Bony Budiman

CHEMICAL PRECIPITATION
IN MERCURY REMOVAL
BONY BUDIMAN
2021
Bony Budiman

COMMON QUESTION

• What is mercury ?
• Why mercury shall be concerned ?
• How to monitor mercury ?
• How to deal with mercury?
• Field cases !
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• CHEMICAL PRECIPITATION APPLICATION
• FIELD CASES
• SUMMARY
 Bony Budiman

OBJECTIVE

• Sharing effect of mercury in

oil and gas field
• Sharing mercury removal
mechanism
• Sharing some field cases

Courtesy picture : https://www.bbc.com/news/magazine-25130770

Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• CHEMICAL PRECIPITATION APPLICATION
• FIELD CASES
• SUMMARY
 Bony Budiman

MERCURY IN OIL AND GAS FIELD

• Mercury is a naturally occurring element, present in

virtually all oil and gas.
• Mercury levels in crude oil and gas can vary widely,
both between and within reservoirs and geographical
areas.
• Concentrations vary from low ppb (parts per billion) to
low ppm (parts per million) levels.
• Mercury compounds in crude are largely elemental and
inorganic compounds such as mercuric sulfide

Courtesy picture : Mercury Monitoring in the Oil and Gas Processing Industry, Warren T.Corns, www.psanalytical.com
Bony Budiman

CHEMISTRY OF MERCURY IN LIQUID

HYDROCARBON
TOTAL
MERCURY

PARTICULATE COLLOIDAL
DISSOLVED
MERCURY MERCURY

Insoluble Mercury
Mercury Elemental
Mercury in Adsorbed to Organomercury Ionic Mercury
Sulphide Mercury
Organic Phase Particulate

Divalent Unknown and

Mercury Complexes
Bony Budiman

IMPACT OF MERCURY

• Corrosion with Aluminum

• Health and Environment
• Poison for catalyst in refinery
• Downstream issues at ethylene producer
• Fouling and plugging (as mercury sulfide) of compact equipment
 Bony Budiman

EXPLOSION CAUSED BY LME

• Moomba Gas Processing Plant is the main

supplier of natural gas to South Australia
and NSW.
• At 02.43, 01st January 2004, an explosion
occurred at Train A cause production
interrupted up to 8 months
• Root cause : Liquid Metal Embrittlement
(LME) caused by mercury contact in
aluminum.
• Found pitting at aluminum surface of the
Heat Exchanger

Courtesy picture : https://ieaghg.org/docs/presentations/PPTPDFs/3rdoxywkss08.pdf

 Bony Budiman

MERCURY TO HEALTH AND ENVIRONMENT

• Mercury is a neurotoxin and could be accumulated in organism

• Some effect of mercury to human :
• Tremors;
• Emotional changes
• Insomnia;
• Neuromuscular changes
• Headaches;
• Disturbances in sensations;
• Changes in nerve responses; and/or
• Poor performance on tests of mental function.
• Higher exposures may also cause kidney effects, respiratory failure and death.

Courtesy picture : https://en.wikipedia.org/wiki/Mercury_in_fish

Bony Budiman

MINAMATA DISEASE

• Minamata disease is a neurological disease caused by severe mercury poisoning, especially methyl
mercury (H3C-Hg-X).
• Symptoms
 Blindness
 Cerebral palsy (movement and coordination problems, and other complications)
 Deafness
 Growth problems
 Impaired mental functioning
 Lung function impairment
 Small head (microcephaly)
• Minamata disease was first discovered in the city of Minamata, Kumamoto Prefecture, Japan, in 1956. It
was caused by the release of methylmercury in the industrial wastewater from a chemical factory
Bony Budiman

THRESHOLD OF MERCURY

• WHO has set 2 μg/L (ppb) mercury as its drinking water standard
• The USEPA Toxicity Characterization Leach Procedure (TCLP) defines solid waste or soil
has hazardous when the acetate buffer lixiviant contains ≥ 0.2 mg/kg (ppmw) total
mercury
• Produced water and wastewater discharge limits in the petroleum industry vary
significantly around the world from <0.1 to as high as 100 μg/L (ppb).
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OUTLINE

• OBJECTIVE
• INTRODUCTION

• MONITORING
• TREATMENT METHOD
• CHEMICAL PRECIPITATION APPLICATION
• FIELD CASES
• SUMMARY
 Bony Budiman

MERCURY ANALYSIS

Courtesy picture : Removal Of Mercury From Water In The Petroleum Industry, Darrell L. Gallup, Thermochem, Inc., Santa Rosa, CA, USA
 Bony Budiman

COLD VAPOR ATOMIC ABSORPTION SPECTROSCOPY

(AAS)
• Use the absorption of light.
• Samples are usually liquid or solids.
• Mercury atoms or ions must be vaporized in a flame or graphite furnace.
• The atoms absorb UV-Vis light and make transitions to higher electronic
energy levels then the detector analyze the intensity of energy absorption.
• The intensity of absorption equal to the mercury concentration.
• Detection limit is from 1 ppt (parts per trillion) to 100 ppm (parts per
million).

