1. Petrochemical analysisQuality assurance of petroleum products
2. Analysis of petroleum productsFormation of crude oil deposits «Lubricant» of the global economyAccording to current knowledge our oil reserves origina- Nowadays crude oil, which consists of at least 500 differ-ted during the Jurassic and Cretaceous periods (200 to ent components, is processed by distillation and refining65 million years ago) from microbial flora and fauna to liquid gas, gasoline, diesel and heating fuel, lubricantsliving in the seas. While some of the dead organic resi- as well as a large variety of other products. As the «lubri-dues were directly mineralized, i.e. decomposed, the cant» of the global economy, crude oil is omnipresent.other part sank to the seabed. There the material was It covers approximately 40% of our energy demand andcovered by other marine deposits and formed a sludge is used in the chemical industry for the production ofwith very fine rock material that slowly converted to plastics, textiles and dyes, cosmetics, fertilizers, deter-crude oil under the prevailing biogeochemical conditions gents, building materials and pharmaceuticals.of increased pressure and salinity. Due to its lower densi-ty the crude oil migrated upwards through fine cracks in The importance of the petroleum products and theirthe rock layers until it accumulated under impermeable derivatives is reflected by the large number of standardscovering rocks and thus formed the oil deposits we know relating to them. Metrohm as a leading manufacturer oftoday. Sometimes above-ground oil deposits were for- instruments for ion analysis offers long-standing applica-med that already allowed our forefathers to use crude oil tion know-how for the quality assurance of petroleumfor heating and lighting, building or lubrication. products.
3. Selected standards from the eld of petrochemicalanalysisThe standards listed below describe numerous interna- minimum requirements and limits stipulated by the res-tional testing and requirement specifications for petro- pective standards.leum products. Metrohm instruments comply with all theParameter Standard Matrix Method Page Petroleum products ASTM D 4739 Potentiometric titrationBase number Lubricants ASTM D 2896 Petroleum products Potentiometric titrationTotal base number DIN ISO 3771 Petroleum products Potentiometric titrationNitrogenous bases UOP269 Petroleum distillates Potentiometric titrationAcid and base number ASTM D 974 Petroleum products Colorimetric titration 4 ASTM D 664 Petroleum products Potentiometric titrationAcid number Petroleum products DIN EN 12634 Potentiometric titration Lubricants Petroleum productsAcid number and naphthenic acids UOP565 Potentiometric titration Petroleum distillates ASTM D 3227 Automotive fuel, kerosene Potentiometric titrationMercaptan sulfur Highly volatile distillates ISO 3012 Potentiometric titration Moderately volatile distillatesH2S ASTM D 2420 Lique ed petroleum gas (LPG) Potentiometric titration 5H2S, mercaptan sulfur UOP163 Petroleum products Potentiometric titrationAlkalinity, H2S, mercaptans Used alkaline petroleum UOP209 Potentiometric titration productsH2S, mercaptan sulfur, Gaseous hydrocarbons UOP212 Potentiometric titrationcarbonyl sul de Lique ed petroleum gas (LPG) ASTM D 94 Petroleum products Potentiometric titrationSaponi cation number Crude oil 6 DIN 51559 Colorimetric titration Insulating oil ASTM D 1159 Petroleum distillates Potentiometric titration Aliphatic alkenesBromine number ASTM D 5776 Aromatic hydrocarbons Potentiometric titration Petroleum distillates 6 ISO 3839 Potentiometric titration AlkenesBromine number and bromine index UOP304 Hydrocarbons Potentiometric titrationBromine index ASTM D 2710 Petroleum hydrocarbons Potentiometric titration Aliphatic and cyclic ASTM E 1899 Potentiometric titration hydrocarbonsHydroxyl number 7 DIN 53240 Resins, raw materials for varnishes, Potentiometric titration primary alcohols, glycols, fatOrganic, inorganic and UOP588 Hydrocarbons Potentiometric titrationtotal chlorine content 