Elemental Analysis of Biofuels with SPECTRO XRF and ICP Spectrometers With a complete range of Energy Dispersive X-ray Fluorescence (ED-XRF) and Inductively Coupled Plasma Optical Emission (ICP-OES) Spectrometers, SPECTRO’s unique solutions for at-line and laboratory elemental analysis are capable of meeting the most demanding product specification testing requirements. To keep pace with the rapidly emerging developments of new biofuels, including second generation bio-materials, one of the key industry challenges is to ensure customer confidence in consistent quality of low sulfur biofuels using advanced, precise, easy to use analytical technology. This ensures extender product or finished blends meet the exacting new ASTM and EN biofuel specifications. This technology allows the industry to measure at sub 10-15 ppm levels of sulfur in biofuels to guarantee meeting federal government agency requirements, but also minimizing and measuring at trace ppm levels, metal elements such as Cu, Ca, Mg, Na, K, and P, to ensure that these biofuels of ‘today and the future’, maintain engine emission optimization, as well as providing trouble free motoring. Like ethanol production, the fast development of bio-materials suitable for diesel engine combustion has rapidly taken off, where the two main approaches have been the use of 100% vegetable oil Demand for automotive fuels is increasing material, in some cases, recycled cooking at a rapid pace, illustrated by the fact that oils, to the more suitable derived ester in 1990 there were around one million oil materials that again can be used at cars in China, by 2004 that number had 100%, but are generally blend back into risen twelve times and in 2005 alone conventional diesel fuels at 5-10 or 20% a further 2.4 million new cars and fuel levels. consumers were added to China’s roads. The demand for continued use and This is a trend which is repeated in many increasing the levels of ethanol used Biofuels today and tomorrow other developing countries, placing in fuels is being pursued by many even greater strains on the goal for government agencies worldwide and it is the downstream oil industry to reduce expected that in the next 5-10 years the emissions of greenhouse gases. alcohol demand for road transport fuels When considering the future of fuels will rise dramatically. Ethanol is now being one must not overlook the fact that made, in many cases, to regional federal Government and industry bodies specifications, which cover a broad range worldwide are firmly predicting that oil of physical and chemical properties to and refined oil products will continue to ensure consistent quality, with minimal form the major global source of fuels for risk of harmful trace contaminants. the next 30 years or more. Therefore providing a finished quality Renewable and other fuels are set to play fuel which can safely be run in advanced a growing role during this period. By far engine technologies without causing the biggest area of biofuel developments any detrimental effects on fuel injection have been for road transport for both (deposits) and engine/emissions gasoline and diesel power technology. The management systems is of paramount use of sugars and other plant materials to importance. manufacture alcohols as 100 % fuels or as extenders to produce bio-gasoline has been around for years and actively applied in countries like Brazil and more recently Sweden. For referenced ASTM standards, Na Mg P S Cl K Ca Cu Pb visit the ASTM website, www.astm.org. For referenced CEN standards, SPECTRO iQ II     ( )  ( )  ( ) visit the CEN website, www.cen.eu/cenorm. SPECTRO GENESIS         For referenced ISO standards, SPECTRO ARCOS      ( )     visit the ISO website, www.iso.org. For referenced IP standards, visit the energy institute website, www.energyinst.org.uk  analysis possible at required levels  analysis possible, test method available ( )  screening possible at required levels Legislation Description Standard Test Methods 2003/30/EC Directive of the European parliament EN 14538 Fat and oil derivatives - Fatty acid methyl ester and of the council of 8 May 2003 on the (FAME) - Determination of Ca, K, Mg and Na promotion of the use of biofuels or other content by optical emission spectral analysis renewable fuels for transport with inductively coupled plasma (ICP OES) 