Advancements in the Removal of

Mercury
From

Crude Oil

pam boschee, oil and gas facilities editor

Production from the Kipper gas field is delayed until ExxonMobil completes the modifications
required for mercury removal at its onshore gas processing facilities. Photo courtesy of ExxonMobil.

lobal awareness of the environmental effects of

mercury has grown significantly over the past
decade. In the oil and gas industry, the presence of
mercury in natural gas, condensate, and crude oil has come
to the forefront in the development, design, and operation of
hydrocarbon processing equipment.
Global exploration and production has expanded to
regions containing hydrocarbons with higher concentrations
of mercury than were previously encountered. Mercury
deposits are often associated with geological plate boundaries,
fold belts, and areas with volcanic or hydrothermal activity.
Table 1 shows the regional estimated levels of mercury in
natural gas and condensates.
Issues associated with mercurys presence in
hydrocarbon processing systems have become more apparent
as deeper and hotter reservoirs (often with higher levels of
mercury) were exploited, and with the low-temperature
gas processing used for liquefied natural gas (LNG) and
natural gas liquids (where mercury accumulates in the lower
and cooler parts of the processing equipment). Increased
offshore processing and the use of lightweight aluminum
cryogenic heat exchangers has revealed the problems
associated with mercury amalgamation with aluminum
and the resultant weakening of the metal through corrosion
andembrittlement.
Mercury presents technical challenges through the
following mechanisms:
Corrosion/embrittlement
- Caused by elemental mercury
- Amalgamation with aluminum, copper, zinc,
othermetals
- Amalgam corrosion
- Liquid metal embrittlement
- Galvanic corrosion
Precipitation of mercury sulfide
- Fouling and plugging of compact equipment
Mercury in most forms (species) is toxic and contributes
to health, safety, and environmental risks. In natural gas,
mercury occurs as the metallic form (species). Various forms
of mercuryelemental, organometallic, and inorganic salt
can be present in natural gas condensates, depending on the
origin of the condensates. Knowledge of the different species
and total mercury content in condensates is important,
because the damage caused to industrial facilities, particularly
petrochemical plants, by the presence of mercury can be
financiallycrippling.
In 1973, recognition of the effects of mercury in natural
gas occurred when a catastrophic failure of aluminum heat
exchangers occurred at the Skikda LNG plant in Algeria
(Spiric 2001). Subsequent investigations determined that
mercury corrosion caused the failure. It was postulated that
the mercury likely came from an accidental source, such
as the testing instruments used in plant and field startup.
Further investigation found that a combination of mercury
and water temperatures around 0C caused corrosion in the
aluminum tubes (constructed of aluminum alloy 6061).

TABLE 1ESTIMATED MERCURY CONCENTRATIONS IN

NATURAL GAS AND CONDENSATE FOR WORLD REGIONS

Mercury Concentration
Location

Gas
(g/m3)

Liquids
(g/kg)

Europe

100150

South America

50120

50100

Gulf of Thailand

100400

4001200

Africa

80100

5001000

Gulf of Mexico (USA)

0.020.4

Overthrust Belt (USA)

515

15

North Africa

5080

2050

Malaysia

1200

10100

Indonesia

200300

10500

Source: Paper SPE 106610.

After the Skikda failure, a study of the Groningen field

in Holland revealed similar corrosion in the gas gathering
system. Carbon dioxide was initially thought to be the
cause, but later investigations pinpointed mercury, with
concentrations ranging from 0.001 to as high as 180 g/Nm3
(Nm3 represents normal m3 under standard temperature
andpressure).
With the realization of the equipment failures and
multimillion-dollar cost implications of mercury in
hydrocarbons came increased efforts to develop mercury
removal technologies and processes.
The processes and technologies used to remove mercury
from natural gas are generally considered mature, but the
industrys experience in the removal of mercury from raw
condensate is limited. Petronas has published its work on
developing mercury removal units for raw and untreated
condensate (Sainal et al. 2007a, 2007b) and is collaborating
with Queens University, Belfast, Ireland, to develop ionic
liquids for mercury removal from natural gas and condensate
(Shariff 2011).
Technologies for the removal of mercury from crude oil
are the least mature and the topic of this article.

