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Investigation of Asphaltene Precipitation Process for Kuwaiti

Reservoir
Article in Petroleum Science and Technology · January 2004

DOI: 10.1081/LFT-120038727
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{MDI}Lft/Lft22(7-8)/120038727_LFT_022_007-008_R1.3dPetroleum Science and Technology (LFT)
120038727_LFT22_07-08_R1_041304
PETROLEUM SCIENCE AND TECHNOLOGY

Vol. 22, Nos. 7 & 8, pp. 1165–1185, 2004
1
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Investigation of Asphaltene Precipitation
10 Process for Kuwaiti Reservoir
11
12
13 E. F. Ghloum and G. P. Oskui*
14
15 Kuwait Institute for Scientific Research (KISR), Petroleum
16 Production Department, Safat, Kuwait
17
18
19
20 ABSTRACT
21
22 As part of an Enhanced Oil Recovery (EOR) research program,
23 Asphalting precipitation processes were investigated for a Kuwaiti
24 dead oil sample using different hydrocarbons and carbon dioxide as
25 precipitants at the ambient and high pressure of 3000 psig conditions.
26
The hydrocarbons used as precipitants were ethane (C2), propane
(C3), butane (C4), normal pentane (n-C5), normal hexane (n-C6),
27
and normal heptane (n-C7). The equipment used for this investiga-
28
tion was a mercury-free, variable volume, fully visual JEFRI-DBR
29
PVT system with laser light scattering. The minimum critical value of
30
precipitants concentration for the oil sample has been identified at
31
the ambient and high-pressure conditions for each precipitant. Our
32 investigation has revealed that for this oil sample the most powerful
33
34
35
*Correspondence: G. P. Oskui, Kuwait Institute for Scientific Research (KISR),
36 Petroleum Production Department, P.O. Box 24885, Safat, Kuwait; E-mail:
37 roskui@prsc.kisr.edu.kw.
38
39 1165
40
41 DOI: 10.1081/LFT-120038727 1091-6466 (Print); 1532-2459 (Online)
42 Copyright & 2004 by Marcel Dekker, Inc. www.dekker.com
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120038727_LFT22_07-08_R1_041304
1166 Ghloum and Oskui
43 asphaltene precipitant were CO2 followed by C2, C3, C4, n-C5, n-C6,
44 and n-C7. Moreover, the effect of pressure and temperature on the
45 asphaltene precipitation has been investigated experimentally for
46 CO2, n-C5, n-C6, and n-C7. The precipitation and redissolution of
47
asphaltene upon the addition and removal of CO2 and light alkanes
(C2–C4), at 3000 psig and ambient temperatures, have shown
48
evidence of reversibility of asphaltene precipitation. A comprehen-
49
sive fluid characterization analysis for the oil sample has been
50 performed including, physical properties of crude oil, compositional,
51 molecular weight (Mw), and SARA analyses. Advanced analytical
52 techniques such as 1H and 13C NMR and IR spectrometers have
53 been utilized to investigate the molecular structure of the asphaltene
54 for this sample. It was concluded that the asphaltene molecules for
55 this oil contain 120 total aromatic carbons with 42 aromatic rings,
56 114 naphthenic rings, and 5–7 sets of condensed aromatic rings.
57
58
59 INTRODUCTION
60
61 The asphaltene deposition problem manifests itself in almost all
62 aspects of production, processing, and transportation of petroleum. The
63 precipitation of asphaltenes in reservoirs, wells, and facilities has a detri-
64 mental effect on the economics of oil production because of reduction in
65 well productivity and clogging of the production facilities. In addition,
66 asphaltene precipitation can occur during acid simulation, gas or other
67 solvent injection for Improved Oil Recovery (IOR). Often the problem is
68 more severe and costly for offshore fields. Problems associated with
69 asphaltene deposition have been well documented in the petroleum
70 industry (Kokal and Sayegh, 1995; Leontaritis and Mansoori, 1989).
71 Asphaltenes are defined as the polar, polyaromatic, and high
72 molecular weight hydrocarbon fractions of crude oil that are generally
73 characterized as insoluble in n-heptane or in n-pentane (Srivastava et al.,
74 1993). They are believed to exist either dissolved or as finely dispersed
75 colloidal suspension in oil stabilized by resins adsorbed on their surface.
76 Asphaltenes are complex organic materials that are thought to be
77 arranged in stacked, multi-ring structures in an oil sample. They consist
78 primarily of carbon, hydrogen, and a minor proportion of heteroele-
79 ments such as oxygen, sulfur, and nitrogen (Yen and Yin, 2001). The AQ1
80 asphaltene molecules are surrounded by the polar heads of the resins and
81 maltenes, while the nonpolar alkyl ends interact with the oil phase.
82 Therefore, oils with a high ratio of resins to asphaltenes are less subjected
83 to asphaltene deposition than oil samples with large amounts of nonpolar
84 saturates compared with aromatics, which are more prone to exhibit
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120038727_LFT22_07-08_R1_041304
Asphaltene Precipitation Process 1167
85 asphaltene-precipitation problems. At normal reservoir conditions, the

