炼油产品中总硫检测方案

智能文字提取功能测试中

analytikjena Fields of Application/Industry：c Chemistry/Polymer Industry Clinical Chemistry/Medicine/Hygiene/Health Care Electronics Semi-Conductor Technology Energy 上Environment/Water/Waste Geology/Mining Food/Agriculture Metallurgy/Galvanization Refineries/Petrochemistry Pharmacy Cosmetics Material Analysis Others Total Sulfur Determination in Petro Industry and Refineries- Competitive， More Reliable and Faster than Ever Before Author： Dr. Angela Grobel， Product Manager， Analytik Jena AG， Konrad-Zuse-Str. 1， 07745 Jena，www.analytik-jena.com This article was published in Petro Industry News July 2013 Abstract The fast， reliable and cost-effective determination of sulfur impurities is an important task in thedaily routine of quality control in refineries and petrochemical industry. As described in crucial regulations like ASTM D7183， D5453， DIN 15486，20846 and others， themost reliable method to do this is the thermal decomposition of samples followed by UV-fluorescence detection of the formed SO，. With conventional sulfur analyzers， the time and effort required to achieve results can varydependent on the sulfur content， digestion behavior and composition of the sample matrix.Especially for the measurement of ultra-low and very high TS quantities， the process time can beremarkably extended.This affects the efficiency of the lab and thereby analysis costs. Where time is money， better solutions are required! The multi EA5000 offers， independent ofsulfur content， fast analysis - thanks to innovative HiPerSens detection. Demand for fast sulfur analysis During refining processes， even very low sulfur contaminations can poison the costly catalyst andthereby affect its effectiveness. Also the allowed quantity of TS in final products is strictly regulatedby ASTM D 4814 and D 6751 as well as DIN EN 590 and 14214 must not be exceeded. That iswhy feed stocks， process streams and final products need to be monitored precisely to avoidproblems. Since the beginning， the determination of sulfur by UV-fluorescence technique has been approvedas a valuable tool for process optimization and quality control. Dependent on the process step， thesulfur contents to be determined can vary in a broad range， from a few ppb (e.g.， raffinate) up tohigh ppm contents (e.g.， intermediates). In quality assurance every minute counts! This requires an analysis technique which enables a fastand correct sulfur determination independent of the concentration. Instrumentation and analysis An elemental analyzer of the multi EA series with an innovative HiPerSens detector was used forthe examination of the samples. This UV-fluorescence detector is based on the intelligent wide-range principle， combining highest sensitivity with an impressively broad operation range (up to10，000 ppm) and linearity. It can measure lowest contents (detection limit： 5 ppb S= 0.2 ng Sabsolute!) without difficulty or time-consuming enrichment procedures like trap and release. Even for the presence of high TN contamination there is a strategy to gain correct results. As anoption， the patented MPO technology renders interfering nitrogen compounds harmless. Fig. 1： multi EA" 5000 with multi matrix sampler The sulfur determination was carried out in a two-phase process at 1050°C. The samples wereintroduced by means of the multi matrix sampler MMS 5000. In the first phase， the liquids are dosed directly into the evaporation zone of the multi purposecombustion tube. There evaporation and pyrolysis takes place in an inert gas stream. The resultinggaseous products are immediately oxidized in the oxygen-rich atmosphere of the combustion zone.This guarantees significant measurement peaks even for the smallest sulfur quantities. The secondphase， which enables complete conversion of pyrolysis products， involves conditioning the analysissystem by flushing it with pure oxygen. The benefit of this "self-cleaning step" becomes obvious when analyzing sulfur contents below 500 ppb(ultra-traces). In this range， process blanks must beas small and stable as possible to gain reliable results. The generated SO2 is introduced to the HiPerSens detector after drying and purification. Thanks toits unique sensitivity and excellent reproducibility， there is no need for high injection volumes andmany replicates. Generally， 2 or 3 analyses per sample are enough to gain reliable results. Flexibility in calibration The calibration of the systemwas carriedl outitvwithliquid standards on the basis ofdibenzothiophene in iso-octane.The flexible multiWin software allows different strategies to easecalibration. Depending on the concentration range， the system can be calibrated with one singlestandard (Fig. 2b) and variable volumes (high contents)， or with different standards (Fig. 2a)andfixed volumes (ultra-trace contents). There is no need to have many methods， one for eachcalibration range. Thanks to the intelligent multi-range principle， up to 5 different calibration rangescan be linked with one and the same method. Depending on the gained integral， the software fullyautomatically selects the suitable calibration to calculate the correct result. This simplifieslaboratory routine and avoids the need for recalculation. Quality of replicatesCorrelation coefficientLinearity Detection limitIdentification limit Quantification limit 0.999930.99996linear93.72ng187.44ng359.96ng Fig. 2a： Calibration curve for ultra-trace contents Fig. 2b： Calibration curve for high contents As a measure of quality and applicability， the multiWinsoftware calculates statistical data incompliance with DIN 32645 fully automatically. Results The examined samples are a representative spectrum of petrochemical matrices. The results ofthe sulfur determination of samples are summarized in table 1. Table 1： Determination of the sulfur contents in petrochemical matrices No. Sample ID TS RSD 1 Raffinate 39.8 pg/I 11.3% 2 Naphtha 116 ug/l 0.36% 3 Gasoline 7.79 mg/l 1.38% 4 Jet fuel 1.91 mg/I 0.80% 5 Diesel fuel 1.61 mg/l 1.61% 6 Light heating oil (HEL) 106 mg/1 0.03% 7 Benzene 384 pg/l 1.79% An analysis time of approximately 3 min can be reached for all analyzed sample matricesindependent of their sulfur content. Thanks to high precision of sampling and optimal combustion，normally 2 or 3 replicates are enough. Fig. 3： TS determination of naphtha (ultra-trace content) Fig. 4： TS determination of HEL (high content) The impressive sensitivity of the HiPerSens detector allows the use of smallest sample quantitiesand thus short analysis times. In addition， its wide operation range enables fast and comfortable analysis of high concentratedsamples without the need of a time-consuming， costly dilution step. Fast， reliable， economic- the three goals of high-throughput labs While sulfur analyzers which are still equipped with common UV-fluorescence detectors needsignificantly longer analysis times for the determination of very low sulfur contents (trap andrelease， multiple injection， extremely high sample volumes) or high sulfur contents (dilution)， themulti EA 5000 with its innovative and maintenance-free HiPerSens detector can make the jobfaster. Integrated features such as Auto Protection， Self Check System， method library and automaticmaintenance counter guarantee fast analysis， low downtime and extremely low running costs. Extension modules like carbon， nitrogen and chlorine detectors or samplers for gases， LPG andsolids enable the owner to benefit even more from his investment. All these benefits turn the multi EA 5000 into an analysis system which is ideally suited to meetthe contemporary requirements of high-throughput analysis centers. Printout and further use permitted with a reference to the source. C 2013 Analytik Jena AG Publisher：Analytik Jena AGKonrad-Zuse-StraBe 1 Telephone +49 (0)36 41/77-7007745 Jena Fax +49 36 4177-92 79 otal Sulfur Determination in Petro Industry and Refineries -Competitive， More Reliable and Faster than Ever BeforeReference： Lit EA_NSCL_e|PIN GRO