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Analytical Instrumentation

article Fuel Cell Technology:

Analyzing Sulfur levels To Improve Efficiency
Dr. Ing. Jens Mathiak,
Project Manager
ZBT, Carl-Benz-Strasse 201,
D-47057 Duisburg,
Drs. Ing. Kees van der Sar
Product Marketing Manager
Thermo Electron Corporation,
Voltaweg 22, 2627 BC Delft,
Germany, The Netherlands,
j.mathiak@zbt-duisburg.de, kees.vandersar@thermo.com,

Ir. Wolfgang Benz Ing. Maurice van Doeselaar,

Project Engineer Research Engineer
authors

ZBT, Carl-Benz-Strasse 201, Thermo Electron Corporation,

D-47057 Duisburg, Voltaweg 22, 2627 BC Delft,
Germany, The Netherlands,
w.benz@zbt-duisburg.de, maurice.vandoeselaar@thermo.com

Loading Total Sulfur XVI+ Analyzer with Lead Acetate Tape

Fuel Cell Technology is a new efficient alternative to fossil fuel combustion for producing electrical power and has the additional benefit that it does not pollute
the environment. The Proton Exchange Membrane Fuel Cell (PEM) has the broadest potential array of applications with fuel cell technologies; yet, it is sensitive
to a wide range of impurities, especially sulfur. The lifetime of fuel cells is mostly dependent on the impurities in the feedstock, such as sulfur. Recent
developments have demonstrated that it is possible to make the feedstock for the fuel cell practically sulfur-free by using a desulfurization unit. A total sulfur
analyzer records the sulfur concentrations in the outlet stream of the desulfurization unit over time - producing "breakthrough curves". As a result of these
measurements the quality (residual sulfur) and the capacity (life cycle time) of the desulfurization unit are evaluated. Breakthrough curve measurements require
not only high sensitivity but also excellent stability. There are some important considerations for the laboratory and chemist to control the reproducibility and the
detection limits of the analysis. Only in-depth analyses can provide information about the factors which significantly affect the measurements.

Fuel Cell Technology

The demands for energy are growing daily while conversely the production of petroleum and natural
gas is declining rapidly due to falling reserves of crude oil. If it is possible to use the energy more
efficiently, petroleum and natural gas reserves can be relied on for a much longer period. This would
also result in less pollution to the environment.
A fuel cell is an electrochemical energy conversion device that converts the chemicals hydrogen
and oxygen into water, and as a result produces electricity. The technology is known for its high
efficiency. The Proton Exchange Membrane
(PEM) fuel cell has the widest range of
applications and thus is subject to extensive
research. However, hydrogen is difficult to store
and distribute due to problems of diffusion and
explosion risks. Consequently it is necessary to
use a specialized high pressure storage tank.
This problem is addressed by utilizing a reformer.
A reformer turns hydrocarbon or alcohol fuels
into hydrogen, which is then fed into the fuel cell.
The reformer extracts hydrogen from hydrogen-
rich fuels like methanol, natural gas, petroleum,
gasoline and even biogas or biodiesel and then Graph 1. Breakthrough curve of a desulfurization unit
directly feeds the hydrogen gas to the fuel cell.
The heart of the PEM fuel cell is the platinum 2. Capacity - How much sulfur the unit can handle until it reaches a predefined sulfur concentration.
ruthenium anode-catalyst (figure 1) however this A breakthrough curve shows the sulfur concentration in the outlet stream of the desulfurization unit
is very sensitive to impurities like sulfur and can over time. Also the shape of the breakthrough curve is of special interest in order to estimate the
easily be damaged. If hydrogen is to be produced tolerance or robustness of the desulfurization unit.
from hydrogen-rich fuels using a reformer, the These characteristics are measured in "breakthrough studies". For example, a unit should
sulfur in the hydrocarbon fuels must be removed desulfurize a gas stream containing 500 ppbv H2S. A total sulfur analyzer monitors the sulfur
from the feedstock to extend the lifetime of the concentration in the outlet stream. Graph 1 represents a typical breakthrough curve.
fuel cell. During this stage of the process, a total The chart shows extremely low sulfur concentrations during the first 60 hours. After this the
sulfur analyzer may be used to analyze the sulfur concentration increases asymptotically until it reaches the input concentration. Graph 1 shows the
content of the hydrogen that is produced. The measurements during 170 hours where the experiment ends. At this point the sulfur concentration
Center for Fuel Cell Technology Ltd. (ZBT GmbH) reaches a typical threshold level of 100 ppbv, .
has great expertise on preliminary and To do a breakthrough curve measurement within a reasonable time, the experimental conditions
subsequent process steps for hydrogen are different from the normal working conditions. In this case the space velocity (gas flow rate divided
production and gas purification. ZBT investigates by volume of catalyst) is 5 times higher and the inlet concentration is 2 times higher than under
different materials for the development of a highly realistic conditions. With the results it is possible to predict the lifetime of the desulfurization unit for
efficient modular desulfurization unit. many applications with less demanding conditions. Since the breakthrough curve depends on the
equilibrium, kinetics and absorption capacity, the predictions are done by computer simulations.
Desulfurization
The quality of a desulfurization unit is based on Sulfur analysis
two characteristics: Since the typical sulfur levels in the outlet stream of the desulfurization unit are very low the total sulfur
1 Residual sulfur concentration - analyzer must have high sensitivity in order to determine the concentrations accurately. (sub-ppb
Figure 1. PEM
How much sulfur is contained in the outlet levels). ZBT GmbH uses the Total Sulfur XVI+ Analyzer, (Thermo Electron Corporation). This analyzer
fuel cell (Image
supplied by SERC) stream of the desulfurization unit. uses the lead acetate tape detection principle:
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Analytical Instrumentation