Mercury in Crude Oil

Mercury in crude oil has received more scrutiny as refineries

seek cleaner oil for their product streams. Among the
problems cited are: excessive levels of mercury in wastewater
streams, preventing discharge in open rivers or oceans;
mercury contamination of products generated from the
refinery streams, such as gas streams, liquefied petroleum gas,
and light or heavy distillate products; hydrotreating catalyst
poisoning or contamination in refined streams because of
metal amalgamation; corrosion of equipment because of
metal embrittlement; and additional expenses in upstream
and downstream facilities because of special disposal
requirements for contaminated mud from tanks, cleaning
April 2013 Oil and Gas Facilities

13

10,000
9,000

Total Mercury, ppbw

8,000
7,000
6,000
5,000
4,000
3,000
2,000
1,000
0
01-Sep

05-Sep

09-Sep

13-Sep

17-Sep

21-Sep

25-Sep

29-Sep

Fig. 1Variation in daily measurements of mercury content. Source: Paper SPE 138333.

of equipment and ships, and restricted product shipping

alternatives.
Although refiners have added processes for mercury
removal in the lighter hydrocarbon product streams, stricter
limits for mercury in crude oils entering the refineries are
being implemented, driving producers to develop approaches
to ensure commercialization of their crude oil.
Two or more types of crude oils are sometimes blended
to moderate the mercury concentrations, but variations
in mercury levels across reservoirs and within reservoirs
prevent this approach from being reliable and do not
eliminate potential restrictions on the acceptance of the
produced crude oil.

T~70-60C
Line Pipe

Fig. 1 shows the wide variation of mercury content in

crude oil from a reservoir in Argentina through a 1-month
period (Salv and Gallup 2010). The total mercury content
ranged from approximately 1,500 to 8,000 parts per billion by
weight (ppbw). In fields related to the Springhill formation
of the Austral basin in Argentina, hydrocarbon liquids are
produced with high mercury concentrations, where the
mean mercury concentration after blending remains close to
3,300ppbw.
Salv and Gallup reported the results of the only
commercially operated upstream mercury removal plant
(MRP) for crude oil. The authors stated that despite the
availability of technologies for mercury removal from liquid

Gas

Gas-Liquid
Separator

Elemental
Mercury

Water
Tubing

Oil

Mercury
T~130C

Oil

Ionic Mercury
Elemental Mercury
Water

Fig. 2Mercury distribution in an oilfield separation system. Source: Paper SPE 138333.

14

Oil and Gas Facilities April 2013

Particulate
(300-10,000 ppb)
Dissolved
(100-1,000 ppb)

hydrocarbons, most of them are applicable to refinery

product streams. Proprietary technologies exist for upstream
removal of mercury from crude oil, but there are no available
data for actual industrial applications.
Developed by Petrobras Argentina and Unocal (now a
subsidiary of Chevron), the onshore MRP began operation in
2006 in southern Argentina. The processes used in the MRP
were originally patented by Unocal and licensed to Petrobras.
Darrell Gallup, consultant at Thermochem, previously
served as senior consultant at Unocal and holds several
patents related to the processes used in the Petrobras MRP.
He said a driver for the removal of mercury from crude oil
was the growing trend by refiners to apply a discount of
USD 2/bbl when purchasing crude oil containing more than
100 ppbw of mercury. A few years ago, the discounts were
more than USD 20/bbl, Gallup said. The goal is to achieve
25 ppbw or less because refiners are shifting from applying
discounts to paying a premium on the cleaner [lower
mercury content] crude.

