JFUE 9591 No.

of Pages 10, Model 5G

8 September 2015

Fuel xxx (2015) xxx–xxx

1

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

5
6

3 Prediction of nitrogen diluted CO2 minimum miscibility pressure for EOR

4 and storage in depleted oil reservoirs
7 Jinjie Wang a,b, Mingzhe Dong a,b,⇑, Yajun Li a, Houjian Gong a
8 a
College of Petroleum Engineering, China University of Petroleum (Huadong), Qingdao 266580, China
9 b
Department of Chemical Engineering, University of Calgary, Calgary, AB T2N 1N4, Canada

11
10
12

1 4
h i g h l i g h t s g r a p h i c a l a b s t r a c t
215
8
29
16
Fifty-five oil samples were modeled Correlation of the ratio of nitrogen diluted CO2 MMP to pure CO2 MMP, Fimp, is developed.
17
31 under six N2 concentrations and 12
18 temperatures. 35
32
19
Mmin without effect on MMP of
20 diluted CO2 under different 30
21 temperatures were found.
22
A chart for oil samples with molecular 25
23 weight of lower than Mmin was
24 invented. K
20
25
An analytical equation for oil samples
26 with MW higher than Mmin was 15
27 created.
10

5
305 310 315 320 325 330 335 340 345 350 355 360
T˄K˅

34
a r t i c l e i n f o a b s t r a c t
3
4 6
9
37 Article history: Injection of CO2 into depleted oil reservoirs can result in incremental oil recovery to help offset the cost of 50
38 Received 29 March 2015 CO2 storage. This paper presents a thorough study of the effects of nitrogen on CO2 minimum miscibility 51
39 Received in revised form 28 August 2015 pressure (MMP) for CO2 storage in depleted oil reservoirs. Nitrogen diluted CO2 MMPs for 55 model oil 52
40 Accepted 31 August 2015
samples were calculated using the Peng–Robinson Equation of State (PR EOS) in the temperature range 53
41 Available online xxxx
of 305–360 K. Based on the modeling results, an analytical equation has been developed for predicting 54
the ratio of impure CO2 MMP to pure CO2 MMP, Fimp. In this equation, Fimp is expressed as a function 55
42 Keywords:
of the pseudo-critical temperature of the impure CO2, the critical pressures of CO2 and N2, and the 56
43 Minimum miscibility pressure
44 N2 diluted CO2 injection
reservoir temperature. For oil samples with molecular weights lower than a certain minimum value 57
45 CO2 flood (Mmin) at various temperatures, a chart has been created for supplying a coefficient in the equation. 58
46 Enhanced oil recovery Compared to commonly used Fimp correlations in the literature, this new correlation yields a more 59
47 CO2 storage accurate match to the Fimp data found in the literature. 60
48 Ó 2015 Published by Elsevier Ltd. 61
62

63
64
1. Introduction 65

There is a growing consensus that global climate change has 66

⇑ Corresponding author at: University of Calgary, Calgary, Albert T2N 1N4, been occurring since the last century. Many climate scientists have 67

Canada. Tel.: +1 403 210 7642; fax: +1 403 284 4852. suggested that the major cause of this global climate change is 68
E-mail address: mingzhe.dong@ucalgary.ca (M. Dong). excessive anthropogenic emission of greenhouse gases (GHGs). 69

http://dx.doi.org/10.1016/j.fuel.2015.08.075
0016-2361/Ó 2015 Published by Elsevier Ltd.

Please cite this article in press as: Wang J et al. Prediction of nitrogen diluted CO2 minimum miscibility pressure for EOR and storage in depleted oil reser-
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 JFUE 9591 No. of Pages 10, Model 5G
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2 J. Wang et al. / Fuel xxx (2015) xxx–xxx