Courtesy picture : https://www.slideshare.net/rajusanghvi1/prasanth-39978892

 Bony Budiman

ATOMIC FLUORESCENCE SPECTROSCOPY (AFS)

AAS • AFS has similar process with AAS.

• Both in AAS and AFS, a light source is used
for excitation of analyte atoms. However, in
AAS this light source is in a straight-line
AFS optical axis configuration, but in AFS the
light source is rotated 90°
• AFS has a detection limit of 5 ng/L / 5000
ppt / 0.005 ppb

Courtesy picture :
https://reader.elsevier.com/reader/sd/pii/B9780124095472053488?token=61F1CCA45F5C67C31C65BBA1E1F3156F8684C2A1474C750CC5FD5018CC03ADE3F49622CA79BB043CF8
D1ACA5B9BBD409&originRegion=eu-west-1&originCreation=20210723065315
Bony Budiman

INDUCTIVELY COUPLED PLASMA AND MASS

SPECTROMETRY (ICP-MS)
• Energy from the plasma ejects
electron from shell (ionization). The
result is positively charged analyte
ion
• Ions are separated by the mass
spectrometer and measured. Ions
measured are directly proportional
to analyze concentration
• ICP-MS has detection limit of 1 ppt
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• CHEMICAL PRECIPITATION APPLICATION
• FIELD CASES
• SUMMARY
Bony Budiman

TREATMENT METHOD

A. Water Re-Injection
B. Adsorption
C. Filtration
D. Chemical Precipitation
 Bony Budiman

A. WATER REINJECTION

• The most effective method for disposing of mercury-

containing waters that have been in contact with
Hg petroleum hydrocarbons is re-injection.
Hg

• In this manner, mercury is returned to the reservoir

from whence it was originally produced.
Hg • In case water re-injection is not practiced for a variety
of reasons (usually the lack of nearby injection wells). In
Hg
these instances, water is usually disposed to the
environment

Courtesy picture :https://www.researchgate.net/figure/Technical-principle-of-water-injection-well-pipeline-in-oil-production-plant_fig1_342665426

 Bony Budiman

B. ADSORPTION

• The vast majority of adsorbents used to remove mercury species from

aqueous solutions in petroleum operations rely on sulfur capture of mercury in
the form of HgS.
• The high affinity of mercury for sulfur normally results in adequate removal
efficiencies.
• The technology is only effective when upstream water is relatively free of solids
and excess chemicals
• Some mercury-specific removal adsorbents are carbon type, silica gel and thiol
compound

Courtesy picture :https://sme-llc.com/product/hga-mercury-removal/

Bony Budiman

C. FILTRATION

• The application of cross-flow microfiltration to metal finishing waste treatment involves the
addition of chemicals to the waste stream to effect precipitation and then continuous dewatering
through the membrane filter which typically has a 0.1 micron pore size
• The microfilter consists of a series of tubes measuring up to 2.5 cm in diameter
• The treated solution is pumped at turbulent velocities down the center of the tubes, and a
downstream valve creates the necessary backpressure to force the clarified water through the
microporous membrane
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• CHEMICAL PRECIPITATION APPLICATION
• FIELD CASES
• SUMMARY
Bony Budiman

CHEMICAL PRECIPITATION - PROCESS

The precipitation process was developed to remove mercury, arsenic and oil from
produced water that was overboard discharged into the ocean. The process consists
of :
a) Treating deoiler water with bleach to oxidize Hg° to Hg2+, and As3+ to As5+
b) Treating with ferric chloride (FeCl3) to co-precipitate Hg2+ and As5+ with
Fe(OH)3,
+ CHEMICALS
c) Treating with a flotation polymer at the inlet to an IGF unit,
d) Skimming off the oily precipitate in the IGF,
e) Sending the skimmings to a small clarifier,
f) Disposing of the Fe-Hg residuals, while reclaiming a little oil or condensate
Bony Budiman

CHEMICAL PRECIPITATION - REACTION

a. Bleaching with Sodium Hypochlorite

NaOCl + Hg°(aq) ⇌ HgO(aq) + NaCl
b. Treating with Ferric Chloride
HgO(aq) + FeCl3 ⇌ Fe-O-HgO (s) + 3Cl-
FeCl3 + 3H2O ⇌ Fe(OH)3(s) + 3HCl
Fe(OH)3(s) + Hg ⇌ chemisorbed Fe-O-Hg(s)
c. Flocculation
The addition of polymer flocculent enhances the consolidation of the hydrocarbon and
mercury-containing precipitates, then separated from partially-cleaned wastewater
stream, usually as a floating sludge.
Bony Budiman

