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Total Mercury Sampling and Analysis Points Regen Gas to Fuel Gas System
To AGRU Train
MDEA Regen
To Waste Water
Flash
Mercury Removal
Drum
To Waste Water
Condensate
Feed Separator
Compression
To Liquefaction
Stabilizer Column
Slug Catcher
Feed Stabilizer
Condensate
Mixing Drum Storage
To Waste Water
MEG Compression
MEG Compression
2 x 50% Stream Paths
MEG
Storage
Lean MEG
Introduction
The distribution of mercury throughout hydrocarbon processing systems varies and requires significant
understanding and planning prior to implementing inspection and maintenance activities. PEI and EFGS
have gained extensive recent experiences in the management of mercury across the petroleum industry
including upstream oil and gas operations, gas gathering, processing and transmission operations, and crude
oil refining operations in the Gulf of Mexico, the Gulf of Thailand, throughout the United States, Alaska,
Canada, the Middle East and Australia.
Improvements in measurement and monitoring methods for assessing mercury in process streams provide
increased confidence in measurement precision and accuracy verified with a robust well defined numerical
data quality performance criteria. Mass balance/flux studies, mercury mapping/partitioning studies and
long term monitoring programs in refineries, gas processing plants, and gas gathering systems, have led to
the development of an improved understanding of the dynamics of mercury accumulation in oil and gas
processing equipment and facilities. Understanding accumulation, distribution and the sorption dynamics
Sampling and analysis methods are critical in determining a management approach and understanding risks
to personnel, products, and process. Mercury is scavenged by carbon steel and is adsorbed/chemisorbed
into the interfacial surfaces and can complex into the scale/metal grain boundary surface requiring special
chemistry and chemical application methods for mercury process system decontamination. In natural gas,
mercury may be present in elemental form and in an adsorbed state on particulates entrained in the gas
stream. In hydrocarbon liquids (e.g., gas condensate), mercury compounds may be present in the dissolved
state and again in an adsorbed state with suspended particulates. Glycol is used to separate the moisture
from the raw natural gas and during the separation process, glycol is in two different stages. In one stage
the glycol contains little or no water (lean glycol). The other stage is after the glycol has absorbed moisture
from the natural gas and in this stage is referred to as rich glycol. Recent experience from mercury mapping
projects throughout the U.S., Asia and Canada
indicate glycol regen streams can be highly concen-
An important part of effective mercury
trated with mercury and often flow to a thermal
management involves use of Mercury oxidizer or directly to atmosphere. PEI and EFGS
Removal Units (MRUs). MRU performance have developed methods and equipment for measur-
monitoring is conducted with the use of ing mercury in this low pressure stream to quantify
mercury released to atmosphere from processing
advanced sampling methods intended to
operations.
quantify total mercury in gas phase streams,
based on EPA Methods 30B which provides Hydrocarbon processing facilities (oil and gas produc-
the highest QA/QC protocol available. tion equipment, gas processing plants, refineries and
Precise data is especially important when petrochemical manufacturing facilities) that handle
hydrocarbons with elevated mercury concentrations
assessing mercury levels in LNG facilities.
are subject to an increased risk for serious occupa-
tional exposure, damage to aluminum process
equipment and the poisoning of precious metal catalysts. The presence of mercury in LNG and NGL plant
feeds and the intermittent performance of mercury removal equipment may suggest the possibility of
mercury deposition in aluminum heat exchangers. Even at low to moderate concentrations, mercury will
accumulate in processing equipment and can cause increased risks to personnel and cryogenic process
equipment.
Sample Point Entry Valve: Minimum diameter, 1-inch, full opening ball valve.
Sample Probe Tip: A liquid exclusion type, sintered stainless steel, Sulfinert™ coated
probe tip is used during the mercury sampling phase as a precaution to help minimize
the potential of a liquid slug pushing liquids into the sampling system.
Due to the potential for amalgamation, and the tendency for mercury to adsorb, and chemisorb to the
surface of stainless and carbon steel the potential for loss of mercury to sample wetted metal components of
sampling systems is significant. To minimize this loss, all sampling system components that come into
contact with the sample gas should be heated and have their sample-wetted surfaces coated with a high
temperature silica coating or be made of a material that is not reactive with mercury. Conditioning (flowing
sample gas through a system for a period of time before active sampling) of installed sampling equipment
including the sample probe is recommended as a means of minimizing mercury sorption/desorption effects
that can adversely affect representativeness of collected samples. Conditioning times may vary and depend
on many factors but typically range from 12 to 24 hours.
