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.
G
lobal awareness of the environmental effects of TABLE 1—ESTIMATED MERCURY CONCENTRATIONS IN
mercury has grown significantly over the past NATURAL GAS AND CONDENSATE FOR WORLD REGIONS
decade. In the oil and gas industry, the presence of
mercury in natural gas, condensate, and crude oil has come Mercury Concentration
to the forefront in the development, design, and operation of Location Gas Liquids
hydrocarbon processing equipment. (µg/m3) (µg/kg)
Global exploration and production has expanded to Europe 100–150 –
regions containing hydrocarbons with higher concentrations
of mercury than were previously encountered. Mercury South America 50–120 50–100
deposits are often associated with geological plate boundaries, Gulf of Thailand 100–400 400–1200
fold belts, and areas with volcanic or hydrothermal activity.
Africa 80–100 500–1000
Table 1 shows the regional estimated levels of mercury in
natural gas and condensates. Gulf of Mexico (USA) 0.02–0.4 –
Issues associated with mercury’s presence in
Overthrust Belt (USA) 5–15 1–5
hydrocarbon processing systems have become more apparent
as deeper and hotter reservoirs (often with higher levels of North Africa 50–80 20–50
mercury) were exploited, and with the low-temperature Malaysia 1–200 10–100
gas processing used for liquefied natural gas (LNG) and
Indonesia 200–300 10–500
natural gas liquids (where mercury accumulates in the lower
and cooler parts of the processing equipment). Increased Source: Paper SPE 106610.
offshore processing and the use of lightweight aluminum
cryogenic heat exchangers has revealed the problems After the Skikda failure, a study of the Groningen field
associated with mercury amalgamation with aluminum in Holland revealed similar corrosion in the gas gathering
and the resultant weakening of the metal through corrosion system. Carbon dioxide was initially thought to be the
and embrittlement. cause, but later investigations pinpointed mercury, with
Mercury presents technical challenges through the concentrations ranging from 0.001 to as high as 180 µg/Nm3
following mechanisms: (Nm3 represents normal m3 under standard temperature
• Corrosion/embrittlement and pressure).
- Caused by elemental mercury With the realization of the equipment failures and
- Amalgamation with aluminum, copper, zinc, multimillion-dollar cost implications of mercury in
other metals hydrocarbons came increased efforts to develop mercury
- Amalgam corrosion removal technologies and processes.
- Liquid metal embrittlement The processes and technologies used to remove mercury
- Galvanic corrosion from natural gas are generally considered mature, but the
• Precipitation of mercury sulfide industry’s experience in the removal of mercury from raw
- Fouling and plugging of compact equipment condensate is limited. Petronas has published its work on
Mercury in most forms (species) is toxic and contributes developing mercury removal units for raw and untreated
to health, safety, and environmental risks. In natural gas, condensate (Sainal et al. 2007a, 2007b) and is collaborating
mercury occurs as the metallic form (species). Various forms with Queens University, Belfast, Ireland, to develop ionic
of mercury—elemental, organometallic, and inorganic salt— liquids for mercury removal from natural gas and condensate
can be present in natural gas condensates, depending on the (Shariff 2011).
origin of the condensates. Knowledge of the different species Technologies for the removal of mercury from crude oil
and total mercury content in condensates is important, are the least mature and the topic of this article.
because the damage caused to industrial facilities, particularly
petrochemical plants, by the presence of mercury can be Mercury in Crude Oil
financially crippling. Mercury in crude oil has received more scrutiny as refineries
In 1973, recognition of the effects of mercury in natural seek “cleaner” oil for their product streams. Among the
gas occurred when a catastrophic failure of aluminum heat problems cited are: excessive levels of mercury in wastewater
exchangers occurred at the Skikda LNG plant in Algeria streams, preventing discharge in open rivers or oceans;
(Spiric 2001). Subsequent investigations determined that mercury contamination of products generated from the
mercury corrosion caused the failure. It was postulated that refinery streams, such as gas streams, liquefied petroleum gas,
the mercury likely came from an accidental source, such and light or heavy distillate products; hydrotreating catalyst
as the testing instruments used in plant and field startup. poisoning or contamination in refined streams because of
Further investigation found that a combination of mercury metal amalgamation; corrosion of equipment because of
and water temperatures around 0°C caused corrosion in the metal embrittlement; and additional expenses in upstream
aluminum tubes (constructed of aluminum alloy 6061). 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

8,000
Total Mercury, ppbw

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. 1—Variation 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.
Fig. 1 shows the wide variation of mercury content in
crude oil from a reservoir in Argentina through a 1-month
period (Salvá 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
3,300 ppbw.
Salvá 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
T˚~70-60˚C Gas-Liquid Elemental
Line Pipe Separator Mercury

