Spe 26604 Ms
Spe 26604 Ms
Spe 26604 Ms
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below the true cloud point. It also means that for low-wax- cloud point determined via CSM. Further discussions
934
SPE 26604 D.D. ERICKSON, V.G. NIESEN, T.S. BROWN 3
The Canoco model is a modification of the model first temperatures for all of the non-normal paraffins, the
proposed by Won4• Won's model calculates equilibrium following formula was used as an average. The exact formula
80*C.
where Xi is the molar concentration of component i in the
f
Ti,non-normal = Tfnonnal - (90 - I ) (4)
100 + C.I
liquid phase, Si is the molar concentration of component i in
the solid phase, T is the temperature, aH fj is the heat of
fusion of pure component i, Yi L and YiS are the activity
coefficients of component i in the liquid and solid phases
respectively, and R is the ideal gas constant. T j is the
freezing/melting point of the pure component i and, for The need to differentiate between normal and non-normal
normal paraffins; is calculated using the following equation. paraffin is also illustrated in the modeling of Blandol.
Blandol is marketed on the basis of its low cloud point (32°F)
and pour point «32°F). Based on detailed compositional
T,! = 374.5 + 0.02617*MW. - 20172 (2) analysis of this oil out to C:,o, the average carbon number
I MW.I present in Blandol is 21 with only 3 weight percent being
normal paraffin and the rest consisting of cyclic and iso-
paraffin components. Normal paraffin ~l has a melting
Where MWj is the molecular weight of the component i. By point of 105°F. As a result, Won's model predicts a cloud
using the melting point temperature, the heat of fusion is point temperature of 107°F and that Blandol is 100% solid at
calculated as follows: 45°F. Fredenslund, et al. 2 presented a paper that stated that
the problem with Won's model is that aromatic components
are responsible for depressing the cloud point. Fredenslund
(3)
developed a complex activity coefficient model for aromatic/n-
paraffin interaction. However, since Blandol contains almost
no aromatic components, Fredenslund's model predicts
The constant 1.14 is a fitting parameter used to obtain a essentially the same behavior as Won's model. The Canoco
better fit with the experimental data. Won's original model model is able to more correctly predict the waxing behavior
uses a value of 1.0. of Blandol (model cloud point=18°F) becauses it uses the
fact that only 3 weight percent is normal paraffin with the
balance consisting of cyclic and iso-paraffinic components.
Differentiation Between Normal and Iso Paraffins
A critical improvement in the model is the identification of You Must Have Accurate, Detailed Compositional Analyses
the need to differentiate between the normal and iso-
paraffins. Won assumed that all components with the same The critical need to differentiate between the normal
carbon number have the same melting temperature Tf. Table paraffins and the iso-paraffins, aromatics, and naphthenics
3 shows that the melting point of several paraffin compounds. necessarily requires a detailed compositional analysis of the
The melting pOint drops significantly when a branch is added crude oil. Accurate compositions at high carbon numbers (at
to a normal paraffin. s For example, the melting point of least 35) are essential since the solubility of normal paraffins
C43H ss is 185°F and one would expect that a Cs2H 104 would decreases exponentially with increasing carbon number;
have an even higher melting point. However, due to the consequently, the cloud point is determined by the higher
branching in the Cs2H 104 compound, the melting point is carbon number, normal paraffins. Other models attempt to
almost 100°F lower than the melting point for C43 Hss. use compositional analyses without isolating the n-paraffins
Because there is such a wide variation in melting point and without differentiation of the Cw+ fraction.
935
4 THERMODYNAMIC MEASUREMENT AND PREDICTION OF SPE 26604
PARAFFIN PRECIPITATION IN CRUDE OIL
Considerable effort was expended to identify an analytical solvent/wax systems (the same systems as listed in Tables 5
and 6) were obtained from the literature and plotted' in
936
SPE 26604 V.G. NIESEN, T.S. BROWN, D.D. ERICKSON 5
changing crude oil composition as paraffin deposits in a to ~s) can make up to 200 P difference. Figures 1 and 7
pipeline. Normally, thermodynamics assumes that the liquid present comparisons between the laboratory data and the
Comparisons between Predictions and Laboratory Data for Conoco Model Predictions for the Mixing or Dilution of
Real Crudes Crudes
The previous comparisons between the Conoco model and In many cases, pipelines do not transport a single crude;
experimental data were for laboratory prepared binary consequently, the cloud point and wax deposition potential
mixtures. This section compares predictions for real fluids must be measured for possible crude oil blends. Because the
(crudes and condensates) with experimental data using the Conoco model does not need to be tuned to individual crudes
Cold-stage microscope described earlier. It is estimated that via a number of fitted parameters, the mixing of crudes,
the microscope is able to detect cloud points to within +/- solvents, and condensates can easily accomplished. As an
3°P and is reproducible to within +/- 30% in estimating the example, laboratory measurements of cloud points and wax
amount of wax formed as a function of temperature. Table contents were performed for a crude oil diluted at different
1 presents the comparison between experimentally concentrations with xylene. Those results were compared to
determined cloud point measurements and the model cloud the model predictions for the same crude oil and xylene
point predictions for a number of crudes and condensates. mixtures. Pigure 9 compare the laboratory results to the
Using only a compositional analysis, no tuning parameters model.