7Organic chlorine content ASTM D 4929 Crude oil Potentiometric titrationSalinity ASTM D 6470 Crude oil Potentiometric titration 7 Petroleum hydrocarbons Coulometric KFTb DIN 51777-1/2a Solvents Volumetric KFT ASTM D 4377 Crude oil Volumetric KFT ASTM D 4928 Crude oil Coulometric KFT Crude oil ASTM E 1064 Organic solvents Coulometric KFTWater content Lubricating oil ASTM D 6304 Petroleum products Coulometric KFT 8 ASTM D 1364 Highly volatile solvents Volumetric KFT ASTM D 890 Turpentine Azeotropic distillation, KFT ASTM E 203 General Volumetric KFT ISO 10336 Crude oil Volumetric KFT ISO 10337 Crude oil Coulometric KFT ISO 12937 Petroleum products Coulometric KFT ISO 6296 Petroleum products Volumetric KFT EN 14112 Fatty acid methyl esters (B100) Oxidation stabilityOxidation stability Fatty acid methyl esters 10 EN 15751 Diesel fuel blends Oxidation stabilityInorganic chloride and sulfate DIN EN 15492 Ethanol as a blending Ion chromatography 12 component in gasolineSulfur, heavy metals Gasoline, ethanol Voltammetry 16pH value, conductivity and Process-dependentparameters that can be determined Petroleum products Process analysis 18 conditionsby titration and voltammetryain revision, bKarl Fischer titration
4. TitrationDetermination of acid and base numbers by compounds (acids, salts) with pKa values <9. The acidpotentiometric titration with the Solvotrode number indicates how many mg KOH are required toWith the base number, alkaline components are deter- neutralize 1 g of sample. The acid number indicatesmined in petroleum products as a sum parameter. These changes during the use of the product.include primary organic and inorganic amino compoundsin particular. However, salts of weak acids, basic salts of Both parameters are determined by potentiometric titra-polycarboxylic acids, a number of heavy metal salts and tion in non-aqueous solvents or solvent mixtures. Thedetergents are also recorded. The base number indicates Solvotrode is a combined pH glass electrode that washow many basic components, expressed as mg KOH, are especially developed for this application. The separablecontained in 1 g of sample. This determination is used for ground-joint diaphragm can be easily cleaned even ofthe immediate detection of product changes during strong contamination. The electrostatic shielding of theuse. electrolyte compartment also ensures a low-noise meas- uring signal.With the acid number, acidic components are measuredin petroleum products as a sum parameter. These are855 Robotic Titrosampler (with 772 Pump Unit) for TAN/TBN determination Solvotrode Standard Parameter Titrant Solvent Electrode (reference electrolyte) ASTM D 4739 Base number HCl in isopropanol Chloroform, toluene, Solvotrode isopropanol, water (LiCl in EtOH) ASTM D 2896 Base number Perchloric acid in Glacial acetic acid, Solvotrode (TEABra >300 mg KOH/g glacial acetic acid xylene in ethylene glycol) DIN ISO 3771 Total base number Perchloric acid in Toluene, glacial acetic Solvotrode (TEABr glacial acetic acid acid, acetone in ethylene glycol) ASTM D 664 Acid number KOH in isopropanol Toluene, isopropanol, Solvotrode water (lubricants) (LiCl in EtOH) Isopropanol (biodiesel) DIN EN 12634 Acid number KOH in TMAHb Dimethylsulfoxide, Solvotrode isopropanol, toluene (LiCl in EtOH) UOP565 Acid number and KOH in isopropanol Toluene, isopropanol, Solvotrode naphthenic acids water (LiCl in EtOH)aTetraethylammonium bromidebTetramethylammonium hydroxide
