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1 Evaluation of Asphaltene Stability of a Wide Range of Mexican

2 Crude Oils

3 Roque Guzmań , Silvano Rodríguez, Pablo Torres-Mancera, and Jorge Ancheyta*

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4 ABSTRACT: Appropriate prediction of asphaltene stability can anticipate operational problems such as plugging of lines and
5 process equipment (pumps, heat exchangers, separation tanks, among others), thus assuring the production, processing,
6 transportation, and storage of petroleum. In the present study, the physical and chemical properties of a series of Mexican crude oils
7 with American Petroleum Institute (API) gravity ranging from 10 to 52 were determined. Based on saturate, aromatic, resin and
8 asphaltene (SARA) analysis, the following indexes were calculated: colloidal instability index, colloidal stability index, Stankiewicz
9 stability criterion, stability cross plot, and oil compatibility model. The stability of crude oils was also evaluated by means of
10 experimental techniques such as spot test, S-value, and static stability test column. No uniform results were obtained when
11 determining the stability of crude oils with different methodologies. Due to the discrepancies disclosed, it is recommended to
12 evaluate stability by various methodologies to adequately predict the stability of asphaltenes in crude oils. Hence, the stability of
13 asphaltenes in a given crude oil may be ascribed based on the average result. However, from a practical point of view, pertinent
14 cautions on the handling of samples must be observed if at least one of the methods classifies the sample as unstable or metastable.

1. INTRODUCTION aromaticity and polycondensation of aromatics, as well as the 46

15 Asphaltenes are the heaviest and most polar fractions of crude solubility of asphaltenes in resins.12−16 47

16 oils. They are compounds insoluble in linear low-molecular- Complications related to the stability of asphaltenes may 48

17 weight alkanes, such as n-pentane (n-C5), n-hexane (n-C6), or appear throughout the production chain. In the upstream 49
18 n-heptane (n-C7) but soluble in aromatic solvents such as sector, it starts at the well where oil recovery can be reduced 50
19 toluene, benzene, xylene, or pyridine.1−3 Some crude oils due to changes in reservoir wettability, clogging of rock pores 51
20 contain high concentrations of asphaltenes depending on their by deposition of asphaltenes, and the formation and 52
21 nature and origin, which may exhibit stability problems under strengthening of oil−water emulsions. In midstream oper- 53
22 certain conditions of pressure, temperature, or flow regime that ations, during storage, blending, and transportation of crude 54
23 in turn cause difficulties during transportation and storage.4−7 oils that may result in damage of pipelines and pumping 55
24 Typically, asphaltene content increases as the crude oil equipment. Finally, in downstream where crude oil is refined, 56
25 becomes heavier, i.e., the lower the American Petroleum since instability of asphaltenes may lead to coking, fouling, and 57
26 Institute (API) gravity, the higher the asphaltenes content. deactivation of the catalysts used in the different refining 58
27 Paradoxically, the precipitation of asphaltenes is often observed processes.8,16 59
28 in light crude oils that have a low content of them, which is due Despite the fact that crude oils own a complex composition, 60
29 to the presence of high amounts of linear alkanes of low compounds in crude oils can be grouped into four main 61
30 molecular weight in which asphaltenes show limited solubility. fractions designated as SARA: saturated, aromatic, resin, and 62
31 In contrast, heavy crude oils contain large amounts of asphaltenes. Regarding their capacity to keep asphaltene in a 63
32 intermediate-molecular-weight components that keep asphal- solubilized state, saturated compounds are considered non- 64
33 tenes in a peptized state,8,9 yielding less stability issues in heavy solvent, while resins and aromatics are solvents. According to 65
34 crude oils despite being generally rich in asphaltenes. the micellar theory, in stable crude oils, asphaltenes are 66
35 Asphaltenes show a natural tendency toward aggregation, associated with resins within a stable equilibrium of solubility. 67
36 which potentially may produce its separation from crude oil The imbalance of the colloidal structure favors the separation 68
37 and their buildup as a solid phase. The phenomenon consists of the phases, causing instability in the medium that in many 69
38 of flocculation/precipitation followed by sedimentation; for
39 this reason, asphaltenes are considered the main precursors of
40 sediment formation.10,11 Asphaltene stability of crude oils also Received: September 30, 2020
41 represents complications during refining. An important Revised: December 3, 2020
42 concern when processing heavy crude oils by catalytic
43 hydrotreating/hydrocracking is sediment formation. It has
44 been reported that during hydrotreating, the most important
45 factors responsible for the generation of sediments are

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.energyfuels.0c03301

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Table 1. Properties of Crude Oils

property C52 C37 C34 C32 C29 C24 C16 C10
API gravity 51.62 37.19 33.65 32.88 29.41 24.69 16.05 9.60
kinematic viscosity, cSt @ 25.0 °C 1.47 5.06 16.28 12.651 24.17 116.52 3293 104 027
sulfur, wt % 0.140 0.931 1.099 2.299 2.252 2.469 4.666 4.540
characterization factor, KUOP 12.23 12.02 12.11 11.96 11.94 11.93 11.63 11.40
acidity, mg KOH/g 0.09 0.47 0.39 0.20 0.27 0.16 0.25 3.61
n-C7 insoluble, wt % 0.95 0.95 1.94 2.96 3.05 3.21 4.05 6.51
nickel, ppm 0.30 3.54 17.03 16.99 24.60 46.62 85.43 89.61
vanadium, ppm 0.25 16.75 23.60 66.02 85.78 131.65 369.11 442.63

