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Metrohm 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 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 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 (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 & 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 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 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 . 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. washed naphtha fraction; sodium biphenyl reduction measured with potentiometry or combustion and Hydrogen Sulfide & Mercaptans by evaluation by microcoulometry. Metrohm Combustion Ion ASTM D3227 Chromatography can be used instead of microcoulometry Sulfur compounds in petroleum products not only have an for this measurement. unpleasant odor, they are also environmentally damaging and promote corrosion. For determining hydrogen sulfide Organic Halides by Combustion IC and mercaptans in gasoline, kerosene, naphtha, and Combustion IC enables the sulfur and halogen content in similar distillates, the sample is titrated with a silver nitrate combustible solids, liquids, and gases to be determined solution. In this titration silver sulfide (Ag2S) and silver mercaptide are produced and two pronounced potential jumps occur. The first endpoint corresponds to hydrogen

sulfide (H2S), the second to the mercaptans. The indicator

electrode for the titration is the Ag-Titrode with Ag2S

coating. Since both H2S and mercaptans are oxidized by atmospheric oxygen and the arising oxidation products cannot be determined titrimetrically, work must be carried out under nitrogen atmosphere.

4 Organic Halides and Sulfur by Combustion IC The parameters that can be determined by NIR The burning of sulfur-containing fuel leads to the emission include: of air-polluting sulfur oxides into the atmosphere. • API gravity Furthermore, high sulfur concentrations have an adverse • Density at 15°C effect on the ease of ignition of fuels and their stability • Aromatic content during storage. Halogen concentrations in the refinery process must also be analyzed due to the corrosion risk. • Cetane index As a result, a fast and reliable method for determining the • Boiling profiles at 10%, 20%, 50% and 90% recovery halogen and sulfur contents is required. • Flash point • Freeze point • Hydrogen content • Viscosity at -20 °C

Liquefied Petroleum Gas (LPG) Water Content in Liquefied Gases Water is a contaminant in fuels and its concentration should be as low as possible. Water promotes corrosion and leads to undesired reactions in the fuel. In the case of liquefied petroleum gas, the challenge lies in the sample measurement and the associated phase transition from liquid to gas. In the sample cylinder, an equilibrium is reached between the liquid and gas phase. Depending on the sample, the water content in the gas phase can be several times higher than that of the liquid phase. Therefore, defined sampling is very important to ensure accurate and reproducible results. The Combustion IC method is captivating, not only due to its outstanding precision, but also because it has higher The 875 KF Gas Analyzer from Metrohm is a fully automated sample throughput. solution to determine trace levels of water in liquefied and permanent gases. Jet Fuel Testing by Near-IR Spectroscopy Monitoring jet fuel properties is important because the Organic Halides and Sulfur in LPG by fuel used in aircrafts must meet rigorous specifications. ASTM D7990 Near-infrared spectroscopy (NIR) is a fast method for fuel Fluorine, chlorine and sulfur contained in LPG can be analysis. Metrohm developed a unique calibration solution harmful to many catalytic chemical processes, lead to for jet fuels testing in the laboratory. corrosion and contribute to emissions pollutants. This test method can be used to determine total fluorine, chlorine and sulfur in processed and finished LPG products.

The Combustion Module (Oven + LPG/GSS) is comprised of the combustion oven and the LPG/GSS module and enables sample digestion during the pyrolysis of liquefied gases and gases under pressure.

