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1 Batch Reactor Study for Partial Upgrading of a Heavy Oil with a

2 Novel Solid Hydrogen Transfer Agent

3 Laura O. Alemań -Vaź quez, Pablo Torres-Mancera, Jose ́ A. D. Muñoz, and Jorge Ancheyta*

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4 ABSTRACT: A novel solid hydrogen transfer agent (SHTA) based on an organic polymer containing fused-aromatic-ring units,
5 supported in an inorganic matrix, was prepared and tested as a hydrogen donor in the upgrading of a heavy crude oil and its 274 and
6 343 °C+ residua. The SHTA performance is compared with that obtained using a conventional liquid hydrogen donor (tetralin).
7 Three sets of experiments were carried out in a batch reactor: (1) hydrovisbreaking (HVB), (2) HVB with added tetralin, and (3)
8 HVB with added SHTA. The results showed that the use of tetralin or SHTA in the HVB reaction enhances upgrading of heavy oils
9 compared with the experiments without a hydrogen donor (HVB alone). Moreover, lower coke formation and a higher yield of
10 liquid products were observed. The results obtained when using the novel SHTA are equivalent to those obtained when using
11 tetralin as a hydrogen donor in the upgrading of a heavy crude oil and its 274 and 343 °C+ residua.

1. INTRODUCTION in the upgrading of petroleum residues by thermal 44

12 The production, transportation, and refining of extremely processing.12 45

13 viscous hydrocarbon liquids, such as heavy and extra-heavy • Crude oil residue can be thermally converted to more 46
14 crude oils and bitumen, present a series of challenges for the oil valuable products by using tetralin, which donates 47
15 industry. hydrogen to the cracked residue.13 Tetralin is dehydro- 48
16 Visbreaking and hydrovisbreaking (HVB), mild thermal genated to naphthalene, and the residue is converted into 49
17 cracking processes in the absence and presence of hydrogen lower-molecular-weight hydrocarbons with a lower 50
18 respectively, are alternatives for the reduction of the viscosity of formation of coke and dry gas. Naphthalene can be 51
19 heavy oils, by means of the partial conversion of residues to light catalytically hydrogenated to tetralin and recycled.7 52
20 and middle distillates. In general, the economy of these In a previous publication, we have emphasized the lack of a 53
21 processes improves with higher conversion to distillates and universal procedure to quantify the hydrogen-donating ability of 54
22 therefore with severity, but this latter is limited by coke laydown either a specific compound or a given oil-derived solvent. The 55
23 and product stability. These two phenomena are strictly linked reason is that hydrogen donation during thermal cracking 56
24 together so that the cracking reactions cannot proceed beyond a reactions in a complex multiphase reaction system strongly 57
25 certain conversion level, which depends on feedstock proper- depends on the process conditions, which define the hydro- 58
26 ties.1 One option to overcome these problems is by using genation−dehydrogenation equilibria of the hydrogen-donating 59
27 hydrogen donor solvents, taking advantage of their ability to species. For that reason, the effectiveness of a hydrogen donor is 60
28 transfer hydrogen to the oil. usually graded qualitatively by comparison of product quality 61
29 Various applications of hydrogen donors have been reported with and without the hydrogen donor. 62
30 in the literature. The main findings are: Hydrogen donors must be capable of releasing hydrogen in an 63
31 • Hydrogen donors enhanced hydrogen transfer to coal activated state to the reaction environment at the operating 64
32 during coal liquefaction.2−5 temperature and pressure conditions. Hydrogen is first obtained 65
by dehydrogenation of the donor. Depending on the reaction 66
33 • Hydrogen transferred from cyclic olefins, such as conditions, the regeneration of the hydrogen donor to its 67
34 1,4,5,8,9,10-hexahydroanthracene and 1,4,5,8-tetrahydro- original hydrogenated state by reaction with molecular H2 is 68
35 naphthalene (isotetralin), to coal.6 possible. This regeneration can provide a continuous hydrogen 69
36 • Paraffins and single-ring naphthenic compounds were not supply by the hydrogen donor by means of hydrogenation− 70
37 active as hydrogen donors, and condensed-ring naph-
38 thenic compounds such as decalin showed some activity, Received: May 25, 2020
39 whereas mixed naphthenic−aromatic condensed-ring Revised: November 6, 2020
40 compounds such as 1,2,3,4-tetrahydronaphthalene (tetra-
41 lin) showed good hydrogen transfer capacity.7−11
42 • Polar hydrogen donors such as tetrahydroquinoline
43 (THQ) and indoline are good hydrogen donor solvents

