Application Note

Merox Process - pH and O2

Oil & Gas: Refinery
Mercaptans (RSH) are organosulfur compounds that are Merox Extraction - A two stage process (caustic + oxidation) used to
often present in unrefined or partially refined hydrocarbon clean lighter molecular weight hydrocarbons such as LPG's (Liquefied
feedstocks. These chemicals have several undesirable Petroleum Gases), pentanes, and NGL's (Natural Gas Condensates).
attributes including strong odor (garlic smell), corrosivity,
and degradation of downstream additives as well as the Merox Sweetening - Single stage process used to directly convert
hydrocarbon end products. For these reasons mercaptans mercaptans to disulfides in jet fuels, naphtha, diesel and kerosenes
must be removed through a catalytic process. In this
paper we will examine the Merox process and the Barben Merox Extraction Process
Analytical products used at different points throughout the Merox extraction processes begin with H2S removal. Often
treatment stages. this is done upstream with an amine treatment unit. In
cases where treatment is not available a caustic pre-wash
Merox Processes is commonly used to remove H2S from LPG feedstock.
Merox is an acronym for "Mercaptan Oxidation". The This sulfur removal step is necessary to avoid secondary
Merox process was first developed by UOP back in reactions downstream when catalysts are introduced. The
1958. Over time, many variations of the Merox process reaction is shown below.
have developed to solve different hydrocarbon refining
applications. Caustic (NaOH) is favored for these H2S + NaOH ► NaSH + H2O
processes since it reacts with both hydrogen sulfide (H2S)
as well as mercaptans (RSH). This paper will focus on The LPG flows from the caustic pre-wash to the bottom of
the two general types of caustic-based Merox processes - the mercaptan extractor vessel (Figure 1). The gas flows
Extraction & Sweetening: upwards through the vessel where it encounters

Figure 1
Water Wash pH Measurement
Used to determine carryover from caustic
settler. Water replaced when > 10pH

Dry Sweetened Salt Bed pH Measurement

LPG Also used to determine carryover from
caustic settler. Should be 7 to 9pH
Water
Salt Disulfide Separator Vent O2
Water Wash

Bed Measurement
Sweetened LPG Monitoring of residual oxygen from
Caustic upstream oxidizer. Typically 5 to 12% O2
Settler

Oxygen 01/06/2017 10:55 AM

% O2 R 850.9 mBar

20.946 67.9°F
Err: 0
„‡‡‡

Drain Drain
§ ¨
ESC

© ª

Lean Merox Caustic

Vent Gas
To Treatment
Mercaptan
Extractor Separator
Caustic Pre-wash

Disulfides Disulfides
To Treatment
Caustic
Oxidizer

Raw LPG Steam

Feedstock Preheater
Rich Merox Caustic

Fresh Catalyst Air

Injection Injection Merox Extraction Process
Application Note
Merox Process - pH and O2
counter-current flow of caustic with entrained Merox mercaptans. The caustic is heated and air is injected
catalyst (metal chelate). A series of perforated trays to convert the mercaptans to organic disulfide oils. The
ensure thorough mixing of LPG and caustic as the two reaction follows:
solutions pass through the vessel. The mercaptans react
with the caustic mixture based on the following reaction: 4NaSR + O2 + 2H2O ► 2RSSR + 4NaOH
"R" denotes an organic group such as methyl, ethyl, or propyl
2RSH + NaOH ► 2NaSR + 2H2O
"R" denotes an organic group such as methyl, ethyl, or propyl Oxidation occurs in a packed bed reactor. Since the
disulfide oils (RSSR) are not soluble in caustic they are
Pressure is kept elevated just above the bubble point so decanted in a horizontal separator vessel. Lean caustic
that the hydrocarbon gases remains in liquid form. The is pumped off the bottom of the vessel for re-use in the
newly sweetened LPG exits from the top of the vessel process. Additional Merox catalyst may be added during
while the mercaptan-rich Merox caustic flows from the regeneration to ensure a mercaptan removal back at the
bottom of the vessel. The sweetened LPG still contains extractor vessel.
caustic thus it is pumped to a horizontal caustic settling
tank. The lighter LPG is pumped off the top of the tank. The disulfide separator vessel will have excess air from
Depending on the feedstock, the LPG will go through the oxidizer stage. The oxygen content of separator
multiple post-treatment steps including a water wash for vent gas is monitored to determine the effectiveness of the
final caustic removal, as well as moisture removal through oxidation stage. It is typically kept at 5 to 12% to ensure
a salt bed dryer. pH levels are closely monitored in these full conversion of mercaptan compounds.
final treatment steps to avoid caustic carry-over in the final
sweetened LPG product. Merox Sweetening Process
Merox sweetening processes (Figure 2) are reserved for
Back at the extractor, the rich caustic solution goes heavier hydrocarbons such as kerosene, aviation fuels,
through a regeneration process to strip off entrained and diesel. These fuels contain longer-chain mercaptans

