attempts to identify and measure significant quantities of
organic mercury species in natural gas have failed and at most only traces have been claimed [4]. In gas
processing condensates organic mercury species have been detected, however, it was shown that they were
formed over time. As a result, for the distribution of mercury in gas processing facilities, metallic mercury
is the main mercury species to be considered

MERCURY RELATED PROBLEMS IN GAS PROCESSING

The presence of mercury in natural gas may lead to the following problems:
• Mercury induced corrosion in process equipment, particularly heat exchangers.
• Exposure of workers to high levels of mercury during maintenance.
• Unwanted presence of mercury in produced gas and in other product streams such as
condensate and LPG.
One of the major problems that may occur is mercury-induced corrosion, particularly in heat
exchangers. Two major types of corrosion can be observed. The first is amalgam corrosion [5] in which the
following reactions (Al taken as example) play an important role:
Hg + Al → Hg ( Al )
Hg ( Al ) + 6 H 2 O → Al2 O3 .3H 2 O + 3H 2 + Hg
For this type of corrosion both the presence of mercury and moisture is required. This type of
corrosion can occur during steaming out of mercury-contaminated equipment or warming up of the main
cryogenic heat exchanger of a LNG plant. Particularly aluminum-based alloys are sensitive for this type of
corrosion.
A second type of corrosion that plays an important role is liquid metal embrittlement (LME). For
this type of corrosion no moisture is required and it produces rapid brittle fracture. It is caused by mercury
diffusion into the grain boundaries forming a liquid amalgam. Consequently cracks usually initiate and
propagate via the grain boundary. This type of corrosion affects a broad range of materials (aluminum
alloys, copper based alloys and some types of steel).
The importance of the presence of metallic mercury in natural gas in LNG operations was first
demonstrated painfully in 1975 by corrosion of aluminum tubes in cryogenic heat exchangers at Skikda,
Algeria [6]. As a consequence one train of the LNG plant was shut down for a period of 14 months. After
this incident the industry paid a lot of attention to understanding the corrosion mechanisms, assessing the
role of mercury in gas processing and finally developed methods for removing mercury from the feed to
the LNG plant to levels down to ≤ 0.01 µg/Nm3.
Mercury is a toxic metal and has a relatively high vapor pressure. Consequently upon opening
mercury contaminated equipment workers will be exposed to mercury vapor levels well in excess to the
Threshold Limiting Value (TLV) or the Maximum Allowable Concentration (MAC-value). Suitable
Personal Protective Equipment (PPE) is required during maintenance work.
The application of the products produced i.e. natural gas; stabilized condensate and LPG may
require the removal of mercury. A predictive tool for the distribution of mercury over the various product
streams will be valuable for:
• Prediction of mercury levels in various products streams for assessment of mercury
removal requirements.
• Prediction of mercury dropout in various types of process equipment.
• Assessment of a design base for mercury removal facilities and prediction of lifetime of
mercury adsorbents.
• Determining the relation between processing conditions and mercury levels in various
process streams.

MERCURY MODEL

Thermodynamic Data
Shell’s Modified and Improved Redlich Kwong (SMIRK) equation of state has been used to
calculate the distribution of mercury between gas, condensate and aqueous streams. This model uses a
specific set of pure component parameters to yield a good description of the vapor pressure of mercury
over a wide temperature range of –30 °C to 300 °C. In addition, the liquid densities of mercury are
accurately described using the same model parameter set. Furthermore the model contains interaction
parameters for all relevant binary systems with mercury i.e. those involving hydrocarbons, water and
TriEthylene Glycol (TEG). These interaction parameters were based on experimental data in temperature
range 0 °C to 150 °C. A generalized expression for the binary interaction parameters of mercury-
hydrocarbon was developed for application to all hydrocarbon types as well as fractions. Model
predictions for the solubility of mercury in methane or a methane rich gas under low-pressure conditions
(say below 10 bar) are accurate as these only rely on the vapor pressure of pure mercury. At higher
pressures gas-phase non-ideality enhances the mercury solubility in dense gas compared to ideal gas (see
section on Mercury Distribution). Unfortunately, no experimental data is available to verify the model
predictions.
 Model predictions for the solubility of mercury in n-octane and water are compared with
experimental data [7, 8] in Figure 1. As can be seen in the figure, the mercury solubility in n-octane at
25 °C is about 1 ppmmol (or 2 ppmwt) whereas the solubility in water is a few orders of magnitude lower
i.e. about 0.005 ppmmol (or 0.06 ppmwt). The mercury solubility in TEG as given in Figure 1 as well, is
derived from data on mercury solubility in various polar solvents, such as water and methanol.

