| CUIDE cxroterzois (J ypsgcanson:DOM Uae ma Proce ee antes eategh chests Bee Kee Wo e cs enna oa See ete Meo Coie et ied Peet ners eee icas on ete eee ed eee ees Sere ee eta) erred ee er eet) ees Vapour pressure and volatility PSUS. | Hise meee Boe cc See ae BRC ACE. (sunt eee tese: eo oar se nang ipo aise re AER iat See ee eee Rare Var ee BB Geta cl oe eee Sh ee eee Raita i eae ee ice cy ae Ponies: Peet: een See ie Gr ah ee Gein CONT ees Bae ee eee ene) Bie oa ny teen Shey eee aaa Ce en aoe Nee M ere pee eee a ae Seen Pree i FRRIRERRRY MM octcter 205ctaber Figure 1. simple repr o @ measurement technique. ‘Table 1 Vapour pressure methoas as™ No. bans 00) baat esr »paara pier bsso7 Method eid vapour pressure (t9o vessels manual Dry Reid vapour pressure [wo | vessels) manual automatic methad (piston method ‘Mini mated (orignal, evsevated chamber out nawalso piston eepnon ini method srmoasherie Peston expansion method Triple petan| ewansion method Mocified Reid fwo vessels) ‘pansion ENGINEERING ‘Scope: Gasoline crude ot |vition gasoline, ‘ther vlatile petroleum products ‘Gains gasoline ‘ovygenate blends vation gasoline, ‘ther vlatile petroleum products Garoing gasoline ‘oxygenate blends, avation Eso, ther volatile petroleum produces Gasoline gating coxygenate blends, Seaton zproine, ‘other volatile petroleum produces ‘Gasoline gasoline fxygenate bende vation gasoline, other volatile petioleumn products ‘ude ci Gatling eating oxygenate blends, aviation gasoline, ther volatile petroleum products ure ure @ -sentation of vapour pressure ‘Test temperature 10°F 578°C) 1o0'F (78°C) 1o0'F 678°C) 1o0'F 78°C) M00 G78") s-80'e HOF 378-70°C a8 T0'C 41 storage applications, and that a plant enginee Understands the ciferent and sometimes seemingly ‘conflicting Standards implemented to measure it Vapour pressure measuréments in the petroleum industry ‘ASTM and other bacis enforce a curnbee of vapour pressure test methods for petroleum products. Devised in the 1920s by German chemist Rel, the earliest standard ‘ASTM D323, otherwise known as Reid vopour pressure (VP) was. a practical way of testing vapour pressure on natural gasoines, and was later extended to other products. The proces is outlined below. Measuring vapour pressure eee eel esse ata constant tempera ec Figue 1h PRPS yale sta ees rele ie ee cee eel eres ncreasing pressure, Eventually this prevents molecules escaping: the ave umber f molecules with energy to escape Is balanced by the number of molecules losing energy and returning ee tothe liquid oF solid state The systems now at equilibrium andl pressure registered by the gauge is the Wopaiepesse) cuit opou pressive conectedio at that temperature, Warming the vessel moves the equilibrium point so the vepour pressure in ce Figure 13). The reverse Vepour pressure cowrectes to an alse applies: cooling reduces vepour pressure. While most petroleum products have an associated VSpSUBISEHE vr speciation it ony comrected to measured at a4 vapour Se liquid rato {the volume of the vapour chamber being our times the volume of the (2.0211 Vapour pressure Stor Vapour pressure Se liquid chamber) at a precise RPE fimessured temperature of 378°C (00°F), at and 100'F) However, vapour pressure Wapolipiesies | ricasured at different ratios comrected cr temperatures does not toDVE represent AVP in adltion, Icompensaiesfor ications are inherent to Secolved a) she method due to loss volatile, high vapour pressure sie ‘components due to coaling, Oto WapourPrESSE known dissolved air omer content, and that the original‘manual method of measurement reared sill but was open to human error in operation, In the 1970s the use of omeenated compounds in gasoline such as ethanol and MTEE meant water soluble ‘onygenates diecolved inthe water traces left in the apparatus after cooling resus = loner vapour pressure results than expected. The anginal method was revised, using a cied apparatus for “cry vapour pressure’ (OVP) or ‘cy Reid ‘vapour pressure (ORVE) measwerents These ASTM 04953 measurements remain the \apour pressure result of interest for gasoline producers. ‘Other automatic or semi automatic methods were {developed with the alm of simplifying the manual tests However, products continue to be specified by ASTM D323 and D4953,s0 while nemer tests produced a vapour pressure resuitin their own right, they ae usualy converted to [ASTM 0323 of D4953 equivalents via 8 conversion factor: Reid vapour pressure equivalent (RVPE), dy vapour pressure ‘equivalent [OVPE) oF ry Reid vapour pressure equivalent [RvPe} ‘Automatic methods either inject a small amount of sample (one volume) into a larger vessel four volumes] at atmospheric pressure, or into a similar vessel held under vacuum (very similar to the example considered