Petrochemical analysis Quality control of petroleum products 02 Metrohm ... • is the global market leader in titration • offers a complete portfolio for NIR and Raman analysis, in addition to all of the methods of • ion analysis – 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 anion chromatography • provides you with unparalleled application expertise • offers you more than 1800 applications free of charge • supports you with dependable on-site service worldwide • is not listed on the stock exchange, but is owned by a foundation • takes a sustainable approach to corporate management, putting the interests of customers • and employees ahead of maximizing profit Metrohm – customized analysis for the petrochemical industry A demanding industry You can count on our support 03 Crude oil is a highly complex mixture of hydrocarbons and Not only do we provide you with the right instrumenta-other compounds that through desalting, distillation, and tion but with complete solutions for the particular task at conversion is transformed into higher quality hydrocarbons. hand. Your partners at Metrohm are experienced profes-This refining is demanding and requires precise and reliable sionals who help you with customized application sup-analysis. port and service. As a leading manufacturer of instruments for chemical On the following pages, discover the solutions Metrohm analysis, we are quite aware of these challenges. We offers the petrochemical industry to ensure the quality offer you state-of-the-art instruments and systems for and safety of your products. monitoring and optimizing the quality of a wide variety of petrochemical products with the required accuracy not only in your laboratory but also in process. Analysis of petroleum products 04 Formation of crude oil deposits «Lubricant» of the global economy According to current knowledge our oil reserves origi- Nowadays crude oil, which consists of at least 500 differ-nated during the Jurassic and Cretaceous periods (200 to ent components, is processed by distillation and refining 65 million years ago) from microbial flora and fauna liv-to produce liquefied gas, gasoline, diesel, heating fuel, ing in the seas. While some of the dead organic resi dues and lubricants as well as a large variety of other products. were directly mineralized, i.e., decomposed, the other As the «lubricant» of the global economy, crude oil is part sank to the seabed. There the material was covered omnipresent. It covers approximately 40% of our energy by other marine deposits and formed a sludge with very de mand and is used in the chemical industry for the pro-fine rock material that slowly converted to crude oil duction of plastics, textiles, dyes, cosmetics, fertilizers, under the prevailing biogeochemical conditions of in - de ter gents, building materials, and pharmaceuticals. creased pressure and salinity. Due to its lower density the crude oil migrated upwards through fine cracks in the Standards for quality control rock layers until it accumulated under im permeable cov-The importance of petroleum products is reflected by the ering rocks and thus formed the oil de po sits we know large number of standards relating to them. Metrohm as today. Sometimes above-ground oil depo sits were a leading manufacturer of instruments for analysis offers formed that already allowed our forefathers to use crude long-standing application know-how for the quality as - oil for heating and lighting, building, or lubri ca tion. sur ance of petroleum products. Selected standards from petrochemical analysis Parameters Standard Matrix Method Page DIN ISO 3771 Petroleum products Base number ASTM D4739 Petroleum products Potentiometric titration Lubricants ASTM D2896 Petroleum products Nitrogenous bases UOP269 Petroleum distillates Potentiometric titration Acid and base number ASTM D974 Petroleum products Colorimetric titration 6 ASTM D664 Petroleum products Potentiometric titration Acid number DIN EN 12634 Petroleum products Lubricants Potentiometric titration Acid number and naphthenic acids UOP565 Petroleum products Petroleum distillates Potentiometric titration ISO 3012 Light and middle distillate fuels, Mercaptan sulfur kerosene ASTM D3227 Automotive fuel, kerosene H S ASTM D2420 Liquefied petroleum gas (LPG) 2 H S, mercaptan sulfur UOP163 Petroleum products Potentiometric titration 8 2 Alkalinity, H S, mercaptans UOP209 Used alkaline petroleum products 2 H S, mercaptan sulfur, 2 carbonyl sulfide UOP212 Gaseous hydrocarbons Liquefied petroleum gas (LPG) ASTM D94 Petroleum products Potentiometric titration Saponification value 10 DIN 51559 Petroleum, insulating oil Colorimetric titration Parameters Standard Matrix Method Page 05 ISO 3839 Petroleum distillates, alkenes ASTM D1159 Petroleum distillates Bromine number Aliphatic alkenes Potentiometric titration ASTM D5776 Aromatic 10 hydrocarbons Bromine number and bromine index UOP304 Hydrocarbons Potentiometric titration ASTM D1492 Aromatic hydrocarbons Coulometric titration Bromine index ASTM D2710 Petroleum hydrocarbons Potentiometric titration ASTM E1899 Aliphatic and cyclic hydrocarbons Hydroxyl number Potentiometric titration 11 DIN 53240 Resins, raw materials for varnishes, primary alcohols, glycols, fats Organic chlorine content ASTM D4929 Crude oil Organic, inorganic, and total Potentiometric titration 11 chlorine content UOP588 Hydrocarbons Salinity ASTM D6470 Crude oil Potentiometric titration 11 ISO 12937 Petroleum products Coulometric KFTa ISO 10337 Crude oil Coulometric KFT ISO 10336 Crude oil Volumetric KFT ISO 6296 Petroleum products Volumetric KFT DIN 51777-1/2 Petroleum hydrocarbons Coulometric KFT Solvents Volumetric KFT 12 ASTM D4377 Crude oil Volumetric KFT Water content ASTM D4928 Crude oil Coulometric KFT ASTM E1064 Crude oil, lubricating oil, solvents Coulometric KFT ASTM D1364 Highly volatile solvents Volumetric KFT ASTM D890 Turpentine Azeotropic distillation, KFT ASTM E203 General Volumetric KFT ISO 10101 Natural gas Coulometric KFT 14 DIN 51869 Gaseous fuels, gases EN 14112 Fatty acid methyl esters (B100) EN 15751 Fatty acid methyl esters and Oxidation stability diesel fuel blends Oxidation stability 16 DIN EN 16568 Fatty acid methyl esters and diesel fuel blends ASTM D7319 Inorganic chloride and sulfate ASTM D7328 Ethanol as a blending DIN EN 15492 component Ion chromatography 18 Free and total glycerol contentb ASTM D7591 Biodiesel blends Ion chromatography 18 ASTM D7359 Aromatic hydrocarbons Halogens and sulfur Combustion IC 22 UOP 991 Halogens in liquid organics Sulfur and heavy metals – Gasoline, ethanol Voltammetry 24 Various parameters (RON, CEN, etc.): Qualitative analysis ASTM E1790 Crude and petroleum as well as Quantitative analysis ASTM E1655 numerous petroleum products Near-infrared spectroscopy 28 Parameters that can be determined Process-dependent by wet chemistry and spectroscopy specifications Petroleum products Process analysis 30 aKarl Fischer titration, bfor details see brochure on biofuel analysis Thermometric titration, corrosion, and service Separate brochure for biofuel analysis The table above lists, amongst others, some standards An additional brochure is available for the analysis of for determining the acid and base number. Thermometric biodiesel and bioethanol. It can be downloaded in PDF titra tion is an interesting alternative. For details, see page format at: 9 of this brochure. biofuels.metrohm.com Pages 26 and 27 cover corrosion research and the Metrohm Autolab potentiostats and galvanostats used in this area. The extensive services offered by Metrohm Service are detailed on pages 36 and 37. Determination of acid and base numbers 06 Potentiometric titration with the Solvotrode easyClean The base number is a sum parameter for alkaline compo- The Solvotrode easyClean is a combined pH glass nents. These include primary organic and inorganic electrode that was especially developed for this amino compounds. However, salts of weak acids, basic application. The easyClean ground-joint dia-salts of polycarboxylic acids, a number of heavy metal phragm can be easily cleaned even of strong salts, and detergents are also determined. The base contamination. The electrostatic shielding num ber indicates how many basic components, ex pres - of the electrolyte compartment also sed as mg KOH, are contained in 1 g of sample. This ensures a low-noise measuring signal. de termination is used for the immediate