Figure 1. Fractionation of the crude oil into its different components.9,10

70 cases leads to the precipitation of asphaltenes.12,17 Accordingly, the proportion of heavy and extra heavy crude oils. For these 99
71 stability is defined as the property of an oil to keep its reasons, the characterization of different types of crude oils and 100
72 asphaltenes in a peptized state, thus avoiding their precip- their influence on the stability of asphaltenes become an 101
73 itation and flocculation.18 important issue. Furthermore, since the blending of crude oils 102
74 Various parameters must be taken into account during the is a common practice to adjust crude oil specifications for sale 103
75 processing, transportation, and storage of petroleum. The or transportation purposes, the compatibility of crude oils also 104
76 following are the most important ones: becomes a pivotal task. 105
77 • Viscosity indicates the relative mobility of crude oils. In the present research, the stability of different crude oils 106
78 • Insoluble in n-C7 reflects the presence of heavy and polar with API gravity ranging from 10 to 52 is determined by both 107
79 hydrocarbons. theoretical and experimental methodologies. Theoretical tools 108
80 • Conradson carbon content correlates with the tendency are based on computing several indexes based on SARA 109
81 to coke formation. analysis, while experimental methods encompass spot test, 110
82 • Acidity is an indication of the corrosive properties of static column, and optical detection of the asphaltene 111
83 crude oils. precipitation onset. Additionally, the model of the compati- 112
84 • Water, salt, and sediment content cause uneven bility of oils is applied to selected blends. The aim of the 113
85 distillation behavior, causing blockage and fouling of present work is to compare various methodologies in the 114
86 heat exchangers and lead to corrosion. evaluation of crude oil stability toward the precipitation of 115
87 • Paraffin content, type of paraffin, crystallization point, asphaltenes. Based on a proper prediction of asphaltene 116
88 gel point, and pour point are important factors for the stability, operational problems such as plugging of lines and 117
89 deposition of waxes during treatment and storage. process equipment can be anticipated, thus contributing to 118

90 Temperature is also important, since it affects some production assurance, processing, transportation, and storage 119

91 properties, especially those related to mobility (density and of petroleum. 120

92 viscosity). In accordance, the most convenient crude oils to

93 refine are those with adequate mobility properties and the 2. EXPERIMENTAL SECTION
94 lowest content of impurities, which are characteristics of light Crude oils employed in the experimental study were recovered from 121
95 and super light crude oils. However, the trend in crude oil different production regions in Mexico and they encompass heavy, 122
96 production, not only in Mexico but also in other countries light, and super light crude oils. They were labeled as C52, C37, C34, 123
97 (Venezuela, Canada, Russia, etc.), corresponds to the shrinking C32, C29, C24, C16, and C10, where the numbers indicate the 124
98 of these types of crude oils with the subsequent increment in approximate API gravity of the crude oil. 125

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126 2.1. Characterization of Crude Oils. The physical and chemical 2.3. Evaluation of the Stability of Selected Crude Oils by 181
127 properties of crude oils were determined by several standardized Indexes and Methods Based on SARA Analysis. 2.3.1. Colloidal 182
128 methods: API gravity by means of an ASTM D1298 method, Instability Index (CII). Asphaltenes and saturates are considered as 183
129 kinematic viscosity at 25 °C by an ASTM D445 method, sulfur compounds that promote asphaltene flocculation, while aromatics and 184
130 content by ASTM D4294, salt content by ASTM D3230, asphaltene resins work as peptizing agents, thus favoring the stability of 185
131 content measured as n-heptane insoluble by ASTM D3279, nickel and asphaltenes. Accordingly, the colloidal instability index (CII) is 186
132 vanadium content by ASTM D5863, characterization factor KUOP by a defined as the quotient between the sum of asphaltenes and saturates 187
133 UOP 375 method, and total acid number by ASTM D-664. The and the sum of aromatics and resins.20−22 188
t1 134 results are presented in Table 1. (% asphaltenes) + (% saturates)
135 The spot test by ASTM D4740 was also used for qualitative CII =
136 determination of the stability of crude oils. A static column was (% resins) + (% aromatics) (1) 189
137 implemented to have a quantitative value of the stability of crude oils. The lower the CII value, the greater the stability of asphaltenes in the 190
138 The column was composed of two concentric tubes, in which the medium; therefore, the stability determined is relative and allows for 191
139 internal tube (110 cm length, 3.8 cm internal diameter) contained the evaluating whether one oil is more or less stable in relation to another. 192
140 oil sample, and the external tube contained the heating liquid Asomaning and Watkinson21 evaluated the stability of oils from the 193
141 (ethylene glycol) to keep to oil sample at the required temperature, SARA analysis determined by liquid chromatography and demon- 194
142 35 °C in this case. A total of 1.25 L can be loaded to the column. The strated experimentally that when CII ≥ 0.9, asphaltenes are unstable 195
143 column had three sampling points located at the bottom, middle (1/3 in the medium, when 0.7 ≤ CII ≤ 0.9, there is uncertainty about 196
144 length), and top (2/3 length). With the static column, crude oil stability, and if CII <0.7, asphaltenes are stable in oil. 197
145 properties during storage were analyzed at two moments of time; just 2.3.2. Colloidal Stability Index (CSI). This index considers that the 198
146 after being introduced in the column and after a certain time of asphaltenes of unstable crude oils are more polar than those of stable 199
147 storage (7 days). The basic idea of the static column is to detect to crude oils and takes into account both the SARA analysis and the 200
148 what extent the value of a chosen property is preserved during sample polarity of the components of crude oils based on the following 201
149 storage. In accordance, a crude oil whose chosen property is unaltered equation23 202
150 during the storage period is considered highly stable. On the contrary,
151 if the value of a given property changes considerably after a period of (ε asph)(% asphaltenes) + (ε sat)(% saturates)
CSI =
152 storage, the crude oil is unstable, since the change of such a property (ε res)(% resins) + (ε arom)(% aromatics) (2) 203
153 is likely the result of asphaltene segregation.
154 2.2. SARA Fractionation of Crude Oils. Separation of where the values of the dielectric constant (ε) of the SARA fractions 204
155 petroleum and residue components is based largely on their solubility are 205
f1 156 properties in different solvents. For instance, Figure 1 shows the εasf = 18.4 and εres = 3.8 for unstable crude oils; εasp = 5.5 and εres = 206
157 fractionation of oil using first n-heptane, which generates two 4.7 for stable crude oils; and εsat = 1.921 and εarom = 2.379 for all of 207
158 fractions, the insoluble one corresponding to asphaltenes and the the crude oils.23 208
159 soluble one corresponding to maltenes.19 Subsequently, by toluene If CSI > 0.95, the crude oil is unstable (asphaltene precipitation will 209
160 addition to asphaltenes, two more fractions are obtained, one that occur). 210