Hg solubility in some liquids

(curves are model predictions)
1.E+03
exp. n-octane
1.E+02 estimated TEG
Hg solubility, ppmmol

exp.water
1.E+01

1.E+00

1.E-01

1.E-02

1.E-03
0 50 100 150
Temperature/degC

Figure 1 – Model Predictions for the Solubility of Mercury in Some Liquids in Comparison
with Experimental Data

Calculation Procedure Mercury Distribution

Using SMIRK’s equation of state, model calculations can be carried out to determine the
distribution of mercury in those parts in the gas treating process where vapor and liquids are in
equilibrium with each other. For separators this is rather straightforward since only one stage needs to
be considered. In contactors and distillation columns this is more complicated and the distribution
needs to be calculated over the whole column using multiple stages. Once the distribution of mercury
over the various gas processing units is known the mass balance for mercury needs to be calculated. To
obtain a mercury distribution over a gas processing plant therefore the following approach was taken:
1. A simplified process flow scheme is derived taking all process units and the corresponding
streams into account that are important for the distribution of mercury.
2. Based on this simplified process flow scheme, model calculations were carried out to establish
the mercury saturation content and distribution between vapor and liquid phases in the various
separators and columns in the gas-processing unit. For columns calculations need to be carried
out for a recreated feed on every tray.
3. The recovery factors (α) of mercury in the output streams of the various units were determined
from distribution coefficients and material balance equations.
4. Finally, the mercury recovery factors (α) were implemented in a HYSYS flow sheet to simulate
 its behavior in the process depending on inlet concentrations.

Simplified Process Flow Scheme of a Gas Processing Plant

A simplified process flow scheme of a gas processing plant is given in Figure 2 and a brief
description of the unit is given below. The process involves both a gas and condensate conditioning
process (in respectively the upper and lower half of Figure 2) to produce sales gas and stabilized
condensate in combination with LPG from inlet gas and condensate streams. The vessels and columns
in the process scheme are further described below.

Flare Gas

V 3104
C 3101
V 2101

V 3101

V 3102

V 3103
Feed

C 3141
Gas

V3141

V4102
V 4104

V 4103

LPG
V 4101

C 4601
C 4101

Feed
Condensate

Stabilised
Condensate

Figure 2 – Simplified Process Flow Scheme of a Gas Processing Plant

Gas processing units:

V 2101: Inlet gas separator. Fluids collected from the wellheads are separated into overhead gas and
liquids. Hydrocarbon condensate reports to the condensate inlet stream for further
processing.
V 3101: TEG unit inlet separator. Gas reports to the TEG contactor and hydrocarbon liquids to
the condensate inlet stream.
C 3101: TEG contactor for drying of the gas to pipeline specification.
V 3141: TEG flash drum for the removal of co-adsorbed gases from water loaded TEG.
C 3141: TEG regenerator for the removal of water and traces of BTX.
V 3104: TEG regenerator gas separator.
V 3102: Low temperature separator inlet separator/scrubber.
V 3103: Low temperature separator. The dew point of export gas is controlled in this part of the
process together with the final mercury content of the export gas.
Condensate processing units:
V 4101: Inlet condensate separator. Overhead gas is recompressed and reports to the gas
processing part of the unit and condensate reports to the stabilizer.
C 4101: Condensate stabilizer. Volatile hydrocarbons report to the overhead section and are
compressed and send to the gas processing part of the plant.
V 4102: Recycle condensate flash vessel. Liquid is fed directly to the stabilizer and overhead gas is
recompressed.
V 4103: First stage flash gas compressor separator. The small amount of liquids is neglected in the
present scheme.
V 4104: Second stage flash gas compressor separator. The small amount of liquid is neglected in
this scheme.
C 4601: Dubutanizer column for the recovery of LPG from stabilized condensate.
The stream data (temperature, pressure and composition) were obtained from a HYSYS flow sheet
model, which applies the Peng - Robinson equation of state for the thermodynamic calculations. The
stream data were used to calculate the saturated mercury content of each stream employing SMIRK. A
summary of the stream data and the predicted mercury saturation contents are given in Table I.