86 asphaltenes, resins, maltenes, and oil phase are in thermodynamic
87 equilibrium. This equilibrium can be disturbed by a number of factors:
88 changes in pressure, temperature, and chemical composition during
89 production and mixing with injection fluids as applied in various EOR
90 techniques and acid simulation.
91 Asphaltene can be classified by the particular paraffin used to
92 precipitate them from the crude oil, and it has been shown that various
93 solvents precipitate different amounts of asphaltene (Kokal and Sayegh,
94 1995). The amounts precipitated with n-heptane and heavier n-alkanes
95 show very little difference, indicating that the most insoluble materials
96 are precipitated by n-heptane and heavier solvents. This is the primary
97 reason for selecting n-heptane as the most logical solvent for obtaining
98 the asphaltene. As these n-alkane molecules get smaller, the amount of
99 asphaltene precipitated increases sharply, (Kokal and Sayegh, 1995).
100 However, their work was limited to C5 and heavier alkanes.
101 The addition of light, paraffinic compounds changes the solubility of
102 the asphaltene component in oil, causing desorbtion of resin molecules
103 from the surface of the asphaltenes in an attempt to re-establish
104 thermodynamic equilibrium. Desorption of the peptizing resins forces
105 the asphaltene micelles to agglomerate in order to reduce their overall
106 surface-free energy.
107 Asphaltene precipitation processes can be reversible or non-
108 reversible. Some researchers such as Pfieffer and Saal (1940), reported
109 that the asphaltene precipitation is irreversible for their oil sample. They
110 based these claims, on certain experimental observations of the colloidal
111 behavior of asphaltene suspensions. Hischberg et al. (1984), however,
112 observed the reversibility of asphaltene precipitation with pressure at
113 367.15 Kpa. Later, Chung et al. (1991) investigated the reversibility AQ1
114 processes using n-pentane and they found that only 23% of precipitate
115 dissolved back in the crude. Rassamdana et al. (1996) performed AQ1
116 experiments at room temperature to study the reversibility with respect
117 to composition. They observed that part of the precipitated asphaltene
118 redissolved into solution and concluded that asphaltene precipitation
119 process is partially reversible. Anderson and Stenby (1996) studied the
120 effect of temperature on asphaltene precipitation/dissolution. They
121 used a mixed solvent (toluene and n-heptane) and performed solvent
122 reversibility runs at 24, 50, and 80 C. Although the reversibility of
123 precipitation with temperature was not explicitly investigated, the results
124 demonstrated that asphaltenes partially redissolve with an increase in
125 temperature. Romoa et al. (1997) in their experiments, verified that the AQ1
126 asphaltene precipitation/dissolution process in liquid titration is reversible.
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120038727_LFT22_07-08_R1_041304
127 The dissolution of the precipitated asphaltene at room temperature is a

128 kinetically slow process and therefore the reversibility may require some
129 time. Hammami et al. (2000) investigated the behavior of asphaltene in
130 live oils through a series of isothermal pressure depletion experiments.
131 They have speculated that pressure depletion induced asphaltene
132 precipitation is a highly reversible process.
133 Many Kuwaiti oil reservoirs have suffered asphaltene precipitation
134 problems. However, very little asphaltene precipitation studies have been
135 reported for such reservoirs. Moreover, the composition of the crude oil
136 and the precipitation agent at high pressure, which has a significant effect
137 on the onset and amount of the precipitated asphaltenes, have never been
138 investigated for Kuwaiti oil reservoirs.
139 In the present work, the asphaltene precipitation for Kuwaiti oil
140 sample was investigated through the injection of a number of asphaltene
141 precipitants by using a high pressure PVT cell equipped with a laser
142 spectroscopy detector. The precipitants used in this work were ethane,
143 propane, butane, n-pentane, n-hexane, n-heptane, and CO2. A fluid
144 characterization study was done for the oil sample and it included
145 density, viscosity, molecular weight, metal analysis, elemental analysis,
146 GC compositional analysis, and SARA analysis (separate the oil into
147 hydrocarbon fractions; Saturate–Aromatics–Resins–Asphaltene). The
148 experimental work was done in Kuwait Institute for Scientific Research
149 (KISR) petroleum laboratories.
150
151
152 2. EXPERIMENTAL METHODOLOGY
153
154 2.1. Crude Oil Characterization
155
156 Initially, the physical properties of the oil sample used in this
157 investigation were measured as shown in Table 1. The composition of the T1
158 sample was measured by Simulated Distillation (SIMDIST) as shown in
159 Table 2. The asphaltene content, measured by IP143, was 3.15% by weight. T2
160 SARA analysis was performed using two different techniques.
161 Results for the conventional chromatography technique are shown in
162 Table 3. Another fractionation method, Modified SARA Analysis T3
163 (Carnahan, 1999) was also used and the results are shown in Table 4. T4
164 In this technique, as shown in Fig. 1, the crude oil was separated into four F1
165 fractions: Asphaltene, Resin 1, Resin 2, and deasphalted-deresined oil. The
166 difference between Resin 1 and Resin 2 fractions is that Resin 1 has higher
167 polarity, closer properties to asphaltene, heptane insoluble and it sticks
168 to asphaltene molecules during precipitation. Conversely, Resin 2
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120038727_LFT22_07-08_R1_041304
169 Table 1. Physical properties of crude oil.

