Determination of Platinum, Palladium, and

Rhodium in Spent Automotive Catalytic

Converters with Thermo Scientific Niton XL3t
Series Analyzers

Introduction The corresponding value in precious metals ranges

More than ever, highly variable compositions and from $25 to a few hundred dollars per vehicle [4].
volatile prices of platinum (Pt), palladium (Pd), and Moreover, the trade of ground-up material sold as
rhodium (Rh) are important factors in the purchase catalysts can be very dangerous because of possible
and recycling of spent catalytic converters. In 2010, alterations, which can mean inclusion of lead or spent
the global sales of Pt, Pd, and Rh totaled, respectively, nickel-cadmium batteries.
245, 299, and 27.2 tons. About 46% of the total Pt,
To avoid considerable financial losses, there is a
57% of the total Pd, and 77% of the total Rh were
definite advantage in having the ability to determine
consumed by the automotive catalyst industry. That
quickly and accurately the contents of Pt, Pd, and
same year, 33.7 tons of Pt, 41.2 tons of Pd, and 7.3
Rh in spent catalytic converters at the collector’s site
tons of Rh were recovered from the recycling of spent
or in the refineries. Thermo Scientific Niton XL3t
catalytic converters [1], representing a total value of
x-ray fluorescence (XRF) Series analyzers are the ideal
$3 billion at the 2010 cumulative average price of fine
instruments for achieving this objective.
metals.
Depending on the supply, the demand, and speculation, Thermo Scientific Niton XL3t and Niton XL3t GOLDD+
the price of these three elements has fluctuated Handheld XRF Analyzers
strongly over the last 20 years (see Figure 1). These Our advanced, Niton® XL3t Series analyzers were
fluctuations, as well as the tightening of emission the first handheld XRF instruments equipped with a
legislation, have had a direct correlation on the
composition of the catalysts, which themselves have
had a strong influence on the demand.
The average concentration and the ratio of Pt and
Rh were more or less constant 20 years ago [2],
so a simple weighting was sufficient to arrive at
a good estimation of the precious metal content.
Currently, the composition, which depends on the
cubic capacity of the engine and the type of fuel used,
varies dramatically. The formulation can consist of
only Pt, or various ratios of Pt-Pd-Rh, Pt-Rh, and
Pd-Rh [2]. Today’s recycled catalytic converters
come from cars manufactured, on average, 10 to 15
years ago [3]. Further, the amounts of recoverable
Pt, Pd, and Rh in each can range from 1-2 grams for
Figure 1: Pt, Pd, and Rh prices from 1992-2011 (data collected from references
a small car to 12-15 grams for a big truck in the US.
[3] and [5])
 this enrichment, the precious metal content of these
wash coat samples is usually much higher than that
for milled ceramics. In both cases, the materials are
pulverized to a maximum 250µm and loaded in XRF
sample cups or sample bags for analysis.
The total measurement time for the Niton XL3t
analyzer and Niton XL3t GOLDD+ analyzer was
120s respectively. Pt was measured with the main
filter for one half of the total measurement time,
whereas Pd and Rh were measured with the high
filter for the second half.

Results
The results for the analysis of three commercially
Materials are pulverized to a maximum 250µm and loaded in XRF sample available certified reference materials (CRMs) are
cups or sample bags for analysis.
shown in Table 1. The values of Pt, Pd, and Rh
measured with the Niton XL3t and Niton XL3t
GOLDD+ analyzers show excellent agreement with
the certified values. Figures 2 through 4 show the
high-performance x-ray tube (50 kV/100µA max.),
correlation curves for certified results (fire assay+ICP)
enabling them to quantify rare earth elements (REEs)
vs. measured concentrations for Pt, Pd, and Rh. The
such as cerium, lanthanum, praseodymium, and 2
coefficient of determination (R ) for each element is
neodymium based on their interference-free K-lines. 2
provided in the figures. The R value is a measure of
Fundamental Parameter (FP) analysis, an algorithm
how closely the data sets correlate with each other,
that corrects using theoretical constants for the 2
where a perfect correlation would have an R of 1.
influence of all elements contained in the sample, is
For all the elements determined in 130 samples, there
used to measure catalyst composition. FP is suitable
is an excellent linear correlation over a wide range of
in the analysis of the spent catalytic materials, which
concentration between certified and measured values:
show unprecedented variability in their composition.
both the slopes and the coefficients of determination
The correct knowledge of the rare earth element, as 2
R are close to 1. The average of the relative difference
well as zirconium, lead, and other elements that are
between certified and measured value was 4.1% for
potentially present at high levels in spent catalysts is a
Pt, 2.8 % for Pd, and 3.7% for Rh. These results
key factor in using FP to obtain accurate results for Pt,
demonstrate the robustness of the analysis against
Pd, and Rh.
considerable matrix changes and sometimes very
Additionally, the Niton XL3t GOLDD+ analyzer with high concentrations of relevant concomitant elements
Thermo Scientific Geometrically Optimized Large such as cerium, lanthanum, zirconium, lead, iron, or
Area Drift Detector (GOLDD™) technology and chromium that were found in the 130 samples (see
higher performing x-ray tube (50 kV/200µA max.) Figure 5).
has light element capabilities (Mg, Al, Si, P) and better
sensitivity.
Materials/ XRF Analyzer Value Certified Value
Elements (ppm) (ppm)
Methodology
Automotive catalyst material is made either of a NIST SRM 2557
ceramic substrate, mostly cordierite coated with Pt 1110 ± 20 (2σ) 1131 ± 11
a precious metal containing a wash coat, or of a
metallic substrate with an aluminum oxide wash Pd 230 ± 10 (2σ) 233.2 ± 1.9
coat also containing precious metals. There is no Rh 130 ± 10 (2σ) 135.1 ± 1.9
technique for analyzing non-homogeneous materials NIST SRM 2556
like catalytic converters directly without sample
Pt 690 ± 30 (2σ) 697.4 ± 2.3
preparation. Therefore, the collected catalysts
with ceramic substrate undergo a “de-canning” Pd 310 ± 10 (2σ 326 ± 1.6
operation, which is the extraction of the ceramic Rh 40 ± 10 (2σ) 51.2 ± 0.5
with a honeycomb structure from the steel case. All
BAM ERM-504
of the ceramic is then sorted crushed, milled, and
mostly blended with other catalysts [2]. In contrast, Pt 1720 ± 60 (2σ) 1777 ± 15
converters with a metallic substrate are first shredded Pd 290 ± 10 (2σ) 279 ± 6
or milled, and then the metallic parts are separated Rh 330 ± 20 (2σ) 338 ± 4
using magnets and winnowing from the wash coat
powder containing precious metals [2]. Because of Table 1. Results of analysis for commercially available automotive catalyst
CRMs
Limits of detection (LODs) for Pt, Pd, and Rh in pure
cordierite are given in Table 2 for both the Niton XL3t
analyzer and the Niton XL3t GOLDD+ analyzer. The
superior sensitivity of Niton XL3t GOLDD+ enabled
us to achieve a higher sample throughput while
halving the measurement time.