Table I – Stream Conditions, Mercury Solubility and K-values

Inlet V3101 V3102 V3103 V4104 V4101 V4103 V4102 Inlet

gas condensate
V2101
Temperature (°C) 95 60 21 6.5 51 56 66 23 51
Pressare (bar) 96.2 94.6 93.1 71.8 38.6 39.1 14.7 39.20 39.2
Normalized stream flow, kgmol/h
Feed 200.0 200.6 198.0 192.3 12.4 20.7 6.4 8.4 7.8
Vapour 188.3 198.6 192.3 189.7 12.2 3.4 6.4 2.6 1.6
L-condensate 9.8 0.4 5.7 2.7 10.2 14.0 0.0 5.8 5.6
Molar mass of streams, kg/kmol
Vapour 20.5 20.6 19.7 19.3 24.2 20.1 28.3 20.6 20.2
L-condensate 99.8 64.5 51.2 49.2 40.3 119.4 - 63.8 125.3
Saturated Hg content ppbmol
Feed 5148 684 58 17 652 2328 3909 326 2060
Vapour 4730 681 50 15 646 880 3909 79 616
L-condensate 13930 2449 299 124 1795 3270 4892 432 2676
L-aqueous 37 14 28 - 11 13 - 17 11
3
Saturated Hg content in µg/Nm
Vapour sat Hg 42335 6095 445 134 5785 7872 34983 706 5510
K-values of Hg (mol/mol)
K (V/L-hc) 0.34 0.28 0.17 0.12 0.36 0.27 0.80 0.18 0.23
K (V/L-aq) 127 47 1.8 - 57 68 - 4.5 55
K (L-hc/L-aq) 375 170 11 - 160 251 - 25 239

It should be noted that the relatively small water streams produced in the various units are not
listed in Table 1. Furthermore, since the rich TEG stream was treated as a product stream in the
HYSYS flow sheet, no stream data was available for the TEG regeneration section (i.e. V 3141, C
3141 and V 3104). In view of the overall low amount of mercury that reports to the rich TEG stream
this is not a problem for the overall mercury mass balance as long as the gas inlet stream to the
contactor remains under-saturated.

RESULTS MERCURY MODELING

Mercury Distribution
The amounts of mercury that end up in the vapor or liquid hydrocarbon streams of the various
vessels depend on the relative phase amounts and the distribution coefficients (or K-values) of mercury
[9]. The K-values of mercury, being the ratio of the mole fractions of mercury in gas and liquid, depend on
temperature and pressure and to a lesser extent on the hydrocarbon gas and liquid phase compositions. All
these variables are different for the individual separators and hence a direct comparison of the results given
in Table I would be difficult or even meaningless.
To illustrate the effect of temperature and pressure, K-values of Hg were computed between vapor and
hydrocarbon liquid for a specific gas-condensate mixture in the relevant temperature and pressure range.
For this purpose the inlet gas separator (V 2101) feed was selected. The results are shown in Figure 3,
which also includes the data-point corresponding to the actual V 2101 conditions.

calculated K-values (V/Lhc) of Hg in V2101 at different conditions

1
T/degC
K-value (Hg) [mole/mole]

95

50

0.1 5

0.01
0 20 40 60 80 100
Pressure [bar]

Figure 3 – Effect of Temperature and Pressure on the K-values of Mercury in a Selected Gas
Condensate System Using V 2101 Feed Composition

In brief these results indicate that higher temperatures lead to higher K-values (driven by the vapor
pressure of Hg). At low pressures (say << 20bar), the K-values vary proportional with the reciprocal
pressure, since non-ideality effects due to pressure in both vapor and liquid phase can be neglected. At
higher pressures, the non-ideality effects due to pressure in both vapor and liquid contribute substantially
to the K-value behavior, notably:
• The gas phase becomes denser which causes an increase of the mercury content (in other words
the gas starts to act as a solvent).
• The liquid phase composition changes drastically due to dissolved gas, which causes a decrease
of the density and the mercury content as well (in other words the liquid looses part of its
solvent power).
Largest pressure effects occur at the lowest temperatures. For the case illustrated here this causes a
minimum in the K-value near 60 bar at 5 °C. At higher temperatures this minimum shifts to higher
pressures.