170
171
Test Unit Amount
172 Density at 15 C g/mL 0.8655
173 Gravity API 31.99
174 Water content %wt 0.072
175 Kinematics viscosity
176 20 C cSt 14.8
177 40 C cSt 8.015
178 Conradson carbon residue %wt 5.47
179 Metal analysis
180
V ppm 26
Ni ppm 8
181
Fe ppm 6
182
Molecular wt. g/gmol 378
183 Element wt%
184 C 84.2
185 H 12
186 N 0.17
187 S 2.2
188 O 0.56
189 H/C 1.81
190
191
192 fraction has lower polarity and is soluble in heptane. Table 5 shows T5
193 densities and molar masses for these fractions. Densities of the liquid
194 mixture were measured with a digital densometer model DMA 48
195 calibrated with mineralized water and air. Density measurements with
196 this instrument are generally accurate to 0.003 kg/m3. All measurements
197 were carried out at 15 0.5 C. Asphaltene and resin densities were
198 calculated indirectly from the densities of mixtures of known concentra-
199 tion of asphaltene in toluene. Molar masses of these fractions were
200 measured by a Vapor Pressure Osmometer K-7000 calibrated with
201 toluene. Measurements in chloroform were made at 50 C. Molar masses
202 of asphaltene in toluene were determined over a range of 1.5–4.5 g.
203
204 2.2. Asphaltene Precipitation Experiments
205
206 I. Determination of Amount of asphaltene Precipitated by
207 Different n-Alkanes at Ambient Conditions
208
209 The precipitants used in these experiments were n-pentane, n-hexane,
210 and n-heptane. Asphaltene onset points with each precipitant were
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120038727_LFT22_07-08_R1_041304
211 Table 2. Simulated distillation data for Kuwaiti dead oil sample.
212
213
Component Boiling Mass Component BP Mass
name point ( C) (%) name ( C) (%)
214
215 C7 98 1 C46 556 84
216 C8 126 2.5 C48 566 85
217 C9 151 6 C50 575 86
218 C10 174 10 C52 585 87.5
219 C11 196 14 C54 592 88.5
220 C12 216 18 C56 600 89.8
221 C13 235 22 C58 608 90
222
C14 254 26 C60 615 91
C15 271 30 C62 622 92
223
C16 287 33 C64 629 92.5
224
C17 302 36 C66 635 93
225 C18 316 39 C68 641 94
226 C20 344 45 C70 647 94.5
227 C24 391 54 C72 653 95
228 C28 431 62 C74 658 95.5
229 C32 466 65 C76 664 96
230 C36 496 74 C82 681 97
231 C40 522 78 C88 695 98
232 C42 534 80 C98 716 99
233
C44 545 82 C110 735 99.5
234
235
236 Table 3. SARA analysis results for Kuwaiti crude oil.
237
238
Fraction name Wt%
239 Saturate 54.82
240 Aromatics 34.49
241 Resin 7.43
242 Asphaltenes 3.260
243
244
245
Table 4. Modified SARA analysis for crude oil.
246
247 Fraction name Wt%
248
249 Asphaltene 3.23
Resin 1 3.75
250
Resin 2 4.89
251
Deasphalted-deresined 88.13
252
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253 Add n-Heptane to Oil

254
255 STO, ratio 1g/30 cc
256
257
258 Filtration with 0.45 micron
259
260
261 Filtrate C7+maltene Asphaltene + Resin 1
262
263
Evaporation Refluxing with hot heptane
264
265
266 Silica Gel Filter Paper with Asphaltene
Maltene Resin 1 + C7
267 (4 spoons to 20g)
268
269 Refluxing with Toluene
270 Refluxing with hot heptane
Evaporation
271
272 Filter cup with Deasphalted –
Silica gel +Resin 2 Deresin oil + C7
273 Pure Asphaltene
274 Resin 1
275 Refluxing with Evaporation

Methanol-Benzene
276 solution (50 %)
277
Deasphalted-
278 Deresin oil
Evaporation
279
280
281
Resin 2
282
283 Figure 1. Schematic diagram for modified SARA analysis.
284
285
Table 5. Physical properties of crude oil fractions.
286
287 Density at Molecular
288 Fraction name 15 C (g/cc) weight (g/gmol)
289
290 Asphaltene 1.213 3245
291
Resin 1 1.09 2535
Resin 2 1.066 2288
292
Deasphalted-deresined 0.924 559
293
Original oil 0.865 378
294
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120038727_LFT22_07-08_R1_041304
295 Table 6. Asphaltene precipitated by different normal alkanes