and a n-paraffin tail out to Cso, in general, the Conoco model
agrees with the microscopic cloud points within lOoP for a Xylene reduces the amount of wax formed for two reasons.
wide variety of condensates and crude oils. In two cases, the The first reason is best illustrated by example. If we had a 10
cloud points are up to 15°P degrees greater than the kg sample containing 10 percent (1 kg) of wax in it and we
microscopic cloud points. For most fluids changing the added 10 kg of xylene, the dilution would be 1 kg of wax in
length of the n-paraffin tail results in only a 0_8°P difference 20 kgs of the mixture resulting in a solid concentration of 5
in cloud point. The exception is for highly paraffinic crudes percent. In other words, the reduction of solid wax is simply
(high pour point) where the length of the tail (say from Cso
937
6 THERMODYNAMIC MEASUREMENT AND PREDICTION OF SPE 26604
PARAFFIN PRECIPITATION IN CRUDE OIL
because of an increase in the overall volume. However, = freezing/melting point of the normal paraffin
938
SPE 26604 V.G. NIESEN, T.S. BROWN, D.D. ERICKSON 7
939
8 THERMODYNAMIC MEASUREMENT AND PREDICTION OF SPE 26604
PARAFFIN PRECIPITATION IN CRUDE OIL
1 79 77 95-99 110
2 92 86 100 114
3 70 <30' 30
4 88 99 137 128
5 77 81 97 102
6 74 74 77
7 92 119 117
8 77 104 108
9 ND 1 53 63
11 70 125 119
12 80 107 104
13 153 170
14 53 ND 1 100 99
15 104 105
16 101 100
1 ND = not detected
940
SPE 26604 D.D. ERICKSON, V.G. NIESEN, T.S. BROWN 9
MAXIMUM APPROXIMATE
NUMBER OF REPORTED MAXIMUM DEGREE
WELL REPORTS DEPTH OF TEMPERATURE CLOUD OF WAX
NUMBER OF PARAFFIN DEPOSITS OF DEPOSITS POINT PROBLEM
HYDROCARBON MELTING-
I I POINT COF) I
Normal tritetracontane, C43H gg
CH3-(CH2)41-CH2 185
Methyl-di-heneicosyl-methane, C44 H 9o
CH3-(CH2)2o-CH-(CH2)2o-CH3 143
I
CH3
Nonyl-di-heneicosyl-methane, Cs2H 104
CH3-(CH2ho-CH-(CH2)20-CH3 91
I
C9H 19
941
10 lliERMODYNAMIC MEASUREMENT AND PREDICTION OF SPE 26604
PARAFFIN PRECIPITATION IN CRUDE OIL
3 0.0004 1.0000
4 0.0223 0.2831
5 0.0596 0.3528
6 0.1280 0.2823
7 0.1987 0.2466
8 0.1557 0.3155
9 0.1139 0.2772
10 0.0759 0.3688
11 0.0535 0.4516
12 0.0418 0.4187
13 0.0320 0.4651
14 0.0129 0.8339
15 0.0128 0.8064
16 0.0209 0.4035
17 0.0170 0.4065
18 0.0141 0.3786
19 0.0055 0.5817
20 0.0065 0.6118
21 0.0037 0.5958
22 0.0040 0.4906
23 0.0030 0.5542
24 0.0026 0.5701
25 0.0018 0.6941
26 0.0021 0.4344
27 0.0017 0.4301
28 0.0013 0.5065
29 0.0013 0.4587
30 0.0012 0.5538
31 0.0008 0.4701
32 0.0008 0.5746
33 0.0004 0.7081
34 0.0009 0.6038
35 0.0006 0.7616
36 0.0021 0.0977
942
SPE 26604 D.O. ERICKSON, V.G. NIESEN, T.S. BROWN 11
TABLE 5: COMPARISON BE:lWEEN EXPERIMENTAL AND PREDICTED CLOUD POINTS· WON'S MODEL
TABLE 6: COMPARISON BE:lWEEN EXPERIMENTAL AND PREDICTED CLOUD POINTS· PARAFFIN MODEL WITH NO ACTIVllY COEFFICIENT
943
12 THERMODYNAMIC MEASUREMENT AND PREDICTION OF SPE 26604
PARAFFIN PRECIPITATION IN CRUDE OIL
1O.,.----:--.,----,----.---r---r---.,-----,------,
I I I I I I I I
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CO • Experiment
;:0.3
....c:
(I)
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a.