Mercury Recovery Factors

From the data presented in Table I, the mercury recovery factors (defined as the fraction of mercury
entering the feed and leaving via the output stream considered) for the co-existing vapor and liquid phases
can be determined in order to calculate the mercury partitioning when streams are under- saturated in
mercury. These factors are listed in Table II. Clearly the amount of Hg that ends-up in the water streams
can be ignored.

Table II Predicted Mercury Recovery Factors for the Various Process Streams

Vessel/Column Mercury recovery factor (α)

Vapor (top) Liquid - condensate Liquid – aqueous

V 2101 0.8641 0.1358 0.00007

V 3101 0.9824 0.0174 0.00017

V 3102 0.8250 0.175 0.00000

V 3103 0.8717 0.1283 -

V 4101 0.0668 0.9323 0.00089

V 4102 0.0728 0.9272 0.00002

V 4103 1.0000 0.0000 -

V 4104 0.9753 0.0246 0.00013

C4601 – tray 14 0.9997

The mercury recovery factors for columns depend on the vapor and liquid flows, compositions and
tray conditions which themselves depend on the location of the trays.
More detailed results for the TEG contactor C 3101 with 2 theoretical stages is given in Table III.
In view of the relatively high vapor flows and merury K-values > 1 it is not surprising to find that almost
all mercury ends up in the top product.
 Table III – Mercury Distribution in the TEG Contactor

Stage Hg K-value Vn Ln α-n α (top, feed n)

1 4.7010 198.5 2.32 0.997522 0.999993

2 5.2420 198.6 2.75 0.997370 0.997363

α-n : fraction of mercury entering tray n, leaving the tray via the vapor phase.
α (top, feed k) : fraction of Hg entering as feed on tray n and leaving the unit via the top.
K-value : mol fraction of mercury in gas divided by the mol fraction in the liquid.
Vn(Ln) : vapor (liquid) normalized mol flow on tray n.
For the more complex stabilizer the details are summarized in Table IV.
Table IV – Mercury Distribution in Stabilizer C 4101

Tray K-values Vn Ln α-n α (top, feed n)

1 0.69 5.47 6.13 0.38 0.77

2 0.78 5.46 6.76 0.39 0.63

3 0.80 6.09 12.89 0.27 0.55

4 1.13 6.55 14.21 0.34 0.51

5 1.52 8.15 1.54 0.89 0.50

6 2.36 8.42 17.21 0.54 0.36

7 2.47 2.87 18.43 0.28 0.19

8 2.58 4.09 19.56 0.35 0.13

9 2.76 5.23 20.74 0.41 0.10

10 3.21 6.40 21.74 0.49 0.07

11 (reboiler) 4.62 7.40 14.34 0.70 0.05

The feed streams enter the stabilizer at tray 1, 3 and 6. Of the mercury present in the feed streams
77 % from tray 1, 55 % of tray 3 and 36 % of tray 6, will report to the top of the column. The overall
mercury recovery over the top of the stabilizer can thus be calculated and amounts to 56 %.
In the Debutaniser, C 4601 mercury will report quantitatively to the top due to the relatively high
K-values of mercury (i.e. above unity on all trays) in combination with the many stripping & rectifying
trays. The fraction of mercury entering via the feed on tray 14, leaving the unit (configured with 23
theoretical trays, reboiler and condenser) via the top can be calculated by solving the material balance
calculations for all separate trays, taking into account the individual recovery factors for all these trays and
amounts to 0.99967.

Calculation of the Mercury Profile in the Simplified Process Flow Scheme

A HYSYS flow sheet was developed to simulate mercury flow in the gas processing plant. The
flow sheet consists of a set of component splitters in which the mercury inlet flow is split into a vapor and
a liquid flow using the recovery factors representative for the various units. Input variables are mercury
flows in the feed gas and feed condensate. The main flow sheet uses ten splitters representing the eight
vessels and two columns, i.e. the TEG contactor and the debutanizer (see Figure 1). The stabilizer is
modeled in a sub flow sheet by means of 3 different splitters representing the feed trays (1, 3, 6), as
indicated in Table IV. A HYSYS TEE-splitter is implemented in the feed to the low-temperature separator
V 3103 to control the amount of mercury. When this amount is above saturation level at V 3103
conditions, then the free mercury ends up in the “Hg-dropout” stream.
Using the model thus developed the following cases were simulated:
1. Case(s) that matched the currently measured 30 µg/Nm3 of mercury in the export gas.
2. A case by which all mercury enters via the gas feed. The total mercury concentration being such
that it is under saturated in all streams (no mercury dropout occurs in any unit).
3. A case by which all mercury enters via the condensate feed. The total mercury concentration being
such that it is under saturated in all streams (no mercury dropout occurs in any unit).
4. Mercury inlet levels at feed gas and feed condensate such that progressively mercury dropout
occurs in various units.

