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Biofuels analysis from Metrohm

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We offer you state-of-the-art instrumentation helping you to check and improve the quality of biofuels and corresponding blends as well as to comply with the standards – in your laboratory but also atline and online in the process environment

Text of Biofuels analysis from Metrohm

  • 1. Biofuel analysisQuality assurance of biofuels

2. 02 Metrohm ... is the global market leader in titration is the only company to offer a complete range of ion analysis equipment titration, voltammetry, and ion chromatography is a Swiss company and manufactures exclusively in Switzerland grants a 3-year instrument warranty and a 10-year warranty on chemical suppressors for ion chromatography provides you with unparalleled application expertise offers you more than 1300 applications free of charge supports you with expert service through local representatives and regional support centers is not listed on the stock exchange, but is owned by a foundation gives the interest of customers and employees priority over maximizing profit 3. Metrohm customized analysis for the biofuel industryA demanding industrySustainable use of biofuels requires reliable and preciseYou can count on our supportNot only do we provide you with the right instrumenta-03analytical methods throughout from the choice of rawtion but with complete solutions for the particular task atmaterials through to process optimization and on to the hand. Your partners at Metrohm are experienced profes-compliant final product.sionals who help you with customized application sup-port and service.As a leading manufacturer of instruments for chemicalanalysis, we are quite aware of these challenges. WeOn the following pages, discover the solutions Metrohmoffer you state-of-the-art instrumentation helping you to offers the biofuel industry in general and you in particu-check and improve the quality of biofuels and corre-lar, to ensure the quality and safety of your products.sponding blends as well as to comply with the standards in your laboratory but also atline and online in theprocess environment. 4. Quality assurance of biofuels04 Keen interest in biofuels Interest in biofuels has greatly increased in recent years.High quality standardsToo much water and the presence of alkali metal or alka- The reasons are the diminishing reserves of crude oil andline earth metal ions as well as sulfate and chloride ions the simultaneous increasing demand for mineral oil ashave a negative effect on the fuel quality and can dam- well as the environmental problems linked with burning age the fuel system of the vehicle. With biofuels based fossil fuels. In addition to a neutral CO2 balance, biogenic on fatty acids, there is an increased risk of polymerization fuels are generally characterized by their very good mi- at higher temperatures in the absence of antioxidants or crobiological degradability, which is why they are suitablein the presence of nonferrous metals. With the aim of for use in ecologically sensitive areas. Furthermore, alter- avoiding these problems, the manufacturers of biofuels native fuels can usually be produced locally and thereby and motor vehicles have developed quality standards in reduce dependence on imported raw materials. which testing methods and quality parameters for bio-fuels are defined. Biodiesel and bioethanol production Biodiesel is usually produced from vegetable oils or ani-A substantial number of the test methods that are stipu- mal fats. In an acid-, base-, or enzyme-catalyzed reaction,lated in international standards can be carried out with the triglycerides of the oil or fat are transesterified with Metrohm instruments and Metrohm application methods. methanol to form fatty acid methyl esters (FAME), which are also known generally as biodiesel. By contrast, bioethanol is made from products that con- tain sugar or starch. Microbial fermentation of the sugar within the biomass with the help of yeast cultures is a technology that is well-established and widely used com- mercially. A great hope for the future is cellulosic ethanol made from lignocellulose-containing waste materials, which has so far only been produced in pilot plants. Cel- lulosic ethanol is characterized by an especially favorable carbon footprint. 5. Selected standards from the eld of biofuel analysisMinimum requirements and test methodsTo ensure the quality of (bio)fuels, there are standards in prescribed test methods listed below to check the limits.05place that set minimum requirements in the form of lim- If an alternative test method is indicated for monitoringits for impurities and the test methods to be used. the limits, this is shown by the symbol.Metrohm instruments are highly suitable to carry out theBiodieselBiodiesel is sold as a pure fuel and in blends with fossilminimum requirements for biodiesel used as heating oil.fuels. The minimum requirements are set out in the spe- EN 590 applies to diesel fuels that contain up to 7% bio-cifications EN 14214 (pure fuel and blend stock) anddiesel and ASTM D 7467 applies to