70 Due to their low cost, high energy density, and existing reliable factors. Simulation methods, on the other hand, require the avail- 136
71 technology and infrastructure for energy production, fossil fuels ability of numerous reservoir fluid-compositional data for them 137
72 currently supply approximate 87% of energy worldwide [1]. Conse- to be reliably validated. However, such data are not always accu- 138
73 quently, environmental effects caused by the emission of GHGs rate or available. Hence, finding a relatively inexpensive, rapid, 139
74 from fossil fuels are becoming serious problems. and widely applicable technique to estimate the gas–oil MMP is 140
75 As world economies and their energy demands grow, fossil fuels desired. The importance of a correlation approach lies in that 141
76 are likely to remain the main energy resource for some time to MMP for a wide range of temperatures and oil/gas fluids can be cal- 142
77 come. Therefore, the discharge of these gases from power plants culated quickly and accurately without introducing uncertainties 143
78 is expected to grow at a rapid rate. It has been reported that inherent in experimental and simulation methods. 144
79 1120–3400 billion tons of CO2 have already been discharged into Many correlations of CO2 MMP have been reported [11–15], and 145
80 the atmosphere, and that more GHGs will be released without many thermodynamic models have also been developed for esti- 146
81 further abatement [1]. Thus, methods for reducing the GHG con- mating the MMP in the literature [16,17]. Several correlations for 147
82 tent in the atmosphere are imminently necessary and imperative. impure CO2 MMP have also been proposed as summarized in 148
83 One effective approach for reducing the atmospheric concentra- Table 1, where Fimp is the ratio of impure CO2 MMP to the pure 149
84 tion of GHG is carbon capture and sequestration (CCS). In particu- CO2 MMP. Coefficients in the correlations of Table 1 are listed in 150
85 lar, CO2 sequestration in geologic formations, such as depleted oil Appendix 1. Johnson and Pollin [18] included seven parameters 151
86 and gas reservoirs, shows great promise as a huge number of in their correlation, considering the effects of reservoir tempera- 152
87 potential geologic sinks already exist. After many years of develop- ture, oil density, and molecular weight (MW). However, their cor- 153
88 ment, exploitation, and accumulation of experience, there is relation is not suitable for high temperatures and/or high 154
89 enough geological analysis data, as well as formation data, that will concentrations of contaminants. The correlation by Alston et al. 155
90 assure the safety and speed of the CCS process. Moreover, CO2 included the effects of reservoir temperature and stock-tank oil 156
91 could still be used in a post-EOR (enhanced oil recovery) process, API gravity on impure CO2 MMP, in which Fimp is a function only 157
92 to maximize the oil recovery after secondary and tertiary exploita- of the pseudo-critical temperature of the injection gas, Tcm [19]. 158
93 tion, before sequestration. Sebastian et al. developed a polynomial correlation for impure 159
94 CO2 injection has been widely used for enhanced oil recovery CO2 MMP, which varies as a function only of the mole-average 160
95 because of its high displacement efficiency and relatively low cost. pseudo-critical temperature [20]. Kovarik proposed an impure 161
96 If the injection of CO2 into the depleting oil reservoirs for storage MMP correlation for a CO2 stream with methane as the only non- 162
97 can further recover some of the remaining oil, achieving large scale CO2 component [21]. In their correlation, Fimp is proportional to 163
98 CCS for acceptable economic and environmental impacts will be the mole fraction of methane in the injection gas. Dong only used 164
99 more promising. This will also facilitate the continuing use of fossil the ratio of pseudo-critical temperature to CO2 critical temperature 165
100 fuels while decreasing the worldwide effect of CO2 emission. to predict Fimp, where a factor fi is used to represent the strength of 166
101 Among CO2 injection methods, miscible flooding is the most effec- different contaminants (namely CH4, H2S, N2, O2, and C2H6) in 167
102 tive process. The cost of CCS is made up of four factors: separating, determining the pseudo critical temperature [22]. Li and 168
103 compressing, pipelining, and injecting [2]. As nitrogen is the pre- co-workers modified Alston et al.’s correlation for achieving a bet- 169
104 dominant component of flue gas, it is, therefore, the most common ter prediction of the CO2 MMP for heavier oil samples [23]. It was 170
105 ‘‘impure” component in the captured CO2. However, it is desirable found in their study that MWC7+ rather than MWC5+ leads to a 171
106 to include as little nitrogen as possible in sequestrated CO2, for the slightly better prediction. Yuan and co-workers proposed a linear 172
107 following reasons: (1) N2 is much more volatile than CO2, so correlation for impure CO2 MMP [24]. However, the parameter m 173
108 including N2 in CO2 will raise the cost of a sequestration operation, in their correlation was calculated by ten regressed coefficients. 174
109 such as for transportation and high pressure storage equipment; Further, the correlation was only valid for streams containing 175
110 (2) N2 will occupy some of the pore space for CO2 storage, so that methane in the CO2 stream. Emera and Sarma developed a correla- 176
111 wasted space reduces the space available for CO2 sequestration in tion to predict the impure and pure CO2 MMP, in which many coef- 177
112 geologic formations; and, (3) it is known that nitrogen in a CO2 ficients were obtained from the regression results [25]. From the 178
113 stream can significantly increase the miscibility pressure. How- above review, it can be seen that the researchers of this area have 179
114 ever, even though obtaining a high purity CO2 stream is technically not reached a consensus on the determinants of impure CO2 MMP. 180
115 feasible, purification steps lead to increased energy requirements Moreover, there is a lack of systematic study on N2 contaminant 181
116 and additional costs. Because of that consideration, purity CO2 MMP for CO2 storage injection. 182
117 standards that are too strict might not be practical, leading to the This study is aimed at developing an accurate and reliable cor- 183
118 conclusion that the CO2 for sequestration in geological formation relation to estimate nitrogen diluted CO2 MMP for an EOR-CO2 184
119 will ultimately contain some nitrogen [2,3]. Therefore, the study storage process. The Peng–Robinson Equation of State (PR EOS) 185
120 of the effect of N2 on the EOR-storage process, especially its effect was used by running the CMG WinProp program [28] to predict 186
121 on the miscibility between the injected CO2 and the residual oil, is the CO2 MMPs and impure CO2 MMPs for 55 model oil samples, 187
122 an important research topic. covering a wide range of molecular weights and a temperature 188
123 Reservoir oil can achieve miscible recovery at pressures higher range between 305 K and 360 K [26,28]. The effects of nitrogen 189
124 than a minimum pressure, which is defined as the minimum mis- mole fraction in the CO2 stream, molecular weight of the depleted 190
125 cibility pressure (MMP) [4–6]. The CO2 MMP is a crucial parameter oil, and the reservoir temperature on MMP were investigated. 191
126 when selecting oil and gas reservoirs for CO2 injection in the EOR Based on the modeling results, the relationship between Fimp and 192
127 process [7]. Three methods of determining the CO2 MMP have been the above factors was established. A comparison of the proposed 193
128 used: experimental, simulation, and correlation. Even though correlation with the experimental data and previously published 194
129 experimental results are the most reliable and comparable with correlations is also performed. 195
130 established industry data, laboratory measurements command a
131 high cost, intensive labor, and a significant time to obtain even a
132 few data sets, making the experimental approach less advanta- 2. MMP calculation 196
133 geous [8–10]. More importantly, each set of experiments test just
134 one condition among many factors, which means that more energy A multiple mixing-cell method has been published to estimate 197
135 and a longer time period are needed for a thorough study of all the MMP [29–31]. The basic concept of this method is to 198