Figure 2
Fixed Bed Regeneration pH Measurement
pH used to determine effectiveness during Hot Water Wash for
catalyst regeneration. 8 to 9pH of hot water Bed Regeneration
wash indicates good contaminant removal.

A secondary acidification step will create 6

to 6.5pH drain effluent for final contaminant
Air
removal. Injection
Water Wash
Fixed Bed
Reactor

Water Wash pH Measurement Salt Bed

Clay Bed
Water washing is used to remove residual
caustic and surfactants. Levels are kept at
Water
<12pH in water wash vessel.

Fresh
Caustic Caustic
Injection
Caustic Pre-wash

Settler Sweetened
Hydrocarbon

Jet Fuel,
Kerosene,
Waste Waste
or Diesel
Water Water
Feedstock
to Drain to Drain

Spent Caustic
Drain Wash Water to Drain

Caustic Recirculation Line

Merox Sweetening Process

2
 Application Note
Merox Process - pH and O2
which are not soluble in caustic. They require the pH Measurement Challenges
conversion of mercaptans to disulfides in a single fixed- Both extraction and sweetening Merox processes
bed reactor in the presences of oxygen, caustic, and present challenges for pH measurement. Excess
Merox catalyst. All of the fundamental chemical reactions caustic combined with mercaptans, disulfides, and other
in the sweetening process remain the same as in the prior contaminants can quickly poison the electrolyte and AgCl
extraction process. element used in most pH sensors. Once the sensor
is poisoned the pH measurement becomes unreliable
Similar to the previously described extraction process; the resulting in more frequent calibration. Residual oil passing
feedstock for a sweetening process must be free of H2S. by the sensor can plug the porous reference junction used
A caustic pre-wash is used for sulfur removal. After pre- in most conventional sensor designs leading to constant
wash, both air and caustic are injected into the feedstock cleaning of the sensor tip and eventual lost measurement.
directly ahead of the fixed bed reactor. As the mixture Entrained catalyst fines can abrade the sensor causing
enters the reactor it is exposed to activated charcoal premature failure of the measurement electrode.
containing the Merox catalyst. The charcoal serves to
extend catalyst life by absorbing phenols, naphthenic acids pH Measurement Solutions
and other contaminants which may harm the catalyst. The Barben Analytical Performance Series pH sensors are
feedstock mixture with entrained caustic and air trickles well suited for the various pH measurements found
through the fixed bed where exposure to the catalyst in refinery processes. The patented Axial Ion PathTM
directly converts the mercaptans to disulfides. It should be reference design (Figure 3) uses multiple internal filtering
noted that these disulfides are soluble in the hydrocarbon chambers to greatly slow the ion transfer of impurities
fuel but not soluble in caustic. They remain with the fuel from the process liquid, reducing contamination of the
throughout the sweetening process and will be removed in internal electrolyte. Each filtering chamber is separated
downstream processing if deemed necessary. with Barben's patented annular AIP seals. The seals
ensure electrolyte flow perpendicular to the length of the
The newly sweetened solution drains from the bottom of sensor thus blocking chemical ingress from the process.
the fixed bed reactor to a caustic settling tank. Caustic The extremely large Teflon junction at the tip of the sensor
is pumped off the bottom of the settling tank for reuse in helps to prevent plugging and coating from hydrocarbon
the process. The sweetened hydrocarbon is pumped to build-up. All features of the Barben reference design
a water wash vessel for removal of any residual caustic. ensure less frequent sensor cleaning and longer intervals
The water wash stage is typically a batch reaction where between calibrations. The end result is the most reliable
pH measurement is used to determine when too much pH sensor for Merox applications.
caustic has carried over and fresh water must be added.
A salt bed following the water wash is used to remove any
Figure 3
residual moisture. pH may be measured on the drain from
the salt bed if caustic carry-over is still a concern. Final
Multiple Axial Ion Paths
treatment involves a clay filtration bed. Clay is used to Plug free communication
absorb oil soluble surfactants, corrosion inhibitors and Seal individual filtering chambers

other final contaminants in the sweetened fuel.