5 Sodium by Online Analysis Iodine Number by EN 14111 The performance and life of combustion engines Iodine number is a test for the number of double bonds in optimized for LPG can severely deteriorate with elevated a sample. It is the amount of iodine (in g/100 g sample) that sodium levels. Determining these levels at the downstream can be added to the sample under the given conditions. stage helps refineries adjust process conditions. Metrohm The determination of the iodine number in fatty acids or Process Analytics technologies use an ion-selective biodiesel is covered by European standard EN 14111. electrode and the dynamic standard addition technique to accurately measure sodium in LPG in the 0-2 ppm range. Oxidation Stability by EN 15751 & EN 14112 Process measurements overcome traditional, lab-based ICP Fatty acid methyl esters are produced from a vegetable oil or AAS, which cannot be implemented in the production and usually obtained from oil seed by transesterification area. with methanol. Both feedstock and biodiesel have a relatively short storage life as they are slowly oxidized by atmospheric oxygen. The resulting oxidation products can Diesel & Biodiesel Blends damage vehicle engines. For this reason, the oxidation stability is an important quality criterion for biodiesel and Biodiesel is sold both as pure fuel and in blends with fossil vegetable oils and must therefore be checked regularly fuels. The minimum requirements for biodiesel are set in during manufacture and storage. The oxidation stability the specifications of EN 14214 (pure fuel and blend stock) of fatty acid methyl esters is included as an essential and ASTM D6751 (only blend stock). EN 14213 describes parameter in EN 15751 & EN 14112 standards. the minimum requirements for biodiesel used as heating oil. EN 590 applies to diesel fuels that contain up to 7% Free & Total Glycerol Content by biodiesel and ASTM D7467 applies to those that contain ASTM D7591 & EN 14214 between 6 and 20% biodiesel. The production of biodiesel from vegetable oils and animal fats leads to the formation of free and bound Acid Number by ASTM D664 & EN 14104 glycerol (monoglycerides and diglycerides) as by-products The acid number is a sum parameter for all acidic after transesterification of the triglycerides. Incomplete components; at the same time it is a measure for the transesterification and/or separation of glycerol causes long-term stability and corrosiveness of the biofuel. The glycerol contamination in the biodiesel, which speeds up smaller the value, the higher the quality. Standard EN fuel aging and leads to deposits in the engine and blocked 14104 stipulates a non-aqueous potentiometric acid-base filters. To ensure engines operate properly, ASTM D6751 titration for determining the acid number. and EN 14214 limit the maximum total glycerol content Moisture Determination (i.e., free and bound glycerol) to 0.24 and 0.25% (v/v), respectively. Free and bound glycerol is determined by ion The presence of water in biofuels reduces their calorific chromatography with subsequent pulsed amperometric value and increases the corrosion rate. Some biodiesel detection. fuels contain additives that can participate in side reactions during the direct coulometric Karl Fischer titration. In this case, Metrohm recommends that the biodiesel sample is not injected directly into the reaction solution. Instead, the Fuel Ethanol & Gasoline water contained in the biodiesel should be driven off in Blends a Karl Fischer oven. The water is driven off at 120 °C and The minimum requirements for fuel ethanol as a blend transported to the titration cell of the KF Coulometer in a component in gasoline are documented in standards EN stream of carrier gas (dry air or inert gas). This process can 15376 and ASTM D4806. ASTM D5798 relates to ethanol- be completely automated with the 874 USB Oven Sample gasoline blends E75-E85. Processor.

6 pHe Value of Fuel Ethanol by ASTM D6432 Water Content by ASTM E1064 & & EN 15490 ASTM E203 A combined pH glass electrode with ground-joint The ASTM E1064 and EN 15489 standards describe diaphragm is recommended for measuring the pH value coulometric Karl Fischer titration for determining water in organic solvents. Because pHe determination according content. For water content >2%, the recommended to ASTM D6423 and EN 15490 is time-controlled, it is test method is volumetric titration as per ASTM E203. essential that the sensor has a rapid response time. The The volumetric KF titrators from Metrohm meet all the Metrohm EtOH-Trode with a special membrane glass and specifications required by the standards and are therefore the very precise fixed ground-joint diaphragm is particularly extremely suitable for this application. suitable for measuring the pHe values of biofuels. Inorganic Chloride Content by ASTM D7179 Conductivity of Fuel Ethanol & ASTM D7328 Electrical conductivity is an important analytical sum Bioethanol is either used in pure form as a fuel or blended parameter for detecting and monitoring corrosive ionic with fossil fuels. Contaminants in the form of inorganic constituents in ethanol and ethanol fuel. Due to the chloride and sulfate salts are corrosive and lead to considerably lower conductivity in non-aqueous systems, deposits and blockages in the fuel filter and injection very sensitive measuring systems are required. The nozzles. The international ethanol specifications EN 15376, stainless-steel conductivity measuring cell with Pt 1000 ASTM D4806, and ASTM D5798 regulate the sulfate and temperature sensor, in conjunction with the flexible 856 chloride content in bioethanol and bioethanol fuel blends. Conductivity Module, is ideally suited for this application in accordance with DIN 51627-4. Total Potential Inorganic Sulfate Content in Fuel Ethanol & Gasoline Blend as per Acidity by ASTM D7795 ASTM D7319 & ASTM D7328 Fuel ethanol is mixed with gasoline in various ratios to According to ASTM D7319, the total content of inorganic reduce both the demand for gasoline and environmental chloride and sulfate is determined by direct injection of the pollution. Denatured fuel ethanol may contain additives ethanol sample, separation on an anion exchange column such as corrosion inhibitors and detergents as well as and measured using conductivity detection. If hydrogen contaminants from manufacturing that can affect the peroxide is previously added, sulfur-containing species acidity of finished ethanol fuel. Very dilute aqueous such as sulfites, sulfides, or thiosulfates can be oxidized to solutions of low molecular mass organic acids, such as form sulfate and are quantified as potential sulfate content. acetic acid, are highly corrosive to many metals, therefore, it is important to keep such acids at a very low level.