0.08 % Flare Gas

7.8 % 30.6 ug/Nm3 Export

gas
V 3104

23 %
C 3101

35 ug/Nm3
V 2101

V 3101

0.7 %
V 3102

V 3103
Feed
C 3141

Gas 23 %
0.08 %

V3141
3%
23 %
0.08 %
V4102
9% 9%
V 4104

0.4 % 400 ppbw

9%
V 4103

3% LPG
4.0 %
V 4101

14 ppbw
C 4601
C 4101

Feed
Condensate
0.4 %
0.32 %

15 ppbw
0.4 % Stabilised
20 ppbw Condensate

Figure 4 – Calculated Mercury Concentration as % of the Saturation Level in Major Streams

The results for Case 1 are given in Figure 4. Using the chosen mercury inlet contents to match the
known mercury contents in sales gas as indicated in the figure, the resulting mercury levels in the two
other main product streams of the processing unit being stabilized condensate and LPG were predicted to
be 15 ppbw and 401 ppbw, respectively (at the current split of condensate to the debutanizer of 20 %). In
actual practice mercury levels in LPG of 200 – 500 ppbw and 25 – 50 ppbw in stabilized condensate have
been measured at mercury levels in the export gas of 10 – 30 µg/Nm3, in reasonable good agreement with
the levels predicted by the model.
The results for Case 2 and Case 3 are collected in Table V. It is clear from the table –Case 2- that
mercury entering with the feed gas reports for almost 80 % to the export gas and for about 20 % in the
condensate downstream the stabilizer; the latter amount is further distributed in accordance with the
condensate split to the debutanizer and as a result 3.7 % ends up in the LPG and 15.6 % in the condensate
product. For Case 3, of the mercury entering with the condensate, 49 % reports to the export gas. The latter
is of course related to the amount of mercury that reports to the overhead vapor stream in the stabilizer
(56 %). A small part of this 56 % will report back via the liquids knocked out in V 3101, V 3141 and
V 3104, giving an overall figure of 49 %. Again as a result of the condensate split to the debutanizer
39.6 % of the mercury will end up in the condensate product and 9.5 % in the produced LPG.

Table V – Mercury Distribution over Product Streams Depending on Feed Streams

Relative molar flow of mercury (%)

Feed gas 100 0

Feed condensate 0 100

Recovery of mercury in product streams in (%) of total inlet

Export gas 79.7 49.0

Condensate 15.6 39.6

LPG 3.7 9.5

Liquid ex V 4103 0.0 0.0

Liquid ex V 4104 0.7 1.7

Absorbed in TEG 0.3 0.2

Mercury Dropout in Process Units

The results for Case 4 are collected in Figure 5. Mercury levels in the streams depend linearly on
the input flows of mercury as long as these streams are all below saturation level. This also means that a
linear relationship exists between the mercury contents in feed gas and feed condensate that yields a
certain mercury level in one of the streams In Figure 5, the first line corresponds to an export gas mercury
concentration of 30 µg/Nm3. The results presented above in Figure 4 (c.q. in Case 1) for a specific
combination of mercury levels in feed gas and feed condensate refer to a point on this line.
In view of the relatively high temperature in the LTS (i.e. about 6.5 °C) relatively high mercury
concentrations in the feed gas and/or condensate are allowed before mercury drops out. In Figure 5 the
second saturation line illustrates at which inlet levels of mercury dropout will occur in V 3103. In the
absence of mercury in the feed condensate, this occurs beyond mercury concentrations of 160 µg/Nm3 in
the feed gas. As can be seen in the figure, this concentration decreases linearly with increasing mercury
concentrations in the feed condensate. The mercury saturation content in the export gas along this line
amounts to 134 µg/Nm3. When the mercury content in the feed gas increases further then also mercury
dropout will occur in V 3102. Line 3 in Figure 5 illustrates this. On the other hand when the mercury
content in the feed condensate becomes rather high then mercury dropout will occur in the LPG stream as
is illustrated by line 4 in Figure 5.