Please cite this article in press as: Wang J et al. Prediction of nitrogen diluted CO2 minimum miscibility pressure for EOR and storage in depleted oil reser-
voirs. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.08.075
 JFUE 9591 No. of Pages 10, Model 5G
8 September 2015

J. Wang et al. / Fuel xxx (2015) xxx–xxx 3

Table 1
Popular correlations from published papers.

Author(s) Equation
h i
Johnson and Pollin 103 y2
Pc;inj þ10:5 1:8þTT ðTT cm ÞþIð0:285MWMW inj Þ
2
cm
F imp ¼ 2
Pc;inj þ18:9ðTT cm ÞþIð0:285MWMW inj Þ

Alston et al. h i168:893

T
F imp ¼ 87:8 cm
T cm
Sebastian et al. F imp ¼ 1:0  2:13  102 ðT cm  304:2Þ þ 2:51  104 ðT cm  304:2Þ2  2:35  107 ðT cm  304:2Þ3
Kovarik F imp ¼ 0:2831½ð548  1:8T cm Þ=MMPpure þ 144:1
Dong P 4
f yT
F imp ¼ i i i ci
304:26

Yuan et al. F imp ¼ 1 þ mðP CO2  100Þ

Emera and Sarma F imp ¼ ð0:068616z3 þ 0:31733z2 þ 4:9804z þ 13:432Þ=MMPpure

250
199 mathematically mix gas and oil in repeated contacts, resulting in a X
45

200 new equilibrium [32]. Utilizing this method, the cell-to-cell simu- MW ¼ MW i  xi ð2Þ
1 252
201 lation from CMG WinProp was run to calculate the miscibility of
202 nitrogen diluted CO2 with oil using the PR EOS [27,28,39]. The where MWi and xi are the molecular weight and mole fraction for 253
203 cubic form of PR EOS is: component i, respectively. Molecular weights of the model oil sam- 254
204
3 2 2 3 2 ples ranged from 120 to 360 g/mol, which represents most of the 255
206 Z  Z ð1  cBÞ þ Z½A  Bð1 þ cÞ  B ð1 þ 2cÞ  ½AB  cðB þ B Þ ¼ 0 ð1Þ
light and medium oils. The temperatures considered in the simula- 256
207 where Z is the compressibility factor, which can be expressed as tion varied from 305 K to 360 K, which covers most oil reservoir 257
208 Z ¼ pv =RT; A and B can be expressed in terms of the critical proper- temperatures. Havens showed that the concentration of N2 in 258
209 ties, the acentric factor, pressure, universal gas constant, and tem- pipelines for transportation is usually no more than 4%, while gas 259
210 perature; and c is equal to 1 for PR EOS. The following procedures from the capture process may require additional purification to 260
211 describe the multiple mixing-cell method to calculate MMP for a meet common oil field injection specifications [36]. Thus, the upper 261
212 reservoir fluid and injection gas at a given temperature [28,32–34]: limit of N2 concentration tested in this study was set to be 10 mol% 262
214
213 (1) Choose a pressure below MMP as the initial input pressure. and, therefore, the pseudo-critical temperature of the CO2 stream 263
215 (2) At the chosen temperature and pressure, the reservoir fluid varied between 304.26 K for pure CO2 and 286.46 K for CO2 with 264
216 and injection gas are mixed at a specified ratio. The flash cal- 10% N2. 265
217 culation for each component is then performed using PR EOS In this paper, more than 4000 modeling runs were carried out to 266
218 and a new two phase region is detected. analyze the effect of N2 concentration on the CO2 MMP for oil sam- 267
219 (3) Repeat the flash calculation by mixing the liquid fraction ples of different molecular weights, at a wide range of reservoir 268
220 from step 2 with the injection gas, until the liquid composi- temperatures. The results are represented by using the ratio of 269
221 tion is same as the vapor composition. This pressure is the the impure CO2 MMP to the pure CO2 MMP, Fimp. Since the model- 270
222 MMP. ing of both pure and impure CO2 MMP were conducted using the 271
223 (4) If the liquid fraction just flashed is the same as that from the same model of the equation of state for the oil and gas compo- 272
224 preceding stage, but the two phase region still exists, the nents, the calculated results for Fimp under each set of oil and reser- 273