CHEMICAL PRECIPITATION - THIOL

• Thiol is organosulfide chemical that contains metal

chelating groups attached to a polymer backbone
which makes it effective in precipitating heavy metal
(such as mercury) ions from solution
• With mercury, thiol behave as ligands to form
transition mercury thiol complex.
• The Hg2+ will be clamped by the S2-.
• Since thiol is more expensive than FeCl3, it usually
injected after FeCl3 to catch the remaining mercury.
• Some patent brands of thiol are Nalmet 1689 (Nalco)
and Metclear 2405 (Suez).
Bony Budiman

THIOL AND FECL3

• Both thiol and FeCl3 used to catch the heavy metal such as mercury.
• Below are the comparison of using thiol from the FeCl3 :
• Advantages
• Better solubility of complex mercury-thiol over wide pH
• Effective in presence of metal chelates.
• Offset potential of coagulant flocculant and/or post-pH adjustment reagent
• Residual more stable under pH variation
• Disadvantages
• More expensive
• Residual more difficult to settle (risk of carryover)
• Residual less stable from oxidator
• Risk of CS2 and H2S evolution
• More toxic
Bony Budiman

CHEMICAL PRECIPITATION : DOSAGE

• Dosage of thiol depend on the type of thiol and concentration of mercury.

• For example, a Proprietary and Patented Polymeric Precipitant thiol named NALMET has
formula dosage as below :
• Above 2 ppm mercury removal : 2 * 6 * Target reduction
• Low Level (ppb) mercury removal : (Up to 10) * 6 ppm * Target reduction
• Example : Calculate how much chemical shall be injected at produced water contain 2000
ppb Hg with KPI <10 ppb
Dosage Nalmet = 10 * 6 * 2000 ppb = 120,000 ppb = 120 ppm
Bony Budiman

FACTOR AFFECTING EFFECTIVENESS OF CHEMICAL

PRECIPITATION
• Good Mixing, Long Retention
• Time Benefits
• pH Should be Optimized
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• CHEMICAL PRECIPITATION APPLICATION

• FIELD CASES
• SUMMARY
 Bony Budiman

1. PETROBRAS MRP PROCESSES

• The mercury removal processes (MRP) were applied

to a blend of black oil and gas condensate that
contained an average of 3,300 ppbw of total mercury
• The crude oil characteristic shown at table beside.
• The treating capacity of the MRP is up to 6,500 BOPD
• The removed waste material containing residual
mercury matter was reinjected in diluted aqueous
form to a deep disposal well near the MRP
• The KPI of mercury in crude oil is max 100 ppbw

Courtesy picture : https://jpt.spe.org/advancements-removal-mercury-crude-oil

 Bony Budiman

1. PETROBRAS MRP PROCESSES

The process steps are described below

• Desanding hydrocyclone : to remove the solid, semisolid,
or liquid droplet mercury initially to minimize chemical
treatment farther downstream in the process
• Stir tank reactor : A sulfur-containing chemical is added
to the stir tank to precipitate the elemental mercury
dissolved in the crude oil
• Filter : The oil was then filtered through a diatomaceous
earth (DE) pre-coated candle filter to remove the mercury
sulfide
• Absorbents : The filtered crude oil was polished by flowing
it over absorbents (copper sulfide-coated or –impregnated
alumina beads)

Courtesy picture : https://jpt.spe.org/advancements-removal-mercury-crude-oil

 Bony Budiman

1. PETROBRAS MRP PROCESSES

• 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%
• When the two types of crude oil are blended, the
mercury sulfide precipitates without the addition of
chemicals
• The final design from the pilot plant and was ultimately
simplified and did not include the hydrocyclone, chemical
treatment, or polishing

Courtesy picture : https://jpt.spe.org/advancements-removal-mercury-crude-oil

Bony Budiman

2. MERCURY-ARSENIC REMOVAL – FIELD

CONDITION
• An oil and gas field at the Gulf of Thailand has specification for contaminant in
discahered produced water as below :
 Mercury (Hg) ….. < 10 ppb
 Arsenic (As) ….. < 250 ppb
 Hydrocarbons ….. < 40 ppm

• The produced water comes from Erawan Produced Water, Platong Produced Water and
Funan Produced Water.
• Mercury mostly exist as elemental mercury, Hgo while arsenic is produced as an AsH3 gas
 Bony Budiman