7 Increase Your Profit Water Content by ASTM D4347 & ASTM D4928 Through Internal Process Crude oil that comes in contact with water carries some Improvement. residual water. If the level of water in crude oil exceeds 0.1 Petroleum refineries are large and complex production to 0.5%, the distillation column will over pressurize. This facilities. Once the crude oil price is fixed the profitability creates unnecessary wear on the column and a potential can only be improved through process optimization. In safety issue. Water content in crude oil is monitored using plant operation, plant integrity and safety, production ASTM D4347 and ASTM D4928 rate, product quality, and costs are primary considerations. Mercaptans & Hydrogen Sulfide These all depend on comprehensive process control Raw oil contains several percent by weight of sulfur through online and near-real-time monitoring of key compounds. These compounds not only have an process variables, often in explosive, dusty, corrosive, and unpleasant smell, they are also environmentally harmful hostile environments. Metrohm provides online analyzers and corrosive which is why they must be largely removed specifically tailored to your process needs. In addition during refining. to dedicated analyzers, we specialize in suitable sample preconditioning systems that allow you to implement a The 2045TI Ex Proof Analyzer with a flexible sample reliable online solution. pretreatment system is found in a very wide variety of refinery applications. It monitors mercaptan and H S Explosion proof analyzers are available in a stainless- steel 2 content in accordance with ASTM D3227 and UOP163 version for Zone I or Zone II according to the European and can also be used for the determination of ammonia, explosive atmosphere directives (ATEX). halogen and phenol content as well as for the bromide index, saponification and acid number. The analyzer fulfills EU Directive 94/9/EC (ATEX95) and is certified for Zones Crude Desalting 1 and 2. Salt Content by ASTM D3230 Chloride Monitoring in Crude Desalting Excessive amounts of chloride salts in crude oil result Monitoring of the chloride in crude and after desalting is in higher corrosion rates in refining units and have a needed to check the desalting process efficiency and to detrimental effect on catalysts. Desalting techniques are overcome corrosion problems in downstream processes. well established, but continuous monitoring of the salt The analytical measuring method is ASTM D3230 by content is needed for process control and cost reduction. conductivity detection. Since the sample take off point Salt in crude oil is determined by titration using ASTM is typically in a hazardous environment the ADI 2045 Ex D6470 or by conductometric measurement with ASTM Proof Process Analyzer is designed and equipped to meet D3230. directives 94/9EC (ATEX95). Desalting Water Analysis A large portion of the water used in the crude desalting process is recycled. The source of wash water for the varies widely; in some cases stripped phonic sour water is used as wash water. Metrohm provides dedicated online solutions for important water analysis parameters such as: Sulfide, Ammonia, Phenol, pH, Alkalinity, Hardness, Conductivity.

8 the amount of organic fluorides in the alkylate product elevates as acid is consumed and exits with the alkylate. Metrohm provides easy to use solutions for the residual organically bound fluoride and sulfur in iso- and olefin feeds by CIC with a gas box that can withstand pressure up to 400 psi. Residual Moisture Content The alkylate is blended to make gasoline with specific Research Number (RON) values and residual water content in the alkylate can induce corrosion. For finished product quality assurance the moisture content determination in the alkylate product is important.