5. Sulfur and sulfur compounds determined bypotentiometric titration with the Ag TitrodeSulfur compounds contained in petroleum products notonly have an unpleasant odor, they are also environmen-tally damaging and promote corrosion. For determininghydrogen sulfide and mercaptans in liquid hydrocarbons(gasoline, kerosene, naphtha and similar distillates), thesample is titrated with silver nitrate solution, wherebysilver sulfide (Ag2S) and silver mercaptide are produced.Two pronounced potential jumps occur. The first end-point corresponds to hydrogen sulfide (H2S), the secondto the mercaptans. The indicator electrode for the titra-tion is the Ag Titrode, version with Ag2S coating. Sinceboth H2S and mercaptans are oxidized by atmosphericoxygen and the arising oxidation products cannot bedetermined titrimetrically, work must be carried out un-der a nitrogen atmosphere.Gaseous sulfur compounds can also be determined withthis procedure. For this purpose they are absorbed in analkaline solution. The first two absorption vessels containKOH or NaOH (for H2S and mercaptans), the third con-tains ethanolic monoethanolamine (for carbonyl sulfide).The results are expressed in mg/kg (ppm) hydrogen sul-fide and/or mercaptan sulfur. Ag Titrode
6. Saponification numberThe saponification number (SN) primarily serves to deter- The 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 which produces the salts of the fatty acids and pounds that are lighter than 2-methylpropane (in-the corresponding alcohol, e.g. glycerine. The method is cluded in this are fuels with and without lead addi-not specific since acidic sample constituents consume tions, kerosene and gas oils).KOH and in so doing increase the saponification number Commercial alkenes (mixtures of aliphatic monoal-(SN). The titrant employed is c(HCl) = 0.5 mol/L in isopro- kenes) with a bromine number from 95 to 165.panol. The SN 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 nonenes, octenes and heptenes.Bromine number and bromine index The BI indicates how many mg of bromine (Br2) areThe bromine number (BN) and the bromine index (BI) bound by 100 g of sample. The method is used forindicate the proportion of unsaturated compounds (usu- «alkene-free» hydrocarbons with a boiling point belowally C-C double bonds) in petroleum products. Here, the 288 °C (550 °F) and a bromine index of between 100double bond is cleaved by bromine addition. The BN in- and 1000. For products with a bromine index of >1000dicates how many g of bromine (Br2) are bound by 100 g the bromine number should be used.of sample.Method Samples Titrant Solvent ElectrodeBromine number Automotive fuels, kerosene, c(bromide/ Glacial acetic acid, Double[g Br2/100 g] gas oils, propene, butenes, bromate solution) = trichloroethane, Pt electrode heptenes, octenes, nonenes 0.08333 mol/L methanolBromine index c(bromide/ Glacial acetic acid, Double[mg Br2/100 g] Olefin-free hydrocarbons bromate solution) = trichloroethane, Pt electrode 0.00333 mol/L methanol
7. Hydroxyl number Chloride and organically bound chlorineThe hydroxyl number (OHN) indicates the number of Organically bound chlorine present in petroleum pro-mg KOH corresponding to the hydroxyl groups in 1 g ducts is decomposed at high temperatures and formssample. The most frequently described method for de- hydrochloric acid, which is highly corrosive and cantermining the hydroxyl number is conversion of the cause damage, for example to the distillation columns.sample with acetic acid anhydride in pyridine with subse-quent titration of the released acetic acid. The one-hour Before measurement the sample is freed of sulfur com-boiling under reflux, the difficulty in automating the pro- pounds and inorganic chlorides by distillation and subse-cess and particularly the use of the health-hazardous quent washing as described in ASTM D 4929. The organ-pyridine are serious disadvantages. ically bound chlorine is converted to NaCl with metallic sodium in toluene. After extraction into the aqueousAn alternative is offered by the considerably simpler phase the NaCl is titrated potentiometrically with silverand more easily automated method according to ASTM nitrate solution.E 1899. Primary and secondary hydroxyl groups are con-verted with toluene-4-sulfonyl-isocyanate (TSI) into anacid carbamate, which is then titrated with the strongbase tetrabutylammonium hydroxide (TBAH) in a non-aqueous medium. The method is especially suitable forneutral raffinates. Acidic products can falsely indicate toohigh values. In the same way products that contain basescan show too low values due to neutralization of thecarbamate formed.