detection of pro duct changes during use. With the acid number, acidic components are measured as a sum parameter. It includes acids and salts with pK s values < 9 and indicates how many mg KOH are required to neutralize 1 g of sample. The acid number reveals changes during the use of the product. Both parameters are determined by potentiometric titra- tion in nonaqueous solvents or solvent mixtures. Titrimetric determinations can be completely automated – from the addition of solvents to the reproducible clean-ing of the electrode. Oil samples can even be weighed in fully automatically by the 864 Robotic Balance Sample Processor before titration. This guarantees complete trace ability. Solvotrode easyClean Determination of acid and base number according to ASTM D974 (photometric titration) The acid and base number may also be determined by photometric titration with color indication of the equivalence point according to ASTM D974. For this applica- tion, Metrohm offers the Optrode, a new sensor for photometric titration. It is 100% solvent resistant thanks to the glass shaft. Another key advantage of the Optrode is its capacity for automation. Optrode Standard Parameter Titrant Solvents Electrode 07 (reference electrolyte) Chloroform, toluene, Solvotrode easyClean ASTM D4739 Base number HCl in isopropanol isopropanol, water (LiCl in EtOH) Base number Perchloric acid in ASTM D2896 Glacial acetic acid, xylene Solvotrode special > 300 mg KOH/g glacial acetic acid Perchloric acid in Toluene, glacial acetic acid, Solvotrode easyClean ISO 3771 Base number glacial acetic acid acetone (LiCl in EtOH) Toluene, isopropanol, Solvotrode easyClean ASTM D664 Acid number KOH in isopropanol water (lubricants), (LiCl in EtOH) isopropanol (biodiesel) Dimethyl sulfoxide, Solvotrode easyClean DIN EN 12634 Acid number KOH or TMAHa isopropanol, toluene (LiCl in EtOH) Acid number and Solvotrode easyClean UOP565 KOH in isopropanol Toluene, isopropanol, water naphthenic acids (LiCl in EtOH) ASTM D974 Acid number KOH in isopropanol Toluene, isopropanol, water Optrode ASTM D974 Base number HCl in isopropanol Toluene, isopropanol, water Optrode a Tetramethylammonium hydroxide 864 Robotic Balance Sample Processor (with 843 Pump Station (peristaltic)) for TAN/TBN determination 08 Sulfur and sulfur compounds determined by potentiometric titration with the Ag Titrode Sulfur compounds in petroleum products not only have an unpleasant odor, they are also environmentally dam- aging and promote corrosion. For determining hydrogen sulfide and mercaptans in liquid hydrocarbons (gasoline, kerosene, naphtha, and similar distillates), the sample is titrated with silver nitrate solution, whereby silver sulfide (Ag S) and silver mercaptide are produced. Two pronoun-2 ced potential jumps occur. The first endpoint corres- ponds to hydrogen sulfide (H S), the second to the mer- 2 captans. The indicator electrode for the titration is the Ag-Titrode with Ag S coating. Since both H S and mer-2 2 captans are oxidized by atmospheric oxygen and the arising oxidation products cannot be determined titri- me trically, work must be carried out under a nitrogen atmosphere. Gaseous sulfur compounds can also be determined with this procedure. For this purpose, they are absorbed in an alkaline solution. The first two absorption vessels contain KOH or NaOH (for H S and mercaptans), the third con-2 tains ethanolic monoethanolamine (for carbonyl sulfide). The Ag-Titrode is a maintenance-free com- bined Ag-ring electrode. During titration, it references the constant pH value of the sam- The results are expressed in mg/kg (ppm) hydrogen sul - ple: therefore, the diaphragm, which is used fide and/or mercaptan sulfur. on other sensors, is no longer required. Compact dimensions: 859 Titrotherm (center) with the 801 Stirrer Thermometric titration: the ideal complement to potentiometric titration Thermometric titration is a determination method suit- thermic reaction) or a decrease (endothermic reaction) of 09 able for a broad range of applications. It substitutes po - the sample solution temperature. The titrant added ten tiometric titration, particularly when potentiometric reacts with the analyte and thereby changes the tem-elec trodes are not suitable for the application at hand. perature in the reaction solution. A bend in the tempera-The only prerequisite for thermometric titration is an ade- ture curve indicates the endpoint when all analyte has quately sufficient temperature change in the sample solu-reacted and allows the calculation of the analyte concention. tration. The advantages of thermometric titration are ease of handling, control via tiamo software, and exceptional y short analysis times. Automation is particularly ad van - tageous here, as it saves a great deal of time. The sensor e [°C] re quires no calibration or maintenance and is ideally atur Endpoint suited to aggressive sample matrices. There are two ver-sions, one for HF-free and the other for HF-containing Temper aqueous/nonaqueous solutions. The principle Volume [mL] Every chemical reaction is associated with a change in reaction enthalpy. This results in either an increase (exo-Temperature curve of an exothermic titration Thermoprobe: a unique sensor for a variety of thermometric titrations Monitoring TAN in refinery operation Sulfur species and naphthenic acids are common corro- than potentiometric titration as it requires fewer resourc-sion contributors from crude oil in the refinery process. es (e.g., sample, solvent, analysis time) and especially no Especially napthenic acids contribute to high TAN value sensor maintenance. The highly sensitive Thermoprobe and can aggressively attack refinery equipment. requires neither a reference electrolyte nor special clean-Therefore, operators need to make quick decisions when ing or conditioning between the titrations and therefore it comes to corrosion. Thermometric titration is the fast-improves operations by avoiding unplanned mainte- er, cheaper and more repeatable test method for moni- nance. toring TAN in crude oil. It is a more economical method 10 Saponification value The saponification value (SV) primarily serves to deterThe method is used for the following products: mine the proportion of fatty acid esters in the sample. • Distillates with a boiling point below 327 °C (620 °F) The fatty acid esters are cleaved by boiling in KOH, a and a volume percentage of at least 90% of com- process that produces the salts of the fatty acids and the pounds that are lighter than 2-methylpropane (included corresponding alcohol, for example, glycerol. The meth- in this are fuels with and without lead additions, kero-od is not specific since acidic sample constituents con-sene, and gas oils). sume KOH and in doing so increase the saponification • Commercial alkenes (mixtures of aliphatic monoalkenes) value. The titrant employed is c(HCl) = 0.5 mol/L in iso-with a bromine number from 95 to 165. propanol. The SV indicates how many mg KOH are con- • Propenes (trimers and tetramers), butene trimers, mix-sumed by 1 g sample under the test conditions. tures of heptenes, octenes, and nonenes Bromine number and bromine index The BI indicates how many mg of bromine (Br ) are bound 2 The bromine number (BN) and the bromine index (BI) by 100 g of sample. The method is used for «alkene-free» indicate the proportion of unsaturated compounds (usu- hydrocarbons with a boiling point below 288 °C (550 °F) ally C-C double bonds) in petroleum products. Here, the and a bromine index of between 100 and 1000. For prod-double bond is cleaved by bromine addition. The BN ucts with a bromine index of > 1000, the bromine number indicates how many g of bromine (Br ) are bound by should be used. 2 100 g of sample. Method Samples Titrant Solvents Electrode Bromine Automotive fuels, kerosene, c(bromide/bromate Glacial acetic acid, Double Pt wire number gas oils, propene, butenes, solution) = trichloroethane, electrode [g Br /100 g] heptenes, octenes, nonenes 0.08333 mol/L methanol 2 c(bromide/bromate Glacial acetic acid, Bromine index Double Pt wire Alkene-free hydrocarbons solution) = trichloroethane, [mg Br /100 g] electrode 2 0.00333 mol/L methanol 11 Hydroxyl number The hydroxyl number (OHN) indicates the number of In comparison to the formerly used 1-hour boiling under mg KOH corresponding to the hydroxyl groups in 1 g reflux, this automated procedure saves time and is more