161 corresponds properly to asphaltenes (soluble fraction) and the second If CSI < 0.95, the crude oil is stable and the risk of asphaltene 211

162 one that represents carbenes and carboids (insoluble fraction). The precipitation is minimal.21 212

163 insoluble fraction is finally separated using carbon disulfide to obtain 2.3.3. Stability Index (SI). The asphaltenes/resins (A/R) ratio is 213

164 carbenes (soluble) and carboids (insoluble). Both carbenes and popular and widely used because asphaltenes and resins form the 214

carboids are considered coke precursors due to their large number of nonvolatile part of petroleum and are therefore accurately measured. 215
165
This relationship makes sense, since resins are the natural peptizers of 216
166 condensed structures. Finally, the fraction soluble in n-heptane
petroleum and keep asphaltenes in solution. Asomaning and 217
167 (maltenes) is further separated by passing through a chromatographic
Watkinson21 reported that if the A/R ratio is lower than 0.35, the 218
168 column packed with alumina; several fractions are obtained using
crude oil will be stable. 219
169 different solvents as eluents. Thus, saturates are obtained by adding n-
170 heptane, aromatics are separated by adding toluene, and resins by (% asphaltenes)
171 adding pyridine. SI =
(% resins) (3) 220
172 In the present study, SARA fractionation was carried out by means
173 of preseparation of asphaltenes from the crude oil by adding an excess 2.3.4. Stankiewicz Stability Criterion. In the Stankiewicz stability 221
174 of n-pentane or n-heptane, using a 40:1 solvent-to-crude oil criterion (SSC), the A/R ratio is plotted against S/Ar. This type of 222
175 volumetric ratio, according to ASTM D-4124. The saturated, representation gives a quick identification of the risks of separation of 223
176 aromatic, and resin fractions were then extracted from the deasphalted asphaltenes by locating the stable and unstable zones.24,25 224
177 oil using the clay−gel absorption chromatographic method (ASTM 2.3.5. Sepúlveda Stability Criterion (Stability Cross Plot). 225
178 D-2007). This fractionation procedure is represented by the shaded According to Sepúlveda et al.,24 the stability cross plot (SCP) 226
179 rectangles in Figure 1. The results obtained from the SARA analysis of method uses four relationships 227
t2 180 the different crude oils are presented in Table 2.
SCP1: [(R/A)/(S/Ar)] versus [Ar/A] (4) 228

Table 2. SARA Analysis of Crude Oils SCP2: [(R/A)/(S/Ar)] versus [R/A] (5) 229

crude saturates aromatics resins asphaltenes inorganics, SCP3: [S/Ar] versus [R/A] (6) 230
oil (S), wt % (Ar), wt % (R), wt % (A), wt % wt %
SCP4: [(R/A)/(S/Ar)] versus [Ar/(S/A)] (7) 231
C52 59.65 3.35 36.95 0.03 0.02
C37 31.85 54.08 13.14 0.91 0.02 In this method, the quotients indicated in eqs 4 and5 are included in 232
C34 50.89 21.95 24.24 2.90 0.02 the four SCP, where a reference curve represents the metastable zone, 233
C32 19.23 42.02 36.35 2.40 0.01 and it also works as the limit between stability and instability zones. 234
C29 26.14 41.23 28.71 3.91 0.01 The method involves the comparison of four parameters, and it is 235
possible that not all of them indicate the same condition of stable, 236
C24 27.80 36.75 27.82 7.20 0.43
metastable, or unstable. In such a case, the sample should be classified 237
C16 10.48 9.00 64.08 16.17 0.27
according to the more repeated condition. For instance, in the case of 238
C10 9.39 31.97 35.20 23.40 0.04 a sample with the following results: SCP1 = metastable, SCP2 = 239