2004/17/EC Council Directive relating to the quality EN 14107 Fat and oil derivatives - Fatty acid methylesters of petrol and diesel fuels (FAME) - Determination of phosphorus content by inductively coupled plasma (ICP OES) USA US Energy Policy Act of 2005 emission spectrometry ISO 10540-3:2002 Animal and vegetable fats and oils — Product Specifications Determination of phosphorus content — ASTM D4806 Standard Specification for Denatured Fuel Part 3: Method using inductively coupled plasma Ethanol for Blending with Gasolines for (ICP OES) optical emission spectroscopy Use as Automotive Spark-Ignition Engine Fuel AOC Ca 17-01 Determination of trace elements (Ca, Cu, Fe, Mg, ASTM D5797 Standard Specification for Fuel Methanol Ni, Si, Na, Pb, Cd) in vegetable oil by ICP-OES (M70-M85) for Automotive ASTM D7111 Standard Test Method for Determination of Spark-Ignition Engines Trace Elements in Middle Distillate Fuels by ASTM D5798 Standard Specification for Fuel Ethanol Inductively Coupled Plasma Atomic Emission (Ed75-Ed85) for Automotive Spectrometry (ICP-AES) Spark-Ignition Engines ASTM D4294 Standard Test Method for Sulfur in Petroleum ASTM D6751 Standard Specification for Biodiesel Fuel and Petroleum Products by Energy Dispersive Blend (B100) for Middle Destillate Fuels X-ray Fluorescence Spectrometry EN 228 Automotive Fuel-Unleaded Petrol-ASTM D7220 Standard Test Method for Sulfur in Automative Requirements and Test Methods Fuels by Polarization X-ray Fluorescence EN 15376 Automotive fuels - Ethanol as a blending Spectrometry component for petrol - Requirements IP 532 Determination of the Sulfur content of and test methods Automotive Fuels-Polarized X-ray Fluorescence EN 14214 Automotive fuels - Fatty acid methyl Spectrometry Method esters (FAME) for diesel engines - EN ISO 20847 Petroleum products- Determination of sulfur Requirements and test methods content of automotive fuels- Energy dispersive DIN 51605 Fuels for vegetable oil compatible X-ray fluorescence spectrometry combustion engines - Fuel from ISO 13032 Petroleum Products: Determination of low rapeseed oil - Requirements and test concentration of sulfur in automotive fuels - methods Energy-dispersive X-ray Fluorescence spectrometric EN 590 Automotive Fuel- Diesel- Requirements method and Test Methods ED-XRF Energy dispersive X-ray fluorescence technology (ED-XRF) provides one of the simplest, most accurate and most economic analytical methods for the determination of the chemical composition of many types of materials. It is non-destructive and reliable, requires no, or very little, sample preparation and is suitable for solid, liquid and powder samples. It can be used for a wide range of elements, provides detection limits in the sub-ppm level and can also measure concentrations of up to 100 % easily and simultaneously. At-line or in the Laboratory, Advanced SPECTRO iQ II Performance ED-XRF Spectrometer The SPECTRO iQ II employs proprietary optic and detector technology yielding performance, especially for light elements like sulfur, that rivals the much more expensive wavelength dispersive X-ray fluorescence spectrometers. The SPECTRO iQ II features a combination of low power X-ray tube and advanced C-Force polarization optical system. It is ideal for analyzing and qualifying biofuel extenders, intermediate and final petrochemical products. Its detection limit for sulfur in fuels, including ethanol and methanol is less than 1 ppm, meeting the requirements for product control and product release analysis. The instrument can be controlled with either a touch screen or standard monitor and keyboard. All important functions for routine analysis are displayed on one screen, making operation uncomplicated and intuitive. For more information about SPECTRO iQ II SPECTRO iQ II, including a – C-Force polarization optical system eliminates detailed brochure and background for superior sensitivity practical biofuels analysis – Powerful Silicon Drift Detector with high resolution reports, please visit www.spectro.com/iq yielding ultra-low detection limits – Precision sample cups and positioning system for better reproducibility – Complete analysis in just a few minutes – Touch screen interface for straightforward, intuitive, operation ICP-OES Over the last 30 years, Optical Emission Spectrometers with Inductively Coupled Plasma (ICP-OES) excitation