The 875 KF Gas Analyzer from Metrohm provides predefined methods for water content determination in Alkylation liquefied and permanent gases. and olefin are feeds into the alkylation unit which combines the olefin with butane to increase octane and lower the vapor pressure of the product for Sour Water Stripping blending. Alkylation is used in combination with fractional Sour water is condensed waste water produced during distillation, catalytic cracking and isomerization to many downstream refining processes containing hydrogen increase the yield of automotive gasoline. Either sulfuric or sulfide, ammonia and other contaminating compounds. It is used as the catalyst for the alkylation is often acidic in nature and can cause corrosion problems reaction. Both catalysts operate at low temperatures and within the refinery’s pipework so it must be treated before high isobutane-to-olefin ratios to reduce the side reactions it can be reused or disposed to the waste water treatment and catalyst consumption. is a liquid under plant. normal operation conditions, while hydrofluoric acid is a gas. Produced alkylates are passed through caustic to remove residual acids. Online Acid Strength Determination Acid acts as a catalyst in a refinery alkylation reaction, therefore, a minimal amount of acid is required to enable the reaction to occur. As acid strength declines, undesirable side reactions increase and can cascade in a runaway manner that consumes all of the acid in the unit. This can lead to undesirable polymer formation or oily sample formation depending on the type of acid used. In the hazardous environment, rugged online analyzers monitor the concentration of acid used in the alklyation Sour water is treated in the Sour Water Stripper (SWS) process. which uses a steam stripping process to remove sulfides and ammonia as gases. At optimum pH the sour water Alkali concentration can be measured using a similar online mixes with steam and the ammonia and hydrogen sulphide analyzer. gas vent to the top of the stripper column to the Sulfur Monitoring Alkylation by CIC Recovery Unit (SRU). The stripped water is either used to produce steam in the reboiler or pumped within control Insufficient acid strength in the HF Alkylation unit can lead limits to the waste water treatment plant for further to flurobutane formation. In an acid runaway situation, processing

9 Online Monitoring of Hydrogen Sulfide and Online Monitoring of Amine Strength Ammonia Determination of free amine is an important parameter Online analysis of ammonia and sulfides increases the to ensure acid gas removal. The alkalinity of gas washing efficiency of the SWS which leads to significant steam solutions containing alkanolamines is measured by reduction and increased energy savings. Effectively potentiometric titration with sulphuric acid using a combined glass electrode. stripping and monitoring H2S and NH3 is an essential operation in the overall pollution reduction program of refineries. The Process Analyzer 2045TI can analyze 2 H S and NH3 simultaneously with automatic cleaning and calibration using absolute wet chemical techniques. Fast and accurate results are continuously transmitted for process control.

Other contaminants that increase the sour water corrosiveness like phenol and cyanide can also be analyzed with Metrohm Process Analyzers. Determination of Anions, Sulfide, and Ammonium by Ion Chromatography Determination of sulfide and other sulfur species is critical for strict SWS process monitoring. While titration A single online analyzer can monitor several sample streams is a suitable technique for the sulfide content, the and determine the binding capacity of several amine other corrosive sulfur species can be determined by ion scrubbers in succession. By implementing Metrohm’s fully chromatography. The degradation products of sulfide, automated online monitoring solution for this process, it such as sulfite, sulfate, thiosulfate and thiocyanate can is possible to optimize the amine activity and measure the be monitored by suppressed ion chromatography. Sulfide efficiency of the acidic gas capture, reducing overall costs content in sour water can be monitored with UV detection while ensuring environmental compliance. while ammonia content can be monitored by cation exchange chromatography. Sample preparation steps such Monitoring Heat Stable Salt Formation by as ultrafiltration and dilution can be automated. Ion Chromatography Heat stable salts are a product of the neutralization reaction between the alkaline amine and an organic or inorganic Amine Treatment acid (the neutralizing agent). Amine solutions extract other contaminants that form salts of organic acids and sulfur An amine treating unit captures hydrogen sulfide and species such as oxalic acid, formic acid, thiosulfate and other acidic gases from the refinery gas streams and thiocyanate. The accumulation of heat-stable salts not only concentrates them into an amine solution. It is also used causes a reduction in CO absorption capacity, but also to capture acidic gases from raw or sour natural gasses. 2 causes a significant increase in the system corrosiveness. Amine gas sweetening is a proven technology that removes Metrohm provides a simple to use Isocractic IC method to H S and CO from natural gas and liquid 2 2 determine heat stable salts. streams through absorption and chemical reaction. The entire process is very energy intensive and results in high Bicine Determination by Ion Chromatography operating costs. Optimizing the amine activity and usage During degradation of these amines they form various by online analysis is a critical step in reducing overall costs products, especially bicine which is corrosive. It is and measuring the efficiency of the CO2 capture at the extremely important to determine the accurate amount of same time. bicine in order to control corrosion and cost. Bicine can be determined using cation exchange chromatography with electrochemical detection.