225 pressure is increased in a setup step. Step 2 and 3 are voir conditions should be theoretically consistent. The calculated 274
226 repeated until the liquid composition is same as the vapor results of Fimp are shown as a function of N2 concentration, oil 275
227 composition, and MMP is the pressure at which this occurs. molecular weight, and reservoir temperature in Fig. 1. The varia- 276
228 tion of Fimp in this three dimensional diagram shows that all three 277
229 The detailed steps used in the cell-to-cell simulation calculation parameters have an impact on Fimp; their effects will be discussed 278
230 can be found in the CMG WinProp manual. in detail in this section. 279

231 3. Modeling results and analysis 3.1. Effect of N2 concentration 280

232 The above equation of state calculation was focused on the Fifty-five sets of modeling runs were carried out to examine the 281
233 effect of N2 on CO2 MMP in depleted oil reservoirs for further effect of N2 concentration on the Fimp of CO2. As an example, the 282
234 CO2 EOR and sequestration. The reliability of the modeling was results of Fimp for MW = 250 g/mol at six reservoir temperatures 283
235 tested by calculating CO2 MMPs of three oil samples in the paper are plotted (intersecting lines on plane A–A in Fig. 1) as a function 284
236 by Srivastava and co-workers and comparing those MMPs with of N2 concentration in Fig. 2. Simulation results show that N2, as a 285
237 their experimental results [35]. For example, the calculated Fimp contaminant whose critical temperature is much lower than that of 286
238 of a particular oil sample (MW = 170, T = 330 K, N2 concentration CO2, decreases the critical temperature of the injection gas and, 287
239 in CO2 = 3%) was 1.14. Compared with the slim tube experimental hence, significantly increases Fimp. 288
240 result of 1.16, the error is 1.7%, which is in the acceptable range of As shown in Fig. 2, Fimp increases dramatically with increasing 289
241 discrepancy. N2 concentration. It is also seen that the relationship between Fimp 290
242 In most published literature, reservoir temperature and oil and N2 concentration is linear, which means that, for a given oil 291
243 composition have been considered to be the most important fac- sample, Fimp is proportional to the N2 concentration at a constant 292
244 tors affecting the CO2 MMP [11,18,24]. The composition of oil sam- temperature. As the reservoir temperature increases, the slope of 293
245 ples and component properties used in this study are shown in the line decreases. 294
246 Appendix 2 (49 model oil samples) and Appendix 3 (6 model oil The above modeling results are consistent with the findings of 295
247 samples), among which the default value for each component is Johnson and Pollin: that N2 diluted into CO2 caused the miscibility 296
248 from CMG WinProp. The molecular weight is calculated by the pressure to increase linearly with the percentage of N2 [18]. Sebas- 297
249 mixing rule: tian and Kovarik have concluded that, for a lower nitrogen concen- 298

Please cite this article in press as: Wang J et al. Prediction of nitrogen diluted CO2 minimum miscibility pressure for EOR and storage in depleted oil reser-
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 JFUE 9591 No. of Pages 10, Model 5G
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4 J. Wang et al. / Fuel xxx (2015) xxx–xxx

299 tration range, Fimp is proportional, or approximately proportional,

300 to the nitrogen mole fraction when the temperature is kept con-
301 stant [20,21]. All the straight lines of Fimp versus N2 concentration
302 have the same y-intercept of unity, which of course represents
303 pure CO2. Thus, a linear relationship could be defined as follows:
304
306 F imp ¼ kyN2 þ 1 ð3Þ

