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Advanced sulphur analysis in

hydrocarbons
Kyle Kuwitzky XOS

P
etra MAX™ delivers advanced D4294 sul- noise and increases signal-to-noise output, ena-
phur analysis in addition to 12 elements bling low detection limits and high precision
from P to Zn including Ca, Fe, K, Ni, and V without the need for consumable helium gas, a
at sub-ppm levels for various applications: vacuum pump, or extensive sample preparation.
• Sulphur in diesel and gasoline using ASTM
D4294 and ISO 8754 Advanced Analysis with HDXRF
• Sulphur and heavy metals in crude using ASTM High Definition X-Ray Fluorescence (HDXRF)
D4294 and ISO 8754 is an elemental analysis technique offering sig-
• Sulphur, Calcium, Phosphorus, and Zinc in nificantly enhanced detection performance over
unused lubricants using ASTM D6481 traditional EDXRF technology. This technique
• Sulphur in bunker fuel and marine diesel using applies state-of-the-art monochromating and
ISO 8217 focusing optics, enabling dramatically higher sig-
nal-to-background ratio compared to traditional
In this whitepaper, we will discuss the follow- polychromatic X-Ray Fluorescence.
ing application studies: Figure 1 shows the basic configuration of
• Application Study #1: S, Ni, V, and Fe Analysis HDXRF and its use of focused monochromatic
of Crude Oil Using HDXRF® excitation. In this system, the diffraction-based
• Application Study #2: Total Sulphur in doubly curved crystal optics capture a wide
Hydrocarbons from 17 ppm to 4.6 wt% angle of X-rays from the source and focus a nar-
row energy band (monochromatic) of X-rays to
Abstract a small spot on a measurement cell. The mon-
Petra MAX is a robust benchtop analyser that ochromatic beam excites the sample and sec-
complies with ASTM D4294 and ISO 8754 ondary characteristic fluorescence X-rays are
for measuring sulphur in hydrocarbons. Petra emitted. A detector processes those secondary
MAX is powered by HDXRF, utilising XOS pat- X-rays and the instrument reports the elemental
ented doubly curved crystal optics coupled with composition of the sample.
a high-performance silicon drift detector and an Figure 2 compares the detector signal of poly-
intense monochromatic excitation beam. This chromatic (competitor) with monochromatic
industry-leading technology reduces background (XOS) XRF to demonstrate how monochro-

Figure 1 HDXRF Technology Figure 2 Superior Signal-to-Noise Ratio

www.digitalrefining.com/article/1001409 September 2017 1


byproducts during transportation and can lead to
pump and exchanger fouling, and off-specifica-
tion coke.
At most refinery and test labs, analysis of S,
Ni, V, and Fe are performed separately. The sul-
phur analysis is performed using EDXRF and
metal content is identified using ICP-OES. While
EDXRF is capable of measuring Ni, V, and Fe in
addition to S, the limits of detection do not meet
the levels needed to control refinery processes.
ICP-OES is able to provide the needed sub-ppm
analysis however; sample preparation is complex
and takes many hours to complete. It involves a
matic excitation reduces background noise and series of heating, acid digestion, and ashing pro-
improves signal definition that enables lower lim- cedures that are quite labour intensive.
its of detection and dramatically better precision. A rapid measurement technique for sulphur
HDXRF is a direct measurement technique that compliance and simultaneous analysis of Ni, V,
requires no sample conversion, equating to no and Fe is necessary to meet the needs of refiners,
consumable gasses, little to no sample prepara- pipelines, terminals, and other petroleum test
tion, and results in just minutes. labs.

Application Study #1: S, Ni, V, and Fe Analysis Application Study


of Crude Oil Using HDXRF In each study, 10 separate aliquots were pre-
Background pared and analysed for five minutes each. Their
Test methods for measuring sulphur content, like individual measurement results and average are
ASTM D4294 and ISO 8754, have become critical reported. Samples were prepared by transferring
for assessing the value of crude oil. The blending 6 mL to a 43 mm XRF sample cup and sealed
of crude oils from different sources has become with an Etnom film. Each refinery or pipeline
more commonplace within the industry to meet location has their own specifications for specific
specifications for the classification of sweet crude elements like S, V, Ni and Fe. The desired level
oil. The introduction of new crudes brings new or limit for each heavy metal may vary depending
challenges, like higher concentrations of metals on the detriment its presence causes to the equip-
such as nickel (Ni), vanadium (V), and iron (Fe). ment, process, or finished product. But in the
Ni and V are known to rapidly deactivate pro- case of V, Ni, and Fe, current methods can take a
cess catalysts in the fluid catalytic cracker (FCC) significant amount of time to prepare, including
and hydrotreaters. This occurs because nickel hours for ashing and analysis, and if outsourced,
and vanadium are often contained in large por- can be quite costly. Table A outlines common
phyrin molecules, which are not able to pene- pipeline feed specifications.
trate into catalyst pores. As a result, the nickel
and vanadium containing molecules end up
depositing on the catalyst and plugging the
pores, which blocks the active sites located
within the catalyst material. There are many
pretreat options for addressing Ni and V, how-
ever these systems require accurate understand-
ing of the Ni and V content to appropriately
treat these metals. In response, many refiners Accuracy Study
have incorporated Ni and V analysis into their To study the accuracy of Petra MAX, 10 repeat
routine crude assay, and pipelines have set spec- measurements were performed on a commer-
ifications for Ni and V in their common stream cially available mineral oil reference material
sweet crude. containing 10,000 ppm of S, and 10 ppm of V, Fe,
Fe is introduced into crude oil from corrosion and Ni. See Table 1 for results.

