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Improving Process Control During

A p p li ca t i on N ot e
Ammonia Production Using the
Thermo Scientific Prima PRO
Process Mass Spectrometer
Graham Lewis, Thermo Fisher Scientific, Winsford, Cheshire, United Kingdom

Key Words
• Steam-to-carbon ratio • H/N ratio
• Air requirement • Rapid multi-stream
sampler (RMS)
• Methane slippage
• Magnetic sector analyzer
• Shift reaction

Introduction as heating fuels, prices tend to be very volatile. This price


Ammonia is one of the most important industrial chemicals volatility means plants must maximize the efficiency
in the world, with demand forecasted to grow 3% of the ammonia production unit to maintain
annually over the next five years. Close to 80% of the a strong bottom line.
ammonia produced globally is used for the production of
The Ammonia Process
fertilizers. Ammonia is also an important component of
The manufacture of ammonia can be described simply
explosives, fibers, plastics, and intermediates for dyes and
by the classic Haber process formula:
pharmaceuticals.
N2 + 3H2 → 2NH3
The first step in ammonia production is the conversion
of natural gas, liquefied petroleum gas or naphtha However, the production of the two reactants from
into hydrogen. Because these raw materials are in high raw materials (i.e. fuel, steam and air) requires a number
demand for many other applications including use of process steps. All of these steps occur during the
gas phase and require fast, accurate gas analysis
to optimize the process.
PRIMARY SECONDARY CO SHIFT WATER
REFORMER REFORMER CONVERTER SEPARATER
Figure 1 is a schematic of a typical ammonia plant
DESULPHURIZATION
HIGH based on natural gas feedstock. The streams
TEMP.

NATURAL GAS
that require analysis are:
STEAM
LOW
• Natural gas • CO2 absorber outlet
AIR
FUEL
TEMP.
• Primary reformer feed • Raw synthesis gas
• Primary reformer effluent • Converter inlet
WATER
• Secondary reformer effluent • Converter outlet
PURGE
HEAT COOL • High temperature shift outlet • High pressure purge
• Low temperature shift outlet • Hydrogen recovery.