sample. The most frequently described method for deter-convenient, and reproducible, as it guarantees that every mining the hydroxyl number is conversion of the sample sample is treated in exactly the same way. with acetic acid anhydride in pyridine with subsequent titration of the released acetic acid. The one-hour boiling Chloride and organically bound chlorine under reflux, the difficulty in automating the process and Organically bound chlorine present in petroleum prod-particularly the use of the health-hazardous pyridine are ucts is decomposed at high temperatures and forms serious disadvantages. hydrochloric acid. This is highly corrosive and can cause damage, for example, to the distillation columns. An alternative is offered by the considerably simpler and more easily automated method according to Before measurement, the sample is freed of sulfur com-ASTM E1899. Primary and secondary hydroxyl groups are pounds and inorganic chlorides by distillation and subse-converted with toluene-4-sulfonyl-isocyanate (TSI) into quent washing as described in ASTM D4929. The or ga - an acid carbamate, which is then titrated with the strong nically bound chlorine is converted to NaCl with me tallic base tetrabutyl ammonium hydroxide (TBAH) in a non-sodium in toluene. After extraction into the aqueous aqueous medium. The method is especially suitable for phase, the NaCl is titrated potentiometrically with the neu tral raffinates. Acidic products can falsely indicate Ag-Titrode. values that are too high. In the same way products that contain bases can show values that are too low due to neutralization of the carbamate formed. Water determination according to Karl Fischer 12 Water occurs as a contaminant in virtually all petroleum Hydraulics, insulation, transformer and turbine products. It reduces lubricant properties, promotes mi - oils cro bial oil degradation, leads to sludge formation in the In these oils the water content is almost always deter-tank, and promotes corrosion of ferrous and nonferrous mined coulometrically using a diaphragm cell. Due to the metals. While water boils and contributes to a partial de - poor solubility in methanol, solubility promoters must be greasing at higher temperatures, temperatures below used (chloroform or trichloroethylene). Since these prod-freezing point lead to the formation of ice crystals and a ucts have very low water contents, it is very important to rapid decrease in lubricity. In addition, insulating and achieve a low and constant drift value. transformer oils used in high-voltage engineering become electrically conducting and are therefore rendered use-Engine oils, lubricating oils, and lubricating less in the presence of water. greases The additives frequently present in these oil samples can Therefore, it is very important to know the water content react with KF reagents and falsify the result. In a KF dry-of petroleum products. Karl Fischer titration, owing to its ing oven, a stream of dry carrier gas transfers the ex pel-excellent reproducibility and accuracy as well as its ease led water into the titration cell. Since the sample itself of use, numbers amongst the most important water de - does not come into contact with the KF reagent, interferter mination methods and accordingly figures in numerous ing side reactions and matrix effects can be excluded. international standards. Measurement can be performed The correct heating temperature lies below the decom-using volumetric or coulometric Karl Fischer tit ra tion. Be - position temperature of the sample and is determined in cause of the low water content in petroleum pro ducts, preliminary tests. KF coulometry is usually applied. Turpentine and its distillation products Aliphatic and aromatic petroleum components After addition of toluene or xylene, the water contained Water determination in these products is simple. They in these products is transferred through azeotropic distil-usually contain only a small amount of water, therefore lation by a stream of dry carrier gas to the titration cell cou lometric Karl Fischer titration is used. If volumetric where it is determined by Karl Fischer titration. titration needs to be carried out, reagents with a low titer must be used. For long-chain hydrocarbons, the addition of a solubility promoter (propanol, decanol, or chloroform) is recommended. In the rare case of interferences by double bonds, one-component reagents should be used. KF Evaporator 860 KF Thermoprep with 851 Titrando 13 Petroleum (crude oil, heavy oil) Water is not homogeneously distributed in these prod- ucts, which means that the petroleum samples must be homogenized before analysis, for example, with the Reaction of a mercaptan with N-ethylmaleimide Polytron PT 1300D. Furthermore, crude and heavy oils contain tars that can seriously contaminate electrodes and titration cells. Reagents must therefore be exchanged regularly and the titration cells must be cleaned fre-Mobile water determination with the quently. To ensure that the sample completely dissolves, 899 Coulometer solubility promoters are added to the methanol: The water content of unstable or hygroscopic samples should be immediately determined. Often, the nearest • Crude oil 10 mL methanol + laboratory is too far away and there might be no socket (in general) 10 mL chloroform + 10 mL toluene around to plug in a power cord either. The compact • Heavy oil 10 mL methanol + 899 Coulometer was designed with this scenario in 10 mL chloroform + 20 mL toluene mind. It can be powered by an optional Power Box which contains a set of rechargeable batteries and enables Fuels mobile measurements at any conceivable location. Fuels contain mercaptans which are oxidized by iodine and thus falsely indicate a water content that is too high. The problem is dealt with by adding N-ethylmaleimide, which causes the SH groups of the mercaptan to add to 899 Coulometer and the double bond of the N-ethylmaleimide. optional Power Box for mobile water determinations far Another option is the separate determination of the mer-away from any power captan component by potentiometric titration with silver supply nitrate. The result of the water determination reduced by this amount corresponds to the actual water content of the sample (1 ppm mercaptan sulfur corresponds to approx. 0.5 ppm water). Normally the water content in fuels is determined by coulometric titration. With volumetric titration, a solubility promoter must be added to the methanol. Water as a contaminant in liquefied gases 14 Water is a contaminant in fuels and its concentration also integrated in the instrument: They guarantee precise should be as low as possible. Water promotes corrosion measurement of the gas flow, even in samples contami-and it leads to undesired reactions in the fuel. In the case nated with oil or stabilizers. For every gas, the MFC is of liquefied gases, also known as LPG, Liquefied Petrocalibrated once using a balance. leum Gas, the challenge lies in the sample measurement and the associated phase transition from liquid to gas: In Trace determination thanks to coulometry the sample cylinder, an equilibrium is reached between Thanks to the proven KF coulometer, the water content the liquid and gas phase. Depending on the sample, the of liquefied and permanent gases can be determined to water content in the gas phase can be several times an extremely precise and accurate level – even for sam-higher than that of the liquid phase. Therefore, defined ples with a very low water content. sampling is very important to ensure accurate and reproducible results. Precise, robust, and fully automatic The 875 KF Gas Analyzer is designed for routine analysis 875 KF Gas Analyzer – a few technical details in the laboratory. The system consists of an operating In the 875 KF Gas Analyzer, defined sampling is achieved unit and an analysis module, which is equipped with a by using a vaporization unit downstream of the sampling base plate to convey the gas and a cell for the water de - module. This rapidly vaporizes the sample and all the termination. The control and database software tiamo water contained within it. An inlet filter for separation of controls the magnetic valves, which take care of the fully particles, an oil filter and a mass flow controller (MFC) are automatic measurement process. The 875 KF Gas Analyzer with operating unit and analysis module. An integrated vaporizer, four magnetic