Hg levels in process streams

1 matching Hg content in export gas (ex-V 3103): 30 ug/Nm3

2 Hg dropout in V 3103
3 Hg dropout in V 3102
4 Hg dropout in LPG (C 4601-condenser)
Hg content in feed condensate, ppbw

2500

3
2000

1500
4
1000 2

500
1
0
0 50 100 150 200 250 300 350 400 450 500
Hg content in feed gas, ug/Nm3

Figure 5 – Inlet Conditions under which Mercury Deposition will Occur in Gas Processing
Equipment

DISCUSSION

The work shows that by making use of a combination of Shell’s SMIRK equation of state to
calculate the distribution of mercury between gas, condensate and aqueous streams and combining this
with a HYSYS simulation of a gas processing plant, the distribution of mercury over the various
process streams can be predicted. By calculating the recovery factors for mercury for each vessel and
column in the gas processing flow sheet and implementing those as component splitters in a HYSYS
flow sheet, the mass balance for mercury over the entire unit can be solved.
The predicted solubility of mercury in n-octane and water is in good agreement with measured
published data, giving confidence that values predicted for hydrocarbon and aqueous streams in the
process flow sheet are reliable. For prediction of the solubility of mercury in TEG the situation is
different. Due to a lack of experimental data a proper comparison between calculated and measured
data is not possible [10]. The solubility of mercury in TEG is derived from data on the solubility of
mercury in various polar solvents such as water and methanol. In addition, by the condensation of
liquid hydrocarbons in the TEG contactor the split of mercury between the vapor and the liquid phase
will change significantly. Fortunately, the amount of hydrocarbons that condense/dissolve in the TEG
contactor is very small (the gas feed to the contactor is under-saturated which avoids potentially large
effects due to the presence of dispersed mercury) and in such a case the influence on the mercury
distribution will be small as well. In the overall process flow scheme only 0.2 – 0.3 % of the mercury
in the input reports to the wet TEG bottom stream in the TEG unit. Even if the calculations would be
wrong by one order of magnitude for the solubility of mercury in TEG, this would have only negligible
influence on the overall mercury distribution and mass balance for the major product streams. This
holds for this process flow scheme only, but can be different for other gas compositions where a large
liquid fraction reports to the TEG stream or when the gas is saturated with mercury and hence may
carry dispersed mercury.
In the first simulations the mercury inlet concentrations were chosen such as to arrive at the
known and measured export gas mercury concentration. However, it is reassuring to see that the
mercury levels as measured in the produced LPG and condensate are in line with the levels predicted
by the model.
The model can be used to assess the behavior of mercury in the gas processing plant and relate
this to problems such as:
1. The requirement for mercury removal from export gas depending on the operating conditions in
the LTS unit.
2. Potential mercury dropout in various process units (in relation with inlet levels and operating
conditions) and as a result the potential exposure of workers to mercury during maintenance. In
addition, an inventory can be made of process equipment susceptible to mercury-induced
corrosion.
3. The requirement for mercury removal from condensate and LPG on the basis of predicted
mercury levels from measured levels in export gas and in the vapor overhead of V 2101 only.
It is clear that under the conditions in this flow scheme a major part of the mercury entering the
unit will be produced with the export gas. This is not a general rule but depends on the mercury inlet
levels in gas and condensate and on the operating conditions. By lowering the temperature in the LTS
unit from 6.5 °C to – 25 °C the mercury saturation content of the export gas will reduce dramatically
from 134 µg/Nm3 to approximately 10 µg/Nm3. In that case part of the mercury would drop out in V
3103 and not be produced with the gas. However, by changing the operating conditions the
composition and the dew point of the export gas will change. This will put a limit on the temperature
range that can be employed. In another example it was predicted that by increasing the top temperature
of a stabilizer by 20 °C this should have a dramatic effect on the mercury recovery with the vapor,
thereby reducing the mercury content of the produced condensate to acceptable levels. In practice this
was observed and controlling the top temperature of the stabilizer controlled the mercury levels in the
produced condensate.