307 where yN2 is the mole concentration of N2 in the CO2 gas stream and
308 k is the slope of the straight line. To represent the properties of the
309 injection gas, the pseudo critical temperatures of the gases were
310 employed. The pseudo-critical temperature of the solvent stream
311 is calculated by the mole-fraction mixing rule [18,37]:
312 X
T cm ¼ yi T ci ð4Þ
314 i Fig. 2. Sensitivity of the miscibility properties to N2 percentage at different
reservoir temperatures (intersecting lines on surface A–A, MW = 250 g/mol).
315 where yi stands for the mole fraction of species i in the gas mixture,
316 and Tci is the critical temperature of species i in Kelvin.
317 Taking the data sets on plane A–A in Fig. 1, for example, the
318 relationship between Fimp and the ratio of the critical temperature
319 of injection gas to that of pure CO2, which is the reduced pseudo-
320 critical temperature, Tcm/304.26, can be obtained, as shown in
321 Fig. 3. The critical temperature of the injection gas decreases as
322 more N2 is mixed into it and Fimp increases with the decrease in
323 the reduced pseudo-critical temperature ratio, Tcm/304.26. It is also
324 noticed that a higher reservoir temperature leads to a relatively
325 lower Fimp; the changing rate of Fimp with N2 concentration
326 decreases with increasing temperature.
327 For pure CO2, the reduced pseudo-critical temperature
328 Tcm/304.26 of course equals 1 and Fimp = 1. Thus, the extended form
329 of Eq. (3) is given as the following:
330  
T cm
F imp ¼ K 1  þ1 ð5Þ
332 304:26
333 where K denotes the slope of the straight line with respect to the Fig. 3. Fimp versus critical temperature ratio of injection gas to pure CO2,
334 dimensionless pseudo-critical temperature of the CO2 stream. As MW = 250 g/mol.
335 can be seen from the three dimensional diagram in Fig. 1, the
336 coefficient K is a function of molecular weight and temperature. calculations for Fimp [4,11,18–21,38]. To investigate the relation- 342
337 The relationship between the coefficient K and these two parame- ship between Fimp and the molecular weight of oil, MMPs were 343
338 ters is analyzed in the next section. predicted for oil samples of 55 different molecular weights. The 344
distribution of the components and the molecular weights used 345
339 3.2. Effects of molecular weight and reservoir temperature in this study cover most oils suitable for CO2 miscible flooding 346
and subsequent sequestration. 347
340 Many researchers have realized that Fimp varies with the molec- For a given average molecular weight, there can exist different 348
341 ular weight of the oil, while others did not include MW in their oil compositions. In order to find out whether or not Fimp changes 349

Fig. 1. Calculation results considering three parameters via CMG WinProp.

Please cite this article in press as: Wang J et al. Prediction of nitrogen diluted CO2 minimum miscibility pressure for EOR and storage in depleted oil reser-
voirs. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.08.075
 JFUE 9591 No. of Pages 10, Model 5G
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J. Wang et al. / Fuel xxx (2015) xxx–xxx 5

Table 2 on the MMP [4]. Therefore, this study focuses on the effect of MW, 360
Calculated values of Fimp for the three groups of oil samples each which have the same rather than the oil composition, on Fimp. 361
MW and different compositions.
To analyze how the MMP ratio Fimp changes with the MW of the 362
N2 (%) 150 (g/mol) 250 (g/mol) 350 (g/mol) oil and with the reservoir temperature, the simulated results of 363
A1 A2 A3 B1 B2 B3 C1 C2 C3 Fimp in Fig. 1 are re-plotted as functions of oil MW and reservoir 364

0 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

temperature at six N2 concentrations in the 3-D diagram of 365
2 1.11 1.10 1.10 1.05 1.05 1.10 1.05 1.10 1.05 Fig. 5. As shown, at a constant N2 concentration, Fimp varies with 366
4 1.21 1.21 1.21 1.09 1.10 1.10 1.10 1.10 1.10 both MW and temperature. It is also seen that, at a constant 367
6 1.32 1.32 1.32 1.16 1.15 1.16 1.15 1.16 1.16 temperature, there exist two ranges of molecular weights in which 368
8 1.43 1.42 1.43 1.21 1.20 1.21 1.20 1.20 1.21
Fimp changes with MW in a different manner. 369
To analyze the change of the Fimp in the aforementioned range 370
of MWs, the results of Fimp at T = 330 K and 350 K are re-plotted 371
in Fig. 6. For each curve in Fig. 6, N2 concentration is constant. At 372
a constant non-zero N2 concentration and temperature, Fimp 373
changes sharply with molecular weight in the low MW range, 374
and remains constant when the molecular weight is higher than 375
a certain value, which is denoted as Mmin. 376
One also observes, in comparing Fig. 6A and B, that Mmin 377
increases as T increases. Fig. 7 shows the change of Mmin with tem- 378
perature; a linear relationship between Mmin and reservoir temper- 379
ature T is obtained as follows: 380
381
Mmin ¼ 0:7762  T  110:59 ð6Þ 383