earlier) A suitable transducer measures the rie in pressure In general, vacuum methods were preferred as equilibrium was faster to achieve, reducing the measurement time but required a vacuum pump. Latest methods have overcome this by fitting the measuring chamber with a moveable piston that incorporates a pressure transducer. The sample is held under the piston the temperature is stabllized and then the piston ‘moved out tothe desired volume /liquid ratio, which can be ratios ether than 4. The transducer then reads the vapour pressure. The measuring chamber Is temperature controlled lining 2 heater and Peltier cooler. Tha chamber te normally ‘controlled at 100°F, but can be varied if measuring the vapour pressure ofa sample over a range of temperatures Is required. True vapour pressure ‘Crucially, neither RYF nor DVP measure what termed tive vapour pressize (TV?) The RVP of a pure liquid measured ata specific temperature results in the true vapour pressure of the liquid only, because there is only one type of molecule present in the vapour. However samples suchas crude ol potentially contain the presence of very volatile components with vey high vapout pressures. The 1 RVP ratio cannot account for these components evaporating to high pressure vapour usually Being so sal as not to very affect the lower pressure generates by the vapour Ftom the concentration of less volatile components that form the bulk ofthe crude oil. different measurement is therefore required to anticipate the dangerous effects these components can generate ‘One property that can express when pumping crude cil and toa lesser extent when storing is Bubble pont: the ‘temperature at which localised boiling causes bubbles of vapour to appear inthe igus f the laud i held under pressure the bubbles connct fom the pressure is reduced, as tis tthe suction niet oF pump, it may be reduced Liquid surface temperature, T (degrees Fahrenheit) i a 2 £ a 5 a Figure 2. API nomograph for TVP of crude oil. 20 Sais ee ‘Vapour Pressure kPa os 4 48 2 25 30 35 40 48 ViL Ratio CRUDE OIL Figure 3. Potential vapour pressure of crude oil at varying ViL ratio (constant temperature) ‘enough 10 allow bubbles to form, causing the pur to be pumping vapour Instead of liquid, resuting in serious damage. Similarly when crude oll is held in a 98% full storage tank the norm) ahigh pressure can Tox in the 2% ullage space due to outgassing ofthe small amount of very high ‘vapour pressive hydrocarbons present, especialy if the tank swarms in the surca problem made worse in floating top tanks by evaporative loss. TVP measurement ASTM D323 is able to measure the vapour pressure of crude ‘ll and, using the romograph published by the EPA and API ppocarson ENGINEERING lal Ostober 2015(Figure 2), can convert the RVPIE} 0 measured at 100°F into a ‘true’ vapour pressure at another temperature, However, the nomagraph is no more than a nominally predicted at another temperature, Since RVP rt mmchnis oF volute 1 capture of small rude ol, TV? fh RUP nay not be 2 predic fg, 8 crude oll snowing RVP of € 60 kPa at 4) could have areal vap kPa ata theoretical 01°V/L ratio. sequence, calculating the vapour pressure of cide oll at various V/L ratios isan important physical ty measurement for shipning and storage, leon piston expantion b -M DS377 method is designed =pecificall for this requirement: the measurement stied out a a4 vapour liquid ratio at 100'F, a correlation factors given sn RVPE [Figure 3), The resutcan beus to predict the accepted vert the res 1 pressure result at another temperature; fer example a vapour liquid rato of 0.021 corresponds tothe 2% of ullage space typically left ina storage vesel, such Related method (V/L) Pay hancement mens ech eas aud Ratio Temperature of Fuels that alternative measurement ASTM 5188 (Vapou FOR SALE re Se ey FROM RECENTLY CANCELLED CANADIAN PROJECTS www.gunningservices.com vacuated Chamber Method} measy the pressure at ich goscline ata V/A. ratio of typically has vapour prbssure of L0 bars, Caried out in a vapour this temperature measurement is essential ta ensure the prevention of vapour lock in engine fuel system: Conclusion pr nethods and correlating conversion chats for different pour pressure test analytical techniques makes selecting the correc syeasuremant technique difficult, However, advances in wave technologies ng these different measurement standards to be led more easly. For instance. Icon's Vapour Pressure environmental or fixed ambient measurement outside the rem h output RUPE at 378 (10DF} for product specifications: for gasoline blending contro the RVP and W/L simultaneously for ahighly accurate jie ite a Fundamental sequirement of ngineer to understand the test method requirements of hydrocarbon proce’ ENIRECAING