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sPE 9421 1

differentiation. Evidently, diflbrentiarion with respevt to

composition provides properties derivatives which are only

slightly aJlected by the normalization in the conceutration of the remaining n-l cornponents. However, as expected such an

effect is negligible.

During an investigation of a large PVT database which



with composition descriptions up to C¡2*, for

plot was generated of the derivatives of the pVT

each fluid', a

properties produced from an EoS, as described above, versus the ascending order of the components' carton number. It was

verified that the change (either positive or negative) in the derivatives values at each carbon number varies smoothly

between different fluids and depends on the overall fluid

cha¡'acterization and on p and T. Let us consider the example illustrated in Figure I with the GOR at the bubble point derivatives plot for a subset of the

available fluids. The values read in the vertical axis indicate the change to tho GOR value which will take place if l% of

each component is added to the system. It

can be readily seen

that all derivatives curves display smooth shapes along the

componcnts axis. Obviously, the higher the volatil§ of the

fluid, the higher the values ofthe derivatives thus rendering iis

GOR more sensitive to composition


The abrupt

decrease in the GOR derivatives with respect to the

concentration ofC12*, as shown in the graph, is due to the fact

that the heavy end is always appreciably heavier than C12.

Furthermorg all curvcs cross the x-axis somewhere between nC5 and C6 depending on the fluid's volatility. Similar curves cffn be obtained for the GOR of the oil phase at lower presswe

steps as well as for the Bo and the other PVT properties.

The derivatives were produced from the purg Robinson

EoSe and the properties oithe componsnts were ñbtained by using the Kesler Leero correlations while those of the heaw

end where obtained fiom the Twuil correlations

using thl

reported molecular weight and specific gravity. The

interaction coefficients used were obtained fiom the Oellrichl2 correlation.

Tuned EoS behavior at extrapolated condit¡on§

The PVT properties preclictions of an Eos model as weil as

their derivatiles depend skongly on the input components

propefiies (T", p", or) as well as on the selected interaction coefficients, the values ofwhich according to currsnt practice are affected by the hrning procedure.

sufficiently well

against a set of lab measurements usually performs fairly

An EoS model which has been tuned

accUretely at the composition a¡d operating conditions region

spanned by the measurements; although the physical

soundness ofthe PVT properties derivatives obtained from it

can be questioned. By forcing the model to pass through the

measurement points, cartceling effects in the de¡ivatives errors

may occur" Let P and s(z¡) denote a specilic PVT propetry and

its partial derivative wiü respect to the mole tiaction of the iú

component produced by tuned EoS. Let us also exptess this

partial derivative as the sum of jts thermodynamicirlly


value s¡(z¡) a¡rd of ar¡ additional term so(zi) which was

generated as a result ofthe tuning :

r(r¡)= r, (r, )+ .o L, )

, ( l)

- For small composition perfurbations, the Taylor expansion indicates that

or = fs(2,)az, =

= Ir,k,hr, *froft,§ri

Equation 2 can be extended úo allow

changes betwee¡r two operating points I integrating both parts :


for larger inuemental

and 2 by simply

& =P.+T,is,(,,






When operating in the "familiar" composition and

operaiing conditions region spanned by the measurements,


second term is negligible due to both ttre integration and the summation, thus leading to accurate prediction§. However, wher¡ PVT properties predictions are required outside this

region, the additional term becomes significantly

to predictions quite offtle correct properties values,

large leading

As it will be slrown in the following sectior¡ different EoS tunings may lead fo entirely different properties derivatives

in Figure l.

By sólely requiring rninimisation of the regression model's

values and deriyatives plots than the ones shown

error with respect to the measwgment§, erroneous derivatives

might be produced. In this case, fhe tuned model could

for iqstancg a larger increase in the oil density by incrqasing the fluid's C¡6 coocentration than by changing C1¡ at an equá mole fraction.


Results and d'rscussion

For demonstrating the principle of

utilizing the PVT properties

derivatives for quatifying EoS hrnings, a flr¡id of medium

volatility has been employed, the mmposition of w!¡ich is

given in Table 1. The Peng Robinson EoS model of a

commercial PVT package was tuned against the bubble point

densíty at its bubble point

of the differential

vaporízation study conducted in üe laboratory at treservoir

temperarure (Table 2).

Three differeüt tunings were performed, More specifically,

pressure and the 8", GOR and oil

and at the first three pressure steps

for tuning 1, the critical pressurs and temperature of the

pseudocomponeÍts from C7 fa C72a, the acentric factor,

molecular weight and volume shift parameterl3 of the C12

interaction cosfficients between Cr; Q,'C: and C1s, Cl,o Cr:* and fheir constant nr2 were used. For tunings 2&3, the acentric

factors and the volume shift paramefers of Cio a¡rd Crrr as w6ll

as the inleraction coefficionts between C¡ and Cro, Cir, Crz*

were ñrrther included. Tunhgs 1&2 were performed allowing five regression parañeters to be aonsidered at each iteratiortr

while tuning 3 was performed allowing for ten. The resulting

values for the regressiou parafireters carr be formd in Table 3.

Il can bs readily scen from F'igures 2 and 3 that aI three

tunings match ac¡rrately the lab measurements for pressures down úo 2328 psi (third pressure step). The ma¡<imum error

eqmls 222Y. and it occurs for the prediction of the GOR ar

fhe third pres$ure step (Table 4). However, the prediction