Therefore, the effect of temperature on Fimp needs to be consid- 384

ered in two MW ranges: MW P Mmin and MW < Mmin. 385
386
For MW P M min 388

For oil samples with a MW greater than Mmin, Fimp is a function 389
Fig. 4. The effect of different oil composition Fimp, T = 330 K.
of temperature and Tcm. Fig. 8 shows the influence of reservoir 390
temperature on Fimp when MW is greater than Mmin. The six curves 391
350 with the oil composition for a fixed average molecular weight, cal- represent the change of Fimp with temperature in Fig. 5, at six N2 392
351 culations were conducted for oil samples with the same MW and concentrations for oils with MW between Mmin and 360 g/mol. 393
352 different compositions, at constant temperature. Three oil samples For CO2 miscible flooding, higher MMPs will result from higher 394
353 were chosen from the 55 model oil samples to represent light, reservoir temperatures. Therefore, deeper, hotter reservoirs 395
354 medium, and heavy oil. For each MW, MMP ratios for three differ- require higher pressures for miscible flooding. All correlations in 396
355 ent oil compositions (Appendix 3) were simulated. The calculated the literature suggest that MMP increases with the reservoir tem- 397
356 results are summarized in Table 2 and plotted in Fig. 4. The results perature. However, the rule is opposite when it comes to Fimp. In 398
357 show that, for oils with the same average MW, even when the Fig. 8, except for the bottom horizontal line, which represents 399
358 composition varies, Fimp does is essentially invariant. Yellig and the Fimp of pure CO2, all curves decrease as temperature increases 400
359 Metcalfe have also stated that oil composition has little to no effect and the rate of change becomes less as temperature increases. As 401

Fig. 5. Effect of MW and T on Fimp at six N2 levels.

Please cite this article in press as: Wang J et al. Prediction of nitrogen diluted CO2 minimum miscibility pressure for EOR and storage in depleted oil reser-
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 JFUE 9591 No. of Pages 10, Model 5G
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6 J. Wang et al. / Fuel xxx (2015) xxx–xxx

Fig. 6. Change of Fimp with MW of oil for different N2 concentrations in CO2 stream. (A) T = 330 K; (B) T = 350 K.

Fig. 7. Mmin as a function of temperature. Fig. 9. Fimp versus N2 concentration at different temperatures.

the effect of a small amount of N2 could be neglected, since the 409

higher T is already the dominant factor affecting Fimp. 410
If the data of Fimp and N2 concentration at different reservoir 411
temperatures are plotted, we have a set of straight lines, as shown 412
in Fig. 9. As was discussed in Section 2.1, there is a corresponding 413
slope for each line, where the values of the slopes for different 414
reservoir temperatures are different. The slopes, K, for the curves 415
in Fig. 9 are listed in Table 3 at different reservoir temperatures. 416
A regression was made using the data in Table 3 to find the 417
expression for K, and, more importantly, to predict the effects of 418
reservoir temperature on Fimp. Considering the critical pressure of 419
the components in the injection gas and the data in Table 3, a 420
correlation representing the relationship between K and T was 421
obtained. 422

Table 3
Parameter K at different temperatures.

T (K) K
Fig. 8. Effect of reservoir temperature on Fimp at different N2 concentrations for oil
with an average MW P Mmin. 305 19.70
310 17.20
315 15.19
320 13.58
402 temperature increases, Fimp appears to be reduced exponentially, 325 12.60
403 but always remains greater than 1. That is, even though 330 11.33
335 10.45
404 temperature will cause a decrease in Fimp, as temperature 340 9.83
405 increases, the effect of N2 on Fimp will become less, and eventually 345 9.15
406 could be seen to be asymptotic. Therefore, an assumption was 350 8.64
407 made that, if the reservoir temperature T were high enough, the 355 7.80
360 7.50
408 Fimp could be taken to be one. This is based on the premise that

Please cite this article in press as: Wang J et al. Prediction of nitrogen diluted CO2 minimum miscibility pressure for EOR and storage in depleted oil reser-
voirs. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.08.075
 JFUE 9591 No. of Pages 10, Model 5G
8 September 2015

J. Wang et al. / Fuel xxx (2015) xxx–xxx 7

25 where Mmin = 0.7762  T  110.59. Here, Fimp is a function of the 437

Eq. (7) reservoir temperature and the pseudo-critical temperature of the 438

20 moedl results injection gas. Accordingly, the diluted CO2–oil MMP can be deter- 439
mined for a given reservoir temperature and pseudo-critical tem- 440
perature of an injection gas, together with the pure CO2 MMP value. 441
15
K 442
10 For MW < M min 444

In the MW range of 120 g/mol and Mmin for different reservoir 445
5 temperatures, the results of Fimp versus reservoir temperature are 446
shown in Fig. 11. Each graph in Fig. 11 shows the relationship 447