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240 unstable, SCP3 = stable, and SCP4 = metastable, the final

241 classification of the sample corresponds to metastable.
242 2.4. Evaluation of the Stability of Crude Oils with
243 Experimental Techniques. Some standardized analytical techni-
244 ques to detect the onset of asphaltene precipitation by means of
245 optical devices are commercially available. Three recognized methods
246 are next listed: a Turbiscan based on the ASTM D7061 method
247 renders a separability number of asphaltenes; a Porla crude oil
248 stability and compatibility analyzer based on the ASTM D 7112
249 method yields solvent equivalence, P-value, and FR5/1; and an ROFA
250 France automated stability analyzer based on the ASTM D7157
251 method whose results are indicated as the intrinsic stability of the oil
252 (S-value), the peptizing power of the oil (So), and the peptizability of
253 asphaltenes (Sa). In the present research, the ROFA France method
254 was employed.26
255 Additional nonoptical-based methodologies can also be used to
256 estimate the stability of crude oils. In this research, two methods were
257 executed: the static column test, based on the degree of modification
258 of a particular crude oil property after a certain time on storage, and
259 the spot test based on the ASTM D4770 method,27 which
260 encompasses visual inspection of the pattern of a drop on the surface
261 of a filter paper.
262 2.4.1. Determination of Intrinsic Stability (S-Value, ROFA).
263 Intrinsic stability was measured by the ASTM D7157 method,
264 which is based on measuring the asphaltene flocculation point in
265 crude oil samples. The method encompasses previous peptization of
266 asphaltenes by adding an aromatic solvent (toluene), and then a
267 constant flow of a paraffinic solvent (n-heptane) is successively added
268 until the asphaltene flocculation point is detected by an optical sensor
269 in an automated integrated analytical measurement system.
270 For the analysis of the stability of a sample, three different dilutions
271 in toluene are prepared. All three dilutions are automatically titrated
272 with n-heptane to detect asphaltene precipitation. The optical sensor
273 monitors the formation of flocculated asphaltenes during the titration.
274 In the first stage, the optical signal is gradually increased due to the
275 clearest sample by consistent addition of n-heptane. In the second
276 stage, aggregation of asphaltenes produces a large and sustained Figure 2. Equipment for the static column test.
277 decrease in light intensity. Hence, the maximum in the signal is
278 ascribed as the flocculation point of asphaltenes.
279 Based on the amount of n-heptane added at the flocculation point,
280 the sample mass, and the volume of toluene used in the three highly stable. On the contrary, if the value of a given property changes 303
281 dilutions, the computation routine calculates the intrinsic stability of considerably after a period of storage, the crude oil is unstable, since 304
282 the oil (S-value), the peptizing power of the oil (So), and the the change of such property is likely the result of asphaltene 305
283 peptizability of asphaltenes (Sa). The calculation of these parameters segregation. 306
284 includes plotting the oil-to-solution ratio (1/X) and the flocculation By the static column test, stability can be evaluated based on 307
285 ratio (FR) and fit the three dilutions data into a straight line to obtain several properties, such as the content of sulfur, metals, and 308
286 the reciprocal critical n-heptane dilution and the maximum asphaltenes; density; or viscosity. In the present study, stability is 309
287 flocculation ratio according to the following equations related to the content of asphaltenes. For such evaluation, an aliquot 310
of the crude oil is transferred and stored in the static column. The 311
1 mass of oil content of asphaltenes is analyzed and then the sample is left to rest 312
=
288 X volume of toluene + volume of n − heptane (8) for 7 days at a temperature of 35 °C and atmospheric pressure 313
(typical operating conditions of storage tanks). Afterward, the crude 314
volume of toluene oil samples taken from the upper, middle, and lower parts of the 315
FR = column are recovered and characterized. The crude oil samples were 316
289 volume of toluene + volume of n − heptane (9)
subjected to the stability test in the static column, and the results 317
S = 1 + X min (10) obtained are presented in Table 9. 318
290
stability =
291 Sa = 1 − FR max (11)
asphaltene content t = 0 − asphaltene content after the storage period
1.0 − [ ]
292 S0 = S × FR max (12) asphaltene content t = 0
293 2.4.2. Stability Evaluation of Crude Oils in a Static Column. A (13) 319
294 simple way to measure the stability in crude oil samples or mixtures is The storage stability of a product is revealed when its properties after 320
295 the so-called “static column stability” test. This method is based on the storage period in the static column are equal to its original 321
296 the analysis of a selected crude oil property in a sample stored in a properties (zero resting time). Hence, the ideal stability value = 1.0, 322
f2 297 stainless steel vessel, as depicted in Figure 2. The sample is analyzed at since it corresponds to the case when the same value of the property 323
298 two moments in time: just after being introduced in the vessel and measured at the beginning and at the end of the storage is observed. 324
299 after a certain time of storage as defined by the researcher. The basic Depending on the property chosen to assess the stability after storage, 325
300 idea is to detect to what extent the value of a chosen property is the value of the property may result in a higher or lower value with 326
301 preserved during sample storage. In accordance, the crude oil whose respect to the value at zero resting time. For this reason, the stability 327
302 chosen property is unaltered during the storage period is considered of the samples by the static column test may take values lower or 328