Annular Filtering Junction
Maintains measurement signal
To keep the sweetening process working smoothly periodic Wood slows process ingress
regeneration of the activated charcoal and catalyst within Highly resistant to strong chemicals

the mixed bed reactor is required. A hot water wash

(approx. 190ºF) is used to unclog pores within the charcoal Teflon Junction Interface
to expose catalyst. Residual caustic keeps pH well above Initial protection against process
Large surface area
neutral during the water wash. The water wash cleaning H+
H+
H+ H+

H+

continues until the effluent water reaches 8 to 9 pH. The

H+
H+
H+

hot water wash is followed by a separate acetic acid wash. H+

The acid removes any leftover salts trapped within the

charcoal. pH of the effluent water will be monitored until is ION PATH®
drops < 6.5pH. At this point, fresh catalyst will be added to
the bed prior to restarting the process.

3
Application Note
Merox Process - pH and O2
Figure 4 pH Sensor Specifications
Performance Series pH sensors should be specified with
“CR” coating resistant glass electrodes. The coat resistant
The 551 Quick Change pH Sensor (left)
with our B4992-1009 Flowcell (right).
layer on the glass provides added protection for exposure
to strong caustic solutions as well as oily build-up. Kynar
Flowcells are available in 316 stainless (PVDF) should be specified as sensor body material due
and titanium with either 1/2" FNPT con- to its chemical compatibility. All seal / o-ring material are
nections or 1/4" tube fittings. A drain port
in the bottom of the flowcell provides an
specified as FFKM (Kalrez) for process compatibility.
option for a sample tap or an easy purge
location for sensor removal. Merox pH measurements are often done on sample lines.
In these applications the Barben 551 Quick Change pH
Sensor with flowcell is recommended (Figure 4). The 551
Quick Change Sensor uses a union nut arrangement to
affix the sensor within the flowcell. This design allows
simple installation and removal of the sensor without
torqueing the sensor body or twisting the cable.

Barben pH sensors easily connect to most modern

pH analyzers in use today, Wiring diagrams for
commonly available instruments can be found on www.
[Link] or by request from technical
support.

551 Quick Change pH Sensor with Flowcell

4
 Application Note
Merox Process - pH and O2
Oxygen Measurement Challenges In disulfide separator applications contaminant gases
Oxygen measurement is typically found on the vent gas within the flow stream continuously penetrate the sensor
of the disulfide separator used in the Merox extraction membrane and react with the electrolyte causing poisoning
process. The vent gas will have traces of hydrocarbons of the oxygen sensor. When this occurs, frequent
and mercaptans which give it a garlic odor. If the sulfur recalibration is required to correct for zero drift caused
content is low the vent gas can be flared. In some by the poisoning of the sensor. Eventually the sensor
applications it may be routed through a carbon filter or response will become erratic and replacement is required.
used a fuel gas for other refinery processes. The gas An electrochemical sensor may require an upstream H2S
content will be primarily nitrogen with oxygen content scrubber to function in these applications. The scrubber
between 5 to 9% O2. Besides vent gas there may also adds to the significant investment in maintenance time and
be trace oxygen measurements on inert gas blanketing spare parts needed to keep the sensor functional.
applications on storage tanks surrounding the Merox unit.
Other downsides of electrochemical oxygen sensors
These oxygen measurement applications can be difficult include error due to changing flow and pressure. In
due to the moisture and contaminant gases in the stream. separator vent gas applications surges of disulfide and
The presence of hydrocarbons eliminates zirconia-based caustic liquids in the tank frequently occur causing
oxygen sensors as due to high internal heat required variable flow and pressure. These two factors affect the
to perform the measurement. Paramagnetic oxygen permeability of the membrane thus creating error in the
technology may be affected by residual water vapor which oxygen reading.
can condense and corrode small moving parts within the
analyzer. Tunable Diode Laser (TDLAS) technology is a A Better Approach to Oxygen Measurement
suitable yet costly solution. Frequently the end user turns Barben Analytical's OXYvisor Optical Oxygen Analyzer
to electrochemical cells for these applications due to their uses a new technology to deal with the challenges of
low cost; however they have multiple issues as well. oxygen measurements within the refinery.