valves, and the control and database software tiamo enable fully automatic and highly sensitive coulometric water determination in both liquefied and permanent gases. Water content in natural and liquefied gas 15 For transport purposes, natural gas is often liquefied to fied and dried before transport. The natural gas drying reduce its volume and allow it to be transported without process can be conveniently monitored with the 875 KF pipelines. Freshly obtained natural gas contains water Gas Analyzer. Other applications include determination vapor as a contaminant. This would freeze when the na - of the water content in liquefied gas with main compo- tural gas is compressed and block the valves. Water also nents propane and butane as well as in other short-chain lowers the calorific value. Therefore, natural gas is puri-hydrocarbons (e.g., according to ISO 10101, DIN 51869). Typical progress of the gas flow and drift curve when determining the water content in propene. When the sample is introduced, the gas flow begins and the drift increases due to the water content. Oxidation stability If stored in such a way that air has access, petroleum 16 sorbed in water and detected there by measuring the un dergoes oxidizing reactions whose reaction products conductivity. The time until formation of these decompo-can cause problems in combustion engines. Polymeric, sition products occurs is referred to as the induction time poorly soluble compounds in particular lead to deposits or the Oil Stability Index (OSI) and characterizes the in and blockages of the fuel injector systems. The aging resistance of the sample towards oxidative aging pro-behavior (oxidation stability) is therefore a very important cesses, i.e., the oxidation stability. property of petroleum products. 893 Professional Biodiesel Rancimat To quantitatively determine the oxidation stability using The 893 Professional Biodiesel Rancimat enables simple the Rancimat method, air is passed through the sample and reliable determination of oxidation stability in pe tro-at an elevated temperature to bring about artificial aging. leum products and biodiesel. Up to eight samples can be During this process, long-chain organic molecules are measured simultaneously. The instrument is con trolled oxidized by oxygen, whereby highly volatile organic sub-via a PC; the computer software records the mea sure- stances form in addition to insoluble polymer com- ment curves, automatically evaluating them and cal cul at-pounds. The former are driven out by the air flow, ab - ing the result. 17 Important applications Biodiesel and biodiesel blends Biodiesel (FAME, fatty acid methyl esters) is usually pro-ultra-low-sulfur diesel fuel is appearing more and more on duced from oilseeds by transesterification with metha-the market. This mineral diesel fuel with a sulfur content nol. It is being added more and more to mineral diesel as of at most 10 ppm (EU) or 15 ppm (USA) is oxidized con-a blending component. Vegetable oils and methyl esters siderably more easily than the formerly used diesel fuels of fatty acids are relatively unstable under storage condi-with a higher sulfur content. This means that oxidation tions since they are oxidized by atmospheric oxygen. Just stability has also become an important parameter for fuel as with oxidation of petroleum, polymer compounds can production. The 893 Professional Biodiesel Rancimat be formed that can cause damage to engines. For this enables easy assessment of oxidation stability. reason, oxidation stability is an important quality criterion for biodiesel and vegetable oils that must be monitored Biologically easily degradable lubricating oils regularly during production according to EN 14112. The Biologically easily degradable lubricants can also be ma - corresponding method for biodiesel blends is described nu factured from natural fat and oils. Like the raw mate-in EN 15751 and EN 16568. The addition of suitable anti-rial, these products are also susceptible to oxidation. oxidants slows down the oxidation process. The 893 Professional Biodiesel Rancimat also enables the effec- Light fuel oil tiveness of antioxidants to be determined. Alongside other methods, the Rancimat method is also used for assessing the oxidation stability of light fuel oil. Ultra-low-sulfur diesel fuel In order to accelerate the reaction, metallic copper is As a result of environmental protection concerns and added to the fuel oil sample to act as a catalyst. technical requirements for motor vehicle manufacturers, 18 Ion chromatographic analyses The quality assurance of petroleum products involves numerous applications of ion chromatography in which inorganic and low-molecular weight organic ions are determined in fuels, lubricating oils, gas-washing solutions, and the so-called «produced water» that is a by- product of crude oil drilling. Anions and cations in «produced water» During oil and gas production, large quantities of «produced water» are transported to the surface. In addition to oil drops and dissolved organic components, «produced water» contains large amounts of inorganic cat- ions such as calcium, magnesium, barium, and strontium as well as anions such as carbonate, bromide, and sul- fate. The resulting salts can cause scaling and ultimately block the piping. For this reason, the determination of inorganic components is of essential importance, not least for the correct dosing of scale inhibitors. Robust analyzers 19 Since determinations occur not only on-shore, but also off-shore, as for example on drilling rigs, robust analyzers that do not need to be serviced frequently are required. This is offered by the 930 Compact IC Flex in combina- tion with the 919 IC Autosampler plus. The system can also be equipped with Metrohm’s patented Inline Dialysis system. The intelligent MagIC Net chromatography software assumes control of the device, the data manage- ment and the system monitoring, and can, if necessary, be configured as «One-button IC» for shift personnel. Anions in «produced water»; column: Metrosep A Supp 4 - 250/4.0; eluent: 1.8 mmol/L Na CO , 1.7 mmol/L NaHCO , 2 3 3 1.0 mL/min; sample volume: 20 μL; sample 1:20 diluted 850 860 870 880 calcium; 662 mg/L 890 sodium; 15290 mg/L potassium; 403 mg/L magnesium; 251 mg/L 900 910 920 ammonium; not quantified 930 Conductivity [µS/cm] 940 strontium; 59 mg/L barium; 88 mg/L 950 960 970 0 4 8 12 16 20 24 28 32 Time [min] Cations in «produced water»; column: Metrosep C 4 - 150/4.0; eluent: 3.0 mmol/L oxalic acid, 3% acetonitrile, 0.9 mL/min; sample volume: 10 μL; sample dilution 1:100 930 Compact IC Flex in combination with 919 IC Autosampler plus, optionally equipped with Inline Dialysis 20 Anions in gasoline-ethanol blends The use of energy from renewable sources and the asso- ciated reduction of greenhouse gases is one of the most pressing goals of our modern industrial society. Ethanol manufactured from waste and renewable plant material, which can be mixed with conventional gasoline in any proportion, is regarded as one of the most promising alternatives. Contaminants in the form of inorganic salts, however, impair engine performance, which is why international standards now specify the chloride and sulfate content of gasoline-ethanol blends in particular. Additional IC applications for petrochemistry • Halogens and sulfur in liquefied natural gas (LNG) and liquefied petroleum gas (LPG) • Halogens, sulfur, and organic acids in crude oil, gasoline, kerosene, heating oil, and coal (ASTM D7359) • Sulfur compounds in amine absorbers (HSS, Heat Stable Salts) • Amines in various matrices from refineries and petrochemical operations • Anions, cations, and amines in process and waste water samples and absorption solutions • Alkali, alkaline earth and transition metals as well as anions in cooling liquids, e.g., monoethyleneglycol «MEG» (ASTM E2469) • Anions in emulsions from drilling oils • Anions and cations in biofuels and fuel blends • Anions, cations, and organic acids in water which is used for the fracking process Simple matrix elimination 21 The anions to be determined are freed from the interferthe preconcentration column using a rinsing solution. ing fuel matrix by Metrohm Inline Matrix Elimination. For Then, the anions are eluted onto the analytical column. this purpose, the fuel is injected directly onto a high- This method allows the additional determination of capacity preconcentration