Mercury Partition in Production Systems

Most of the mercury species are not stable and undergo

changes in their physical states and chemical compositions
as they go through the processes in the production system.
The metallic form is the predominant form at the wellhead
in the southern Argentinean fields. Mercury drops are
frequently observed in the gas separator equipment. Metallic
mercury is a liquid at room temperature, but may remain in
the vapor phase at reservoir conditions. During the lifting
process from the bottom of the well to the production gas/
liquid separator, the product stream is often cooled down.

TABLE 2CRUDE OIL CHARACTERIZATION

Crude Oil Type

Black oil-condensate blend

Viscosity, cSt

1.9

API

50

Water, %

< 0.1

TSS, ppm

100200

Other

Paraffins and some asphaltenes

Source: Paper SPE 138333.

Small drops of mercury are condensed and tend to coalesce

and form larger drops in the separator. The larger drops tend
to separate toward the water phase in the dehydration tanks.
The smaller drops remain suspended in the hydrocarbon
phase, producing the observed contamination of the export
crude oil (Fig. 2).
Drops of elemental mercury condense and adhere to
the walls of the pipelines and vessels, creating mud deposits
in association with other solids, such as oxides, sand, and
clay. The mud deposits are released or removed by the use of
cleaning pigs, causing an increase in total mercury content at
downstream receiving facilities.

Petrobras MRP Processes

The mercury removal processes were applied to a blend

of black oil and gas condensate that contained an average
of 3,300 ppbw of total mercury. Table 2 shows the
characteristics of the crude oil treated in the MRP. The
treating capacity of the MRP is up to 6,500 BOPD using
250

5,000

Left axis, inlet total mercury, ppbw

4,000

200

3,000

150

2,000

100

1,000

50

0
1-Dec

6-Dec

11-Dec

16-Dec

21-Dec

26-Dec

31-Dec

Total Mercury at Outlet, ppbw

Total Mercury at Inlet, ppbw

Right axis, outlet total mercury, ppbw

Fig. 3Mercury removal performance trend at MRP. Source: Paper SPE 138333.

April 2013 Oil and Gas Facilities

15

Untreated
surge
tank

Chemical
Reactor
mixer

Inlet
oil

Filter
Production
water

Heater
Treated
oil tank
Outlet
clean oil

Diatomaceous
earth
Solids
to disposal

Fig. 4Mercury removal plant process flow diagram. Source: Paper SPE 138333.

a continuous process that operates 24 hr/d. The average

mercury content at outlet was less than 100 ppbw. The
removed waste material containing residual mercury matter
was reinjected in diluted aqueous form to a deep disposal
well near the MRP.
Gallup said the original concept design for the MRP was
first pilot tested at an oil storage terminal near the producing
oil fields and was based on a patented Unocal method. The
process steps are described below:
1. Desanding hydrocyclone. Crude oil is delivered to a
desanding hydrocyclone. In many cases, the mercury in
crude oil is predominantly elemental, but sometimes it is
present as droplets or is encapsulated in wax, or absorbed
onto sand particles. Gallup said, We wanted to remove
the solid, semisolid, or liquid droplet mercury initially
to minimize chemical treatment farther downstream in
theaprocess.
2. Stir tank reactor. A sulfur-containing chemical is added
to the stir tank to precipitate the elemental mercury
dissolved in the crude oil. Gallup said, The solubility of
elemental mercury in typical hydrocarbons in crude oil
at room temperature is approximately 1.53 ppm. We
removed the elemental mercury by adding the chemical
and stirring it up in the reactor. When the elemental
mercury was precipitated as mercury sulfide, the crude
oil was moved to a special filter.
3. Filter. The oil was then filtered through a diatomaceous
earth (DE) precoated candle filter to remove the mercury
sulfide precipitate from the crude oil. During the filtering
process, body feed made up of additional DE was pushed
into the crude oil to maintain flow and prevent plugging
of the filter.

