Analytical Standards and CRMs for the Petroleum Industry Dr. Lisa Fitzpatrick EMEA Tactical Marketing Manager, LT&D. sigma-aldrich.com 2013 Sigma-Aldrich Co. LLC. All rights reserved.
Brands and WW Product Manager for Standards & Certified Reference Materials (CRMs) Evakatharina Richter Matthias Nold Buchs (Fluka) Pat Brumfield Laramie (RTC) mainly secondary pharma & environmental matrix standards, PT mainly neat standards & CRMs Vicki Yearick Bellefonte (Supelco) mainly standard solutions & mixtures Inside Sales Cambridge UK (Cerilliant) mainly pharmaceutical certified reference material solutions 2013 Sigma-Aldrich Co. LLC. All rights reserved.
Crude oil lifecycle 3
Physical tests on Crude Oil Inspection assays are used to monitor a supply for any major changes which affect suitability for refinery use, and may be routinely carried out when a batch of crude is received at a refinery. The tests involved check the bulk properties of the crude to ensure suitability for refinery processing and may involve the following tests: Density/API gravity Pour point Distillation Viscosity 4
Physical Tests on Blending / Finished Products Gasoline (product spec. ASTM D4814, EN228) Blending and monitoring tests - density, distillation, research octane number (RON) Shipment certification, additional tests RON, Motor octane number (MON), density, atmospheric distillation, vapour pressure (DVPE) Kerosene, regular burning oil, (product spec. ASTM D4054, EN2869, Class C-2 Blending and monitoring tests - density, atmospheric distillation, Abel flash point Shipment certification, additional tests viscosity Jet A1 kerosene, (product spec. ASTM D1655, Defence Standard 91-91) Blending and monitoring tests - density, atmospheric distillation, Abel flash point, mercaptan sulphur %, total acidity, aromatic content, freezing point, viscosity, aniline point, colour Diesel (product spec. ASTM D975, EN590) Blending and monitoring tests - density, atmospheric distillation, flash point, cloud point, cold filter plugging point (CFPP) Shipment certification, additional tests Cetane number, colour viscosity 5
Application Areas & Market Segments Our offering Forensics Cosmetics Food & Beverage Standards Petrochemical Environmental Pharmaceutical
We offer Standards for several Analytical Techniques Physical Properties Viscosity Melting Point Conductivity Density Particle Size... Standards Chromatography GC HPLC IC SEC/GPC ICP AAS XRF qnmr Spectroscopy Other Techniques Titrimetry TOC TIC...
Neat Standards -for Chromatography (typically 10 100mg) -quantitative NMR (1g) Standard Solutions (Single or Multicomponent) -Chromatography (typically 1mL) -> ampoules or CERTAN bottles -ICP / AAS / IC (100mL / 250mL) Matrix Materials -e.g. Soils, Food... -Certified Content of Components / Contaminants -RTC / IRMM 8
TraceCERT Organic CRMs TraceCERT certified reference materials (CRM) are developed and produced in an accredited laboratory, fulfilling both ISO 17025 (General Requirements for the Competence of Testing and Calibration Laboratories) and ISO Guide 34 (General Requirements for the Competence of Reference Material Producers). TraceCERT products are characterized by: Highest-purity starting materials available Superior (Swiss metrological) level of accuracy, very low uncertainties and lot-specific values Traceability to at least two independent references (i.e. NIST, BAM or SI unit kg) Comprehensive documentation (certification according to ISO Guide 31) 9
Petrochemical Standards We have a large range of petrochemical standards: These can be found under www.sigma-aldrich.com/chemistry/petrochemical Neats and Solution 10
Detailed Hydrocarbon Analysis Widely used to characterise light petroleum fractions with boiling points up to 450 F/225 C. Comply with ASTM methods D5134, D6729, D6730 and D6733 which use single-column gas chromatography (GC) to group the hydrocarbon components by structure. Applied to petroleum streams comprising naphtha, alkylate, reformer feed, reformate, isomerate, gasoline and compressed liquids. Characterisation is based on the Kováts Index differentiates the composition and concentrations into five groups that are collectively called PIANO: Paraffins, Isoparaffins, Aromatics, Naphthenes and Olefins. 11