column. While the anions are ace tate and formate. retained on the column, the fuel matrix is removed from Schematic representation of Metrohm Inline Matrix Elimination Anions in an E85 gasoline-ethanol blend (85% ethanol, 15% gasoline); column: Metrosep A Supp 7 - 250/4.0; eluent: 3.6 mmol/L Na CO , 2 3 7.5% acetone, 0.8 mL/min; column temperature: 45 °C; sample volume: 10 μL; matrix elimination: transfer solution 7.5% acetone, sample enrichment with Metrosep A PCC 1 HC/4.0 Anion system with Metrohm Inline Matrix Elimination 22 Combustion ion chromatography The burning of sulfur-containing fuels leads to the emis-Combustion IC enables the sulfur and halogen content in sion of air-polluting sulfur oxides into the atmosphere. combustible solids, liquids, and gases to be determined Furthermore, high sulfur concentrations have an adverse by combining combustion digestion (pyrolysis) with sub-effect on the ease of ignition of fuels and their stability se quent ion chromatography. It can be fully automated during storage. Halogen concentrations in the refinery and excels in its high sample throughput, large measur-process must also be analyzed due to the corrosion risk. ing range, and excellent precision and accuracy. As a result, a fast and reliable method for determining the halogen and sulfur contents is required. The Combustion Ion Chromatography system includes a 930 Compact IC Flex, a 920 Absorber Module, and a Combustion Module from Analytik Jena equipped with Autosampler MMS 5000. In combustion digestion (pyrolysis), sulfur compounds are converted into sulfur dioxide, and halogen compounds are converted into hydrogen halides and elemental halogens. These gaseous combustion products are fed into an oxidizing absorption solution and detected as sulfate and halide by way of the ion chromatography that follows. 23 a) Crude oil desalter b) Biodiesel blend B5 340 1.8 sulfate 320 1.7 1.6 280 1.5 sulfate; 10.4 mg/kg 240 phosphate 1.4 200 1.3 160 1.2 chloride; 1.1 mg/kg 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1.1 120 Conductivity [µS/cm] Time [min] Conductivity [µS/cm] 1.0 chloride; 5 mg/kg 80 chloride 0.9 40 0.8 0 0.7 0 2 4 6 8 10 12 14 16 18 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Time [min] Time [min] Determination of the chlorine and sulfur content by Combustion IC in a) crude oil desalter output sample and b) B5 biodiesel blend; column: Metrosep A Supp 5 - 150/4.0; eluent: 3.2 mmol/L Na CO , 1.0 mmol/L NaHCO , 0.7 mL/min; column temperature: 30 °C; 2 3 3 sample volume: 100 μL Voltammetry 24 Voltammetric trace analysis is used for determining elec-Voltammetry is particularly well-suited to laboratories in tro chemically active substances. These can be inorganic or which only a few parameters need to be monitored in organic ions or even neutral organic compounds. Vol tam-combination with a moderate sample throughput. It is metry is often used for supplementing and vali dating frequently used for special applications which cannot be spectroscopic methods and is characterized by a minimum performed using other techniques or only with a great amount of equipment, comparably low in vest ment and deal of effort. operating costs, short analysis times, and a high accuracy and sensitivity. In addition, unlike spectroscopic methods, 884 Professional VA voltammetry can distinguish bet ween different oxidation The 884 Professional VA is a flexible measuring instru-states of metal ions as well as between free and bound ment for accurate and sensitive voltammetric and polaro-metal ions. This is referred to as speciation analysis. graphic analyses. The analyses can be easily automated by adding Dosinos and a sample changer. The accompa- Broad application range nying viva software enables individual optimization of Voltammetric measurements can be carried out both in methods. aqueous solutions and in organic solvents. Heavy metal determinations are usually carried out in aqueous solu- tions after digestion of the sample. 25 Some application examples Elemental sulfur in gasoline Heavy metals in petroleum products The total sulfur content in petroleum products is widely The determination of heavy metals in petroleum prod-defined by law and is therefore routinely controlled. It is ucts by voltammetry is usually carried out after digestion. also of interest to see in which form the sulfur is actually The samples are mineralized by microwave digestion or present. By using voltammetry, the proportion of elemen-combusted. Alternatively, the metal ions can be deter- tal sulfur can be determined directly and simply. In this mined after extraction with a mineral acid. way, inferences can be drawn about the influence of gasoline on corrosion processes, for example, regarding sensors in the fuel tank. Copper in ethanol Ethanol is increasingly used in gasoline as a blending component. Contaminants can cause problems in the engine. For example, traces of copper catalyze the oxidation of hydrocarbons. As a consequence, polymer compounds can form which can lead to deposits and blockages in the fuel system. Using voltammetry, copper can be mea- sured without any sample preparation in pure ethanol or ethanol-gasoline blends (E85, 85% ethanol + 15% gasoline) in the range between 2 μg/kg and 500 μg/kg. Voltammetric determination of copper Corrosion 26 Corrosion – a universal problem Linear polarization and impedance spectroscopy All industries which work with materials that are suscep-Metrohm Autolab offers a complete product range for tible to corrosion have to fight this form of electrochem-investigating the corrosion properties of materials, both ical decay. Contact and pitting corrosion are particularly for pure and applied research. A common feature of all problematic: they have a negative impact on the me - methods is that they relate to the interface between the chan ical properties of the material without causing obvi-material and the corrosive environment and that they can ous changes. be easily adapted to suit the analytical problem in question. The measuring instruments from Metrohm Autolab Petrochemistry – an easy target for corrosion use a variety of different electrochemical methods, pri-Corrosion is common in the petrochemical industry, par- marily linear polarization and electrochemical impedance ticularly in the areas of production, transport, and refin-spectroscopy (EIS). ery. The chemical composition of the raw materials, high pressure, and high temperature along with the use of salt Fast, accurate, and standard-compliant: water all promote corrosion. PGSTAT204 Together with the FRA32M impedance analyzer module Electrochemistry in corrosion research and the ASTM-compliant 1 L corrosion cell, the Autolab Corrosion not only leads to increased production costs, it PGSTAT204 is ideal for carrying out fast and accurate also represents a constant danger for man and machine. corrosion measurements. To prevent it, it is essential to have an in-depth understanding of the corrosion process. As corrosion is an electrochemical process, it is best described using electrochemical methods. These are described in depth in nu - me r ous specialist publications as well as many international standards. The Autolab PGSTAT204 and corrosion cell for corrosion research 27 Fuels change the corrosion behavior The material-fuel interface (substratum) The corrosion resistance of storage tanks, process lines, Electrochemical methods allow you to easily and conve-and pipelines is a key material prerequisite for the storage niently determine the corrosion resistance of various and transport of fuels. Fuel-conveying materials, in par-materials in contact with fuels. The Autolab PGSTAT100N ticular, can suffer considerable damage due to stress potentiostat/galvanostat together with the FRA2 imped-corrosion cracking (SCC) and microbial-induced corrosion ance analyzer module is a powerful analysis system with (MIC). In comparison to fossil fuels, biodiesel exhibits a several preprogrammed methods. It allows you to effec-higher risk of corrosion. tively detect corrosion processes occurring on the con- ductive material-fuel interface by linear polarization or electrochemical impedance spectroscopy. The Autolab PGSTAT100N – a potentiostat/galvanostat for carrying out electrochemical determination (max. 100 V compensation voltage) in matrices with low conductivity www.metrohm-autolab.com Near-infrared spectroscopy 28 NIRS – interaction