296 at ambient conditions.
297
Precipitated asphaltene (wt%)
298 Dilution ratio
299 (cc/g oil) n-C5 n-C6 n-C7
300
301 0.3 0.1 0 0
0.8 1.1 0.1 0
302
1 1.75 0.85 0.1
303
3 2.97 2.45 2.00
304 5 3.90 3.06 2.33
305 10 4.69 3.46 2.64
306 15 4.73 3.58 2.93
307 20 4.96 3.62 2.98
308 25 4.99 3.79 3.11
309
310
311
312 obtained by the filter drop spreading method (Fourest, 1995). The
313 amount of asphaltene precipitated was gravimetrically determined
314 for each precipitant as shown in Table 6. T6
315
316
317 II. Investigation of Asphaltene Precipitation Onset Point at
318 High Pressure
319
320 Instrumentation
321 The Solid Detection System (SDS) is used to measure the asphaltene
322 onset point in this work. It consists of a mercury-free, fully visual, PVT
323 cell equipped with fiber optics light transmission probes (source and
324 detector) to measure the onset of organic solids precipitation (due to
325 temperature, pressure, and compositional change) concurrently with fluid
326 volumetric data (P, V, T ). The system has been well described in open
327 literature (Hamami et al., 2000; Lira-Galeana and Hammami, 2000). A AQ1
328 schematic of the SDS system, including the fiber optic probes mounted
329 across a standard PVT cell and a solvent injection cylinder and a Back
330 Pressure Regulator (BPR) is illustrated in Fig. 2. F2
331 The ultimate interpretation of asphaltene behavior is done through
332 inspection of the resulting ‘‘light transmittance’’ plots, which show the
333 amount of light received by the detector (i.e., transmitted through the
334 sample) as a function of solvent volume during titration experiments.
335 Therefore, it is useful to summarize some of the main factors known to
336 influence light transmittance through an optically dense fluid such as
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120038727_LFT22_07-08_R1_041304
Schematic diagram for SDS system used in this study. (View this art in color at www.dekker.com.)
Figure 2.
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120038727_LFT22_07-08_R1_041304
337 crude oil. The Power of Transmitted Light (PTL) refers to the amount of
338 light that passes through the oil sample and is detected through the fiber
339 optic cable.
340
341 . PTL is inversely proportional to density; hence, if the density
342 decreases (during solvent injection), then PTL increases.
343 . PTL is inversely proportional to particle size; hence, if the particle
344 size increases then PTL decreases.
345 . PTL is inversely proportional to the nucleation density of solids;
346 hence, if the number of particles per unit volume of fluid increases
347 then PTL decreases.
348
349
350
351 Solvent Titration Experiment Procedure
352 The precipitant or gas is charged into the sample cylinder in the PVT
353 oven, then heated to the desired titration temperature using a
354 displacement pump to maintain the solvent and sample in equilibrium
355 during the heating process. The BPR is set to the desired titration
356 pressure (3000 psig), and then any increase in pressure in the PVT cell will
357 be maintained by BPR. The solvent is injected at a predetermined
358 injection rate (10 cc/h). The PTL is measured and recorded continuously
359 (in real time) while the solvent is being injected and the resulting cell
360 content is vigorously mixed. The onset point is obtained on observation
361 of a dramatic drop in PTL is.
362 Four series of experiments were conducted for oil sample using the
363 high pressure, PVT-SDS system to investigate the effect of the addition of
364 number of alkanes and CO2 on asphaltene precipitation. In the first series
365 of measurements, the oil was diluted with three liquid alkanes: n-C5, n-
366 C6, and n-C7, all under the same conditions, 3000 psig, 20 C and dilution
367 ratio of (5cc of alkane/g of oil). Also the amounts of asphaltene
368 precipitated by different alkanes were determined by normal filtration,
369 with filter size of 0.45 mm.
370 In the second series of experiments, the oil sample was diluted with
371 different alkanes such as ethane (C2), propane (C3), butane (C4), and
372 carbon dioxide (CO2) at 3000 psig and ambient temperature.
373 In the third series of measurements, the effect of temperature on the
374 asphaltene precipitation at high pressure has been investigated for CO2.
375 The last series of experiments were designed to quantify amounts of
376 the precipitates from all titration tests done at high pressure. For liquid
377 alkanes, n-C5, n-C6, and n-C7, the solvent–crude oil solutions were
378 filtered using 0.45 m filter paper and then the unwashed asphaltenes were
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120038727_LFT22_07-08_R1_041304
379 analyzed for SARA analysis. For the cases with C2, C3, C4, and CO2,
380 once the oil sample was flashed, the dissolved gas in oil was released,
381 which, in turn, changes the solubility parameter of oil. Once again, this
382 change causes redissolution of the precipitated asphaltene in oil. After
383 several filtration attempts, we observed that no solid precipitates were
384 seen in the filter papers, which means that all the precipitated asphaltenes
385 were again redissolved in the oil sample. Therefore, we decided to
386 measure the precipitated asphaltenes by these solvents based on the
387 original content, i.e., reprecipitating with C7 in a ratio (1:30) and
388 proceeding with the modified SARA analysis.
389
390
391 3. RESULTS AND DISCUSSION
392
393 3.1. Determination of Amount of Asphaltene Precipitated by
394 Different n-Alkanes at Ambient Conditions
395
396 Figure 3 shows the weight percentage of asphaltene precipitated F3
397 using different alkanes (n-C5, n-C6, and n-C7) at ambient conditions. It is
398 evident from this figure that n-pentane is the most powerful precipitant in
399 asphaltene precipitation comparing to C6 and C7. As shown in Table 6,
400 for n-C5, asphaltene precipitation started at dilution ratio of 0.3 cc/g
401 of oil, while for n-C6 and n-C7, these values were 0.8 cc/g and 1 cc/g,
402
403
404
5
405
Wt.% of asphaltene precipitated
406
407 4
408
409 3
410
411 n-C7
2
412 n-C6
n-C5
413
1
414
415
416 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
417
Solvent to Crude Ratio (cc of n-Cm/g)
418
419 Figure 3. Gravimetric measurement of asphaltene precipitation using different
420 normal alkanes at ambient conditions. (View this art in color at www.dekker.com.)
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120038727_LFT22_07-08_R1_041304
421 7
422
423 6
Precipitated Asphaltene, wt%
424
425 5
426
4
427
428 3
429
430 2
431
432 1
433
434 0
60 70 80 90 100 110
435
Solvent Molecular Weight
436
437 Figure 4. Effect of precipitant molecular weight on the amount of asphaltene
438 precipitated at ambient conditions.
439
440
441 respectively. Also, as shown in this table, the total content of asphaltene
442 precipitated for n-C5, n-C6, and n-C7 at the dilution ratio of 25 cc/g of
443 oil was 4.9, 3.79, and 3.11%, respectively. That means as the molecular
444 weight of n-alkanes decreases from n-C7 to n-C5, the onset point of
445 asphaltene precipitation decreases, and the amount of asphaltene
446 precipitated increases, as illustrated in Fig. 4. The reason for the greater F4
447 precipitation is that lighter alkanes might cause precipitation of resins
448 in addition to asphaltenes (Firoozabadi, 1999).
449
450
451
452 3.2. Investigation of Asphaltene Precipitation
453 Onset Point at High Pressure
454
455 Figure 5 shows the precipitation on set curves for C5, C6, and C7 at F5
456 3000 psig and 21 C. As precipitant is added, the light transmittance
457 increases due to the dilution. The sharp decline in direction of the
458 titration curve (maximum point) is the asphaltene onset point. As shown
459 in this figure, the onset points for n-C5, n-C6, and n-C7 were 18, 21,
460 and 25 cc respectively. This means that at high-pressure condition, as
461 molecular weight of the precipitant is decreasing the onset point will
462 decrease as found in the ambient conditions.
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120038727_LFT22_07-08_R1_041304
463 1.40E-08
464
n-C6
465 1.20E-08
n-C5 n-C6 n-C7 n-C7
Light Transmitted, Watt
466
1.00E-08 n-C5
467
468 8.00E-09
469
470 6.00E-09
471
4.00E-09
472
473 2.00E-09
474
475 0.00E+00
476 0 5 10 15 20 25 30 35 40 45 50
477 Solvent Volume, cc