Detailed Hydrocarbon Analysis Calibration of equipment: Precise calibration is critical for running successful DHA applications. Calibration utilises a set of six complex, quantitative analytical standards known as the PIANO standards. These standards can difficult for a laboratories to prepare due to their complexity and the lack of commercial sources of the many branchedchain hydrocarbons in the mixtures. 12
Detailed Hydrocarbon Analysis P-I-A-N-O (Paraffins-Isoparaffins-Aromatics-Napthenes-Olefins) standards are complex mixtures of known quantities of hydrocarbons, accurately prepared by weight to three decimal places. These mixes are used to determine retention times and indices, and to monitor response factors for components of complex mixtures of hydrocarbons. Formulations are weight percent. Each mix includes a detailed data sheet listing components by weight percent, mole percent, and liquid volume percent, retention indices for each component and other information. A chromatogram from a 100-meter capillary column (including conditions) is provided. Products are supplied in a crimp-top vial with hole caps and septa. 36 month shelf life from date of manufacture 13
New standards. July 2013 - Sigma-Aldrich announced a new strategic alliance with Paragon Scientific, with a global distribution agreement in place. They are based in the North West of the UK, near Liverpool. Paragon Scientific specialise in the production of premium quality reference materials that include Density, Flash Point, Liquid Colour, Refractive Index, TAN/TBN and Viscosity standards. They supply CRMs that are all certified in accordance with the requirements of ISO-IEC 17025 + ISO Guide 34 Gold Standard Accreditation. Our dedicated web page is page available www.sigmaaldrich.com/paragon 14
Total Acid Number (TAN) The total acid number (TAN) Is a measurement of acidity that is determined by the amount of potassium hydroxide in milligrams that is needed to neutralize the acids in one gram of oil. Is an important quality measurement of crude oil. Indicates to the crude oil refinery the potential of corrosion problems. Is usually the naphthenic acids in the crude oil that causes corrosion problems. This type of corrosion is referred to as naphthenic acid corrosion (NAC). We can supply Paragon TAN standards that are specifically manufactured for the verification of analytical instruments used to determine acid number by potentiometric titration. They are tested and certified in accordance with ASTM D644/IP177 15
Total Base Number (TBN) Total base number (TBN) Is a measure of a lubricant's reserve alkalinity. It is measured in milligrams of potassium hydroxide per gram (mg KOH/g). Determines how effective the control of acids formed will be during the combustion process. high TBN = more effective in reducing the corrosive effects of acids We can supply Paragon TBN Standards that are specifically manufactured for the verification of analytical instruments used to determine base number by potentiometric titration. Total Base Number (TBN) tested and certified in accordance with ASTM D2896 / IP 276 16
Paragon Scientific is a UKAS accredited CRM manufacturer with 20 years of experience in the production and certification of quality reference materials. The products are certified in accordance with the requirements of ISO-IEC 17025 and ISO Guide 34. All products are now available world-wide from Sigma Aldrich. www.sigmaaldrich.com/paragon 17
Where do Paragon standards fit in our portfolio? In the following areas: Physical properties calibration standards, viscometry Titration TAN (total acid number), TBN (total base number) Optical measurements refractive index, colour measurements Elemental analysis x-ray spectroscopy Water analysis conductivity, refractive index More information can be found at sigmaaldrich.com/paragon 18
Standards search tool at www.sigmaaldrich.com/standards_explorer 19
Standards Explorer Criteria Search available by Product number/name CAS number probably most accurate Molecular formula Agency; most agencies are included e.g. ASTM, CARB, EPA, DIN, EEC, EU etc. BUT Please be aware that not all methods for Europe are included. Most US agency methods are available, e.g. EPA, but only a few have been populated for DIN and EEC. 20
Summary Premier supplier of analytical standards and CRMs Broad range covering a variety of applications & areas of interest Standards for analyte identification, as well as material physical properties Standards explorer to help wit searching for the most suitable standard More information can be found at sigmaaldrich.com/standards 21