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329 higher than 1.0, and the criterion employed is that when the stability solution. Based on SI, all the samples are ascribed as stable and 378
330 value is closer to 1.0, the stability degree is higher. only the C10 sample is characterized as unstable. 379
331 By considering the possible stratification of heavy components in The CII can also be represented graphically by plotting the 380
332 the crude oil sample, the design of the static column shown in Figure sum of saturates and asphaltenes (S + A) as a function of the 381
333 2 includes valves for sampling at three different heights in the column:
334 at the top, in the middle, and at the bottom of the column.
sum of resins and aromatics (R + Ar), as shown in Figure 3. In 382 f3

335 2.4.3. Spot Test. This method is used to quickly identify possible
336 risks of operation during the transportation and storage of oils (sludge
337 settlement in storage tanks, plugging in process lines, etc.), caused by
338 the incompatibility between the different streams, which by presenting
339 notable differences between their chemical nature lead to the
340 separation and precipitation of heavy species (asphaltenes).
341 The test consists basically of placing a drop or drops of the sample
342 under evaluation on a filter paper, drying it to defined conditions, and
343 at the end, visually observing the stain left by the drop and classifying
344 it according to reference numbers.
345 By direct observation of the stain pattern left by each oil on the
346 filter paper, crude oils can be qualitatively classified within five groups
347 of samples as a function of the asphaltene flocculation degree. From 1
348 to 5, the asphaltene state may be ascribed as high peptized asphaltenes
349 (level 1) to precipitated asphaltenes (level 5). According to the
350 method, if a sample leaves spots that are classified as 3 or more, the
351 said sample presents instability, and evidently, it grows as approaching Figure 3. Graphical representation of CII with data from the SARA
352 the maximum value of 5. analysis of crude oils.

3. RESULTS AND DISCUSSION

353 3.1. Stability of Crude Oils by Methods Based on such a representation, CII falls into the reference dotted line 383

354 SARA Analysis. From the results shown in Table 2, it can be and three zones are readily identified: (1) a zone of instability 384

355 seen that the highest asphaltene content corresponds to C10 at the left-hand side of the curve, delimited by (S + A) ≥ 47.4 385

356 and C16. The asphaltene fraction is the only one that shows a wt % corresponding to (R + Ar) ≤ 52.6 wt % (CII ≥ 0.9), (2) 386

357 correspondence with respect to API gravity of crude oils, the a zone of metastability at the middle, where 47.4 wt % > (S + 387

358 heavier the crude oil (lower API), the higher its asphaltene A) > 41.1 wt % and 52.6 wt % < (A + R) < 58.9 wt % (0.9 > 388

359 content. In the case of saturated compounds, it is normal to CII >0.7), and (3) a zone of stability at the right-hand side of 389

360 find them more concentrated in light crude oils. Regarding the the curve, delimited by (S + A) ≤ 41.1 wt % corresponding to 390

361 content of resins and aromatics, a clear trend with API gravity (R + Ar) ≥ 58.9 wt % (CII ≤ 0.7). Figure 3 allows for a better 391

362 is not observed, maybe because of the different oil fields from visualization of the nature of the studied crude oils. It is 392

363 which the crude oils were recovered. observed that most of the samples are located within the 393

364 Based only on crude oil characterization by SARA analysis, stability zone, which includes C24, C10, C37, C29, C16, and 394

365 the behavior in terms of the stability or instability of their C32. Samples C52 and C34 are located in the zone of unstable 395

366 asphaltenes cannot be established. For this reason, the SARA- crude oils. 396

367 based stability/instability parameters were calculated. CII also allows to ascertain the degree of stability, since, for 397

t3 368 Table 3 presents the values obtained for stability index (SI), the stable samples, they exhibit the following stability order: 398

369 colloidal instability index (CII), and colloidal stability index C32 > C16 > C29 > C37 = C10 > C24. Such an affirmation is 399
based on the statement that the higher the CII value, the worse 400

Table 3. Results of SI, CII, and CSI the colloidal stability. The Stankiewicz criterion (SSC), where 401
the A/R ratio is plotted against S/Ar, is shown in Figure 4. It is 402 f4
crude observed that C52, C32, C37, and C39 are stable, with C32 403
oil SI designation CII designation CSI designation
being the most stable crude oil, as it corresponds to the 404
C52 0.001 stable 1.48 unstable 0.78 stable furthest point from the curve limiting the stable zone curve. 405
C37 0.069 stable 0.49 stable 0.35 stable Accordingly, C16 and C34 are unstable, with C34 being the 406
C34 0.120 stable 1.16 unstable 1.05 unstable
C32 0.066 stable 0.28 stable 0.19 stable
C29 0.136 stable 0.43 stable 0.31 stable
C24 0.259 stable 0.54 stable 0.43 stable
C16 0.252 stable 0.36 stable 0.34 stable
C10 0.665 unstable 0.49 stable 0.61 stable

370 (CSI), which were calculated with the SARA analysis of the
371 crude oils. The stability index accounts for the asphaltene/
372 resins (A/R) ratio, and it has been stated that crude oils with
373 SI values lower than 0.35 can be considered as stable.23 The SI
374 index is simple and is broadly used because both asphaltenes
375 and resins are heavy, nonvolatile, and can be precisely
376 quantified. It is based on the consideration that resins act as
377 natural peptizers of asphaltenes, maintaining them in the oil Figure 4. Criteria of stability of Stankiewicz for crude oils.