478
Figure 5. Comparison of titration tests of STO with different liquid alkanes at
479 3000 psig. (View this art in color at www.dekker.com.)
480
481
482
8.0E-09 C3
483
C2
484 7.0E-09 CO2
C5
485 6.0E-09 CO2 C3 C2 C4 C5 C6 C7 C6

486 C4
5.0E-09 C7
487
488 4.0E-09
489 3.0E-09
490
2.0E-09
491
492 1.0E-09
493 0.0E+00
494 0 5 10 15 20 25 30 35 40
495 Solvent Volume, cc
496
Figure 6. Comparison of titration tests for STO with different precipitants at
497
3000 psig and ambient temperature. (View this art in color at www.dekker.com.)
498
499
500
501 Figure 6 shows the precipitation onset curves for different alkanes and F6
502 CO2 at 3000 psig and 21 C. As shown in this figure, CO2 has the lowest
503 onset point (5.5 cc) followed by C3 (9.5 cc), C2 (11 cc) etc. The onset values
504 in terms of (cc of solvent/g of oil) for all precipitants are tabulated in
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120038727_LFT22_07-08_R1_041304
505 Table 7 along with the solubility parameters for each precipitant. Figure 7 T7 F7
506 presents the effect of precipitant carbon number vs. the asphaltene
507 precipitation onset point (cc/g) at 3000 psig. As shown in this figure, as the
508 precipitant carbon number increases, the asphaltene precipitation onset
509 point increases. This is according to the solubility theory. As the solvent
510 carbon number increases, the solubility parameter of the solvent delays the
511 flocculation process of Asphaltene, as shown in Fig. 8. F8
512
513
514 Table 7. Asphaltene precipitation onset values for different
515 precipitants.
516
517 Onset value
518 Precipitant name (cc solvent/g of oil) ( j/cc)1/2
519
Carbon dioxide 0.347 14.56
520
Ethane 0.632 12.4
521 Propane 0.544 13.1
522 Butane 0.789 13.7
523 Pentane 1.097 14.4
524 Hexane 1.328 14.9
525 Heptane 1.45 15.2
526
527
528
1.4
Asphaltene precipitation onset point (cc/g)
529
530
1.2
531
532 1
533
534 0.8
535
536 0.6
537
0.4
538
539 CO2
0.2
540
541 0
542 0 1 2 3 4 5 6 7 8
543 Solvent Carbon Number
544 Figure 7. Effect of precipitant carbon number on the asphaltene precipitation

