Mercury Management White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas with Sorbent Traps

White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

Mercury is a naturally occurring trace constituent of crude oil, natural gas, and

natural gas condensate. Virtually all geologic hydrocarbons contain measurable quantities of mercury. The concentration of mercury in natural gas and associoccurring in SE Asia (Thailand and Indonesia), North Africa (Algeria), Egypt, ated liquids varies with geology and reservoir conditions with high concentrations South America (Venezuela, Bolivia), China, and the Netherlands. Certain oil and gas reservoirs in the United States, including at least one located in the Gulf of Mexico, are known to produce natural gas and condensate with mercury concentrations that are orders of magnitude greater than those of typical gas reservoirs. Hydrocarbon processing facilities (oil and gas production equipment, gas processing plants, refineries and petrochemical manufacturing facilities) that handle hydrocarbons with elevated mercury concentrations are subject to an increased risk for serious occupational exposure, damage to aluminum process equipment and the poisoning of precious metal catalysts. Even at low to moderate increased exposure risks during maintenance activities.

concentrations mercury will accumulate in processing equipment and can cause

Since 2005 Portnoy Environmental, Inc (PEI) and Frontier Global Sciences (FGS) have worked on the development of improved sampling and analysis white paper presents an overview of the current industry standard methods streams. An improved sorbent trap method based on the modification of a USEPA (United States Environmental Protection Agency) method is also presented and compared to the current industry standard methods. methods for the measurement and monitoring of mercury in natural gas. This for the measurement of mercury in natural gas and other gas phase process

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White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

Sample Point Design

The collection of representative samples is one of the most important steps in producing analytical results that meet project data quality objectives and accuand the design of the sample point/probe are key components of a sampling rately report mercury concentrations. The selection of the sample point locations approach that will facilitate the collection of representative samples. The gas from any fittings or appurtenances that may disturb laminar flow. The industry

sample should be collected via a insertion type sample probe located well away standard rule of thumb is: Collect the sample at a distance of five (5) inside pipe

diameters away from 90 tube turns, valves, and any other discontinuities. The tip of the insertion probe should be inserted well away from the walls of the process piping, the rule of thumb is in the middle one-third of the process pipe. Any pressure reductions (through valves, regulators, reducers or other fitting) should be designed so as to minimize Joule-Thompson cooling. Additionally, the sample the potential for debris or liquids to enter the sample probe.

point entry valve should be located on the top of a horizontal pipe run to minimize

Portable insertion probes are typically used for short term assessments of mertrain should decontaminated to less than 10 ng/scm before installation at each sample point.

cury in natural gas and process streams. The probe as well as the entire sample

Typical Insertion Probe Design Specifications

Material: Stainless Steel Maximum Operating Pressure: 2500 PSIG Maximum Operating Temperature: 225 F Internal Coating: Sulfinert Pipe Connections: 1-inch NPT or -inch NPT Sample point entry valve: Minimum diameter, 1-inch, full opening ball valve. Integral Probe Regulator: A. Maximum Inlet Pressure: 3000 PSIG B. Maximum Outlet Pressure: 500 PSIG (pressure reduction required for mercury sampling equipment) 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.
Table 1.

Figure 1. Portable Insertion Probe

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White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

Sample Collection Methods

Typically, mercury samples are collected from natural gas by the use of a solid in natural gas (ASTM D6350 and ISO 6978) both specify gold in the form of sorbent trap (Figure 2). Two standard methods for the measurement of mercury gilded silica as the solid sorbent for the collection, via amalgamation, of mercury from a sample gas stream. After sample collection, both procedures specify a double amalgamation step whereby
Figure 2. Sorbent Traps: (Top) Carbon based sorbent, and gilded silica sorbent

the mercury is thermally desorbed (sorbent trap heated to ~ 800 C) onto another gold sorbent trap, and then thermally desorbed into the ana-

lyzer cell, and analyzed by either Cold Vapor Atomic Fluorescence Spectrometry (CVAFS), or Cold Vapor Atomic Absorption Spectrometry (CVAAS).