of light and physical matter Advantages of NIRS analysis in petrochemistry Near-infrared spectroscopy (NIRS) is an analytical tech-Near-infrared spectroscopy has been successfully used in nique based on the absorption of radiation by matter. oil refineries for years, as shown by the example of mo - Molecular vibrations are induced in the near-infrared ni toring the blending of a range of fuels. NIRS detects region of the electromagnetic spectrum (800–2500 nm) numerous parameters in a single measurement in less – i.e., from the end of the visible to the mid-infrared than a minute. The cost savings are enormous. Further (MIR) range. The main absorption bands of the func-ad vantages are: tional groups of chemical substances are located in the • no chemicals or reagents necessary MIR range and are very strong. The absorption bands of • short response times and fast quality control the harmonics, however, and the combinations of the • improved product quality and process optimization fundamental molecular vibrations are in the NIR spectral • reduced investment, analysis, and maintenance costs region. They are significantly weaker and allow direct • accurate and precise measuring results. measurement without sample preparation. This enables in-depth insight into the chemical and physical properties From the laboratory to the process of the sample. The strongest overtone absorptions in the Initially, NIRS analysis was used purely for offline deter-NIR range are displayed by OH, CH, NH, and SH bounds. minations in the laboratory, however, as it matured tech-A NIR spectrum is the result of numerous overlapping nically, its potential for use in the harsh process environ-absorption bands; evaluation is therefore carried out ment was recognized, especially for online and inline using multivariate chemometric methods. monitoring. The NIRS XDS Rapid Liquid Analyzer can analyze petrochemical samples either offline in the laboratory or atline. The measure-NIR spectra of diesel fuel samples ment can be made in cuvettes or vials. Real-time monitoring with NIRS process analyzers NIRS process analyzers guarantee real-time monitoring of the sample flow in the process and thereby enable optimum product quality. Robust and versatile NIRS is an extremely robust and versatile method that is suitable for all sample types, from clear solutions and sus pensions through to solids. By selecting a suitable fiber-optic interface, the process analyzer can be per-fectly adjusted to suit the required application. Single-Fiber, MicroBundle, and DirectLight/NonContact are Calibration model for quantitative determination of the research available. octane number (RON). The RON determined according to ASTM D2699 is plotted against the RON determined by NIRS. NIRS for optimizing refinery processes 29 In order to refine crude oil and natural gas into diverse to reforming. All these processes rely on NIRS analysis – petrochemical products, complex processes are required, whether to determine characteristics or the composition from crude oil distillation, cracking, and desulfurization of petroleum products. Where What • API gravity1 • PIANO3 Crude oil distillation • Density • Reid vapor pressure (RVP) • Distillation of crude oil (TBP2) • API gravity • PIANO Cracking and reforming • Distillation analysis4 • Reid vapor pressure • Aromatic content • Flash point • PAH5 Lubricating oil • Density • Nitrogen • Pour point • Distillation analysis • Oil content • Viscosity • API gravity • Benzene content • Alcohols & ether • Density • Research octane number Gasoline blends (MTBE, etc.) • Motor octane number (RON) • Alkene content (MON) • Reid vapor pressure • Aromatic content • Octane index number • Boiling point • Cold filter plugging point • Flash point • Cetane number (CFPP) • Pour point Diesel blends • Cloud point • Density • Specific weight • Color • FAME6 content • Viscosity Diesel Gasoline Mobile fuel analysis • Cetane number • FAME content • Alcohols & ether • BTX7 «On-site testing» • Density • Flash point • Aromates • Density • Distillation analysis • Viscosity • Alkenes • Octane rating 1 Degree of density according to the American Petroleum 4 Boiling behavior according to ASTM D86: Institute (API) verification by NIRS 2True Boiling Point distillation 5Polycyclic Aromatic Hydrocarbons 3 Paraffins, Isoparaffins, Aromatics, Naphthenes, or 6Fatty Acid Methyl Ester (FAME) Olefins (alkenes) 7Benzene, Toluene, Xylene Atline, online, and inline analysis systems from Metrohm Process Analytics 30 Atline, online, and inline analysis systems from Metrohm the field. We offer, under the brand of Metrohm Process Process Analytics are the preferred solution for process Analytics, a broad program of process analyzers and monitoring in a wide range of industries. Reliable analysis sample preparation systems for a large array of applica-results are determined directly in-process with the latest tions in a wide number of industries. met hods of ion analysis and spectroscopy: measurement of pH value, conductivity, redox potential, and TOC, as Metrohm Process Analytics – globally present well as titration, Karl-Fischer titration, photometry, ion-Metrohm Applikon, with the brand name Metrohm selective electrode measurement (dynamic standard ad - Process Analytics, is part of the Metrohm Group support-dition), ion chroma tography, voltammetry, and near-in - ing you globally with offices in 45 countries. Our special-fra red spec troscopy. ists offer you advice during the planning and de vel- opment of your own custom-designed analysis system, Metrohm Process Analytics is an inline, online, and atline commission the system, and provide professional mainte-analysis specialist with more than 40 years’ experience in nance and service during routine operations (see pages 36–37). 4 Offline analysis • Manual sample collection during operation 3 • Transport of the sample to the Atline analysis laboratory • Manual sample collection during • Registration and analysis in the operation laboratory • Automatic analysis directly in the production process • Determination of one or more parameters • Numerous measuring points • Low to medium frequency of analyses • Rapid onsite analytical results 2 Online analysis • Sample collection via bypass line • Automated sample preparation • Fully automated analysis • Fastest response time and high frequency of analyses 1 • Results as controller input Inline analysis • No sample collection required • Sensor located directly at reactor • Real-time results • Fastest response time and high frequency of analyses • Results as controller input ADI 2045PL ProcessLab – atline routine analysis in production The ADI 2045PL ProcessLab is by far the most robust ments. The ADI 2045PL ProcessLab guarantees the high-31 routine system for atline analysis in everyday use in the est level of reliable analytical results. The new ProcessLab plant and in control labs. Metrohm Process Analytics’s 40 Manager software offers a user-friendly interface in com-years experience with online analysis has resulted in a bination with the well-proven tiamo lab software. new system for custom-made atline process measure- Determination of acid and base numbers Production of standard mixtures with a defined The determination of the acid and base numbers is of octane rating essential importance for the quality control of petroleum The octane rating is a measure of a gasoline’s resistance to products. The acid number records components that engine knock. In order to assess the octane rating, the re - react acidically as a sum parameter and allows conclu- sis tance to engine knock of a gasoline sample is deter-sions regarding the corrosion of plant or engine compo- mined in comparison with standard mixtures showing a nents. Over the longer term, petroleum products with predefined octane rating. The standard mixtures, consisting high base numbers offer protection from the corrosive of n-heptane, isooctane (2,2,4-trimethylpentane), and tol-influence of any generated acids. By measuring sum pa ra-uene, must be prepared with the highest accuracy and meters, product alterations can also be quickly and di rec tly precision. ProcessLab is ideal for this thanks to its range of recorded during use. options for liquid handling. The automatic production of dilutions and dilution ranges as well as the doping of addi-The determination of acid and base numbers is carried tives can be carried