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Figure 5. Stability cross plot for different relationships based on SARA analysis.24

Table 4. Behavior of Crude Oils in SCP charts

crude oil SCP1 SCP2 SCP3 SCP4 average
C52 stable stable stable stable stable
C37 stable stable stable stable stable
C34 stable stable stable stable stable
C32 stable stable stable stable stable
C29 stable stable stable stable stable
C24 stable stable stable stable stable
C16 unstable metastable metastable metastable metastable
C10 metastable unstable stable metastable metastable

Table 5. Comparison of Stability Results Based on SARA Fractions

crude oil CII CSI SI SSC SCP average
C52 unstable stable stable stable stable stable
C37 stable stable stable stable stable stable
C34 unstable unstable stable unstable stable unstable
C32 stable stable stable stable stable stable
C29 stable stable stable stable stable stable
C24 stable stable stable metastable stable stable
C16 stable stable stable unstable metastable metastable
C10 stable stable unstable metastable metastable metastable

407 most unstable crude oil, while C10 and C24 crude oils have a that on average, the most stable crude oils are C37 and C32 419
408 metastable character. (which are the lightest crude oils), since the five compared 420
f5 409 Figure 5 shows the graphical representation of these four methods agreed on the stable characteristic. The crude oils 421
410 relationships. It is necessary to examine the behavior of each with less stability are C16 and C10, since the average of the 422
411 sample in the four graphs to obtain a single result that four compared methods characterizes them as metastable. 423
412 characterizes the state of the asphaltenes contained in the In general, the results do not show a correlation between the 424
413 sample. It was observed that most of the crude oils are stable, type of crude oil according to its API gravity and its 425
414 and only C16 and C10 oils are metastable. The behavior of classification as stable or unstable. In spite of the high content 426
t4 415 each of the samples in the four graphs is presented in Table 4. of asphaltenes, heavy crude oils were found as stable given 427
416 The results obtained with the different methods were their high content of resins that preserves the colloidal system 428
417 compared to verify the effectiveness of the different criteria, steady. On the other hand, instability was observed in the case 429
t5 418 which are summarized in Table 5. In general, it can be seen of some light crude oils. In general, as the crude oils become 430

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431 lighter, the relative amount of saturates grows and the content samples can be qualitatively classified within five groups as a 474
432 of asphaltenes diminishes. Light crude oils with a minimal function of the asphaltene flocculation degree, with level 1 475
433 amount of asphaltenes may be classified as unstable by some being the case when the asphaltene state may be ascribed as 476
434 indexes, but the precipitation of asphaltenes is not quantifiable. high peptized asphaltenes, while level 5 corresponds to 477
435 This is the case of the C52 sample. However, light crude oils precipitated asphaltenes. The characteristics of the spot pattern 478
436 with a significant amount of asphaltenes, as in the C34 sample, according to the scale referred in the method are included in 479
437 usually are prone to deactivation as a result of the high amount Table 6. By such an approach, it was determined that C52, 480 t6
438 of saturates.
439 Some variations in the prediction of crude oil stability Table 6. Spot Test Scale
440 measured by the different indexes based on SARA analysis
spot
441 were observed. In this sense, it is important to highlight that reference spot characteristics
442 SARA analysis groups hydrocarbons according to their 1 homogeneous stain (no presence of inner ring)
443 solubility/insolubility behavior (Figure 1). In a broad sense, 2 very thinly defined inner ring
444 the stability condition of crude oils depends on the equilibrium 3 well-defined inner ring, faint and only slightly darker than the
445 among the SARA fractions where the polar asphaltenes are background or rest of the stain
446 stabilized by resins within the less polar aromatic and saturate 4 well-defined inner ring, slightly denser than reference spot 3 and
447 components in the crude oils; in such a case, molecular somewhat darker than the background or rest of the spot
448 interactions reach a balanced colloidal system. Unbalance of 5 solid or almost solid area, very dark in the center; the central area
is much darker than the background or rest of the stain
449 such a system may result in aggregation of asphaltenes and
450 eventually in solid precipitation. Accordingly, disturbance of C32, C29, C24, C16, and C10 crude oils are stable. C37 481
451 the crude oil colloidal system is usually produced by changes in presents a stain corresponding to level 2 (very dimly defined 482
452 composition, temperature, or pressure. inner ring), but it is also stable. C34 crude oil has a stain 483
453 The assessment of stability using SARA-based method- pattern of level 3 that corresponds to the crude oil with 484
454 ologies is based on the solubility behavior of the components flocculated asphaltenes and therefore is unstable. 485
455 of the crude oil. However, chemical and structural parameters The values of S, Sa, and So obtained with an ROFA 486
456 of the molecules and molecular interactions are not considered equipment for all crude oils are presented in Table 7. The 487 t7
457 within SARA-based indexes, and it may explain the lack of
458 uniformity by several indexes for predicting stability in some Table 7. Intrinsic Stability Parameters
459 crude oil samples. In this sense, it is important to consider the
460 properties of asphaltenes such as the type of molecular crude S Sa So condition
461 structure, elemental composition, aromaticity, and self- C52 2.62 0.02 2.56 stable
462 aggregation phenomena in the stability character of crude C37 2.70 0.84 0.44 stable
463 oils.30 For instance, the unstable character of crude oil samples C34 3.61 0.75 0.89 stable
464 was related to low hydrogen-to-carbon ratios and high C32 3.90 0.79 0.81 stable
465 aromaticity of asphaltenes.31,32 Accordingly, further research C29 2.70 0.72 0.76 stable
466 efforts are necessary to include the properties of asphaltenes C24 3.65 0.76 0.88 stable
467 within indexes or methodologies to count on reliable and C16 2.89 0.65 1.00 stable
468 universal tools to predict the stability of crude oils. C10 3.22 0.69 1.00 stable
469 3.2. Stability of Crude Oils Obtained with Exper-
470 imental Techniques. The results obtained by means of the
471 standard test method for cleanliness and compatibility of minimum value of S is 1, which indicates that the sample is 488