The sample collection process is the most difficult and critical aspect of accurately quantifying mercury concentrations in gas phase streams. Mercury can form amalgams with many metals and alloys commonly used in gas sampling systems including stainless steel, brass, copper, nickel, chromium and aluminum. Due
Primary By-pass Pressure Regulator

Valve Flow Indicator Rotameter

Vent

Filter

Spiking Port

Sorbent Trap

Dry Gas Meter

Figure 3. Sorbent Trap Sampling System

to the potential for amalgamation, and the tendency for mercury to adsorb, and chemicsorb to the surface of stainless and carbon steel the potential for loss of mercury to sample wetted metal components of sampling systems (Figure 3)

is significant. To minimize this loss, all sampling system components that come surfaces coated with a silica type coating or be made of a material that is not

into contact with the sample gas should be heated and have their sample-wetted reactive with mercury. Conditioning (flowing sample gas through the 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 the representativeness of the collected samples.
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White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

Mercury Sampling and Analysis Methods for Gas Phase Matrices

ASTM D 6350
Standard test method for mercury sampling and analysis in natural gas by atomic fluorescence spectroscopy.
Table 2.

ISO 6978
Natural Gas, determination of mercury, Part 3: Sampling of mercury by amalgamation on gold/platinum alloy.

EPA Method 30B

Determination of total vapor phase mercury emissions from coal fired combustion 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 amalgamation process results in

the desorption of all of the collected mass from a single trap into the analyzer at that the upper range of the analytical instrument is not exceeded. This limits the sample time and the sample volume.

once, the sampler must limit the amount of mercury mass loading on the trap so

The Modified EPA Method 30B

The method, referred to as Modified Method 30B is based on the EPA reference method (30B) for the measurement of total vapor phase mercury in flue gases.

The Modified EPA Method 30B was developed by the PEI-FGS team to provide industry clients with a method that: Includes a rigorous, performance based QA/QC protocol that validates the Utilizes sorbent traps with an increased mercury loading capacity useful for continuous monitoring through the collection of long term (730 days) samples. accuracy and precision of the sample collection procedures.

Minimizes the loss of mercury to sampling system components. in harsh weather conditions and hydrocarbon mists.

Is highly portable and robust enough for deployment at remote locations and And is relatively unaffected by gas stream contaminants such as H2S, CO2,

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White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

Features of the Modified Method 30B

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.
Table 3.

The PEI-FGS Team

The PEI-FGS team began field testing the method in 2005 on natural gas production platforms offshore Texas and natural gas collection and transmission lines both offshore and onshore extending from South Texas used in natural gas fields in Wyoming, Colorado, West Texas, South Texas, Louisiana, Mississippi, and Alaextensively in gas processing plants and refineries Canada, and Saudi Arabia. bama. The Modified Method 30B has also been used including, California, Texas, New Mexico, Wyoming, to Alabama. To date the Modified Method 30B has been

Sorbent Traps
FGS custom makes carbon type traps with National Institute of Standards and Testing (NIST) traceable spiked section mercury mass. The analytical system used is a sorbent trap acid digestion method based on the prinof proven laboratory testing. ciples of EPA Method 1631. This method has 17 years

Modified Method 30B: Three Section Sorbent Trap

A-Section B-Section C-Section

Mod. Method 30B: QA/QC Performance Criteria

A-Section QA/QC Test or Specification Acceptance Criteria
Primary Collection

B-Section
Breakthrough

C-Section
Spiked (Field Recovery Test) Average Recovery Between 75% and 125% for Hg(0)

Duplicates
Duplicate Agreement

95% of Total Collected mass

10% of A-Section Hg Mass For Hg concentration > 1 g/dcm 20% of A-Section Hg Mass For Hg concentration 1 g/dcm

10% RD mass for Hg concentration > 1 g/dcm 20% RD or 0.2 g/dcm absolute difference for Hg concentrations 1 g/dcm

Table 4.

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White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

Sorbent Trap Mercury Sampling Methods Comparison

Feature Comparison
Analytical Detection Method

Modified Method 30B

Acid DigestionCVAFS CombustionCVAAS

ISO 6978
Thermal DesorptionCVAFS

ASTM D6350
Thermal DesorptionCVAFS

Lower Detection Limit

0.001 g/scm

0.001 g/scm

0.001 g/scm

0.001 g/scm

Number of Analyses From One Zample Sample Collection Phase QA/QC NIST Traceable Standard

Multiple

Yes

Yes

No

No

Yes

Yes

No

No

Sorbent Trap Hg Mass Loading Limit

No limit (dilution of extract)

No limit

Limited by instrument saturation

Limited by instrument saturation

Sample Collection Duration

8 168+ hours, depending on Hg loading Up to 10,000 liters

8 168+ hours, depending on Hg loading Up to 10,000 liters

Limited by Hg mass loading (typically less than 4 hours)

Limited by Hg mass loading (typically less than 4 hours)

Sample Gas Volume

< 500 liters

< 500 liters

Analysis On-site

No

Yes

Yes

Yes

Table 5.

