Total Sulfur Analysis
Total Sulfur (TS) stands for the sum parameter of all organic and inorganic sulfur compounds. Trace levels (0.02 – 10.000 mg/kg or ppm by weight) of Total Sulfur are measured with an elemental combustion analyzer according to UV-Fluorescence detection technique or Microcoulometric detection technique. Common ASTM methods for sulfur testing include: ASTM D5453-19a, ASTM D6667, and ASTM D7183. All TSHR Total Sulfur Analyzers provide a reliable and robust solution for labs.
Environmental regulations like the TIER III and EURO VI wield a maximum of 10 mg/kg of Total Sulfur or ppm by weight in diesel oils. The maximum amount of 10 ppm is also included in the Chinese norms GB 19147-2013 for Diesel fuels and GB 17930-2013 for Gasoline, deriving from the CHINA 5 environmental program.
Total Sulfur (TS) stands for the sum parameter of all organic and inorganic sulfur compounds. Trace levels (0.02 – 10.000 mg/kg or ppm by weight) of Total Sulfur are measured with an elemental combustion analyzer according to UV-Fluorescence detection technique or Microcoulometric detection technique. Common ASTM methods for sulfur testing include: ASTM D5453-19a, ASTM D6667, and ASTM D7183. All TSHR Total Sulfur Analyzers provide a reliable and robust solution for labs.
Environmental regulations like the TIER III and EURO VI wield a maximum of 10 mg/kg of Total Sulfur or ppm by weight in diesel oils. The maximum amount of 10 ppm is also included in the Chinese norms GB 19147-2013 for Diesel fuels and GB 17930-2013 for Gasoline, deriving from the CHINA 5 environmental program.
White Papers
Combustion and Ultra Violet Fluorescence (UV-F) have been used for accurate analysis of sulfur in motor fuels as per ASTM D5453. However, even an optimized detector may identify nitrogen oxide as Sulfur dioxide, which emits at the same wavelength as sulfur dioxide, into positive interferences and biased sulfur data.
TSHR has developed an integrated tunable Nitrogen Oxide Interference Elimination Module, so-called the TRINITY Module, this in order to ensure there is no interference of high nitrogen containing samples and to deliver an accurate and precise Total Sulfur data…
ASTM Method D5453-19a describes the combustion and Ultra Violet Fluorescence (UV-F) detection of Sulfur in light hydrocarbons, engine fuels and oils. However, even an optimized detector may identify nitrogen oxide as Sulfur dioxide, as they both emit at the same wavelength. This problem can result in false positives or biased total sulfur data. EST Analytical has developed an integrated tunable Nitrogen Oxide interference elimination module, called the TRINITYTM Module. This new module ensures there is no interference when analyzing high nitrogen containing samples thus delivering accurate total Sulfur data.
This application note shows the analytical data and achieved LOD’s for both nitrogen and sulfur with the NEXIS VP model based on ISO ISO11843-2 methodology and the use of the NEN 7777 method which is incorporated in the NEXIS LINK operating software.
Labs around the globe share a common need to enhance lab productivty and stability when analyzing Total Sulfur, Nitrgen and Chlorine. Today, that process consumes too much time and money. When done improperly it can also contribute to poor data outcomes requiring labs to repeat calibrations and delay much needed sample analysis.
The oxidative combustion analysis of a wide range of petroleum samples which may contain high sulfur and/or nitrogen content may result into potential carry-over effect issues that can result in downtime for this analysis. The EST NEXIS VP model with AS120 liquid autosampler uses a direct injection technique combined with a high efficiency combustion tube design to avoid the risk of incomplete combustion and therefore demonstrates a very low carry-over effect. This application note describes the practical lab study for the “carry-over effect” and the degree to which the NEXIS VP TN/TS elemental combustion analyzer manages1) the “carry-over” effects which is based on a reference definition. Extreme high sulfur/nitrogen concentrations of 10,000 ppm as well as middle high ppm concentrations 100 ppm of nitrogen and sulfur samples were analyzed multiple times and multiple sets followed by a set of blank solvent injections to determine the “carry-over” effects.