2. MERCURY-ARSENIC REMOVAL – CURRENT

PROCESS
Operations Mercury Arsenic • Table beside summarizes water filtration data from
Concentration Concentration three processing platforms
(ppb) (ppb)
• Mercury is largely removable by filtration, while
Erawan Produced Water
As Received 191 – 235 arsenic is not
3.0 micron filtrate 69 • Water reinjection will be a good option to solve
0.45 micron filtrate 10
the contaminant problem. Unfortunately, the re-
Platong Produced Water injection of all produced water is not a simple task
As Received 155
given the large geographic area over which gas
3.0 micron filtrate 12
0.45 micron filtrate <1 production occurs
Funan Produced Water • A chemical treatment than considered as a quick
As Received 11 382 solution
3.0 micron filtrate 3.7 255
0.45 micron filtrate 1.9 251
 Bony Budiman

2. MERCURY-ARSENIC REMOVAL – CHEMICAL

PROCESS
• The process consists of a three-phase separator to remove gas and condensate.
Water from
Retention
Deoiler Degasser
Tank • Water leaves the bottom of the separator and passes through desanding and
deoiling hydrocyclones.
Bleach FeCl3 • The water then enters the chemical treatment process
• InChemical
the chemical treatment process, an oxidator (NaOCl), ferric ions and a
Treating
flocculant are sequentially added to the wastewater to form a floatable sludge
Process
Thiol
consisting of ferric hydroxide, chemi-sorbed mercury, ferri-arsenate, and
hydrocarbons.
(Hg/As
Removal)
GLCC • Bleach is added at the inlet to a Degasser, ferric chloride is injected into the
To Sludge Clarifie r Retention Tank, and cationic polymer is added just upstream of the IGF (Induced
Gas Flotation) unit
In du ced Gas
Flotation (IGF)
Un it
• Thiol injected downstream of retention tank as polishing.
To Sump Caisson Polymer

Courtesy picture : https://www.researchgate.net/publication/242293227_Removal_of_Mercury_and_Arsenic_from_Produced_Water

Bony Budiman

2. MERCURY-ARSENIC REMOVAL - RESULT

• Most result meet requirement

(max 10 ppb for mercury, max 250
ppb for arsenic and max 40 ppm
TPH.
• On September 2004, the arsenic
not meet specification due to weak
bleach injection.
Bony Budiman

3. MERCURY REMOVAL IN IAF SYSTEM

• A refinery in Thailand wanted to process an opportunity crude containing heavy metals

with very high Mercury content.
• The mercury in the wastewater came from the crude slate, via the desalter brine.
• The existing system did not have the capability to remove the heavy metal and hence the
plant had a limitation in accepting this crude slate.
• The organic coagulant effectively addressed the suspended solids, oil and grease at the
Induced Air Floatation (IAF) unit; and its mercury removal efficiency was close to 90%.
 Bony Budiman

3. MERCURY REMOVAL IN IAF SYSTEM

• A combination of organic coagulant and thiols/ organosulfide

chemicals (Metclear MR2405) resulted in mercury removal
greater than 98%.
• Mercury discharge in the effluent was brought well within
the stipulated control limit of <5 ppb and was maintained at
levels below 0.045 ppb
• As seen at table beside (Trend of % Hg removal), since mid
of September 2002, the mercury removal effectiveness
could be keep ≥ 90%

Courtesy picture : Article MetClear* MR2405 improves mercury removal in IAF System, CH1060EN.docx
Bony Budiman

OUTLINE

• OBJECTIVE
• INTRODUCTION
• MONITORING
• TREATMENT METHOD
• CHEMICAL PRECIPITATION APPLICATION

• FIELD CASES

• SUMMARY
Bony Budiman

SUMMARY

• Mercury is an unwanted contaminant that shall be removed once exceed

the maximum allowable limit
• Physical and chemical method may applied to reduce the mercury content
• Routine monitoring and process review shall be conducted for process
improvement.
 Bony Budiman

REFERENCES

• Production Chemicals for the Oil and Gas Industry, 2nd Edition, Malcolm A. Kelland, CRC Press, 2014
• Mercury Monitoring in the Oil and Gas Processing Industry, Warren T.Corns, www.psanalytical.com
• https://www.thermofisher.com/blog/metals/xrf-and-the-impact-of-mercury-in-the-oil-and-gas-
industry/#:~:text=Mercury%20is%20a%20naturally%20occurring,within%20reservoirs%20and%20geographical%20areas.
&text=Mercury%20compounds%20in%20crude%20are,compounds%20such%20as%20mercuric%20sulfide.
• Removal Of Mercury From Water In The Petroleum Industry, Darrell L. Gallup, Thermochem, Inc., Santa Rosa, CA, USA
• https://jpt.spe.org/advancements-removal-mercury-crude-oil
• Emerging Technologies and Approaches to Minimize Discharges Into Lake Michigan Phase 2, Module 3 Report, M.C.
Negri, P. Gillenwater, and M. Urgun Demirtas , 2011
• https://www.researchgate.net/publication/242293227_Removal_of_Mercury_and_Arsenic_from_Produced_Water