Lead acetate, Pb(CH3COO)2, is a white salt. Light illuminating the tape reflects on the white surface
and a photodiode detects the reflected light. The H2S reacts with the lead acetate to produce lead
sulfide (PbS) which forms a dark brownish stain on the white tape. Less light reflects when the color
of the tape changes from white to brown due to H2S. The decreasing amount of reflected light is
proportional to the amount of sulfur in the sample. The computer program records the signal and
produces an absorbance curve (graph 2). The measurement can be the rate of color change or the total
change of color, according to the ASTM D4045, D4084, D4323, D4468, D6212 and D6313 standard
methods.

Graph 4. Relative deviation plot of calibration measurements

This high level of reproducibility extends the possibility for extreme low level sulfur analysis. As a
consequence ZBT has examined the response of the Total Sulfur XV1+ Analyzer to H2S concentration
from 1 to 23 ppbv. Graph 5 plots the calibration line for this concentration range.

Graph 5. Calibration curve for sulfur concentrations at sub-ppb level

To achieve such low sulfur level measurements it is very important to have full control over the analysis.
During the preparation of the calibration gases the chemist should take extra care to work cleanly and
precisely. Also extreme care is necessary in relation to the temperature and pressure of the samples.
Since the samples are gases, fluctuations on pressure and temperature increase the standard deviations
of the measurements, giving more uncertainty about the results and degrading the detection limit.
Graph 2. Typical detector response Studies at ZBT GmbH even show significant effects on the data caused by flow fluctuations in the
laboratory ventilation system in which the exhaust of the analyzer is fed.
To measure the sulfur content in the outlet stream of the desulfurization unit the total sulfur analyzer
needs to be calibrated. Diluting a certified 10 ppmv H2S gas with pure hydrogen gives a set of calibration
standards. Graph 3 shows the correlation between the detector signal and the concentration of H2S. Each Conclusions
point represents the mean value of three measurements. A wide application of fuel cells mainly depends on the ability of decentralized generation of hydrogen by
a reformer. The hydrogen generated must be free from impurities like sulfur to extend the lifetime of the
fuel cell. Desulfurization units can reduce the sulfur concentration in the hydrogen stream to almost zero.
With breakthrough curve studies and computer simulations the lifetime of a desulfurization unit can be
predicted. Since the sulfur concentration in the outlet stream of the desulfurization unit is down to sub-
ppb level, the breakthrough curve measurements rely on a very sensitive and accurate total sulfur
analyzer. The Total Sulfur XVI+ Analyzer (Thermo Electron Corporation) consists of a sophisticated
detector which can measure sulfur concentration as low as 1 ppbv and is applicable for advanced
laboratories for fuel cell technologies.

About Thermo Electron Corporation’s Total Sulfur XVI+ analyzer

The XVI+ analyzer has been developed to provide the petrochemical, automotive and food and beverage
industries with a complete solution for fast and accurate low detection analysis.

In addition to offering a completely versatile solution – the XVI+ can analyze liquid and gas/LPG samples
from very low levels (ppb) to high concentration (ppm) – the lead acetate detection methodology
contained within the instrument has several immediate notable advantages:
- It is the only known method capable of determining H2S without any interference
making the XVI+ Analyzer H2S specific
- It allows the XVI+ Analyzer to measure total color and color change rates

Thermo’s XVI+ Total Sulfur Analyzer has been engineered to optimize the analysis of sulfur, especially in
extremely low concentrations. The novel lead acetate detector ensures unparalleled levels of accuracy.
Graph 3. Calibration curve of H2S in hydrogen
ThEuS Analytical Software streamlines all aspects of the analysis enabling scientists to achieve routine
total sulfur analysis in an efficient, fast and reliable way. Clear icons enable the user to operate the
instrument at a glance. The software has been configured to allow the operator to multi-task without
The calibration fits to a linear correlation up to 300 ppbv under optimized measurement conditions for
affecting the analyses in progress. Thus, sample queues can easily be modified or data and calibration
the XVI+. This calibration curve is valid for measurements in the range of 25 to 300 ppbv. Error analysis
lines independently evaluated. Results are typically presented in customized print reports or exported in
is plotted in graph 4. The uncertainty is within ±3% in the range up to 300 ppbv.
a variety of data formats.

As seen in PIN Volume 6.1 www.iet-pub.com