The future requirements of Total Sulfur/Nitrogen analysis in light liquid hydrocarbons such like petrochemical base, intermediate and final products are heading towards very low concentration levels (ppb). This application note shows the precision, Level of Detection (LOD) and repeatability performance when a simultaneous analysis of Total Nitrogen and Sulfur is conducted using the NEXIS Combustion analyzer equiped with both ONE-Cal™ functionality and Digital Signal Prcoessing Technology (DSP). DSP Technology will enhance the Sulfur/Nitrogen detector performance resulting in a level of high sensitivity and repeatability.
This note shows the raw analytical calibration data and achieved LOD’s for both Nitrogen and Sulfur using the NEXIS model equipped with the AS120 liquids autosampler in the range of 0 – 1000 ppb.
Over the recent years, there have been major advancements in the development of biofuel diesel and gasoline. The use of sugars and other plant materials to manufacture alcohols as 100% fuels or as extenders to produce bio-gasoline has been around and actively applied in a number of countries globally. There were regionalized programs started to make bio-gasoline available. This has resulted in a large number of investments in bio-ethanol plant production. Elemental analysis is required to control fuel quality and show compliance with actual specifications. For ethanol and methanol fuel, ASTM, amongst others, has published sulfur content specifications which are laid down in ASTM D5453 method [1].
This application note describes the direct analysis for the routine measurement of Total Sulfur content in ethanol blends. The TSHR TS 7000 model Total Sulfur combustion analyzer fitted with the TSHR HR 7000 model autosampler was used to measure the Total Sulfur (TS) content in a set of ASTM Crosscheck ethanol (EtOH) samples. Sulfur detection was conducted using high temperature combustion connected to ultraviolet fluorescence detection in accordance with ASTM D5453. The standard test method ASTM D5453 is applicable to hydrocarbons with a sulfur content of 1 – 8000 mg/kg, boiling in the approximate range of 25 – 400 oC and with approximate viscosities between 0.2 – 20 cSt. The results obtained in this application note were compared with results obtained from ASTM Crosscheck Programs.
Crude oil is composed mainly of hydrocarbons mixed with a variation of nitrogen, sulfur and oxygen. The differences in the nitrogen, sulfur, and oxygen content can be attributed to where the crude oil originates. After drilling, crude oil is usually refined in order to create fuel, lubricants, etc. Due to the use of processing catalysts in the refining method, determining the nitrogen and sulfur content is very important. Trace amounts of sulfur and nitrogen can be very detrimental. Thus, determining the nitrogen and sulfur content is very important. This application will examine total sulfur and nitrogen in light hydrocarbon samples using the NEXIS combustion elemental analyzer, complete with a novel multilayer combustion tube.
ASTM Method D5453 is commonly used to determine Total Sulfur in liquid hydrocarbons. The boiling range of these hydrocarbons can vary from 25 to 400ºC. This method calls for the sample to be directly injected or placed in a sample boat and then inserted into a high temperature tube for combustion where the sample is oxidized into sulfur dioxide (SO2). The sample is exposed to ultraviolet light and detected by a photomultiplier. This application note will examine the Total Sulfur content of diesel fuel samples using the NEXIS Total Nitrogen/Total Sulfur combustion analyzer.
The analysis of total sulfur in automotive fuels and related refinery products which is defined in ASTM D5453 method requires an easy to use, reliable and accurate lab analyzer from operator, laboratory and refinery operations perspective. The TSHR TS 7000 model, Total Sulfur analyzer, demonstrates an enhanced performance and fully compliance solution towards ASTM D5453 method.
Having minimum sample volumes but keep the same detection performance at low ppm level sulfur content within the scope of above ASTM method will have significant user advantages such as high productivity, less downtime and precise sulfur data.
This Note described the total sulfur performance data on the TSHR TS 7000 instrument, equipped with an auto injector (AI 7000 model) or with a liquids autosampler, HR 7000 series, to test the use of typical sample volumes and verify the calibration curves performance as per ASTM D5453 method. Also a set of CRM ultra-low sulfur diesel samples (ULSD) have been analyzed to show the correlation reference of these CRM samples when using the TS 7000.