sources have become an indispensable tool for chemical elemental analysis. Their ease of use, high sensitivity and precision, plus relative freedom from interferences have made ICP-OES systems the analytical method of choice for a wide range of applications. SPECTRO GENESIS – A powerful alternative to conventional sequential ICP and Atomic Absorption spectrometers – High speed analyses using simultaneous measurement The SPECTRO GENESIS offers a real of the complete spectrum economic alternative to sequential ICP-OES and Atomic Absorption spectrometers, – Factory calibrated, norm-conforming methods for enabling those who are unfamiliar with environmental and industrial applications ICP-OES to profit from the advantages of – Minimal installation and training requirements leading CCD ICP-OES technology and to – Compact design enables seamless integration into use a powerful, low cost and user friendly analytical system. the laboratory – Excellent price/performance ratio An extensive package of accessories is available for the SPECTRO GENESIS to further expand its application range. This includes, but is not limited to, a wide range of sample introduction systems, autosamplers, an autodilutor, an ultrasonic nebulizer and a hydride generator. The SPECTRO GENESIS is equipped with SPECTRO GENESIS powerful automation functions for the safe unattended analysis of a large number of samples. With an optional autosampler, several hundred samples can be processed without operator intervention. If the relevant methods are available, simply import or define a sample list. For more information about SPECTRO GENESIS, including a detailed brochure and practical biofuels analysis reports, please visit www.spectro.com/genesis The SPECTRO ARCOS is different from conventional ICP spectrometers. Hidden inside the prominent left side of the instrument is the unique optical system – a major development with unbeatable resolution, accuracy and stability. Available with an interface for either axial or radial plasma observation, the new CCD optic system with Paschen-Runge mount assembly delivers a matchless resolution of 8.5 picometer in the important wavelength range from 130 to 340 nm. Additional SPECTRO ARCOS strengths include the extremely robust, free-running generator and the low maintenance and economical UV-PLUS system for high VUV transparency down to 130 nm. The combination of these components deliver SPECTRO ARCOS powerful analytical performance for difficult organic matrices like ethanol, methanol, biodiesel and biofuel blends. The generator has the power needed to analyze difficult organic samples “straight-up” without dilution, resulting in better sensitivity, precision and better recoveries. Flexibility, transparent structure and simple operation characterize the SMART ANALYZER VISION software interface. Whether setting up norm-compliant methods or quantitatively reprocessing stored spectra, operators appreciate the straightforward SPECTRO ARCOS and easily accessible functions. They enable – High ICP-OES Performance class for the SPECTRO ARCOS to be perfectly tuned to the applicable analytical regulations and complex matrices and analytical tasks requirements. – Stable plasma conditions due to the robust free-running generator For more information about SPECTRO – Extended spectral range from 130-770 nm ARCOS, including a detailed brochure and practical biofuels analysis reports, please for perfect line selection visit www.spectro.com/arcos – Low maintenance UV-PLUS system with minimal operating cost www.spectro.com GERMANY U.S.A. HoNG KoNG (Asia-Pacific) SPECTRO Analytical Instruments GmbH SPECTRO Analytical Instruments Inc. AMETEK, Inc. SPECTRO Analytical Boschstrasse 10 91 McKee Drive Instruments (Asia-Pacific) Ltd. 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SPECTRO operates worldwide and is present in more than 50 countries. For SPECTRO near you please visit www.spectro.com/worldwide. © SPECTRO 2012, Subject to technical modifications • H-12, Rev.0. Photos: SPECTRO, GettyImages, Corbis. Registered trademarks of SPECTRO Analytical Instruments GmbH EU(005673694), USA(3,645,267); „SPECTRO“ (009693769); SPECTRO iQ EU(004206181), USA(3,906,817); SPECTRO Genesis EU(004206165), USA(3,170,644); iCAL D(303 15 391), EU(003131919), USA(3,189,726), Arcos EU(005326566), USA(3,451,924), Japan(5085474)