Table 2: Mercury Sampling & Analysis Methods for Gas Phase Matrices
Standard test method for Natural Gas, determination Determination of total vapor
mercury sampling and analysis of mercury, Part 3: Sampling phase mercury emissions
in natural gas by atomic of mercury by amalgamation from coal fired combustion
fluorescence spectroscopy. on gold/platinum alloy. sources using carbon
sorbent traps.
While both of these methods perform reasonably well, they lack a well defined QA/QC component for the
validation of the precision and accuracy of the field sampling procedures. Also, since the double amalgama-
tion process results in the desorption of all of the collected mass from a single trap into the analyzer at once,
the sampler must limit the amount of mercury mass loading on the trap so that the upper range of the
analytical instrument is not exceeded. This limits the sample time and the sample volume.
The method, referred to as Modified Method 30B is based on the EPA reference method (30B) for the measure-
ment of total vapor phase mercury in flue gases. The Modified EPA Method 30B was developed by the PEI-EFGS
team to provide industry clients with a method that:
• Includes a rigorous, performance based QA/QC protocol that validates the accuracy and precision
of the sample collection procedures
• Utilizes sorbent traps with an increased mercury loading capacity useful for continuous monitoring
through the collection of long term samples that provide an integrated average mercury concentration
• (7-30 days) samples depending on mercury mass loading rates and other operational factors
• Is highly portable and robust enough for deployment at remote locations and in harsh weather conditions
• And is relatively unaffected by gas stream contaminants such as H2S, CO2, and hydrocarbon mists
PEI and EFGS have used EPA 30B independently and in conjunction with both ISO 6978 and ASTM D6350
methods on over 100 sites globally (upstream, midstream and at downstream processing plants).
» Robust QA/QC protocol with numerical performance criteria (Table 4) for the evaluation of the precision and
accuracy of the sample collection process. NIST traceable spiked sorbent traps.
» Sorbent media with increased mass loading capacity, unaffected by common natural gas contaminants such as
acid gases, H2S scavengers and corrosion inhibitors as well as entrained hydrocarbon mists
» Long-Term Sampling Capability: Large mercury loading capacity (up to 50,000 micrograms per trap) allows for
a longer sampling period and a larger total volume of sample gas. Improved representativeness.
» Acid digestion of carbon based traps allows multiple analytical runs of the sample, and the ability to archive the
sample extract for future analysis. Gold trap samples allow for one analytical run only.
» Streamlined sample collection procedures, which is one of the primary advantages of the Modified Method 30B.
This approach eliminates the expense and effort associated with the setup, calibration and maintenance of an
analyzer in the field.
Functional speciation of mercury in gas phase streams includes a) particulate bound mercury (PHg), b)
elemental mercury and c) ionic mercury. Functional and molecular speciation of mercury in process streams
is critical to developing appropriate mercury management plans and MRU design.
Acceptance 95% of Total ≤ 10% of A-Section Hg Mass Average Recovery Between ≤ 10% RD mass for Hg
Criteria Collected Mass For Hg concentration > 1 µg/dcm 75% and 125% for Hg(0) concentration > 1 µg/dcm
Lower Detection Limit 0.001 µg/scm 0.001 µg/scm 0.001 µg/scm 0.001 µg/scm
Up to 10,000 Up to 10,000
Sample Gas Volume <500 liters <500 liters
liters liters
All wetted surfaces of the sampling apparatus are treated with Sulfinert™ coating, a high-temperature silica
coating process designed to minimize the sorption or adherence of mercury to the sample-wetted surfaces. For
safety purposes all electrical components (heated sampling enclosure, regulators, and heat traced sample lines)
are rated for Class 1 Division 1 service.
Mak2™ Deployment
PEI has deployed 2 each complete Mak2 mercury sampling systems and CVAFS analyzers to our alliance partners
CR Asia, Rayong Thailand base of operations and CR Australia Perth facility for use throughout southeast Asia and
Australia (including offshore assets throughout the northwest shelf).