8. Water determination according to Karl FischerWater occurs as a contaminant in virtually all petroleum Hydraulics, insulation, transformer and turbineproducts. It reduces lubricant properties, promotes micro- oilsbial oil degradation, leads to sludge formation in the tank In these oils the water content is almost always deter-and promotes corrosion of ferrous and nonferrous met- mined coulometrically using a diaphragm cell. Due to theals. While at higher temperatures water boils and con- poor solubility in methanol, solubilizers must be usedtributes to a partial degreasing, temperatures below (chloroform or trichloroethylene). Since these productsfreezing point lead to the formation of ice crystals and a feature a very low water content, it is very important torapid decrease in lubricity. In addition, insulating and achieve a low and constant drift value.transformer oils used in high-voltage engineering becomeelectrically conducting and are therefore rendered use- Engine oils, lubricating oils and lubricatingless in the presence of water. greases The additives frequently present in these oil samples canIn view of this, knowledge of the water content in petro- react with KF reagents and falsify the result. If a KF dryingleum products is of prime importance. Karl Fischer titra- oven is used, a stream of dry carrier gas transfers thetion, owing to its excellent reproducibility and accuracy expelled water into the titration cell. Since the sampleas well as its ease of use, numbers amongst the most itself does not come into contact with the KF reagent,important water determination methods and accordingly interfering side reactions and matrix effects can be ex-figures in numerous international standards. Measure- cluded. The correct heating temperature lies below thement can occur by volumetric or coulometric Karl Fischer decomposition temperature of the sample and is deter-titration. Because of the low water content in petroleum mined in preliminary tests.products, KF coulometry is usually applied. Turpentine and its distillation productsAliphatic and aromatic petroleum components After addition of toluene or xylene, the water is trans-Water determination in these products is simple. They ferred by azeotropic distillation to the titration cell whereusually contain only little water so that the coulometric it is determined by Karl Fischer titration.Karl Fischer titration is used. If volumetric titration has tobe carried out, reagents with a low titer must be used.For long-chain hydrocarbons the addition of a solubilizer(propanol, decanol or chloroform) is recommended toimprove solubility. In the rare case of interferences bydouble bonds, the use of one-component reagents isrecommended.KF Evaporator 860 KF Thermoprep with 756 KF Coulometer
9. 841 TitrandoPetroleum (crude oil, heavy oil)Water is not homogeneously distributed in these pro- Another option is the separate determination of the mer-ducts, so that the petroleum samples must first be homo- captan component by potentiometric titration with silvergenized before analysis, e.g. with the Polytron PT 1300D. nitrate. The result of the water determination reduced byFurthermore, crude and heavy oils contain tars that can this amount corresponds to the actual water content ofseriously contaminate electrodes and titration cells. the sample (1 ppm mercaptan sulfur corresponds toReagents must therefore be exchanged regularly and the approx. 0.5 ppm water). Normally the water content intitration cells must be cleaned frequently. In order to fuels is determined by coulometric titration. With volu-ensure that the sample completely dissolves, solubilizers metric titration a solubilizer must be added to the metha-are added to the methanol: nol.- Crude oil (in general) 10 mL methanol + 10 mL chloroform + 10 mL toluene- Heavy oil 10 mL methanol + 10 mL chloroform + 20 mL toluene.FuelsThis group contains mercaptans that are oxidized byiodine and thus produce too high water contents. Theproblem is dealt with by adding N-ethylmaleinimide,which causes the SH groups of the mercaptan to attachthemselves to the double bond of the N-ethylmalein-imide. Reaction of a mercaptane with N-ethylmaleinimid
10. Oxidation stabilityIf stored in such a way that air has access, petroleum driven out by the air current, absorbed in water andundergoes oxidizing reactions whose reaction products detected there by measuring the conductivity. The timecan lead to problems in combustion engines. Polymers until formation of these decomposition products occursand poorly soluble compounds in particular lead to de- is referred to as the induction time or the Oil Stabilityposits in and blockages of the fuel injector systems. The Index (OSI) and characterizes the resistance of theaging behavior (oxidation stability) is therefore a very sample towards oxidative aging processes, i.e. the oxida-important property of petroleum products. tion stability.In order to quantitatively determine the oxidation stabili- 873 Biodiesel Rancimatty using the Rancimat method, air is passed through the The 873 Biodiesel Rancimat allows the simple and re-sample to be examined at an elevated temperature to liable determination of oxidation stability in petroleumbring about artificial aging. During this process long- products and biodiesel. The device is controlled via a PC;chain organic molecules are oxidized by oxygen, the PC software records the measurement curves, auto-whereby highly volatile organic substances form in addi- matically evaluating them and calculating the result. Uption to insoluble polymer compounds. The former are to eight samples can be measured simultaneously.