Niton XL3t GOLDD+ Niton XL3t

Element (30s/filter) (60s/filter)

The limits of detection depend on the testing time, the

interferences/matrix, the level of statistical confidence
Pt 10 ppm 16 ppm
Pd 5 ppm 7 ppm Figure 2. Correlation curve for Pt – CRM vs. Niton XL3t Series analyzers
Rh 5 ppm 6 ppm

Table 2. LODs (3σ) of precious metals in pure cordierite (common ceramic

substrate of catalysts)

Conclusions
Exploration catalysts from gasoline engines with
various ratios of Pt-Pd-Rh, Pt-Rh, or Pd-Rh, as well
as catalysts from diesel engines containing higher
amounts of Pt only or wash coats from catalysts
with metallic substrates were all analyzed with good
accuracy. The analysis results were comparable to
lab assays, showing that Niton XL3t Series XRF
analyzers can be used successfully in the field to
provide a good estimation of the value of spent
catalytic converters.
Important benefits derived from using Niton XL3t Figure 3. Correlation curve for Pd – CRM vs. Niton XL3t Series analyzers
Series analyzers include:
• Analyses take only one or two minutes vs.
time-consuming lab assays
• Ease of use with little training vs. lab analysis
requiring specialized knowledge
• Robust FP-calibration is insensitive to matrix
changes
• Cost efficient with reduced price per analysis

To discuss your particular applications and

performance requirements, or to schedule an on-site
demonstration, please contact your local Thermo
Scientific portable XRF analyzer representative or
contact us directly by email at niton@thermofisher.
com, or visit our website at www.thermoscientific.
com/niton.
Figure 4. Correlation curve for Rh – CRM vs. Niton XL3t Series analyzers
 In addition to these
offices, Thermo Fisher
Scientific maintains a
network of representative
organizations
throughout the world.

Americas
Boston, MA USA
+1 978 670 7460
[email protected]

Europe
Munich, Germany
+49 89 3681 380
[email protected]

Asia Pacific
New Territories, Hong Kong
+852 2885 4613
[email protected]

www.thermoscientific.com/niton

Figure 5. Range of concentration for Pt, Pd, Rh and relevant matrix elements found in the investigated samples

References ©2012 Thermo Fisher

Scientific Inc. All rights
reserved. All trademarks are
[1] Loferski, P., “Platinum-Group Metals,” in 2010 Mineral Yearbook, US Geological Survey, 2011. the property of Thermo
Fisher Scientific Inc. and its
[2] Hagelüken, C., “Der Kreislauf der Platinmetalle – Recycling von Katalysatoren,“ Autoabgaskatalysatoren, Expert Verlag, 2005. subsidiaries.
Specifications, terms and
[3] Hagelüken, C., The PGM-markets and their interdependencies with the autocatalyst. Presented at the CTI Forum Material in Exhaust Gas pricing are subject to
Technology, Stuttgart, Germany. May 2008. Available at http://www.autocatalyst-recycling.umicore.com/ change. Not all products are
available in all countries.
[4] Tollefson, J. , Worth its weight in platinum, Nature 450, 2007, 334-335. Please consult your local sales
representative for details.
[5] http://www.kitco.com

8-316 07/2012