f6 472 residual fuels are shown in Figure 6. By direct observation of unstable and its asphaltenes are already precipitated without 489

473 the stain pattern left by each crude oil on the filter paper, the the addition of paraffin. As the value of S increases, the crude 490
oil achieves a greater degree of stability. Hence, the method 491
allows for comparing the relative stability among crude oil 492
samples. However, the definite character of being stable or 493
unstable of a sample cannot be assigned. In this sense, the 494
order of stability of the samples measured by this technique is 495
C52 > C37 = C29 > C16 > C10 > C34 > C24 > C32. In all 496
cases, the S-value was higher than 2.5. In an arbitrary way, by 497
considering samples with S > 2.5 as stable, all crude oils of the 498
present study may be classified as stable according to this 499
technique. 500
The results shown in Table 8 include stability data for the 501 t8
top, middle, and bottom of the static column. By considering 502
the asphaltene content, the results fall within a 5 wt % of error. 503
C37, C32, C29, C24, C16, and C10 samples clearly show 504
values of stability close to 1 along the column, thus implying 505
stability and that a stratification process did not occur. The 506
results of C34 crude oil exhibit a clear trend in the asphaltene 507
content and consequently in the stability values along the 508
column height. Hence, C34 crude oil results as an unstable 509
Figure 6. Spot test for crude oils. sample during storage. 510

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Table 8. Results Obtained in the Static Column Test 3.3. Oil Compatibility Model. The oil compatibility 547
model was applied to the hypothetic blends of C52 with all of 548
stability at the stability at the stability at the
crude top of the middle of the bottom of the the crude oil samples studied. Based on Sa and So parameters 549
oil column column column condition obtained from the ROFA equipment, the insolubility number 550
C52 1.000 0.667 1.333 stable (IN) and the solubility blending number (SBN) can be 551
C37 1.011 1.011 1.033 stable calculated to employ the oil compatibility model by the 552
C34 0.901 0.956 1.148 unstable following equations28,29 553
C32 1.004 1.008 1.008 stable IN = (100)So (14) 554
C29 1.003 1.003 1.008 stable
C24 0.986 0.992 0.969 stable SBN = 100(1 − Sa) (15) 555
C16 1.002 1.011 1.017 stable
C10 0.993 0.996 0.996 stable The SBN/INmax ratio is a criterion for compatibility between two 556
crude oils. A high value of this ratio indicates greater stability. 557
When this ratio is less than 1, the corresponding blend is 558
incompatible. A value slightly greater than 1 represents 559
511 C52 crude oil is a special case, since it has the lowest content uncertain compatibility and a value greater than 1 indicates a 560
512 of asphaltenes (0.03 wt %), and the values of the asphaltene compatible blend. The values of IN, SBN, and SBN/IN are 561
513 content at different positions range from 0.02 to 0.04 wt %. reported in Table 9. 562 t9
514 Such values fall within the experimental error, so the stability The maximum IN value (INmax = 98) corresponds to the C52 563
515 calculated by eq 13 (1.0−1.333) must be taken into account sample. SBN/INmax values slightly higher than 1 were obtained 564
516 for this type of low-asphaltene crude oils. It should be noted for the case of blending C52 with C16 and C10, which 565
517 that small values of the asphaltene content might yield to suggests uncertain compatibility. In the case of C52 with C37, 566
518 classified samples as unstable due to errors in the experimental C34, C32, C29, and C24, values lower than 1 were obtained, 567
519 determination and not necessarily to asphaltene aggregation. which indicates a higher probability of incompatibility. Since 568
520 Hence, it is important to consider the accuracy of the property the insolubility value of C52 is higher than the SBN determined 569
521 employed to estimate stability by the static column method. In from the other crude oils, it denotes the existence of 570
522 accordance, C52 is qualified as stable crude oil. incompatible mixtures. This agrees with the results of the 571
523 Methodologies for the experimental assessment of stability spot test shown in Figure 7, in which it is clearly observed that 572 f7
524 employed in the present research include several approaches. C52 crude oil in different proportions with other crude oils is 573
525 The static column test is focused on analysis in static mode capable of causing the instability of the asphaltenes. 574
526 (storage). Nonetheless, storage implies perturbation-free Prediction of the compatibility of crude oils is still a pending 575
527 conditions resulted in the stable character of most of the issue, since a common practice in crude oil processing includes 576
528 samples. The spot test is a simple and fast test, including blending of two or more streams, sometimes of considerably 577
529 evaporation of light components of an oil drop over a filter different characteristics. There are additional methods to the 578
530 paper, which implies changes in the composition of the leftover oil compatibility model in the scientific literature.40−46 579
531 sample during the process, and the interpretation of the result Validation of such methods and/or generation of new ones 580
532 depends on the visual acuity of the observer. The S-value with application to domestic crude oils are desirable. 581
533 method encompasses modification of the sample by addition of
534 an aromatic solvent to assure peptization of asphaltenes and 4. CONCLUSIONS
535 then titration of such a modified sample with a paraffinic
536 solvent to provoke asphaltene flocculation. The process is According to the use of different methods to determine the 582