11. Important applicationsBiodiesel and biodiesel blendsBiodiesel (FAME, fatty acid methyl esters) is usually ex- acid methyl esters) is usually ex free diesel fuel is appearing more and more on the markettracted from oilseeds by transesterification with methanol. (ultra-low-sulfur diesel). This mineral diesel fuel with a sulfurIt is being added more and more to mineral diesel as a content of at most 10 ppm (EU) or 15 ppm (USA) is oxidizedblending component. Vegetable oils and methyl esters of considerably more easily than the formerly used diesel fuelsfatty acids are relatively unstable under storage conditions with a higher sulfur content. This means that oxidationsince they are slowly oxidized by atmospheric oxygen. Just stability has also become an important parameter for fuelas with oxidation of petroleum, polymer compounds are production. The 873 Biodiesel Rancimat allows a simpleformed during the oxidizing of biodiesel that can cause assessment of oxidation stability.damage to engines. For this reason oxidation stability is animportant quality criterion for biodiesel and vegetable oils Biologically easily degradable lubricating oilsthat must be controlled regularly during production accord- Biologically easily degradable lubricants can also be manu-ing to EN 14112. The corresponding method for biodiesel factured from natural fat and oils. Like the raw material,blends is described in EN 15751. The addition of suitable these products are also susceptible to oxidation.antioxidants slows down the oxidation process. The 873Biodiesel Rancimat also allows to determine the effective- Light fuel oilness of antioxidants. Alongside other methods the Rancimat method is also used for assessing the oxidation stability of light fuel oil. In orderSulfur-free diesel fuel to accelerate the reaction, metallic copper is added to theAs a result of environmental protection concerns and tech- fuel oil sample to act as a catalyst.nical requirements for motor vehicle manufacturers, sulfur-
12. Ion chromatographic analysesThe quality assurance of petroleum products involvesnumerous applications of ion chromatography in whichlow-molecular inorganic and organic ions are determinedin fuels, lubricating oils, gas-washing solutions and theso-called «Produced water» that is a by-product of crudeoil drilling.Anions and cations in «Produced water»During oil production large quantities of «Producedwater» are transported to the surface. In addition to oildrops and dissolved organic components, «Producedwater» contains large amounts of inorganic cations suchas calcium, magnesium, barium and strontium as well asanions such as carbonate, bromide and sulfate. Theresulting salts can cause scaling and ultimately block thepiping. For this reason the determination of inorganiccomponents is of essential importance, last but not leastalso for the correct dosing of scale inhibitors.
13. necskilled personnel. CO , optionally equipped with dialysis
14. Anions in gasoline-ethanol blendsThe use of energy from renewable sources and the asso-ciated reduction of greenhouse gases is one of the mostpressing goals of our modern industrial society. Ethanolmanufactured from waste and renewable plant material,which can be mixed with conventional gasoline in anyproportion, is regarded as one of the most promisingalternatives. Contaminants in the form of inorganic salts,however, impair engine performance, so that various in-ternational standards now regulate particularly the chlo-ride and sulfate content of gasoline-ethanol blends.
15. Simple matrix eliminationThe anions to be determined are freed from the inter-For this purpose the fuel is injected directly onto a high-caretained on the column, the fuel matrix is removed fromThis method allows the additional determination of ace- Schematic representation of Metrohm Inline Matrix Elimination Anions in an E85 gasoline-ethanol blend (85% ethanol, 15% CO acetone, sample preconcentration with Metrosep A PCC 1 HC ProfIC 8 Anion System with Metrohm Inline Matrix Elimination
16. VoltammetryVoltammetric trace analysis is used for determining elec- Voltammetry is suitable in particular for laboratories introchemically active substances. These can be inorganic which, with a medium sample throughput, only a fewor organic ions or even neutral organic compounds. Vol- parameters need to be controlled. It is often used fortammetry is often used for supplementing and validating specific applications that are either not feasible or toospectroscopic methods and is characterized by low costly using other techniques.equipment costs, comparably low investment and oper-ating costs, short analysis times and a high accuracy andsensitivity. Unlike spectroscopic methods, voltammetry 797 VA Computracecan also differentiate between different oxidation states The 797 VA Computrace is a modern voltammetricof metal ions or between free and bound metal ions. This measuring stand that allows voltammetric and polaro-is referred to as speciation analysis. graphic determinations to be carried out. The analyses can also be easily automated by adding Dosinos and aBroad application range sample changer.Voltammetric measurements can be carried out both inaqueous solutions and in organic solvents. Heavy metaldeterminations are usually carried out in aqueous solu-tions after digestion of the sample.
