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Special Report

LNG, NGL and Alternative Feedstocks


S. HAMMOND, Barben Analytical, Reno, Nevada

Optimize amine sweetening with an optical


O2 analyzer
After extraction, raw natural gas must go through processing
before it is suitable for industrial, commercial and residential
usage. The first stage of gas processing is known as sweetening, where hydrogen sulfide (H2S) and carbon dioxide (CO2 )
are removed through exposure to amines (FIG. 1).
Here, the negative effects of entrained oxygen (O2 ) on the
amine sweetening process are examined, and the use of an optical O2 analyzer as a measurement solution is explored.
Gas contaminants. Purified, or pipeline-quality, natural gas

typically consists of 95% methane (CH4 ). However, raw gas


from the wellhead is actually a mixture of many components:
Methane (CH4 ): 70%90%
Ethane (C2H6 ): 5%15%
Propane and butane: < 5%
CO2 , nitrogen (N2 ), H2S, O2 and helium (He): balance.
As a contaminant, H2S has multiple negative attributes. It is
a well-known toxin and is lethal at high levels. If condensation
is present in the pipeline, water will absorb H2S to form sulfuric
acid (H2SO4 ), resulting in pipeline corrosion. When H2S levels
exceed 4 ppm/100 cf, the natural gas is considered sour gas
and must be treated to meet US EPA standards per 40CFR72.2.
CO2 , while not quite as undesirable as H2S, also can cause
similar acidic conditions in pipelines through the formation of
carbonic acid (H2CO3 ). Excess CO2 also creates problems in
the cryogenic processing of LNG, since it has a melting point
above that of CH4. Pipeline companies strive to achieve less
than 2 vol% of CO2 in natural gas, while LNG facilities will
further remove CO2 to less than 50 ppm.
What role does O2 play? Amine

sweetening is a frequently used method


for removing H2S and CO2 from natural
gas. Most amines have some selectivity toward one of the contaminant gases;
therefore, a blend is typically used to
knock out both H2S and CO2 . Methyldiethanolamine (MDEA) is the primary
amine for absorption of H2S, while diethanolamine (DEA) and monoethanolamine (MEA) remove CO2 .
Oxidation is the enemy of amines.
The presence of O2 causes amines to
degrade into heat-stable amine salts
(HSAS) such as acetate, oxalate, glyco-

late, bicine and formate. The formation of these salts creates


multiple problems. The acid-removal capabilities of an amine
solution decrease due to the conversion to salts. Chemical usage must increase to reduce the risk of contaminants passing
through to the dehydrator.
A second problem is the corrosive nature of the newly
formed HSAS. Since moisture is present, the salts can dissolve in condensation. The result is acidic corrosion, which
will damage the absorber and related piping in much the same
way that H2S and CO2 would damage them. If these salts precipitate in downstream piping, they can create harmful buildup
in pumps and valves, while reducing the efficiency of heat exchangers. Furthermore, HSAS promote excess foaming in absorber towers, thereby reducing the contact area of the amines
and inhibiting gas flow.
Causes of O2 in gas. Trace-level O2 may be found in the wet

natural gas coming directly from the wellhead. More commonly, however, O2 gets into the piping through leaks in the system
at common intrusion points:
Separation/water knockout: stuck separator dump valves
Vapor recovery unit: poorly sealed or open tank hatch
(thief hatch), or leaking relief valves
Compressors: leaking seals, worn piston packing
Piping: flanges, threaded connections and valves.
The gas processing plant is at the mercy of the gathering
wells and midstream suppliers, making the sour gas pipeline the
final measurement point for catching O2 contamination.
Acid gas to are or SRU
Condenser

Sweet gas to dehydrator

Cooler

Sweet gas O2
measurement
Sour gas O2
measurement

Lean
amine
storage

Amine
absorber

Acid gas
stripper

Heat
exchanger
Steam

Sour gas from wellhead

Reboiler
Rich amine
solution

Condensate

FIG. 1. In gas sweetening, H2S and CO2 are removed through exposure to amines.
Hydrocarbon Processing|JANUARY 201551