....
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•
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-;0.1
•
;: iII
1
I
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0.0 -t----+---+----;--'--~~----4--=:::::---1
50 55 60 65 70 75 80
Temperature (OF)
Figure 2: Cloud Point and Wax Content for Oil #6
944
SPE 26604 D.D. ERICKSON, V.G. NIESEN, T.S. BROWN 13
.-
86
AC36
••
; .. .1)
0
a. 77
+.,.., .. .a-..,JiI
• ••
.
III.
68
••• • .,::
-0
-
:::s
0 59
• •••
(.)
50
•• •
0.00009 0.0009 0.009 0.09
Mole Fraction Wax
Figure 3 : Experimental Cloud Points of Wax in Various Solvents
....r::
.-
o 5.4 - + • Pentane
+
a. + Xylene
-0 3.6 - !A
T Heptane
+
::J_ • 0 •• 0 0 + + • 0 Decane
1.8 -
0
..2 u.. 0 T 'ta o 0 0 . !A n-C 12
(.)0 !AlA tv AI~~~6"'6~!,
:V
c: '-" 0 ·.1/\ ~ "
1\
<Q
IT •T
<II
0
-1.8 - T
T
945
14 THERMODYNAMIC MEASUREMENT AND PREDICTION OF SPE 26604
PARAFFIN PRECIPITATION IN CRUDE OIL
.....r::
.....c
.-o 3.6 • Pentane
a. + Xylene
"0 +
1.8 o "Iff Heptane
::s
0"-"
_U- ¢ Decane
• ~ n-C
O~ 12
x Octane
.-c'- -1.8
o Hexane
o
'-
'- 0.00007 0.0007 0.007
w
Mole Fraction Wax
Figure 6 : Prediction for Solvent / n-C36 using Conoco Model
946
SPE 26604 D.D. ERICKSON, V.G. NIESEN, T.S. BROWN 15
40 I
I
I
I
I • Oil #13 Microscope
35 ~,~~-=~-----~------------~------------~--
3: 30 ____________ I
~------L-----------L-
I I
I I I
25 I I
------------r------ - . -----------T-- I
X Oil #5 Microscope
en I I
....c I
:
I
I
I
: ··_·_·"Oil #5 Model
Q)
20 ------------r------------l ~----1:--L--------~------------~------~
0
J-
:
I
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I . I I I
Q)
15 -----~------------~------ -Jl-~-----------~-----------~------------
a. I I • I
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:
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_______I~___________ IL
:
~
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:
:
~
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0) 10 I I I
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Q)
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I ~.
:
I
: . :
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:
I
6 80
I
I. • _ _
");-,",...,;*~
~ >'~'-*
1do 1 0
: -,...
.. _
:-.....:.... I
160
Temperature ( OF )
Figure 7: Comparison of Model Predictions with Microscope
.....~20 - , - - - - - - - - - - - - - - - - - - - . - - - - - - - - - - .
Ccn - - 0 % Xylene
Q)ea
Om •••,._,,",W>·k" 25 % Xylene
CD Q) 15
D.Q) ."'-."'-."'-."'-.~ 50 % Xylene
.... 1-
.c LL . - - - 7 5 % Xylene
0l1-10 .
- - G) -..,........
Q) .... ••.".... ~.
;:::.. •.c-
::> -.. .
"'C:E 5 ~ .
•- s:::: ~ .
"0 - ........... .....~=" .... -
en oc 0 J~----,--__r--~-=-:-:;.:-~..:..:;:.~~
-..~..-~. . ~.......
-;;.~-~~~~~--r---._J
..:a.... ~."' .....
35 45 55 65 75 85 95 105 115
Temperature ( OF )
Figure 10 : Calculations for Oil #7 / Xylene Mixtures
948