17. Interesting application examples Heavy metals in petroleum productsElementary sulfur in gasoline The determination of transition metals in petroleum pro-The total sulfur content in petroleum products is nor- ducts by voltammetry is usually carried out after diges-mally defined by law and is therefore routinely con- tion. Usually the samples are mineralized or combustedtrolled. It is also of interest to see in which form the sulfur by microwave digestion. Alternatively the metal ions canis actually present. By using voltammetry the proportion also be determined after extraction with a mineral acid.of elementary sulfur can be determined directly andsimply. In this way inferences can be drawn about theinfluence of gasoline on corrosion processes, e.g. regard-ing sensors in the fuel tank.Copper in ethanolEthanol is used increasingly in gasoline as a blendingcomponent. Contaminants can cause problems in theengine. For example, traces of copper catalyze the oxida-tion of hydrocarbons. As a consequence, polymer com-pounds can form that can lead to deposits and blockagesin the fuel system. Using voltammetry, copper can bemeasured without any sample preparation in pureethanol or ethanol-gasoline blends (E85, 85% ethanol+ 15% gasoline) in the range between 2 g/kg and500 g/kg. Voltammetric determination of copper
18. Atline process analysis In distillation columns, refineries and petrochemical in- ProcessLab was deliberately designed to be modular; it is stallations, crude oil is processed in sometimes complex configured according to analytical requirements and can processes to numerous intermediates and end products. be ideally integrated into the process communication Product quality and the economics of the manufacturing network via inputs/outputs (typically 4...20 mA). Just a processes depend absolutely on in-process analysis. few minutes after sampling, the relevant process infor- Samples must be analyzed within the shortest of times in mation is available to a LIMS or the master display. The order to rapidly register changing process conditions. process conditions can be rapidly and efficiently altered However, qualified laboratory personnel are not always wherever the need arises. ProcessLab is therefore ideally available around the clock and there are often long dis- suited for rapid and independent process monitoring in tances to the laboratory, which prevents rapid sample an industrial environment. analysis. A ProcessLab analytical system consists of an LCD control If it were possible to analyze the sample directly on-site unit and an application-specific, customized analytical during the process, this would present a considerable module. For even simpler and more convenient opera- advantage. This is possible with Metrohm ProcessLab, a tion, the control unit is also available with a touch-sensi- robust and easy to operate analytical system that can be tive screen. Owing to its splashproof housing, ProcessLab installed directly adjacent to the process. The sample is is ideally suited for application in rough production envi- brought to the ProcessLab and the analysis is started with ronments. a single push of a button. ProcessLab is based on proven Metrohm components for titration and voltammetry.ProcessLab analytical system with a touch-sensitive monitor and analytical module
19. Determination of the total acid and base Production of standard mixtures with a definednumbers octane ratingThe determination of the acid and base numbers is ofessential importance for the quality control of petroleum to engine knock. In order to assess the octane rating, theproducts. The acid number records components that resistance to engine knock of a gasoline sample is deter-react acidically as a sum parameter and allows conclu- mined in comparison with standard mixtures showing asions concerning the corrosion of plant or engine com- predefined octane rating. The standard mixtures, consist-ponents. Over the longer term, petroleum products with ing of n-heptane, isooctane (2,2,4-trimethylpentane) andhigh base numbers offer protection from the corrosive toluene, must be prepared with the highest precision andinfluence of any generated acids. By measuring sum pa- correctness. ProcessLab is ideal for this thanks to itsrameters, product alterations can be quickly and directly range of options for liquid handling. The automatic pro-recorded during use. duction of dilutions and dilution ranges as well as the doping of additives can be carried out without anyThe determination of acid and base numbers is carried further ado. The production of test mixtures is preciselyout automatically in the ProcessLab by potentiometric documented and the report can be used as a certificate.titration in non-aqueous solvents. Because of its proximi-ty to the process, the analytical results are available In the same way one can also prepare standard mixtureswithin minutes. for measuring cetane numbers with diesel fuels.