ASTM D5453 covers the determination of Total Sulfur in concentrations ranging from about 1 to 8000 mg/kg in a wide range of liquid hydrocarbons and automotive fuels having a boiling point range of 25˚C to 400˚C and viscosities between 0.2 and 20 Cst (mm²/s) at ambient temperature.
Sulfur compounds can have detrimental effects on many environmental and industrial processes and are undesirable in finished products. This supports the need and importance to monitor trace level sulfur concentration of various type of automotive fuels and related products. This Application Note shows the analysis performance of a set of automotive fuel samples. The system design and methodology of the EST NEXIS Total Sulfur analyzer is thoroughly tested for response linearity and repeatability, to validate its performance according to ASTM D5453.
Simultaneous analysis of total sulfur and nitrogen in liquid hydrocarbon samples are widely used in R&D, production and routine quality control labs in compliance with several ASTM methods. Combustion and Ultra Violet Fluorescence (UV-F) have been used for accurate analysis of sulfur in motor fuels as per ASTM D5453. However, even an optimized UV-F detector may identify nitrogen oxide as Sulfur dioxide, which emits at the same wavelength as sulfur dioxide, into positive interferences and biased sulfur data. TSHR has developed an integrated TRINITY solution in their TN/TS analyzer, in order to have maximum flexibility when it comes to accurate and interference free total sulfur analysis as well as simultaneous analysis of total sulfur and nitrogen with minimum user handling.
The TSHR Total Sulfur Analyzer, TS 7000, is ideal for the determination of total sulfur particular in an extensive range of liquid hydrocarbon samples such as automotive fuels and high-grade chemicals in compliance with ASTM D5453 and SHT 0689 methods. The TSHR TS 7000 model Total Sulfur combustion analyzer fitted with the HR 7000 autosampler series, is able to accommodate syringes of 25ul, 50 ul and 100 ul in order customize certain application needs while achieve high precision data.
This note described the performance data of the TS 7000 analyzer configuration when the HR 7000 liquids autosampler is fitted with a 25 ul syringe for direct injection of small sample volumes as per ASTM D5453 methodology. The injection port design is maintained at 500°C to ensure a proper introduction of the sample. Once the liquid sample is evaporated it enters the oxygen rich combustion zone to ensure a oxidative conversion of the sulfur components into SO2 (sulfur dioxide) at 1000oC. Water and interferences (if any) are removed by the conditioning stage, which involves a permeable membrane dryer tube.
The dried gas with SO2 is led to the UV-F detector for the excitation of SO2 (SO2*) and a photomultiplier tube (PMT) which detects the light emitted by SO2* returning to its ground state. The automatic gain control (AGC) ensures a constant energy level of the UV lamp for excellent long-term stability and to reduce the need for frequent lamp calibration.
Base oils having applications to manufacture products including lubricating greases, motor oil and metal processing fluids and is produced by means of refining crude oil. During the refining process, light and heavy hydrocarbons are separated – the light ones can be refined to make petrol and other fuels, while the heavier ones are suitable for
bitumen and base oils.
By using hydrogenation technology in this process, in which sulfur and aromatics are removed using hydrogen under high pressure, extremely pure base oils can be obtained, which are suitable when quality requirements are particularly stringent. The sulfur content in these high-quality base oils will be very low ppm or ppb level. This application note describes the principle of operation and performance of the TSHR 7000 Total Sulfur Analyzer for the determination of Trace Level Total Sulfur analysis in these type of base oil samples according to ASTM D7183 methodology.
The EST NEXIS GM model, Gas & LPG Sample introduction module, is able to accurately sample and automatically introduce Gases and LPG samples into the EST NEXIS model Total Sulfur Analyzer. This feature results into a fully automatic calibration and sample analysis for trace level Total Sulfur content with the EST NEXIS series TS analyzers. Liquefied Petroleum Gas (LPG) is a group of hydrocarbon gases easily liquefied at moderate pressures which typically comprise C1 up to C10 hydrocarbons and S hetero compounds. The most common forms of LPG are methane (CH4),
Ethane (C2H6), propane (C3H8), propylene (C3H6), butanes (C4H12) and butylenes (C4H8). The most common S compounds found in LPG are sulfides, thiophenes and mercaptans.