those that containASTM D 6751 (only blend stock). EN 14213 describes thebetween 6 and 20% biodiesel. Requirements and test methods EN 14214ASTM D 6751 EN 590Test method Method EN 14213ASTM D 7467PageAcid number Titration EN 14104ASTM D 6647Iodine number Titration EN 14111 Water content KFTcoulometric EN ISO 12937EN ISO 12937 10EN 15751 EN 15751Oxidation stability Oxidation stability EN 15751a12 (EN 14112) (EN 14112)Free and total glycerol content Ion chromatographyASTM D XXXXb 14Alkali metal and alkaline earth metal content Ion chromatography15Antioxidant content Ion chromatography recommended recommended recommended 15Sulfur contentCIC 18KFT = Karl Fischer Titration, CIC = Combustion ion chromatographya Applies to pure biodiesel and blends that contain at least 2% (v/v) biodieselb Test method is currently being validated in a round robin test and is only referenced in ASTM D 6751BioethanolThe minimum requirements for bioethanol as a blend com- and ASTM D 4806. ASTM D 5798 relates to ethanol-gaso-ponent in gasoline are documented in standards EN 15376 line blends E75-E85.Requirements and test methodsASTM D 4806EN 15376Test methodMethod ASTM D 5798 PagepHe valuepHe valueEN 15490ASTM D 64236Conductivity ConductivityDIN 51627-4Total acid number and acidityTitrationEN 15491ASTM D 1613Inorganic chloride content TitrationEN 15484 ASTM D 512 8Total inorganic sulfate contentTitration ASTM D 7318 KFTcoulometric EN 15489ASTM E 1064Water content11 KFTvolumetricASTM E 203ASTM D 7319Inorganic chloride content Ion chromatography EN 15492 16ASTM D 7328Total and potential inorganic ASTM D 7319 Ion chromatography EN 15492 16sulfate content ASTM D 7328Sulfur content CIC 18Copper content Voltammetry 20KFT = Karl Fischer Titration, CIC = Combustion ion chromatography 6. pHe value and conductivity measurement06 Bioethanol pHe value Conductivity A combined pH glass electrode with ground-joint dia-Electrical conductivity is an important analytical sum phragm is recommended for measuring the pH value in parameter for detecting and monitoring corrosive organic solvents. Because pHe determination according ionic constituents in ethanol and ethanol fuel. to ASTM D 6423 and EN 15490 is time-controlled, it is Because of the considerably lower conductivity essential that the sensor has a rapid response time. Thein nonaqueous systems, very sensitive meas- EtOH-Trode with a special membrane glass and the very uring systems are required. The stainless- precise fixed ground-joint diaphragm is particularly suit-steel conductivity measuring cell able for measuring the pHe values of biofuels. The double-(6.0916.040) with Pt 1000 temperature junction system allows the free choice of the electrolyte sensor, in conjunction with the flexible (e.g., 3 mol/L KCl in ASTM D 6423 and 1 mol/L LiCl in EN856 Conductivity Module, is ideally 15490). The pH meter used for the measurement shouldsuited for this application in accor- possess the following GLP functions, among others:dance with DIN 51627-4. Three-point calibration with automatic buffer recognition Temperature compensation Calibration data monitoring Automatic measured value recording Result memory with identification The pH meter 827 pH lab for laboratory use and the handy, battery-operated 826 pH mobile offer all these functions with extremely comfortable operation. The electrode for measuring pHe values in ethanol The laboratory pH meter 827 pH lab 7. 07TitrationBiodieselAcid number Iodine numberThe acid number is a sum parameter for all acidic com-The iodine number is a measure for the number of doubleponents; at the same time it is a measure for the long-term bonds in a sample. It is the amount of iodine (in g/100 gstability and corrosiveness of the biofuel. The smaller the sample) that can be added to the sample under the givenvalue, the higher the quality. Standard EN 14104 stipu- conditions. The determination of the iodine number inlates a nonaqueous potentiometric acid-base titration for fatty acids or biodiesel is covered by European standarddetermining the acid number. This involves dissolving the EN 14111.sample in a bioethanol-diethyl ether mixture and titrat-ing it with potassium hydroxide dissolved in 2-propanol An aliquot of the fatty acid or biodiesel sample is dis-(0.1 mol/L).solved in a mixture of cyclohexane and glacial acetic acidand treated with Wijs reagent. After a defined time hasAs organic solvents are used, the manual working stepselapsed, potassium iodide and water are added. The re-should be reduced to a minimum. With its space-saving leased elemental iodine is then titrated with sodium thio-Dosino technology, the Titrando allows fully automaticsulfate solution. EN 14111 allows both optical (withand safe solvent addition. The Solvotrode, an excellently starch solution as the indicator) and potentiometric end-shielded combined pH glass electrode, has been speciallypoint determination.developed for nonaqueous titrations. The separable ground-joint diaphragm guarantees stable potentials and is easyto clean. 8. 08 Bioethanol Chloride contentSulfate content The chloride content in bioethanol fuels is the subject ofA proven method for sulfate determinati