CONCLUSIONS

Shell’s Modified and Improved Redlich Kwong equation of state can be used successfully to calculate
the distribution of elemental mercury between gas, condensate and aqueous streams for the various process
units at the conditions of interest. For each main unit (eight vessels and three columns) mercury recovery
factors (α) can be calculated.
Using a developed HYSYS process flow sheet the flow of metallic mercury in the gas processing plant
can be simulated. The calculated recovery factor α for each vessel and column is now used as split factors
in the HYSYS flow sheet to calculate the split of mercury between the product streams of the unit at a
certain mercury inlet level of the feed gas and feed condensate. In this way a mass balance for mercury
over the entire unit can be generated and the concentration of mercury in the individual major streams can
be calculated.
Using this approach it was possible to generate the current situation in which the mercury content of
the export gas is 30 µg/Nm3. Using these inlet concentrations the model predicts mercury levels for the
produced LPG and condensate that are close to the levels actually measured, thereby validating the current
model.
Using the model it can be concluded that for the process streams studied above:
1. Under the conditions as specified in Table 1 the streams in the LTS unit will be saturated at a
level of 134 µg/Nm3 of mercury in the sales gas and deposition of liquid mercury in the unit will
start. Consequently, measuring the mercury contents of export gas is a good method to
determine the requirement of mercury removal facilities in the LTS unit (for dispersed mercury
droplets).
2. At conditions below saturation all mercury concentrations in the major streams of the process
flow scheme are directly proportional to the inlet mercury concentrations is the feed condensate
and feed gas and consequently mercury levels of all streams can be estimated by measuring the
sales gas mercury contents and the mercury contents in the overhead vapor of V 2101.
3. Under current operating conditions 80 % of the mercury present in the feed gas will report to the
sales gas and 20 % to the condensate. The latter is further split into 4 % to the LPG and the
remainder remains in the condensate (at the current split of condensate to the debutanizer).
4. All mercury in the condensate sent to the debutanizer will report to the LPG.
5. Under current operating conditions 49 % of the mercury present in the feed condensate will
report to the sales gas and 50 % to the stabilized condensate. The latter is further split into
10 % to the LPG and the remainder remains in the condensate (at the current split).
6. Liquid mercury deposition will first occur in the LTS unit, the unit with the lowest operating
temperature in the process flow scheme.
7. The amount of mercury reporting to the wet TEG in the glycol contactor is small in comparison
to the amount reporting to the dry gas stream.

REFERENCES CITED

1. Cameron, C., Blaise, D., Benayoun, D. and Dorbon, M., “Mercury: A Trace Contaminant in
Natural Gas and Natural Gas Liquids”, Paper presented at Eurogas 96, 3 – 5 June 1996.

2. Wilhelm, S.M. and Bloom, N., “Mercury in Petroleum”, Fuel Processing Technology, 63, 1 – 27,
2000.

3. Snell, J., Johansson, M., Frech, W. and Smit, K., “Stability and Reactions of Mercury Species in
Organic Solutions”, Analyst, 123, 905, 1998.

4. Frech, W., Baxter, D.C., Balke, B., Snell, J, and Thomassen, Y., “Determination and Speciation of
Mercury in Natural Gases and Gas Condensates”, Analytical Communications, 33, 7H, May 1996.
5. Lund, D., “Wyoming Operator Solves Mercury Exposure Problems”, Oil and Gas Journal, May 13
1996, 70 – 77.

6. Dolle, J. and Gilbourne, “LNG Startup of the Skikda LNG Plant”, Chem. Eng. Progress 72, 39,
1976.

7. Clever, H.L., “Mercury in Liquids, Compressed Gases, Molten Salts and Other Elements”, IUPAC
Solubility Date Series, 29, 1987.

8. Migidisov, A.A., Kister, P and Williams-Jones, A.E., “An Experimental Study of the Solubility of
Liquid Mercury in Octane and Dodecane at Temperatures up to 200°C”, J. of Conf. Abstracrs”, 5
issue 2, 706, 2000.

9. Edmonds, B., Moorwood, R.A.S. and Szczepanski, R., “Mercury partitioning in Natural Gases and
Condensates”, Paper presented at the GPA European Chapter Meeting in London 21 March 1996.

10. Wilhelm, S.M., “Mercury in Petroleum & Natural Gas: Estimation of Emissions from Production,
Processing and Combustion”, USA EPA R&D Report, EPA/600/R-01/066, September 2001.