LPG originates from two main sources: Associated gases in crude oils and gases produced in the refining processes. Because of its origin the composition of LPG varies in a wide range of components and concentrations. When processed industrial and domestic use as a fuel, hydrocarbons >C3 are removed since they are very valuable in petrochemical processes and gasoline blending operations. This type of fuel is a colorless and odorless mixture to which a certain amount of S compounds odorants is added to facilitate its detection. The determination of the total sulfur (TS) content in LPG streams is important to prevent sulfur related pipelines and equipment corrosion; to improve the quality of final products and to reduce pollutant emissions into the atmosphere.
LPG and other light hydrocarbons also find use as feedstocks for a variety of new refining catalytic technologies. The need for low sulfur measurements in this part of the industry is of growing importance since sulfur compounds poison the catalysts and negatively impact the economics of the processes. Furthermore, LPG is increasingly used as an automotive fuel and must therefore comply with stringent legislations concerning their Total Sulfur content.The Total Sulfur analysis of LPG by UV-Fluorescence detection is governed by ASTM D6667 and is applicable to samples containing sulfur in the range of 1.0 to 100 mg/kg. This application note describes a direct sampling and injection technique, which is fully compliant with ASTM D6667, for measuring low level sulfur in LPG using the EST NEXIS model Total Sulfur Analyzer in conjunction with the EST NEXIS GM model, Gas & LPG Sample introduction module.
ASTM D5453 covers the determination of Total Sulfur in concentrations ranging from about 1 to 8,000 mg/kg in a wide range of liquid hydrocarbons and automotive fuels having a boiling point range of 25˚C to 400˚C and viscosities between 0.2 and 20 Cst (mm²/s) at ambient temperature.
Sulfur compounds can have detrimental effects on many environmental and industrial processes and are undesirable in finished products. This supports the need and importance to monitor trace level sulfur concentration of various type of automotive fuels and related products. This application note shows the analysis performance of a set of automotive fuel samples. The system design and methodology of the EST NEXIS Total Sulfur analyzer is thoroughly tested for response linearity and repeatability, to validate its performance according to ASTM D5453.
Sulfur content in vegetable oils, animal fats, and waste vegetable oils varied greatly among these samples. Oil seeds can contain sulfur as high as a few thousand ppm.
In many countries the sulfur content standard allows maximum levels to be 10 or 15 ppm in automotive fuels, which includes biodiesel. It is known that when animal fats and waste vegetable oils are used for biodiesel production, the sulfur content is expected to be high, due to the presence of sulfur-containing compounds such as proteins. In addition to this, water-washing of the biodiesel may be a critical step for sulfur removal to obtain a good fuel quality biodiesel which does meet the respective allowable sulfur limit. This application note described the analysis and sulfur content in set of undiluted fatty acids which contains partly waste vegetable oils with low and high ppm sulfur content. With use of the TSHR TS 7000 model equipped with heated autosampler tray to maintain the sample in liquid form, this configuration enables customers to analyze the samples fully automatic in compliance to ASTM D5453 method.
Liquefied Petroleum Gas (LPG) is a group of hydrocarbon gases typically compromising three or four carbon atoms. The most common forms of LPG are propane (C3H8), propylene (C3H6), butane (C4H12) and butylenes (C4H8). Being colourless and odourless necessitates the addition of odourants to LPG to aid detecting unsafe situations. These odourants are normally the sulfur containing compounds mercaptanes, which are added at an approximate concentration of less than 10 ppmS. Measurement of the Total Sulfur (TS) content in natural gas streams is important both in avoiding sulfur related pipeline corrosion and for the determination of precise quantity of odorant that must be added to the LPG. LPG and other light hydrocarbons are also finding use as feedstocks for a variety of new refining technologies. The need for low sulfur measurements in this part of the industry is of a growing importance. Furthermore, LPG is increasingly used as an automotive fuel and must therefore comply with legislations concerning the sulfur content of automotive fuels, the limits of which are decreasing in last decade.