545 onset point at 3000 psig and ambient temperature. (View this art in color at www.
546 dekker.com.)
+ [13.4.2004–3:09pm] [1165–1186] [Page No. 1179]
120038727_LFT22_07-08_R1_041304
547 16
548
Solvent Solubility Parameter, (j/cc)1/2
549 15 CO2
550
551 14
552
553 13
554
555 12
556
11
557
558
10
559
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2
560
Asphaltene Precipitation Onset point, (cc/g)
561
562 Figure 8. Effect of the precipitant solubility parameters on the asphaltene
563 precipitation onset point at 3000 psig and ambient temperature. (View this art in
564 color at www.dekker.com.)
565
566
567 3.3. Influence of Temperature on Asphaltene Precipitation
568
569 The sample was titrated with CO2 at 3000 psig and different
570 temperatures of 20, 35, and 48 C, as shown in Figs. 9 and 10. As F9 F10
571 shown in these figures, as temperature increases the onset point increases
572 or the tendency of asphaltene flocculation decreases. This could be
573 referred to as a change in asphaltene solubility, because as the temperature
574 increased the solubility of asphaltene in crude increases. This will delay
575 the precipitation.
576
577
578
579 3.4. Determination of Crude Oil Fractions after the
580 High-Pressure SDS Tests
581
582 Table 8 summarized the SARA Fractionation of crude oils after SDS T8
583 tests for different solvents. Comparing the amount of asphaltene
584 percentage for C5, C6, and C7 with a dilution ratio of 5 cc/g at high
585 pressure (Table 8) with the same precipitants at ambient conditions
586 (Table 6) it is evident that the higher pressure of 3000 psig increases the
587 asphaltene content by maximum 0.9% for C5, while the difference for
588 C6 and C7 were 0.3 and 0.7%, respectively.
+ [13.4.2004–3:09pm] [1165–1186] [Page No. 1180]
120038727_LFT22_07-08_R1_041304
589 3.5E-10
590 CO2 at 20C
591 3.0E-10
592 CO2 at 48C
593 2.5E-10
CO2 at 35C
594
2.0E-10
595
596
1.5E-10
597
598 1.0E-10
599
600 5.0E-11
601
602 0.0E+00
0 2 4 6 8 10 12 14
603
Solvent Volume, cc
604
605 Figure 9. Titration of STO with CO2 at different temperatures and high
606 pressure. (View this art in color at www.dekker.com.)
607
608
11
609
610 10
611 9
Onset point (CO2 %)
612
8
613
7
614
615 6
616 5
617 4
618
3
619
620 2
10 15 20 25 30 35 40 45 50 55 60
621
Temperature, C
622
623 Figure 10. Effect of temperature on asphaltene precipitation, with CO2 as a
624 solvent, at high pressure. (View this art in color at www.dekker.com.)
625
626
627 It should be noted that for lighter precipitants such as (C2, C3, and
628 C4) and CO2, the asphaltene contents were measured after each titration
629 test by using C7 (IP 143) technique. As shown in Table 8, the amount of
630 asphaltene percentage with C7 was less than those measured after C2, C3,
+ [13.4.2004–3:09pm] [1165–1186] [Page No. 1181]
120038727_LFT22_07-08_R1_041304
631 Table 8. SARA fractionation of crude oils after titration tests for
632 different solvents (5 cc/g) at 3000 psig and 70 F.
633
Deasph.-
634
Solvent Asph. Resin 1 Resin 2 deresin-oil
635
used (wt%) (wt%) (wt%) (wt%)
636
637 C1 4.51 3.58 5.90 79.09
638 C2 4.14 3.82 5.78 72.79
639 C3 3.67 4.56 3.67 67.49
640 C4 3.52 4.04 5.49 63.13
641 C5 4.79 5.49 6.36 71.58
642
C6 3.33 4.13 6.14 68.10
C7 3.04 4.34 6.36 68.28
643
644
645
646
Precipitated Asphaltene, wt%
647 5.5
648 5.0
649 4.5
650 4.0
651
3.5
652
3.0
653
2.5
654
2.0
655
0 1 2 3 4 5 6 7 8
656
Alkanes Carbon Number
657
658 Figure 11. Effect of precipitant carbon number on the asphaltene precipitation
659 contents at 3000 psia and ambient temperature. (View this art in color at www.
660 dekker.com.)
661
662
663
664 C4, and CO2 tests by maximum 1.5%. This change can be explained as
665 the asphaltene precipitates by lighter hydrocarbons of (C2, C3, C4) and
666 CO2 are left in monomers form with less resins (unlike the original
667 asphaltene micelles) that can easily aggregate to form the asphaltene
668 precipitates.
669 Figure 11 shows the effect of alkane carbon number and CO2 on the F11
670 amount of asphaltene precipitated at 3000 psig. As we can see in this
671 figure, the amount of asphaltene precipitated increases with decreasing
672 solvent carbon number.
+ [13.4.2004–3:09pm] [1165–1186] [Page No. 1182]
120038727_LFT22_07-08_R1_041304
673 Table 9. Infrared spectral region assignments.