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White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

Sampling System and Equipment

The PEI-FGS team uses the MAK II Mercury Sampling Systems manufactured by the PEI subsidiary, Measurement and Monitoring Solutions.

VENTS TO ATMOSPHERIC STACK

SAMPLE GAS VENT LINE

HEATED SAMPLING ENCLOSURE AND CONTROL PANEL (CLASS 1 DIV 1 HEATED ENCLOSURE)

METERING PANEL (FIREPROOF METERING ENCLOSURE)

SORBENT TRAP (TYP) D

PI

TI

TI

FL
PI TI

M
TI

FL
PI TI

M
TI

D SAMPLE GAS SUPPLY LINE PI

FL FL FL
BYPASS LINE

BYPASS LINE

ADJUSTABLE SAMPLE PROBE

TO PLANT

Figure 3. MAK II Mercury Sampling System Flow Schematic

The MAK II Mercury Sampling Systems are designed and manufactured expressly for the natural gas industry for the collection of mercury samples from high-pressure natural gas. MAK II systems meet all of the requirements for mercury sampling

equipment specified in the most recent versions of ASTM (American Society of Testing Methods), ISO (International Standards Organization) and EPA standard methods for the sampling and analysis of mercury. In addition, the procedures and equipment that Research Institutes publication GRI-94/0243.2.

PEI uses are consistent with those procedures detailed and recommended in the Gas

MAK II Sorbent Trap Sampling System

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White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

Each MAK II sampling unit consists of four primary components: 1) A portable insertion type sampling probe (stainless 2) A heat-traced Sulfinert treated sample gas line 3) A heated sampling enclosure consisting of three sampling manifold, sample train control valves, (-inch stainless steel); steel, Sulfinert treated, 2500 psig MAOP);

sample trains with heated pressure regulation and primary and secondary bypass, and Class 1 Division 1 heater and thermostat with explosion proof connectors and power cords (see Figure 4); and,

Figure 4. MAK II Sorbent Trap Sampling System

4) A sample gas metering unit consisting of prec-

sion control flow meters, calibrated dry gas meters and -inch braided stainless steel hoses for connection to the heated sampling enclosure (Figure 4).

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 poses all electrical components (heated sampling enclofor Class 1 Division 1 service (Figure 3).

of mercury to the sample-wetted surfaces. For safety pursure, regulators, and heat traced sample lines) are rated

MAK II with Carbon Traps

MAK II with Gold Traps

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10

White Paper 2012

The Measurement and Monitoring of Mercury in Natural Gas

James H. Vickery, Jr.

The MAK II Mercury Sampling Systems have proven their reliability, precision and

robustness in the toughest environments. The design includes features and components that make it the most reliable, maintenance free, easily operated, and flexible mercury in gas sampling system available in the industry.

Contacts
James Vic Vickery Vice President, and Technical Director of Mercury and Chemical Services Group Portnoy Environmental, Inc. 1414 W. Sam Houston Pkwy. N. Suite 170 Houston, TX 77043 USA 281-536-0899 www.pei-tx.com vvickery@pei-tx.com Bob Brunette Frontier Global Sciences, Inc. 11720 N. Creek Pkwy. N. Suite 400 Bothell, WA 98011 USA 206-660-7307 www.frontiergeosciences.com/ Bobb@frontiergeosciences.com Ron Radford Director of Chemical Cleaning Operations Portnoy Environmental, Inc. 1414 W. Sam Houston Pkwy. N. Suite 170 Houston, TX 77043 USA 713-503-6803 www.pei-tx.com rradford@pei-tx.com Roberto Lopez-Garcia Chief Scientist Portnoy Environmental, Inc. London, England 44-7791904-977 www.pei-tx.com rgarcia@pei-tx.com

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Copyright 2012 Portnoy Environmental, Inc. All Rights Reserved. PEI-FGS 2/2012