Metrohm Petroleum Refinery Applications Innovation to fuel profitability Innovation to Fuel Profitability Whether it is simply running a standard method or Impacting the Entire Refining implementing a customized process system, Metrohm is Process ready to partner with you to help drive productivity and Refineries are complex operations that convert crude profitability in your operation. oil into a range of products. Optimizing the production process to improve yield and maximize profitability is a key objective of any refinery. A recent study found that losses Driving Global Standards due to corrosion alone can approach $12 billion USD per Standard methods are more important than ever before year. Metrohm offers innovative analytical methodologies because these industry validated solutions streamline to improve process efficiency, protect against corrosion testing, making it consistent in labs all over the world. and maximize profitability. ASTM, UOP, ISO, IP and other global standards are commonly used for product quality control testing as they From crude oil to highly refined petroleum products, facilitate global commerce and are the basis of sound Metrohm offers solutions that deliver value across the economies. refinery. The testing of crude and refined oil products is demanding The table on the following page demonstrates the utility and requires precise and reliable analysis to meet regulatory of Metrohm products across the entire refining operation. demands. Metrohm is actively involved with ASTM and This brochure connects the regulatory needs of the helps drive method development. We take on these industry to our quality titration, ion chromatography, near- challenges and deliver solutions that improve accuracy and infrared and process products. efficiency. 1 PRODUCT PARAMETER TECHNOLOGY METHOD REFERENCE PAGE # Crude Oil Total acid number Thermometric titration ASTM D8045 3 Total acid number Potentiometric titration ASTM D664 3 Water content KF volumetric titration ASTM D4377 3 Water content KF coulometric titration ASTM D4928 3 Salt content Potentiometric titration ASTM D6470 4 Organic halides Potentiometric titration ASTM D4929 4 Organic halides Combustion IC AN-CIC-14 4 Jet Fuel & Kerosene Acidity Potentiometric titration ASTM D3242 4 Hydrogen sulfide and Potentiometric titration ASTM D3227 4 mercaptans Organic halides and sulfur Combustion IC AN-CIC-14 4 Water content KF volumetric titration ASTM D4377 4 Water content KF coulometric titration ASTM D4928 4 Liquefied Petroleum Gas (LPG) Hydrogen sulfide Potentiometric titration ASTM D2420 5 Water content KF coulometric titration AN-K-058 5 Organic halides and sulfur Combustion IC AN-CIC-018 5 Diesel & Biodiesel Blends Total acid number Potentiometric titration ASTM D664 6 Iodine number Potentiometric titration 8.000.6020 6 Water content KF coulometric titration 8.000.6077 6 Oxidation stability Oxidation stability EN15751(EN 14112) 6 Free and total glycerol content Ion chromatography ASTM D7591 6 Antioxidant content Ion chromatography TA-005 6 Sulfur content Combustion IC TA-049 6 Fuel Ethanol & Gasoline Blends pHe pH measurement ASTM D6432 7 Total acid number and acidity Potentiometric titration ASTM D7795 7 Water content KF volumetric titration ASTM E1064 7 Water content KF coulometric titration ASTM E203 7 Inorganic chloride content Ion chromatography ASTM D7319 & ASTM D7328 7 Total and potential inorganic Ion chromatography ASTM D7319 & ASTM D7328 7 sulfate content PROCESS PARAMETER TECHNOLOGY METHOD REFERENCE PAGE # Crude Desalting Total acid number of crude oil Online titration AN-PAN-1037 8 Salt in crude oil Online titration AN-PAN-1014 8 Desalted water anlaysis Online and lab titration AN-T-076 8 Mercaptans and hydrogen Online titration AN-PAN-1026 8 sulfide Salt content (salinity) Conductometric method ASTM D3230 8 Organically bound halides in Alkylation Combustion IC AN-CIC-018 9 feed, process and alkylates Acid strength Online titration AN-PAN-1006 9 Residual moisture in alkyate gas KF gas analyzer AN-K-058 9 Sour Water Stripping Hydrogen sulfide and ammonia Online titration AN-PAN-1001 10 Anions, sulfide and Ion chromatography AW IC-US-0218 10 ammonium in sour water Amine Treatment Heat stable salts Ion chromatography AN-S-343 10 Bicine Ion chromatography AW IC-US-0215 10 Amine strength Online titration AN-PAN-1003 10 Cetane number, density, Diesel & Gasoline Blending FAME, flash point, pour point, Online near-IR AN-NIR-022 11 Monitoring viscosity, cloud point Ethylene Cracking Various parameters Online near-IR AN-NIR-US-073 12 Water & Waste Water Analysis Various parameters Various technologies Various methods 13 Corrosion Monitoring Corrosion determination Electrochemistry Various methods 14 Crude Oil Crude oil assays evaluate the physical