Water Oil
Tubing

Particulate
(300-10,000 ppb)
Mercury

Dissolved
T˚~130˚C Oil (100-1,000 ppb)
Ionic Mercury
Elemental Mercury

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

14 Oil and Gas Facilities • April 2013

hydrocarbons, most of them are applicable to refinery TABLE 2—CRUDE OIL CHARACTERIZATION
product streams. Proprietary technologies exist for upstream Crude Oil Type Black oil-condensate blend
removal of mercury from crude oil, but there are no available
data for actual industrial applications. Viscosity, cSt 1.9
Developed by Petrobras Argentina and Unocal (now a API° 50
subsidiary of Chevron), the onshore MRP began operation in Water, % < 0.1
2006 in southern Argentina. The processes used in the MRP
were originally patented by Unocal and licensed to Petrobras. TSS, ppm 100–200
Darrell Gallup, consultant at Thermochem, previously Other Paraffins and some asphaltenes
served as senior consultant at Unocal and holds several
Source: Paper SPE 138333.
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 Small drops of mercury are condensed and tend to coalesce
USD 2/bbl when purchasing crude oil containing more than and form larger drops in the separator. The larger drops tend
100 ppbw of mercury. “A few years ago, the discounts were to separate toward the water phase in the dehydration tanks.
more than USD 20/bbl,” Gallup said. “The goal is to achieve The smaller drops remain suspended in the hydrocarbon
25 ppbw or less because refiners are shifting from applying phase, producing the observed contamination of the export
discounts to paying a premium on the cleaner [lower crude oil (Fig. 2).
mercury content] crude.” Drops of elemental mercury condense and adhere to
the walls of the pipelines and vessels, creating mud deposits
Mercury Partition in Production Systems in association with other solids, such as oxides, sand, and
Most of the mercury species are not stable and undergo clay. The mud deposits are released or removed by the use of
changes in their physical states and chemical compositions cleaning pigs, causing an increase in total mercury content at
as they go through the processes in the production system. downstream receiving facilities.
The metallic form is the predominant form at the wellhead
in the southern Argentinean fields. Mercury drops are Petrobras MRP Processes
frequently observed in the gas separator equipment. Metallic The mercury removal processes were applied to a blend
mercury is a liquid at room temperature, but may remain in of black oil and gas condensate that contained an average
the vapor phase at reservoir conditions. During the lifting of 3,300 ppbw of total mercury. Table 2 shows the
process from the bottom of the well to the production gas/ characteristics of the crude oil treated in the MRP. The
liquid separator, the product stream is often cooled down. treating capacity of the MRP is up to 6,500 BOPD using

5,000 250

Left axis, inlet total mercury, ppbw

Right axis, outlet total mercury, ppbw
4,000 200

Total Mercury at Outlet, ppbw

Total Mercury at Inlet, ppbw

3,000 150

2,000 100

1,000 50

0 0
1-Dec 6-Dec 11-Dec 16-Dec 21-Dec 26-Dec 31-Dec
Fig. 3—Mercury removal performance trend at MRP. Source: Paper SPE 138333.

April 2013 • Oil and Gas Facilities 15

 Untreated
surge
tank
Inlet
oil
Heater
Treated
oil tank
Outlet
clean oil
Fig. 4—Mercury 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
the aprocess.”
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 1.5–3 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
Chemical
Reactor
mixer
Filter
Production
water
Diatomaceous
earth
Solids
to disposal
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 For Further Reading
to other sites and sectors of the value chain, such as
transportation, shipping, and refineries. ETCE2001-17085 Innovative Approach to the Mercury
Control During Natural Gas Processing by Z. Spiric, INA
What Lies Ahead Naftaplin.
Gallup, who is involved in the continued development
of the technology for Chevron licensing, said two SPE 106610 Mercury Removal System for Upstream
additional companies are interested in crude oil mercury Application: Experience in Treating Mercury From Raw
removal applications. Both are onshore projects in Condensate by M.R. Sainal, A. Shafawi, and I.A.J. Mohamed,
the Patagonia region and have injection wells for Petronas.
waterflooding and will likely be able to reinject the DE
with residual mercury into the reservoir. SPE 110118 Mercury Removal Project: Issues and
A goal in advancing the technology for wider Challenges in Managing and Executing a Technology
applicability is to reduce the footprint of the mercury Project by M.R. Sainal, T.M.U.T. Mat, and A. Shafawi,
removal equipment to allow its installation on offshore Petronas et al.
platforms or floating storage and offloading vessels,
Gallup said. “We are trying to miniaturize the process. SPE 138333 Mercury Removal Process is Applied to Crude
One idea, for which a patent has been filed, is to add bulk Oil of Southern Argentina by C. Salvá, Petrobras, and D.
iodine to the crude oil to oxidize the mercury from an Gallup, Chevron.
elemental to an ionized form. The complexed ionized form
will go into the aqueous phase during separation, instead of Shariff, S.M. 2011.Mercury Removal From Gas Streams
remaining in the oil phase.” Using New Solid Adsorbents. Presentation given at the
A water treatment system would remove the International Gas Union Research Conference, Seoul, Korea,
small amount of highly concentrated mercury 19–21 October.
precipitant, which would be sent to a hazardous
material facility.
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
use product. “We have used sludge from sources other
than this crude oil mercury removal process that
had mercury and other metals in it for cement. We have
a special formulation that allows it to be included in a
nonshrinking cement that passes California’s stringent
regulatory standards better than many types
of shrinking cements.” OGF

April 2013 • Oil and Gas Facilities 17