674
675
IR bands Assignments regions Asphaltene
676 OH,NH (stretch) 3300–3600 3400 (w)
677 C-H (stretch) 2800–3000 2924 (s)–2850 (m)
678 SH 2500 2720 (s)
679 C¼O 1600–1800 1690 (w)
680 C¼C (stretch) 1620–1590 1590 (w)
681 C-H, CH3 1375–1450 1375 (m)–1452 (s)
682 (C-S, C-O, C-N) 1000 1050 (w)
683 C-H (aromatic) 700–900 750 (m)–858 (w)
684
685
686
687 3.5. Characterization of Asphaltene Molecule
688
689 Different advanced analytical techniques such as 1H and 13C NMR
690 and IR spectrometers were used to characterize the asphaltene sample
691 precipitated by n-C7 for this crude. Major bands of asphaltene are shown
692 in Table 9. The chemical shift assignments and average structural param- T9 AQ2
693 eters were obtained from 1H and 13C NMR spectroscopy and are shown
694 (Table 10). The H/C ratio was calculated to be 1.12 using elemental T10
695 analysis.
696 Table 11 shows the total Double Bond Equivalent (DBE) (Calemma T11
697 et al., 1995), Aromatic Double Bond Equivalent (ArDBE) (Bekear et al., AQ3
698 1999), and Aliphatic Double Bond Equivalent (AlDBE) (Ignasik et al.,
699 1977) per 100 carbon atoms. It is clear that there are some aliphatic
700 double bonds in the asphaltene, which are most likely due to cycloalkanes
701 and condensed aliphatic rings. It was concluded that for this sample the
702 total number of carbon atoms was 220 of which 120 were associated with
703 aromatic and the rest were aliphatic rings. The numbers of aromatic and
704 naphthenic rings were estimated to be 42 and 114 rings respectively.
705
706
707 4. CONCLUSIONS
708
709 1. Asphalting precipitation processes were investigated for Kuwaiti
710 reservoir oil sample using different hydrocarbons and carbon
711 dioxide as precipitants at the ambient conditions and high pressure.
712 2. The minimum critical value of precipitants concentration for the
713 oil sample has been identified at the ambient and high pressure
714 conditions for each precipitant.
+ [13.4.2004–3:09pm] [1165–1186] [Page No. 1183]
120038727_LFT22_07-08_R1_041304
715 Table 10. Average structural data for asphaltene fraction from Kuwaiti STO.
716
717
Average structural data Wt% No. of atoms
718 Total hydrogen 247
719 Aromatic hydrogen 9.56 10
720 Aliphatic hydrogen 90.44 90
721 Aliphatic hydrogen in the position 30.15 30
724 Total carbon 220
725 Aromatic carbon (Car) 44.2 120
726
Aliphatic carbon (Cal) 37.3 100
Quaternary aromatic carbon (Car;q) 35.4 96
727
Tertiary aromatic carbon (Car;t) 8.8 24
728
Alkyl-substituted aromatic carbon (Cars ) 12.43 33.62
729 Degree of substitution () 0.51 0.51
730 Bridged aromatic carbon (Cbar ) 30.9 62.38
731 Aromatic rings (Rar) 15.95 42.29
732 Naphthenic rings (Rna) 40.17 114
733 n-Alkyl carbon 28.1 76
734 Total carbon in CH3 group 8 22
735 Average no. of carbon per alkyl substitutes (n*) 3
736 Degree of condensation ( ) 0.7
737
{H/C} al 2.23
Aromaticity ( fa) 54 0.54
738
739
740
741
742 3. For this oil sample the most powerful asphaltene precipitant
743 were in order of CO2 followed by C2, C3, C4, n-C5, n-C6, and
744 n-C7.
745 4. The effect of pressure and temperature on the asphaltene
746 precipitation has been investigated for CO2, n-C5, n-C6, and n-C7.
747 5. The precipitation and redissolution of asphaltene upon the
748 addition and removal of CO2 and light alkanes (C2–C4), at
749 3000 psig and ambient temperatures, have shown evidence of
750 reversibility of asphaltene precipitation.
751 6. Comprehensive fluid characterization analysis for the oil sample
752 has been performed, including physical properties of crude oil.
753 Comprehensive fluid characterization analysis for the oil sample
754 has been performed including physical properties of crude oil.
755 7. Analytical techniques indicated that for this sample the
756 asphaltene molecule has a total number of carbons atoms of
+ [13.4.2004–3:09pm] [1165–1186] [Page No. 1184]
120038727_LFT22_07-08_R1_041304
757 Table 11. Properties of asphaltene deduced from