10 Diesel & Gasoline Blending Monitoring

• API • Benzene content • Research octane number • Alcohols & ether (MTBE, etc.) • Density Gasoline Blends (RON) • content • Motor octane number (MON) • Reid vapor pressure • Aromatic content • Octane index number

• Boiling Point • Flash point • Cold filter plugging point (CFPP) • Cetane number • Pour point Diesel Blends • Density • Cloud point • Specific weight • FAME content • Color • Viscosity

During the blending process, different fractions of the Advantages of NIR Analysis in crude oil distillation are mixed together to produce Petrochemistry ready-to-sell diesel or gasoline. This process is the most Near-infrared spectroscopy has been successfully used in economical when it is carried out in automated process oil refineries for years. NIR detects numerous parameters systems that work online. The endpoint of the blending in a single measurement in less than a minute. The cost process is reached when the required fuel specifications savings are enormous. Further advantages are: are achieved. Key characteristics, which indicate the • short response times and fast quality control progress of the blending process, are the cetane number • improved product quality and process optimization for diesel blends and the for gasoline blends. • reduced investment, analysis, and maintenance costs Near-infrared spectroscopy (NIR) sensors located directly in • accurate and precise measuring results. the process enable the entire process to be controlled and ensure a high-quality end product. Real Time Blending Process Monitoring by NIR Parameters that can be monitored in parallel and inline are Monitoring the blending of a range of fuels is a direct listed in the table above. example of the success of NIR in the refinery. NIR detects numerous parameters in a single measurement in less than a minute.

Metrohm manufactures dedicated lab and process NIR analyzers for diesel and gasoline analysis and blend monitoring. These dedicated analyzers are provided with start-up calibration that eliminates time-consuming calibration development.

11 Ethylene Cracking Approaching 150 million tons per year, ethylene is the NIR process analysis is a key component of process largest volume industrially produced organic material. optimization, because it provides process control with real- Feedstock, typically naphtha or light gases (e.g., ethane, time gas concentrations at various points in the process. ), is first heated to high temperatures to break The use of fiber optics enables real-time sequential down the feed into small hydrocarbon molecules. After measurements of up to 9 positions (e.g., feed, recycle being cooled, the products are then sent through a variety streams, product streams) with a single instrument. This of separation processes with high purity ethylene being allows for rapid adjustments of the process to account one product stream among many. for changes such as differences in feed or temperature. The net results of incorporating NIR into the process are Process optimization focuses on maximizing the output increased capacity, improved process reproducibility and of ethylene and other profitable products. Typically, a product quality. Further, the amount of process testing can Process GC is utilized for monitoring the cracking process. be shortened while enhancing plant safety. In combination However, these measurements are time-consuming and with a high pressure cell, NIR spectroscopy can also be maintenance-heavy. Near-IR with multicomponent analysis used as a tool for online, real-time analysis of industrial capability can be used for real-time cracking process gases. monitoring.

12 Water & Waste Water Monitoring Many of the processes in a petroleum refinery use water in large quantities. Refineries also generate a significant amount of waste water that has been in contact with . In addition, most organic and inorganic compounds found in the refinery accumulate in this process water. To sustain this resource, refineries treat the waste water and reuse it for various process applications. This requires treatment utilizing reliable analyses that monitor the composition of the water continuously.

Raw water or source water for refineries could come from lakes, rivers, ground water or sea water. Due to the specific requirements of process water in the refinery, all source water needs to be treated before being used for refinery applications.

Waste water from refineries contains high levels of pollutants and is characterized by the presence of large quantities of oil products and other chemicals that are hard to degrade. With increasing regulatory limits and stringent monitoring requirements, most refineries are forced to use advanced water treatment, recovery and process monitoring technologies. Major waste water streams in refineries include water, sour water, spent caustic formed in the extraction of acidic compounds from products, tank bottoms, and condensate blow down. Below is a table listing analytical parameters monitored in various water sources within the refinery.