out easily. The production of test mix-out automatically in the ProcessLab by potentiometric tures is precisely documented and the report can be used titration in nonaqueous solvents. Because of its proximity as a certificate. to the process, the analytical results are available within minutes. In the same way, standard mixtures can also be prepared for measuring cetane numbers with diesel fuels. Online and inline process analysis: wet chemistry 32 Online process analyzers Explosion-proof systems for petrochemistry In the (petro)chemical industry, continuous control of the In many cases, the IP66-NEMA4 housing of the analyzers production process, the quality of the product and the will be sufficient. In some cases in the petrochemical in - composition of any waste streams is of utmost impor- dustry, however, explosion-proof systems are required. tance. With the online process analyzers from Metrohm For those circumstances, the ADI 2045TI Ex proof Process Analytics, this is possible 24 hours a day, 7 days Analyzer is available in a stainless-steel explosion-proof a week. The analyzers are used directly on-site, as close version for Zone I or Zone II according to the European as possible to the process, and run completely stand-explosive atmos phere directives (ATEX). alone without operator intervention. The Metrohm Process Analytics analy zers are based on wet-chemical analysis techniques such as titration, colorimetry, or ion-selective electrode measurements. Analyzers are available for single method, single-stream purposes as well as for complex multiple methods and multiple streams. Importance of sampling In online analysis, sampling and sample preparation are at least as important as the analyzer itself. Metrohm Applikon has a lot of expertise in this area and is capable of offering custom-made sampling systems, for example, for pressure reduction, filtering, and degassing. Powerful interfaces Analysis alone is of no use for process control, and that is why the analyzers are all equipped with possibilities for digital as well as analog outputs. Results, for example, can be transferred via 4–20 mA outputs, whereas alarms can be transmitted via digital outputs. Digital inputs, in turn, can be used for remote start-stop purposes. ADI 2045TI Process Analyzer for online monitoring of various parameters Many of the analysis methods that are used in the labo- 33 ratory can be transferred to an online analyzer. Typical applications are: Water content A very important factor in quality control of the petrochemical industry is the determination of the water content in oil. A water content that is too high has a negative impact on the oil quality. As in the laboratory, Karl Fischer titration (coulometry) is the method of choice for the online determination of the water content in any oil product. Sampling system for determining the water content in hydrocarbons Hydrogen sulfide and mercaptan determination Sulfur compounds in oil and oil products cause corrosion and pose an environmental hazard. Determination of H S 2 as well as mercaptans is done by titration with silver nitrate using a sulfide-coated silver electrode serving as the indicator electrode. Cuvette module for photometric measurements TBC in styrene In styrene production, the addition of 4-tert-butylcateSalt in crude oil chol (TBC) as a stabilizer is critical to prevent the styrene Excessive amounts of chloride salts in crude oil result in from polymerization during storage and transport. TBC higher corrosion rates in refining units and have a detri-levels need to be maintained above 10–15 mg/L. The mental effect on the catalysts used. Desalting techniques prob lem is that the TBC concentration in styrene will are well established, but continuous monitoring of the slowly decrease in the presence of oxygen. By using an salt content is needed for process control and cost reduc-ADI 2045TI Process Analyzer with colorimetric technique, tion. With the ADI 2045TI Process Analyzer equipped TBC levels can be monitored continuously to maintain with special heavy duty sample valves, the salt content the concentration at the proper level. can be monitored by measuring the conductivity or by titration. After each analysis, the measurement vessel is cleaned and a blank measurement is performed before the next sample is taken. For this type of application, the analyzers are configured in an explosion-proof housing. Online and inline process analysis: NIRS 34 NIRS – from the laboratory to the process NIRS: the key to process understanding With progressive technological development, NIRS has To optimize a process, you need to understand it. You increasingly established itself as an in-process technolo-need to know as much as possible about it and this is gy. Just a few decades ago, many users were put off by only possible when you are in the middle of the action. the range of information combined in a spectrum: the spectra were considered unclear and were hard to inter- NIRS is in the thick of it. Everything is available at a glance, pret using classical methods. This view changed dramati-in a matter of seconds, thanks to sensitive sensors which cally with the arrival of powerful computers. The enor-are directly atline or inline. There is no need for complex mous potential of NIR spectroscopy was recognized, final checks. NIRS is also nondestructive, and requires no par ticularly for process applications. sample preparation or chemical reagents. Several parameters – with just one measurement Real-time monitoring of the sample stream Today, NIRS is a robust and extremely versatile method, NIRS is now an essential part of process control in petro-which enables simultaneous, real-time monitoring of chemistry. The key properties of petroleum products can diverse process parameters with a single measurement. be tracked directly in-process, whether it be the water Fiber-optic data transfer means that the measuring ins-content, flash point, or cold filter plugging point. The trument and measuring cell can be spatially separated – same applies to the chemical composition of the petro-even by hundreds of meters if required. This is a huge leum product during fractionation: from aromatics, alco-advantage, especially in environments with high explo- hol, and ether to BTEX or FAME content in biodiesel, the sion protection requirements, such as petrochemistry. composition can be determined in a matter of seconds. Numerous measuring points – with just a single Key characteristics such as the octane rating, cetane or instrument hydroxyl number are also easy to track live. The same Metrohm process analyzers are real multitaskers: 4 or applies to physical parameters such as density, viscosity, even 9 measuring points can be connected (multiplexing) or vapor pressure. to a single measuring instrument. The NIRS XDS Process Analyzer (left) and the NIRS Analyzer PRO allow real-time analysis within seconds from process flows or batch reactors. 35 Blending process: straightforward with NIRS During the blending process, different fractions of the the progress of the blending process are the cetane crude oil distillation are mixed together so as to produce number for diesel blends and one of the octane ratings the ready-to-sell diesel or gasoline grades. This is most for gasoline blends. NIRS sensors located directly in the economical when it is carried out in process systems that process enable the entire process to be controlled and work online and can be automated. The endpoint of the ensure a high-quality end product. Additional para meters blending process is reached when the required fuel speci-can also be monitored in parallel and inline de pending on fications are achieved. Key characteristics which indicate the application. Process image of the Research Octane Number (RON) and Reid vapor pressure control parameters determined during the blending process of gasoline using NIRS. Both parameters can be tracked simultaneously via the live view on the control panel (the black/green section between the two trend curves). 