537 optically monitored, and the results imply extrapolation of the stability of a wide variety of crude oils, the following can be 583

538 quantities measured to those of the sample nonmodified by concluded: 584

539 aromatic solvent addition. The S-value stability results are • Based on SARA analysis, C32 crude oil shows the 585
540 useful to compare the relative stability among different greatest stability due to its relatively low content of 586
541 samples. The obtained parameters are not readily translated asphaltenes, high content of resins, which are the 587
542 to a stability/instability degree of practical significance. compounds that help asphaltenes remain in a peptized 588
543 Due to the complexity of the peptization, flocculation, and state, and also high content of aromatics. Both resins and 589
544 precipitation of asphaltene phenomena, several attempts of aromatics aid to keep the asphaltenes in solution in the 590
545 alternatives or modified methodologies for the measurement of crude oil. For these reasons, this crude oil is the most 591
546 crude oil stability have been reported.33−39 stable. 592

Table 9. Results of the Oil Compatibility Model

crude S Sa So SBN = 100(So) IN = 100(1 − Sa) SBN/IN SBN/INmax

C52 2.62 0.02 2.56 256 98 2.61 2.61
C37 2.7 0.84 0.44 44 16 2.75 0.45
C34 3.61 0.75 0.89 89 25 3.56 0.91
C32 3.9 0.79 0.81 81 21 3.86 0.83
C29 2.7 0.72 0.76 76 28 2.71 0.78
C24 3.65 0.76 0.88 88 24 3.67 0.9
C16 2.89 0.65 1.00 100 35 2.86 1.02
C10 3.22 0.69 1.00 100 31 3.23 1.02

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Figure 7. Spot test of blends of C52 with other crude oils. Reference numbers of the type of spot obtained according to ASTM D4740: 1 and 2
(dispersed asphaltenes), 3 (asphaltenes starting to flocculate), 4 (flocculated asphaltenes), and 5 (precipitated asphaltenes).26

593 • The colloidal instability index and the Stankiewicz plot produced by addition of solvents into crude oils. 612
594 provide uncertain results, while the stability cross plot Nonetheless, the result is displayed as a relative 613
595 method renders higher certainty for estimating the parameter. The spot test is revealed as a quick and 614
596 stability of asphaltenes in crude oils. effective technique, but it depends on the visual 615
597 • All approaches are recommended to be used to obtain a perception of the observer. The static column test has 616
598 better prediction of the stability of asphaltenes in crude several advantages: it is effective, it does not require 617
599 oils. The average result can be assumed as the solvent incorporation, and it is possible to measure the 618
600 characteristic that best defines the stability character of stability of asphaltenes at any pressure and temperature. 619
601 asphaltenes in crude oils. Nonetheless, the stability is determined indirectly by 620
602 • The intrinsic stability results obtained using the ROFA means of a chosen property, and the procedure is time- 621
603 equipment determined that all crude oils are stable and consuming. 622
604 that C32 crude oil is the most stable, while the lowest • The application of the different approaches is useful in 623
605 stability is found for C52 crude oil. the determination of the stability of asphaltenes in crude 624
606 • The spot test and the static column test classified C34 oils or blends. The stability character of asphaltenes in a 625
607 crude oil as unstable, unlike the stability predicted by the given crude oil may be established by averaging the 626
608 ROFA equipment. The other crude oils were classified results from different methodologies. 627
609 as stable by the three experimental methods. • From the practical point of view, pertinent cautions on 628
610 • The ROFA method measured stability by optical the handling of samples must be observed if at least one 629
611 detection of the flocculation of asphaltenes artificially of the methods classifies the sample as unstable or 630

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636 mode technique is a better option if the concern is the isolated from crude oil production facilities. Energy Fuels 2001, 15, 698
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642 AUTHOR INFORMATION Fathinasab, M. A literature review of asphaltene entity, precipitation, 706
643 Corresponding Author and deposition: introducing recent models of deposition in the well 707
644 Jorge Ancheyta − Instituto Mexicano del Petróleo, Mexico City column. J. Oil Gas Petrochem. Sci. 2018, 1, 83−89. 708
645 07730, Mexico; orcid.org/0000-0001-9626-637X; (17) Matsushita, K.; Marafi, A.; Hauser, A.; Stanislaus, A. Relation 709
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649 City 07730, Mexico Separation of Asphaltene-Containing Heavy Fuel Oil as Separability 714
650 Silvano Rodríguez − Instituto Mexicano del Petróleo, Mexico Number by an Optical Scanning Device. ASTM International: West 715

651 City 07730, Mexico Conshohocken, PA, 2019. 716

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