LNG, NGL and Alternative Feedstocks


O2 measurement challenges. Electrochemical cells are the
traditional method for O2 measurement. These sensors function in a similar manner as a battery using a cathode and a lead
(Pb) anode in an electrolyte solution. An O2 -permeable membrane allows O2 molecules to enter the cell, where they react
with the electrolyte, creating a voltage response to the changing O2 level (FIG. 2).
This design is not without downsides. H2S and CO2 , the
two culprits of gas processing, also create considerable problems with the electrochemical O2 sensors. Both contaminant
gases continuously penetrate the sensor membrane and react
with the electrolyte, causing poisoning of the O2 sensor. When

Cathode
Electrolyte

Anode

O2-permeable membrane

this occurs, frequent recalibration is required to correct for the


zero drift caused by the poisoning of the sensor. Eventually,
sensor response becomes erratic, and replacement is required.
To function properly in these applications, an electrochemical sensor may require an upstream H2S scrubber that also requires significant investment in maintenance time and spare
parts to keep the sensor functional.
A better approach to O2 measurement. An optical O2
analyzer that uses fluorescence quenching technology takes
advantage of a different sensing technology to deal with the
challenges of O2 measurement in natural gas. Fluorescence
quenching technology provides trace ppm O2 measurement
with no risk of damage to the sensor in the application.
An O2 -sensitive luminophore sensor provides the measurement technology. A blue light source is used to excite the
luminophore sensor located in the process gas. Once excited,
the luminophore emits light back at a specific wavelength
and intensity (FIG. 3). When O2 is present, the emitted light
is quenched, causing a phase shift in the time domain and reduced light intensity. The change in the luminophore output
can be directly correlated to the partial-pressure O2 levels in
both the gas and liquid phases.

FIG. 2. An O2-permeable membrane allows O2 molecules to enter the


cell, where they react with the electrolyte, creating a voltage response
to the changing O2 level.

Excitation spectrum
Emission spectrum

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Luminophore dye at tip of ber optic

O2

FIG. 3. An O2-sensitive luminophore sensor provides measurement.

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FIG. 4. A pre-engineered sample calibration panel can be provided


with connections for calibration gases, along with flow and pressure
instruments.

LNG, NGL and Alternative Feedstocks


Advantages of the optical sensor design include no interference due to moisture, H2S, CO2 and other contaminant gases.
The O2 measurement is independent of flowrate. The luminophore can withstand condensation and mild particulate buildup. The response time is extremely quick (T90 < 6 sec), as is
calibration time (35 min).
Due to these advantages, an optical O2 analyzer simplifies
the sample system design. Contaminant gases do not need to
be scrubbed prior to the measurement. The end result is increased reliability, better accuracy and faster response in sour
gas processing applications.
O2 sensor installation. There are several options for the in-

stallation of an optical O2 analyzer. A basic system includes the


analyzer and an optical sensor. The analyzer typically provides
for a local human-machine interface and has agency approvals
for non-incendive installations (i.e., explosive, Class 1, Division 2 installations in the US), and the optical sensor will have
several measurement range options depending on the amount
of O2 in the natural gas.
The sensor will consist of an armored fiber-optic cable connected to a probe with the luminophore sensing element on
the tip. The sensor is available with mating flow cell in 316
stainless steel, Titanium Gr. 2, and Hastelloy C-276 for full
material compatibility. Temperature compensation of the O2
measurement is provided by an external PT1000 RTD reference temperature detector for quick response.

A pre-engineered sample calibration panel, or SCP (FIG. 4),


can be provided with connections for calibration gases as well
as flowmeters, pressure regulators and a fast loop for quick response. The O2 sensor and temperature sensor are pre-wired to
the analyzer, which is mounted directly to the panel. An SCP
panel can save considerable engineering and design work, especially in new installations.
Takeaway. Entrained O2 in sour gas can create a wide variety of

problems for the amine sweetening process. Optical O2 sensing


technology, using fluorescence quenching, can provide many advantages over traditional electrochemical sensors:
Increased reliability
Reduced maintenance
Quicker calibration times
Fewer spare parts
Simplified sample systems.
Reliable O2 measurement allows workers at the gas processing
plant to determine leak sources and increase uptime for the plant,
while providing better pipeline-quality sales gas for customers.
STEVEN HAMMOND is the product manager for Barben
Analytical, a unit of AMETEK Process and Analytical Instruments.
His prior experience includes 20-plus years of product
development and sales/marketing of analytical sensors and
instrumentation for gas and liquid measurement. Mr. Hammond
holds an engineering degree from Michigan State University in
East Lansing, Michigan and an MBA degree from DePaul
University in Chicago, Illinois.

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