and chemical composition of crude oil feedstock. Each type of crude oil has unique chemical characteristics that are important to refiners, oil traders and producers globally. Crude oil measurements can vary from a simple yield determination to a complex evaluation of the quality of the crude oil and all of its refined fractions. These evaluations are critical to control corrosion in the refinery and greatly impact the profitability of all refining operations given the potential for significant loss in crude investments and disruptions in the refining process that influence yield, quality, production and environment. Total Acid Number by ASTM D664 Even though it is not as effective or reliable as ASTM D8045, many laboratories still measure Acid Number using ASTM D664. Metrohm has proven potentiomentric systems that yield the most accurate results from D664 and provide a high level of automation for worry free analysis. Water Content by ASTM D4377 & D4928 The determination of the amount of water in crude oil and petroleum products has always been important. Karl Fischer (KF) titration is the best water determination method due to its excellent reproducibility and accuracy as well as its ease of use. For these reasons, KF is called out in numerous international standards. Water is not homogeneously distributed in these products, which means that the petroleum samples must be homogenized Total Acid Number by ASTM D8045 before analysis. Furthermore, crude and heavy oils contain Acid Number (AN) is a critical quality control parameter for tars that can contaminate electrodes and titration cells crude oil and petroleum products. The accuracy of the AN leading to frequent reagent exchange and titration cell results has significant influence on the commercial value of crude oil and the profitability of a refinery. Moreover, acidic compounds lead to corrosion in petroleum refining and transportation infrastructure, therefore accurate AN measurements are necessary for safe operation. Given the commercial and corrosion impact of acidic compounds monitored by AN titrations, new method ASTM D8045 is critical to quality control laboratories throughout the industry. ASTM D8045 uses thermometric titration and improves upon the traditional D664 analysis technique by utilizing a sensor that is unaffected by difficult matrices, requires lower solvent volumes, and completes sample analysis in often less than two minutes. 3 cleaning. These additional steps add time and complexity by combining combustion digestion (pyrolysis) with to these measurements. To ensure that the sample subsequent ion chromatography. completely dissolves, solubility promoters are added to the methanol. Combustion IC can detect of individual halides without the interference that is encountered in any of the competing Metrohm offers both volumetric and coulometric KF detection methods for ASTM D4929 titrators for moisture determination in crude oil samples. Chloride by ASTM D6470 & D3227 Jet Fuel & Kerosene Chlorides in crude oil form areas of salt accumulation in processing units. These salt accumulations corrode key Total Acid Number by ASTM D3242 equipment, especially those that run in low-temperature The acid and base number may also be determined ranges where hydrogen chloride forms. Refineries by photometric titration with color indication of the constantly optimize the production process to improve the equivalence point. Metrohm offers a unique optical yield of high value products. They lose their profit due to electrode called the Optrode, a new sensor for photometric the corrosion to the level of 1 billion per year. Protecting titration. It is 100% solvent resistant thanks to its inert plants against the corrosion caused by sulfur, chloride and glass shaft. Another key advantage of the Optrode is its other organic acids is important in the context of safety capacity for automation. and profitability. Water Content in Jet Fuel by ASTM D4377 Chloride in crude oil is determined by potentiometric & D4928 and conductometric methods in accordance with ASTM Fuels contain mercaptans that are oxidized by iodine and methods. can falsely indicate a high water content. Organic Chlorides by ASTM D4929 The problem is addressed by adding N-ethylmaleimide, Organic chlorides in crude oil are known to cause severe which causes the SH groups of the mercaptan to add to corrosion in crude tower overhead systems, therefore, the double bond of N-ethylmaleimide. Normally the water most refineries allow no more than 1 ppm (mg/L) organic content in fuels is determined by coulometric titration. chlorides in the crude charge. There are two alternative With volumetric titration, a solubility promoter must be test methods for determination of organic chloride in added to the methanol.