CO2 AMMONIA
CO2 ABSORBER METHANATOR NH3 CONVERTER SEPARATOR PURIFICATION

Figure 1.
Typical ammonia process based on natural gas feedstock.
2 Process Analytical Requirements to form hydrogen and carbon monoxide:
The analysis of these 12 streams requires a wide CH4 + H2O → 3H2 + CO. Some of the CO will react
range of compounds to be analyzed, including: with the steam to form even more hydrogen: CO + H2O
→ CO2 + H2. The steam-to-carbon gas ratio requires
• Organics: C1 to C5
tight control because energy is wasted when excess steam
• Inorganics: N2, H2, NH3, CO, CO2, O2, Ar, H2S.
is produced unnecessarily. In addition, excess methane
Concentrations range from tens of percent down to requires more energy for compression and causes
parts per million (ppm). In theory, a set of discrete inefficient catalyst activity.
analyzers can be used to measure some of the required
components. However, installation Air Requirement
and maintenance costs will be In addition to being the source of hydrocarbon for the
extremely high and vital analysis process, natural gas is also used as fuel. The physical
information will be missing. properties of the fuel gas must be measured accurately.
Alternatively, a process gas Doing so ensures the air requirement for combustion
chromatograph (GC) can be used, control optimizes the energy consumption of the unit.
but long analysis cycle times and
Methane Slippage
frequent calibration and maintenance
Only 30 to 40% of the hydrocarbon is converted in the
intervals limit the usefulness of this
primary reformer. The exhaust is therefore fed into a
technique. This application note will
secondary reformer where the conversion to CO and H2
discuss the advantages gained by
continues. Air (the source of N2) is introduced at this stage
using a multi-point, multi-component
and combustion takes place at around 1250°C (2282°F).
solution: the Thermo Scientific™
Prima™ PRO Process Mass It is important to minimize the amount of unreacted
Spectrometer. This field-proven methane, or methane slippage, from the secondary reformer.
analyzer provides fast, accurate and If it is not minimized, this methane builds up in the
reliable data that can be ammonia converter loop. Because this process takes place
Thermo Scientific used as part of a dynamic at high pressure, the methane needs more compression
Prima PRO Process process control model. energy which ultimately reduces ammonia yield.
Mass Spectrometer
Shift Reaction
Advantages of Mass Spectrometry It is important to remove all CO from the process before
The Prima PRO process mass spectrometer offers it enters the ammonia converter, or catalyst poisoning
analysis times measured in seconds rather than minutes will occur. This removal takes place by ‘shifting’ the
and the ability to measure both inorganic and organic CO to CO2 after which the CO2 is absorbed. This shift
species over a wide dynamic range. One Prima PRO mass occurs in two steps during high and low temperature
spectrometer can therefore monitor all sample points, shifts. If the CO is not properly removed, it can shift
from feedstock to final product, in the ammonia process. back to methane, creating a highly exothermic reaction
that can damage the next process stage, the methanator.
Key Control Parameters
Steam-to-Carbon Ratio H/N Ratio
Steam and natural gas (or another source of The methanator is designed to remove any residual
hydrocarbon) react together in the primary reformer CO and CO2. The syn-gas output from the methanator
should be ideally comprised of 75% H2 and 25% N2.
In practice, there will also be some residual CH4 and
argon from the air. The production of ammonia takes
place over an iron oxide catalyst in the converter. During
this process, it is vital to maintain the ratio of H2 and N2
as close as possible to the stoichiometric ratio of 3-to-1.
Analyzer Requirements
While the ammonia process presents a series of challenges
to a typical process mass spectrometer, the Prima PRO
mass spectrometer has been designed to overcome these
challenges and offers a unique set of capabilities.
Rapid Multi-Stream Sampling
To effectively monitor all process streams, the mass
spectrometer requires a fast, reliable means of switching
between streams. Other technologies use solenoid valve
manifolds that have too much dead volume or rotary
Figure 2. Rapid multi-stream sampler within the Prima PRO Process Mass valves that suffer from poor reliability. Figure 2 is a
Spectrometer. schematic of the rapid multi-stream sampler (RMS) of the
Prima PRO mass spectrometer.
which offers an unmatched combination of sampling 3
speed and reliability and allows sample selection from TYPICAL LEVEL PRECISION
one of 32 or one of 64 streams. Stream settling times are %mol %mol
application-dependent and completely user-configurable. CH4 80 - 95 0.02
The RMS includes digital sample flow recording for C2H6 1-5 0.005
every selected stream which can be used to trigger an C3H8 1-3 0.005
alarm if the sample flow drops or if a filter in the sample N-C4H10 1-2 0.005
conditioning system becomes blocked. CO2 1-3 0.003
N2 2-5 0.01
The RMS within the Prima PRO mass spectrometer
Ar 0.5 0.001
can be heated to 120°C (248°F) and the stream selector
H2 0-1 0.002
position is optically encoded for reliable, software-
controlled stream selection. Temperature and position Natural Gas Stream (Primary Reformer Feed)
control signals are communicated via the internal
network. The RMS has a unique standard three year TYPICAL LEVEL PRECISION
%mol %mol
warranty. There are no other multi-stream sampling
CH4 0.5 - 2 0.002
devices that offer the same level of guaranteed reliability.
CO 10 - 14 0.03
Precision of Analysis CO2 8 - 10 0.01
The mass spectrometer is required to monitor a wide N2 23 - 24 0.02
range of component concentrations. To be used as part Ar 0.1 - 0.5 0.001
of a dynamic plant control strategy, the data must H2 55 - 65 0.03
be reliable and available.
Secondary Reformer Effluent
The heart of the Prima PRO mass spectrometer is
TYPICAL LEVEL PRECISION
a magnetic sector analyzer which offers unrivalled
%mol %mol
precision and accuracy compared with other mass
CH4 3 - 10 0.01
spectrometers. Key advantages of magnetic sector
N2 20 - 26 0.01
analyzers include improved precision, accuracy, long
Ar 0.1 - 5 0.002
intervals between calibrations, and resistance to
H2 65 - 75 0.02
contamination. Typically, analytical precision is between
He 0.5 - 1 0.002
two and 10 times better than a quadrupole analyzer,
depending on the gases analyzed and the complexity Synthesis Gas
of the mixture. A unique feature of the Prima PRO mass
TYPICAL LEVEL PRECISION
spectrometer magnet is that it is laminated. It scans %mol %mol
as fast as a quadrupole analyzer, offering the unique CH4 5 - 10 0.01
combination of rapid analysis and high stability. This N2 15 - 22 0.01
capability allows for the rapid and extremely stable Ar 1-5 0.002
analysis of an unlimited number of user-defined gases. H2 55 - 60 0.02
The scanning magnetic sector is controlled with 24-bit NH3 10 - 15 0.01
precision using a magnetic flux measuring device for
Convertor Outlet
extremely stable mass alignment.
The Prima PRO mass spectrometer features an enclosed
Figure 3. Typical stream performance specifications
ion source that provides high sensitivity, minimum
for the Prima PRO Process Mass Spectrometer.
background interference and maximum contamination
resistance. The high-energy (1000 eV) analyzer offers
extremely rugged performance in the presence of gases A guaranteed performance specification for the
and vapors that have the potential for contaminating the Prima PRO mass spectrometer is issued based on an
analyzer. individual customer’s specific stream details. This
performance will be demonstrated during start-up by a
A set of typical performance specifications for the Prima
trained Thermo Fisher Scientific service engineer.
PRO mass spectrometer on ammonia process streams
is shown in figure 3. It indicates an 8-hour analysis Analysis of Low-Level Carbon Monoxide
precision (single standard deviation) based on an analysis The gas exiting the low temperature shift reactor
time of 15 seconds. Thermo Scientific™ GasWorks contains minimal levels of carbon monoxide, typically
software permits analysis optimization on a per stream between 0.1% and 0.5%. The analysis of trace levels
basis, enabling selection of the most appropriate of carbon monoxide in the presence of percentage levels
‘speed versus precision’ setting depending on process of carbon dioxide and nitrogen presents a problem to all
control requirements. Similarly, the most efficient peak process mass spectrometers because these spectra overlap
measurements for each stream and the most appropriate with one another. In all other process streams containing
display units (% or ppm) can also be selected. these three species, the CO levels are high enough to
allow the use of fragment peaks. While it is possible
in the low temperature shift, it is not measurable with the Improving H/N Ratio
necessary precision. In this case, analysis of CO in the The Prima PRO mass spectrometer measures the
low temperature shift by NDIR is recommended. It is easy H/N ratio to a relative precision of 0.05% (i.e. precision