36 Service you can rely on – Metrohm Quality Service Reliable measurement results during the entire Metrohm Compliance Service lifetime of the instrument You can trust Metrohm Compliance Service when it comes From the production of the crude oil to the refining pro-to the professional qualification of your analyzers. Ins tal - cess and the quality control of the final products, lation Qualification/Operational Qualification (IQ/OQ) or che mical analysis is in constant demand in the oil indus-Certified Installation (CI) saves you time and money be - try. Those responsible for the accuracy of the results in cause we configure the system according to your re quire-the laboratory must not make compromises. Be ensured ments and ensure quick and reliable commissioning. that systems installed and maintained by professionals on a regular basis eliminate threats of instrument failure User instructions lay the foundations for safe, error-free and profit loss. operation. The Metrohm Compliance Service also includes comprehensive documentation and guarantees com pli-With Metrohm Quality Service you are on the safe side ance with the standards of quality management systems from day one. From installation and start-up, such as GLP/GMP and ISO. to regular maintenance and fast repair – if problems arise – we guarantee that you can rely on your ins tru- ment and gain maximum up - time from your instrument. Metrohm Quality Service 37 Metrohm’s global Quality Service, and regularly sched- particular need. With a Total Care Contract, for example, uled preventive maintenance in particular, extends your you can rely on the optimum performance of your instrument’s lifetime and ensures trouble-free operation. Metrohm instruments at all times, incurring no additional Maintenance work is carried out by qualified and certi-costs whatsoever and benefit from complete and com- fied service engineers. You have the option of selecting pliant documentation. different types of service contracts depending on your Metrohm Quality Service Customer benefits • Minimizes downtime through preventive maintenance • Cost control and savings through free or discounted replacement materials Metrohm Care Contracts and consumables • Guaranteed reaction times and rapid on­site repair • Documented instrument certification as an ideal preparation for audits • High data security and maximum system performance through regular, Metrohm Software Care professional software maintenance • Customized services and documentation for analytical instrument qualification (AIQ) Metrohm Compliance Service • Professional start-up (IQ/OQ or Certified Installation) and requalification or recertification by specifically trained employees Metrohm Remote Support • Quick resolution of software and application issues directly at the workplace • Calibration of burettes (e.g., dosing and exchange units) with certification Metrohm Dosing Test • Accurate measurement results • Verification documentation for compliance with regulations and efficient audits • Rapid availability of repaired instruments thanks to decentralized repair workshops around the world and a central workshop at the manufacturer site Metrohm Repair Service • Highly qualified service technicians ensure sustainable repair success • Rapid resolution of problems and minimized downtimes through on-site emergency services and express repairs • Original spare parts, made in Switzerland and available worldwide • Short delivery times through warehousing from local distributors Metrohm Spare Parts • Investment security through ten-year spare parts guarantee after discontinuation • Free access to the Metrohm Application Finder (www.metrohm.com/en/ applications/) with more than 1800 applications (Application Bulletins, Application Notes, monographs, technical posters, and technical articles) Metrohm Application Support • Rapid and professional resolution of any application issues through personal consultations with our specialists by e-mail, telephone, or remote support • Support for the solution of complex analytical problems, as well as method optimization on-site or at our application laboratories • Basic and advanced training with local representatives, at the Metrohm Academy or directly on-site Metrohm Training Programs • Efficient and proper use of all analytical methods, as well as results reliability through competently trained users • Training documentation and certificates for trouble-free audits Ordering information 38 Titration 2.848.3010 Oil Titrino plus 2.905.3010 Oil Titrando 2.916.3010 Oil Ti-Touch 2.859.1010 859 Titrotherm complete with tiamo 2.855.2010 Robotic TAN/TBN Analyzer 2.864.1130 Robotic Balance Sample Processor TAN/TBN 6.0229.010 Solvotrode easyClean, 1 m cable 6.0229.020 Solvotrode easyClean, 2 m cable 6.0430.100S Ag-Titrode with Ag S coating 2 6.1115.000 Optrode 6.6040.00X «Oil PAC» application collection Water determination according to Karl Fischer Coulometric KF titration 2.831.0010 831 KF coulometer including generator electrode with diaphragm and 728 Stirrer 2.831.0110* 831 KF coulometer including generator electrode without diaphragm 2.756.0010 756 KF coulometer with built-in printer including generator electrode with diaphragm and 728 Stirrer 2.756.0110* 756 KF coulometer with built-in printer including generator electrode without diaphragm 2.851.0010 851 Titrando including generator electrode with diaphragm and 801 Stirrer 2.851.0110* 851 Titrando including generator electrode without diaphragm 2.852.0050 852 Titrando including generator electrode with diaphragm and 801 Stirrer 2.852.0150* 852 Titrando including generator electrode without diaphragm 2.899.0010 899 Coulometer with built-in stirrer including generator electrode with diaphragm 2.899.0110 899 Coulometer with built-in stirrer including generator electrode without diaphragm 2.875.9020 875 KF Gas Analyzer with TFT monitor (incl. tiamo) 2.875.9050 875 KF Gas Analyzer without TFT monitor (incl. tiamo; monitor and keyboard are required) * The magnetic stirrer has to be ordered separately. Volumetric KF titration 2.870.1010 870 Titrino plus complete 2.890.0110 890 Titrando with Touch Control 2.901.0010 901 Titrando including titration cell and indicator electrode 2.915.0110 915 Ti-Touch with built-in stirrer Sample preparation 2.136.0100 Polytron PT 1300 D 2.860.0010 860 KF Thermoprep 2.874.0010 874 Oven Sample Processor 2.885.0010 885 Compact Oven Sample Changer 2.136.0200 KF Evaporator Oxidation stability 2.893.0010 893 Professional Biodiesel Rancimat (230 V) including software and accessories Ion chromatography Anions and cations in «produced water» 2.930.2560 930 Compact IC Flex SeS/PP/Deg 2.930.2160 930 Compact IC Flex Deg 2.850.9010 IC Conductivity Detector (2 ×) 2.919.0020 919 IC Autosampler plus 39 6.1006.430 Metrosep A Supp 4 - 250/4.0 6.1050.420 Metrosep C 4 - 150/4.0 6.2832.000 MSM Rotor A 6.2842.020 Adapter sleeve for suppressor Vario to MSM and MSM-LC 6.6059.312 MagIC Net 3.1 Professional Anions in gasoline-ethanol blends 2.940.1500 940 Professional IC Vario ONE/SeS/PP 2.850.9010 IC Conductivity Detector 2.858.0030 858 Professional Sample Processor – Pump – Injector 6.2041.390 Sample Rack 16 × 120 mL 6.2842.000 MSM-HC Rotor A 6.1006.630 Metrosep A Supp 7 - 250/4.0 6.1006.310 Metrosep A PCC 1 HC/4.0 6.6059.312 MagIC Net 3.1 Professional Options 2.800.0010 800 Dosino 6.3032.210 Dosing unit 10 mL 6.5330.100 IC equipment: Inline Dialysis 6.5330.190 IC equipment: Dosino Regeneration 6.5330.130 IC equipment: Liquid Handling Station 6.2844.000 MSM-LC Rotor A 6.2842.200 MSM-HC Rotor C Combustion IC 2.930.9010 Metrohm Combustion IC 6.1006.520 Metrosep A Supp 5 - 150/4.0 Voltammetry 2.884.0110 884 Professional VA manual for Multi-Mode Electrode (MME) 2.884.1110 884 Professional VA semiautomated for MME consisting of 884 Professional VA, measuring head for MME and two 800 Dosinos. MVA-22 Fully automated Professional VA system consisting of 884 Professional VA, measuring head for MME, 919 IC Autosampler plus for VA and two 800 Dosinos for automatic addition of auxiliary solutions. Allows the automatic processing of up to 28 samples. This system is the optimum solution for automatic analysis of small sample series. Required Accessories 6.5339.030 VA-Elektrodenkit with Multi-Mode Electrode 6.6065.202 viva 2.0 Full Near-infrared spectroscopy – laboratory, atline 2.921.1410 NIRS XDS RapidLiquid Analyzer 2.921.0510 NIRS XDS Interactance Optiprobe Analyzer 2.921.1520 NIRS XDS Transmission Optiprobe Analyzer Near-infrared spectroscopy – Process 2.928.0110 NIRS XDS Process Analyzer – Microbundle SinglePoint 2.928.1120 NIRS Analyzer PRO – FiberSystem petro.metrohm.com ­9100 Herisau G, CH ohm A witzerland at Metr , printed in S SW Subject to modifications Layout by Ecknauer+Schoch A 8.000.5143EN – 2015-09