Water Source Parameters of Interest Technology Source water: Ground water, River water, pH, Conductivity, Hardness, Alkalinity, Chloride, ISE Measurement; Titration & Online Analyzer Sea water, Rain water Sulfate, COD, Chloride, Sulfate, Nitrite, Nitrate, Phosphate & Ion Chromatography; Online IC other anions Sodium, Potassium, Calcium, Magnesium, Ion Chromatography; Online IC Ammonium, Barium pH, Conductivity, Hardness, Alkalinity, Chloride, Process Water: Hydrocracking steam condensate Titration Sulfate, COD Ammonia, Nitrite, Phosphate, Silica, Iron, Dedicated Online Analyzers Cobalt, Sulfide, Fluoride, Hypochlorite pH, Conductivity, Chloride, Sulfide, hardness, ISE Measurement; Titration; Dedicated Online Desalter waste water alkalinity analyzer Sulfide, Ammonia, Phenol Dedicated Online Analyzers Sour water Ammonia, Sulfide, Chloride Dedicated Online analyzers; Ion Chromatography Cooling water & cooling tower blow down Calcium, Magnesium, Zinc, Phosphate, Silica Dedicated Online analyzers; Ion Chromatography Dedicated Online analyzers; Titration; Spent caustic Cyanide, Phenol, Sulfide, Ammonia, ISE Measurement Ammonia, Sulfide, Cyanide, Phenol, Nitrite, Nitrate, Total Nitrogen, Sulfate, Calcium, Waste water treatment Dedicated Online Analyzers Magnesium, Barium, COD, Phenol, Total phosphate pH, Conductivity, Alkalinity, Hardness, Chloride, Measurement & Titration Sulfate Fluoride, Chloride, Sulfate, Nitrite, Nitrate, Phosphate, organic acids, hexavalent chromium, Ion Chromatography Sodium, Ammonium, Potassium, Calcium, Magnesium and other amines, Cobalt, Zinc

13 Corrosion Monitoring Reliable Corrosion Measurements via Electrochemistry

Refineries are complex systems of multiple operations that depend on the type of crude refined and the desired products. They constantly optimize the production process to improve the high value products yield that maximizes profitability. Refineries lose their profit due to the corrosion to the level of $1 billion per year. Protecting refinery plants against corrosion due to the sulfur, chloride and other organic acids is important in regard to safety and profitability.

Metrohm offers innovative and improved analytical methodologies to improve process efficiency and to protect against corrosion to maximize profitability.

Over the past three decades, several methods have been introduced to measure and monitor corrosion. While many of these traditional methods such as weight loss or spray test analysis are quick and cost-effective, they can only offer a qualitative overview of the process. In comparison, electrochemistry techniques are accurate, reproducible and often the only method to measure corrosion rates on a quantitative basis. Electrochemistry has not only made it easy and direct to measure the parameters governing the corrosion processes but has also helped greatly in the overall development of the novel corrosion resistant films and corrosion inhibitors.

Depending on the nature of the application, different electrochemical techniques are needed to determine specific parameters of interest. Metrohm instruments and pre-programmed methods provide ready-to-use tools to determine these parameters. Metrohm offers fully customized corrosion analyzers to evaluate corrosion parameters for specific ASTM methods. A corrosion software package with pre-programmed protocols is provided with every analyzer at no charge. Corrosion parameters of interest and the relevant ASTM methods are summarized in the table below.

Electrochemistry Techniques Parameters of Interest ASTM Reference Methods DC Techniques Polarization resistance (Rp) Linear sweep voltammetry Corrosion rate (mm/Year) ASTM G102 Tafel slope analysis Corrosion current ASTM G59 Potentio-dynamic polarization (LPR) Corrosion potential Film resistance & conductivity AC Techniques Charge-transfer resistance ASTM G59 Electrochemical impedance analysis (EIS) Solution resistance ASTM G106 Polarization resistance Chrono & other Techniques ASTM G150 Redox kinetics Electrochemical noise (ECN) ASTM G148 Pit initiation Critical pitting technique (CPT) ASTM G100 Crevice progression Hydrogen permeation study ASTM G61 Hydrogen resistance Cyclic potentiodynamic polarization ASTM F746 Surface morphology Hydrodynamic linear sweep ASTM F2129

14 Partner with Metrohm for Quality Service Profitability Metrohm Quality Service begins before you purchase your instrument and continues throughout its entire lifecycle. Petroleum refining is demanding and requires precise and Instrument experts help you make the right decisions to reliable analysis. As a leading manufacturer of instruments satisfy your analytical and environmental requirements. for chemical analysis we are aware of these challenges. Application chemists assist you in every technical aspect, We work closely with the petroleum refineries and with from support in method development to troubleshooting the regulatory agencies such as ASTM and EPA to come up and process optimization. Our certified service engineers with new and improved analytical methods that improve are always on alert to provide emergency service in the overall product quality and profitability. Your partners at shortest possible time – wherever you are. Metrohm Metrohm are experienced professionals who help you with provides the same high standard of service all over the customized application support and service. world by trained and certified service engineers based at local Metrohm offices. After all, who is better qualified to care for your instruments than the people who built them?

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