A p p li ca t i on N ot e
to integrate the NDIR CO analysis with the Prima PRO of 0.0015 on a ratio of 3). In figure 4, the blue trend
mass spectrometer data: a connector is fitted to the RMS indicates the H/N ratio immediately after the mass
to select the sample for the mass spectrometer to analyze spectrometer was installed while the red trend indicates
and, at the same time, to divert the fast loop to the external the H/N ratio after implementing process control based
NDIR analyzer. The Prima PRO mass spectrometer on data provided by the mass spectrometer.
can also be used to provide a backup alarm for CO
breakthrough.
Using Mass Spectrometry
Data to Control the Process
The unique combination of magnetic sector stability, Figure 5.
fast multi-stream switching and GasWorks quantitative Prima PRO Process Mass
Spectrometer service kit.
software ensures the process data produced by the
Prima PRO mass spectrometer is accurate and reliable.
A range of industry standard communication protocols
enable transfer of this data to process control systems to
optimize the ammonia process.
Steam-to-Carbon Ratio
A detailed evaluation of the Prima PRO mass
Summary
spectrometer was conducted by an accredited fuel
gas calibration laboratory. The performance was The Prima PRO mass spectrometer offers the best
benchmarked against a range of gas compositions in available online measurement precision and stability
combination with an ISO 17025 accredited calibration for ammonia process monitoring and control. Its fault
cylinder. The Prima PRO mass spectrometer provided tolerant design combined with extended intervals
exceptional analytical performance, ensuring confidence between maintenance as well as simplified maintenance
in the data. In addition, GasWorks software easily procedures ensure maximum availability of the analyzer.
calculates the steam-to-carbon ratio with just two analog The plug-n-play standard service kit that is shipped
inputs; one for the steam flow in weight per unit time with each analyzer is shown in figure 5. The reliability
and the other for natural gas flow in weight per unit of the Prima PRO mass spectrometer is reflected in its
time. Alternatively, the Prima PRO analyzer can simply industry-best three year parts and labor warranty.
transfer the composition data to the DCS using one of its
Advantages of the Prima PRO
industry standard communication protocols.
Process Mass Spectrometer
• Optimizes processes, including:
After start-up After implementation
3.05 - Gas mixing and burner control in reformer
- Steam/carbon ratio
3.00
- Optimization of H/N ratio
2.95 - 0.05% RSD
- Methane slippage to ±20 ppm accuracy
H/N Ratio

2.90
• Facilitates monitoring of:
2.85 - H2S in natural gas
- Inert gas build-up in synthesis loop
2.80
- Catalyst activity to schedule plant outages
2.75
0.00 0.50 1.00 1.50 2.00 2.50 3.00

Time

Figure 4. Improvements achieved in the H/N ratio using


the Prima PRO Process Mass Spectrometer.

thermoscientific.com/primapro

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