2 September 2017 www.digitalrefining.com/article/1001409


Precision Study
To study the precision of Petra MAX, 10 repeat
measurements were performed on two different
crude oil samples containing S, V, Fe and Ni. The
results shown in Tables 2 and 3 demonstrate that
Petra MAX delivers precise measurement results Conclusion
well below desired specifications, and therefore In response to the increased blending of sweet
is a valuable tool for monitoring trends as well crude oil with crude containing higher levels of
as identifying materials that simply do not meet metals and S, petroleum labs are beginning to
specification. see the need to measure other elements, in addi-
tion to S, as a part of their crude assay. This study
Limit of Detection demonstrates that Petra MAX delivers simultane-
By incorporating patented doubly curved crystal ous trace metals and ASTM D4294 or ISO 8754
optics to monochromate and focus the excitation analysis of S, in a single measurement. Petra
beam, Petra MAX is able to achieve low limits MAX performs this analysis without the difficult
of detection without the assistance of a vacuum ashing sample preparation that makes the analy-
pump or consumable helium. sis of metals like V, Ni, and Fe in crude oil so dif-
ficult today.

Application Study #2: Total Sulfur in


Hydrocarbons from 17 ppm to 4.6 wt%
Background
Recent international trends across a majority of
fuel types have focused on lowering specifications
for total sulphur. These changes in regulation are
in response to public health and environmental
concerns. Examples include:
• The International Maritime Organization’s
announcement that MARPOL Annex VI, a reg-
ulation intended to control airborne emissions
from ships, will reduce the total limit on sulphur
content of fuel oil used on ships from 3.5 wt% to
0.5% by January 1, 2020.
• In India, all automotive diesel and gaso-

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line was transitioned to
Bharat IV with a 50 ppm
maximum sulphur in April 2017. available mineral oil reference material contain-
• Jet fuel specifications such as ASTM D1655 and ing 20,000 ppm of S. Samples were run on four
D6615 require a maximum sulphur of 3000 ppm. analysers by five different users. Results can be
To demonstrate compliance with these regu- found in Table 4, and demonstrate the accuracy
lations, refinery and independent laboratories achievable with Petra MAX.
have long relied on standard methods such as
ASTM D4294 and ISO 8754. These labs operate Precision Study
in fast-paced environments that require instru- To study the precision of Petra MAX, various
ments that can provide rapid, precise results and hydrocarbon samples were analysed. These sam-
are increasingly relying on solutions that provide ples include heating oil, kerosene, jet A, vacuum
simple, direct integration with laboratory infor- gas oil (VGO), and crude oil. The analyses were
mation management systems (LIMS). performed at separate laboratories with unique
instruments and users. The results shown in Table
Application Study 5 demonstrate that Petra MAX delivers precise
In this study, various hydrocarbon matrix sam- measurements across a wide range of hydrocarbon
ples were analysed to demonstrate the expected sample types. In addition, Petra MAX is a valuable
performance of Petra MAX utilising ASTM tool to monitor trends and identify materials that
D4294 methodology. Separate aliquots were pre- simply do not meet specification.
pared and analysed for five minutes each. Their
individual measurement results and average are Conclusion
reported in the tables below. Samples were pre- Sulphur analysis using ASTM D4294 and ISO
pared by transferring 6 mL to a 43 mm XRF sam- 8754 continues to be an important measurement
ple cup and sealed with an Etnom film. for refinery and independent laboratories around
the world. Global regulation trends toward lower
Accuracy Study sulphur fuels demonstrate the need for a rapid
To study the accuracy of Petra MAX, 10 meas- and precise analysis solution. That solution is
urements were performed on a commercially Petra MAX. Utilising the most advanced optics
technology, Petra MAX delivers accurate meas-
urement across various hydrocarbons without the
need for complex sample preparation or consum-
able gasses.

LINKS
More articles from: XOS
More articles from the following categories:
Sulphur Removal and Recovery
Laboratory, R&D and Quality Control
Instrumentation, Automation and Process Control

4 September 2017 www.digitalrefining.com/article/1001409

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