20. Online process analysisIn the (petro)chemical industry, continuous control of theproduction process, the quality of the product and thecomposition of any waste streams is of utmost impor-tance. With the online process analyzers of ApplikonAnalytical this is possible 24 hours a day, 7 days a week.The analyzers are used directly on-site, as close as possi-ble to the process, and run completely stand-alonewithout operator intervention. The Applikon analyzersare based on wet-chemical analysis techniques such astitration, colorimetry or ion-selective electrode measure-ments. Analyzers are available for single method, single-stream purposes as well as for complex multiple methodsand multiple streams.In online analysis, sampling and sample preconditioningare at least as important as the analyzer itself. ApplikonAnalytical has a lot of expertise in this area and is capa-ble of offering custom-made sampling systems, forexample for pressure reduction, filtering and degassing.Analysis alone is of no use for process control, and thatis why the analyzers are all equipped with possibilities fordigital as well as analog outputs. Results, for example,alarms can be transmitted via digital outputs. Digitalinputs, in turn, can be used for remote start-stop purposes.inputs, in turn, can be used for remote start-stop purpo-ses.In many cases the IP66-NEMA4 housing of the analyzerswill be sufficient. In some cases in the petrochemicalindustry, however, explosion-proof systems are required.stainless-steel explosion-proof version for Zone I or ZoneII according to the explosive atmosphere directives(ATEX). ADI 2040 explosion-proof with reagent cabinet
21. Many of the analysis methods that are used in the labo-ratory can be transferred to an online analyzer. Typicalapplications are:Water contentA very important factor in quality control of the petro-chemical industry is the determination of the watercontent in oil. A too high water content has a negativeimpact on the oil quality. As in the laboratory, Karl Fischertitration (coulometry) is the method of choice for theonline determination of the water content in any oil Water in a hydrocarbon sampling systemproduct. TBC in styrene In styrene production, the addition of tertiary-butylcate- chol (TBC) as a stabilizer is critical to prevent the styrene from polymerization during storage and transport. TBC levels need to be maintained above 10...15 mg/L. The problem is that the TBC concentration in styrene will slowly decrease in the presence of oxygen. Using an ADI 2040 with a colorimetric method, TBC levels can be monitored continuously in order to maintain the concen- tration at the proper level.Cuvette module for colorimetric measurementsSalt in crude oilExcessive amounts of chloride salts in crude oil result inhigher corrosion rates in refining units and have a detri-mental effect on the catalysts used. Desalting techniquesare well established, but continuous control of the saltcontent is needed for process control and cost reduction.With the ADI 2040 equipped with special heavy dutysample valves, the salt content can be monitored bymeasuring the conductivity or titration. After each analy-sis, the measurement vessel is cleaned and a blank meas-urement is performed before the next sample is taken.For this type of application, the analyzers are configuredin an explosion-proof housing.Hydrogen sulfide and mercaptane determinationSulfur compounds in oil and oil products cause corrosionand pose an environmental hazard. Determination of H2S Applikon belongs to the Metrohm group. The companyas well as mercaptans is done by titration with silver produces online analytical instruments.nitrate, a sulfide-coated silver electrode serving as theindicator electrode. www.applikon-analyzers.com
22. Technical speci cations and ordering informationTitration2.848.3010 Oil Titrino plus2.809.3010 Oil Titrando2.855.2010 Robotic TAN/TBN Analyzer6.0229.100 Solvotrode6.0430.100 Ag Titrode6.6040.00X Application collection «Oil PAC»Water determination according to Karl FischerCoulometric KF titration2.831.0010 831 KF Coulometer including titration cell with diaphragm and 728 Stirrer (magnetic stirrer)2.831.0110 831 KF Coulometer including titration vessel and generator cell without diaphragm, stirrer has to be ordered separatelyor2.756.0010 756 KF Coulometer with built-in printer including a titration cell with diaphragm and 728 Stirrer (magnetic stirrer)2.756.0110 756 KF Coulometer with built-in printer including a titration vessel and generator cell without diaphragm, stirrer has to be ordered separately2.728.0010 728 Stirrer (magnetic stirrer)Volumetric KF titration2.870.0010 870 KF Titrino plus2.890.0110 890 Titrando with Touch Control2.841.0010 841 Titrando including titration cell and indicator electrodeKF Oven2.860.0010 860 KF Thermoprepor2.774.0010 774 Oven Sample Processor2.136.0200 KF EvaporatorVoltammetry2.797.0010 797 VA Computrace for manual operationMVA-2 VA Computrace system with automatic standard addition. Consisting of 797 VA Computrace with two 800 Dosinos.MVA-3 Fully automated VA Computrace system. Consisting of 797 VA Computrace with 863 Compact VA Autosampler and two 800 Dosinos for automatic addition of auxiliary solutions. Allows the automatic processing of up to 18 samples. This system is the optimal solution for the automatic analysis of small sample series.Oxidation stability2.873.0014 873 Biodiesel Rancimat (230 V) including software and accessories2.873.0015 873 Biodiesel Rancimat (115 V) including software and accessories
23. Ion chromatographyAnions and cations in «Produced water»OptionsAnions in gasoline-ethanol blends ®OptionsProcess analysis
24. Subject to changeLayout Ecknauer+Schoch ASW, printed in Switzerland by Metrohm AG, Herisau www.metrohm.com