16

Oil and Gas Facilities April 2013

4. Absorbents. The filtered crude oil was polished by

flowing it over absorbents (copper sulfide-coated or
impregnated alumina beads), similar to those used in
gas and condensate treatment.
The precipitated mercury and DE was pulsed into a flow,
dropping it into a hopper below the filter. The DE was pushed
through a screw conveyor into a produced water stream
to create a slurry, which was then injected into an offset
injection well.
The pilot tests demonstrated that at an average mercury
feed concentration of approximately 2,000 ppbw, the treated
effluent contained an average of approximately 80 ppbw. The
mercury removal efficiency was about 96% (Fig. 3).
The final design of the industrial plant incorporated
learnings from the pilot plant and was ultimately simplified
and did not include the hydrocyclone, chemical treatment, or
polishing (Fig. 4).
A slightly sour mercury-free crude oil is produced in the
same vicinity as the high-mercury content crude oil. When
the two types of crude oil are blended, the mercury sulfide
precipitates without the addition of chemicals. A stir tank
reactor was installed to ensure that the two crude oils are
thoroughly blended to promote a complete reaction between
them. The blended crude oil is pushed through the DE filter
and is ready for sale without polishing.

Conclusions

The installed MRP successfully treated the crude oil to meet

the mercury level requirements for whole export gross sale
price. In accordance with Petrobras Argentina health, safety,
and environmental policies, the MRP contributed to the
reduction of mercury emissions related to the source crude

oil fields and reduced the spread of mercury contamination

to other sites and sectors of the value chain, such as
transportation, shipping, and refineries.

What Lies Ahead

Gallup, who is involved in the continued development

of the technology for Chevron licensing, said two
additionalcompanies are interested in crude oil mercury
removal applications. Both are onshore projects in
the Patagonia region and have injection wells for
waterfloodingand will likely be able to reinject the DE
withresidual mercury into the reservoir.
A goal in advancing the technology for wider
applicability is to reduce the footprint of the mercury
removalequipment to allow its installation on offshore
platforms or floating storage and offloading vessels,
Gallupsaid. We are trying to miniaturize the process.
One idea, for which a patent has been filed, is to add bulk
iodineto the crude oil to oxidize the mercury from an
elemental to an ionized form. The complexed ionized form
will go into the aqueous phase during separation, instead of
remaining in the oil phase.
A water treatment system would remove the
smallamount of highly concentrated mercury
precipitant,whichwould be sent to a hazardous
materialfacility.
Gallup said that sludge with residual mercury
has been used as an augment for cement. Mercury
residual precipitant is encapsulated by combining
sand,aggregate,and cement to make a beneficial
useproduct. We have used sludge from sources other
thanthis crude oil mercury removal process that
hadmercury and other metals in it for cement. Wehave
a special formulation thatallows it to be includedina
nonshrinking cement that passes Californiasstringent
regulatory standards better than many types
ofshrinkingcements. OGF

For Further Reading

ETCE2001-17085 Innovative Approach to the Mercury
Control During Natural Gas Processing by Z. Spiric, INA
Naftaplin.
SPE 106610 Mercury Removal System for Upstream
Application: Experience in Treating Mercury From Raw
Condensate by M.R. Sainal, A. Shafawi, and I.A.J. Mohamed,
Petronas.
SPE 110118 Mercury Removal Project: Issues and
Challenges in Managing and Executing a Technology
Project by M.R. Sainal, T.M.U.T. Mat, and A. Shafawi,
Petronas et al.
SPE 138333 Mercury Removal Process is Applied to Crude
Oil of Southern Argentina by C. Salv, Petrobras, and D.
Gallup, Chevron.
Shariff, S.M. 2011.Mercury Removal From Gas Streams
Using New Solid Adsorbents. Presentation given at the
International Gas Union Research Conference, Seoul, Korea,
1921 October.

Society of Petroleum Engineers

th

THE
MIDDLE EAST HEALTH, SAFETY,
ENVIRONMENT & SUSTAINABLE DEVELOPMENT
CONFERENCE & EXHIBITION (MEHSE)

PLAN
TO
ATTEND
www.spe.org/events/mehse
w
w w s pe o rg

24 September 2013
Qatar National Convention Centre, Doha

April 2013 Oil and Gas Facilities

17