758 the elemental and 13C NMR.
759
Asphaltene properties
760
761 Molecular weight 3245
762 Wt% 3.2
763 H/C 1.12
764 fa 54
765 DBE 45a
766 99b
767 ArDBE 31.4
768
68
AlDBE 13.6
769
30.8
770
771 Wt%: relative to crude oil.
772 fa: percent of aromatic carbon.
a
773 : per 100 carbon atoms.
b
774 : per 220 carbon atoms.
775
776
777 220 of which 120 were associated with aromatic and the rest were
778 aliphatic rings. The numbers of aromatic and naphthenic rings
779 were estimated to be 42 and 114 rings respectively.
780
781
782
783
ACKNOWLEDGMENTS
784
785
The authors are grateful to Kuwait Institute for Scientific Research
786 (KISR) management for their financial support during this study.
787
788
789
790 REFERENCES
791
792
Anderson, S. I., Stenby, E. H. (1996). Thermodynamics of asphaltene
793 precipitation and dissolution investigation of temperature and
794 solvent effects. Fuel Science Technology Intl. 14(1&2):231–287.
795 Bekerar, S., Lehmann, T., Mondez, B. (1999). Energy & Fuels
796 13:305–308.
797 Calemma, V., Iwanski, P., Nail, M., Scotti, R. (1995). Energy & Fuels
798 9:225–230.
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799 Carnahan, N., Salager, J., Antone, R., Davila, A. (1999). Properties of
800 resins extracted from boscan crude oil and their effect on stability of
801 asphaltenes in boscan and hamaca crude oils. Energy Fuels 13:309.
802 Firoozabadi, A. (1999). Thermodynamics of Hydrocarbon Reservoirs.
803 Chapter 5. New York City: McGraw-Hill.
804 Fourest, J. M. Study of Asphaltenes Precipitation from Hamaca Crude
805 Oil, Technical Report of FIRP-ELF Aquitan Project; Merida,
806 Venezuela: University of the Andes.
807 Hamami, A., Phelps, H., Little, T. M. (2000). Asphaltene precipitation
808 from live oils: an experimental investigation of the onset conditions
809 and reversibility. Energy Fuels 14:14–18.
810 Hirschberg, A. et al., (1984). Influence of temperature and pressure on AQ4
811 asphaltene flocculation. SPEJ June:283–293.
812 Ignasik, R. K., Kemp-Jones, A. V., Strauz, O. P. (1977). Jornal Org.
813 Chem. 42:312.
814 Kokal, S. L., Sayegh, S. G. (1995). Asphaltenes: The Cholesterol of AQ5
815 Petroleum. In: SPE Paper 29787, presented at the SPE Middle East
816 Oil Show in Bahrain. March 11–14.
817 Leontaritis, K. J., Mansoori, G. A. (1989). Asphaltene Flocculation
818 During Oil Production and Processing: A Thermodynamic-Colloidal
819 Model. In: SPE Paper 16258 Presented at the SPE International
820 Symposium on Oilfield Chemistry. San Antonio, TX, Feb. 4–6.
821 Mansoori, G. A., Jiang, T. S., Kawanaka, S. Asphaltene deposition and AQ6
822 its role in petroleum production and processing. The Arabian
823 Journal for Science and Engineering 13(1).
824 Pfeiffer, J. P., Sual, R. N. (1940). Asphaltic bitumen as a colloid system.
825 Journal of Physical Chemistry 44:139.
826 Speight, J. G. (1980). The Chemistry and Technology of Petroleum. AQ7
827 New York City: Marcel Dekker Inc., 192.
828 Srivastava, R. K., Huang, S. S., Dyer, S. B. (1993). Quantification of
829 Asphaltene Flocculation During Miscible CO2 Flooding in Weyburn
830 Reservoir. In: Paper no. 28, Presented at the Fifth Petroleum
831 Conference of the South Saskatchewan Section, The Petroleum
832 Society of CIM, held with CANMET in Regina. Oct. 18–20.
833
834
835
836
837
838
839
840
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Investigation of Asphaltene Precipitation Process for Kuwaiti

Article in Petroleum Science and Technology · January 2004

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PETROLEUM SCIENCE AND TECHNOLOGY

1166 Ghloum and Oskui

Asphaltene Precipitation Process 1167

85 asphaltene-precipitation problems. At normal reservoir conditions, the

1168 Ghloum and Oskui

127 The dissolution of the precipitated asphaltene at room temperature is a

Asphaltene Precipitation Process 1169

169 Table 1. Physical properties of crude oil.

1170 Ghloum and Oskui

Asphaltene Precipitation Process 1171

253 Add n-Heptane to Oil

275 Refluxing with Evaporation

1172 Ghloum and Oskui

295 Table 6. Asphaltene precipitated by different normal alkanes

Asphaltene Precipitation Process 1173

1174 Ghloum and Oskui

Asphaltene Precipitation Process 1175

1176 Ghloum and Oskui

Asphaltene Precipitation Process 1177

477 Solvent Volume, cc

485 6.0E-09 CO2 C3 C2 C4 C5 C6 C7 C6

1178 Ghloum and Oskui

543 Solvent Carbon Number

544 Figure 7. Effect of precipitant carbon number on the asphaltene precipitation

Asphaltene Precipitation Process 1179

1180 Ghloum and Oskui

Asphaltene Precipitation Process 1181

1182 Ghloum and Oskui

673 Table 9. Infrared spectral region assignments.

Asphaltene Precipitation Process 1183

1184 Ghloum and Oskui

757 Table 11. Properties of asphaltene deduced from

Asphaltene Precipitation Process 1185

Article No. 120038727

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