0 between Fimp and temperature at six nitrogen concentrations for 448

300 310 320 330 340 350 360 one particular molecular weight. 449
T (K) The four graphs in Fig. 11 were taken from the 3D diagrams of 450
Fig. 5, when MW was equal to 125, 135, 145, and 155 g/mol, 451
Fig. 10. Comparison between model results and calculation results from Eq. (7).
respectively, showing the effect of reservoir temperature on Fimp. 452
423
The curves in Fig. 11 show that, for oils with a MW less than Mmin, 453
PCO2
 ð10ð Þ  1Þ
304:26 3

425
K¼ T ð7Þ Fimp exhibits various types of changes for different MWs in the 454
PN2
temperature range of 305–360 K. At a constant MW, the coefficient 455
426 where PCO2 and PN2 stand for the critical pressures of CO2 and N2, K (the slope of Fimp versus N2 mole fraction in a CO2 stream) in Eq. 456
427 respectively, and T is the reservoir temperature. A good agreement (5) changes with the reservoir temperature, as shown in Fig. 12. 457
428 of correlation results and the data in Table 3 is shown in Fig. 10. The curves in Fig. 12 show that, for each MW, K rises slowly 458
429 The root-mean-square error (RMSE) of Eq. (7) to the data in with temperature, at first. After exceeding the peak values, K 459
430 Table 3 is 0.15, indicating that Eq. (7) is accurate in calculating decreases with the increase in temperature. To have a complete 460
431 the value of K for substitution into Eq. (5) for calculating Fimp. chart for the coefficient K with MW < Mmin, 11 curves in the tem- 461
432 Therefore, combining Eqs. (5)–(7), the ratio of the impure CO2 perature range tested in this study were plotted in Fig. 13, along 462
433 MMP to the pure CO2 MMP for a depleted reservoir oil is given by: with the line that can analytically represent MW P Mmin at differ- 463
434     ent temperatures. As shown in the chart of Fig. 13, the curves of 464
P CO2 T cm
 10ð T Þ  1  1 
304:26 3
F imp ¼ þ 1 for MW > M min 125 g/mol, 130 g/mol and 135 g/mol merge into the curve of 465
PN2 304:26
120 g/mol, at 334 K, 341 K and 353 K, respectively. The K values 466
436 ð8Þ for those joint parts should be read in the curve for 120 g/mol. It 467

Fig. 11. Effect of reservoir temperature on Fimp for different N2 concentrations in the CO2 stream, (A) MW = 125 g/mol; (B) MW = 135 g/mol; (C) MW = 145 g/mol;
(D) MW = 155 g/mol.

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30 As is shown in Fig. 13, the error of K read from the chart is no 478
larger than 1. According to Eq. (5), the largest error for Fimp calcu- 479
25 lation happens when 10 mol% N2 was contained in CO2 and the 480
smallest K is happened. When we consider the simulation under 481
20 360 K for model oil sample with MW of 170 g/mol, the smallest 482
K is obtained, i.e., 7.8. Thus, the largest error of 4% for Fimp could 483
K 15 be reached, which is in the acceptable range of discrepancy. 484

10
MW=125g/mol 4. Comparison and discussion 485
MW=135g/mol
5 MW=145g/mol Correlations by Alston et al. and Sebastian et al. have been con- 486
MW=155g/mol sidered the best models for Fimp prediction [40]. A comparison 487
0
300 310 320 330 340 350 360 between the correlation developed in this paper and those two cor- 488
T (K) relations is presented in this section. Fig. 14 shows the Fimp pre- 489
dicted by the three models as a function of Tcm of the injection 490
Fig. 12. K values for different reservoir temperatures for four MWs. gas at different temperatures and oil molecular weights. In 491
Fig. 14A, Fimp was calculated as a function of Tcm using the three 492
correlations for oil with a MW of 180 and at temperatures of 493
305, 330, and 360 K. Although the curves from Alston et al.’s and 494
Sebastian et al.’s equation show a different trend, their results have 495
the same problem – that reservoir temperature has no effect on 496
Fimp at all – due to the fact that their correlations do not include 497
the temperature. Nevertheless, based on a literature analysis and 498
proof of the results presented by this paper, it is clear that reservoir 499
temperature has a significant influence on Fimp [13,23]. For the 500
same oil sample, the greater the reservoir temperature, the lower 501
the miscibility pressure ratio Fimp will be. 502
Fig. 14B shows the results of the three correlations for Fimp as a 503
function of Tcm, at a constant temperature of 330 K, for three differ- 504
ent molecular weights: 130, 180, and 350 g/mol. Similarly, because 505
neither Alston et al. nor Sebastian et al. included MW in their cor- 506
relations, the calculated Fimp for the three molecular weights is the 507
Fig. 13. The chart of parameter K in Eq. (5) (see Appendix 4 for original data of this
chart).
same. However, according to the results in the literature and the 508
calculations of this study, MW does affect the Fimp when MW is 509
smaller than Mmin [40,41]. As to these oils, the lighter the oil, the 510
468 should be pointed out that Eq. (7) can be used to predict Fimp for greater the ratio of miscibility pressure Fimp. 511
469 approximately 90% of cases considered in this study. A comparison between the experimental data from the litera- 512
470 As an example, the following steps show how to obtain the Fimp ture and the calculated results using the three correlations was 513
471 for an oil sample using the chart of Fig. 13: MW = 170 g/mol, performed. The results are shown in Table 4 and plotted in 514
472 T = 330 K, and N2 concentration = 6%: Fig. 15. Alston et al.’s correlation shows increasingly greater devi- 515
ation from the experimental results when N2 concentration 516
473 (1) Obtain the coefficient K from Fig. 13; K = 11.1. increases (Fig. 15A), while Sebastian et al.’s correlation always 517
474 (2) Calculate the pseudo-critical temperature of the injection underestimates Fimp (Fig. 15B). The results from the correlation 518
475 gas using Eq. (4); Tcm = 293.58 K. developed in this paper (Fig. 15C) showed a much better agree- 519
476 (3) Calculate the Fimp using Eq. (5); Fimp = 1.39 (the reported Fimp ment than the other two correlations. 520
477 in the referenced paper [38] was 1.392). As shown in Table 4, the correlation of this study has a much 521
lower RMSD (root mean square deviation, 0.25) and MAPE (mean 522