Electrochemical Sensor Issues Quenched luminescent technology provides accurate

Electrochemical oxygen sensors function similar to a oxygen measurement with no risk of damage to the sensor
battery using a cathode and a lead (Pb) anode in an in the application. An oxygen sensitive luminophore
electrolyte solution. An oxygen permeable membrane sensor provides the measurement technology for the
allows oxygen molecules to enter the cell where they react OXYvisor. Blue light is used to excite the luminophore
with the electrolyte creating a voltage response to the sensor located in the process gas (Figure 6). Once
changing oxygen level (Figure 5). excited, the luminophore emits red light back at a specific

Figure 6
Electrochemical Cell O2 Sensor

Cathode Anode

Electrolyte + -

Oxygen Permeable
Membrane

• Sensitive to flow and pressure changes

• Membrane sensitive to fouling, coating and attack Pulsed light from the analyzer excites the luminophore oxygen sensor. Once excited, the
luminophore emits light which is measured back at the analyzer. The duration and wavelength
• Electrolyte poisoning of the light will vary depending on the oxygen concentration in the liquid.
Figure 5

5
Application Note
Merox Process - pH and O2
wavelength and intensity. In the presence of oxygen, Figure 7
the emitted light is quenched, causing a time domain
phase shift and reduced light intensity. The change in
the luminophore output can be directly correlated to the
partial pressure oxygen measurement. Advantages of
the optical sensor design include no interference due
to moisture, H2S, and other contaminant gases. The
oxygen measurement is independent of flow rate. The
luminophore can withstand condensation and mild
particulate build-up. The response time is extremely quick
(T90 < 6 seconds) as is calibration time (3-5 minutes).

Because of these advantages, the OXYvisor Optical

Oxygen 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 Merox gas
measurement applications.

Installation
There are several options for installation of an Optical
Oxygen Analyzer. A basic system includes the OXYvisor
Analyzer, BOS Optical Sensor and Flow Cell (Figure 7).
The OXYvisor Analyzer provides a local HMI interface and
agency approval for non-incendive installations (Ex nA,
Class I Division 2). The BOS Optical Sensor has several
measurement range options depending on the amount of
oxygen in the natural gas.

Sensor Range
BOS1 0 - 4.2% O2 The OXYvisor Optical Oxygen Analyzer, BOS Sensor & Flow Cell
(loose) shown above.
BOS2 0 - 25% O2
BOS3 0 - 300 PPM O2 (1000 PPM over-range)

The BOS sensor consists of an armored fiber optic cable

connected to a 12mm probe with the luminophore sensing
element on the tip. Barben Analytical offers the 12mm
probe and mating flow cell in 316 stainless steel, Titanium,
and Hastelloy C-276 for full material compatibility.
Temperature compensation of the oxygen measurement is
provided by a external PT1000 RTD for quick response.

Barben Analytical also offers a pre-engineered sample

calibration panel (Figure 8 & 9). The SCP panel provides
connections for zero/span calibration gases as all related
hardware for a proper installation. The panel design
includes a fast loop to increases gas flow. The fast loop is
a valuable feature to improve response time in applications
where there process sample point is a long distance from
the analyzer. The analyzer and related sensors ship pre-
wired and mounted directly to the panel. The SCP panel
can save considerable engineering and design work in
new installations.

6
 Application Note
Merox Process - pH and O2
Figure 8

24"

33.7"

30.5"

Part #B6001-1293 Pre-Engineered Sample Calibration Panel with integrated OXYvisor, designed for use in Merox processes.

Figure 9

Part #B6001-1293 Sample system flow diagram.

7
Application Note
Merox Process - pH and O2
Summary Contact Us
Barben Analytical pH and oxygen measurement products
offer many benefits for improved measurement in the Barben Analytical is a leading supplier of analytical mea-
Merox process. surement technology targeting the industrial
marketplace. It is a wholly owned subsidiary of AMETEK,
pH Measurement Inc., a leading global manufacturer of electronic instru-
• Less frequent cleaning and calibration intervals ments and electromechanical devices.
• High pH measurement accuracy
• Increased sensor lifespan AMETEK has over 15,000 colleagues at more than 120
• Less MRO inventory manufacturing locations around the world. Supporting
those operations are more than 100 sales and service lo-
Oxygen Measurement cations across the United States and in 30 other countries
• Increased reliability versus competing technology around the world.
• Reduced analyzer complexity
• Fully integrated sampling solutions Barben Analytical
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