Fig. 14. Relationship between Fimp and Tcm for three correlations. (A) MW = 180 g/mol; (B) T = 330 K.

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J. Wang et al. / Fuel xxx (2015) xxx–xxx 9

Table 4
Comparison of three correlations for predicting MMP ratio Fimp.

mol (%) T (K) Tcm (K) MW (g/mol) Reference Experimental This paper Alston et al. Sebastian et al.
a a
Fimp Fimp APE (%) Fimp APE (%) Fimp APEa (%)
3 330 298.92 170 [35] 1.14 1.19 4.39 1.16 1.75 1.12 1.75
5 316 295.3 118 [17] 1.59 1.90 19.50 1.31 17.61 1.21 23.90
6 301 293.58 240 [35] 1.81 1.75 3.31 1.40 22.65 1.26 30.39
6 330 293.58 170 [35] 1.36 1.39 2.21 1.40 2.94 1.26 7.35
8 314 290.02 156 [16] 1.44 1.72 19.44 1.64 13.89 1.36 5.56
10 316 286.46 118 [17] 2.24 2.80 5.00 1.99 11.16 1.46 34.82
11 301 284.67 240 [35] 2.39 2.37 0.84 2.23 6.69 1.52 36.40
14 301 279.33 240 [35] 2.87 2.74 4.53 3.37 17.42 1.69 41.11
19 314 270.43 156 [36] 2.4 2.71 12.92 10.23 326.25 2.02 15.83
20 316 268.65 118 [17] 3.24 4.60 41.98 14.16 337.04 2.09 35.49
RMSDb 0.25 4.26 0.68
MAPEc (%) 13.40 75.74 23.26
a
APE: absolute percentage error.
b
RMSD: root mean square deviation.
c
MAPE: mean absolute percentage error.

(2) At a fixed temperature, there exists a minimum MW of oil, 542

A B
Results by Sebastian et al.

14 3 Mmin, at or above which Fimp can be calculated directly by 543

an analytical equation. This equation relates Fimp with the 544

13 2 critical properties of the components of the injection gas 545

and the reservoir temperature. The equation predicts Fimp 546
Correlation results by Alston et al.

and the subsequent N2 diluted CO2 MMP much better than 547
12 1
most of the existing popular correlations. 548
(3) For oil samples with a MW less than Mmin, Fimp changes with 549
11 0
0 1 2 3 the MW of the oil. Accordingly, a chart has been developed 550
Experimental data for supplying a coefficient used in the Fimp correlation. 551
10 552

3 3 C
Results by this paper

Acknowledgements 553
2 2
This study is financially supported by the National Basic 554
Research Program of China (No. 2014CB239103), ‘‘973 Program” 555
1 1
(No. 2014CB239103), the Natural Science Foundation of China 556
(No. 51204197), and the Natural Sciences and Engineering 557
0 0 Research Council of Canada (NSERC). 558
0 1 2 3 0 1 2 3
Experimental data Experimental data
Appendix A. Supplementary material 559
Fig. 15. Experimental data and modeling results from three correlations.

Supplementary data associated with this article can be found, in 560

the online version, at http://dx.doi.org/10.1016/j.fuel.2015.08.075. 561
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voirs. Fuel (2015), http://dx.doi.org/10.1016/j.fuel.2015.08.075
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