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.energyfuels.0c01680

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71 dehydrogenation cycles. Both steps provide activated hydrogen 2.1. Preparation of the SHTA. The polymer used for preparing the 120
72 released from the hydrogen donor, thus enhancing hydro- SHTA contains naphthalene units in its structure. It was physically 121
73 genation reactions.14 mixed with boehmite as support to improve its mechanical and textural 122
74 To achieve cyclic hydrogenation−dehydrogenation of the properties. Boehmite (59 g), 80 mL of distilled water, and 35 mL of a 123
5% nitric acid solution were mixed to obtain a homogeneous paste. 124
75 hydrogen donor, this reaction must be reversible at the reaction After that, 50 g of polymer, ground to a 100 μm size, was added and the 125
76 conditions. For a given reaction, reversibility is achieved at a mixture was put into an extruder with a 2 mm nozzle. The extruded 126
77 temperature and pressure that lead to an equilibrium constant material was then dried at 100 °C for 12 h. 127
78 around 1, implying that the logarithm of the equilibrium 2.2. Activation of the SHTA. Prior to the activity tests, SHTA was 128
79 constant (ln Ke) is around zero. activated. The material was first cured at 380 °C in a stainless steel 129
80 The effect of tetralin, decalin, and naphthalene as hydrogen autoclave-type reactor in a N2 atmosphere and then activated at 380 °C 130
81 donors was studied in the thermal cracking of a 12.1°API crude in a H2 atmosphere (Figure 2). 131 f2
82 oil in the presence of hydrogen or methane as reducing agents.15
83 The results indicate that the combination of the H-donors and
84 reducing agents leads to a significant reduction of coke
85 formation compared with using only reducing agents under
86 the same conditions. The reduction in coke formation was
87 similar for tetralin, decalin, and naphthalene.
88 In the upgrading of heavy oils using liquid hydrogen donors,
89 the reaction product contains a hydrogen donor. The industrial
90 application of the conventional hydrogen donors has been
91 limited by their high cost, if they are allowed to remain in the
92 product mixture, or by the difficulty and cost of their recovery
93 and separation from the upgraded oil.
94 To overcome this problem, a novel type of solid hydrogen
95 donor or solid hydrogen transfer agents (SHTA) has recently
96 been proposed.15−17 SHTAs are solid polymers having in their
97 structure units with hydrogen transfer capabilities, particularly Figure 2. Procedure for curing and activating SHTA.
98 solid polymers containing in their structure units with two or
99 more fused aromatic rings.
100 Solid hydrogen transfer agents represent a new alternative in For the activation, 20 g of SHTA was placed in the reactor and a 132
101 the field of processing of heavy oils that could lead to improved nitrogen flow was used for purging. The temperature was increased to 133
102 upgrading processes. Further studies on their hydrogen transfer 380 °C, and the reactor was pressurized with hydrogen to 8.11 MPa. 134
103 mechanism and on their application to different hydrogenation The reactor was kept at these conditions under agitation (750 rpm) for 135
18 h and then cooled in an ice−water bath. 136
104 reactions are required.
2.3. Characterization of the STHA. The following key properties 137
105 The objective of this work is to apply SHTA as a hydrogen of the SHTA were determined: elemental analysis, average molecular 138
106 donor in the hydrovisbreaking of a heavy crude oil and two of its weight, textural properties, functional groups, thermal stability, 139
107 residues with different boiling ranges. A series of hydro- crystalline structures, infrared spectroscopy, and resistance to fracture. 140
108 visbreaking experiments were carried out, in which thermal Fourier transform infrared spectroscopy was carried out in a Thermo 141
109 cracking of crude oil and residua occurs in the presence of Nicolet PROTEGÉ 460 FTIR spectrometer with a spectral resolution 142
110 molecular hydrogen. Some experiments include a hydrogen of 4 cm−1, 75 scans, and a DTGS Nicolet Magna 560 detector, with 143
111 donor additive to enhance transfer hydrogen reactions. sample preparation in KBr tablets. All of the samples were analyzed 144
using the diffuse reflectance technique (DRIFT). For this purpose, a 145
Harrick Praying Mantis accessory in nitrogen atmosphere was used. 146
2. EXPERIMENTAL SECTION Elemental analysis of polymer and SHTA was performed in an 147
112 An organic polymer was synthesized according to the procedure Elementar Vario micro cube equipment for microanalysis CHONS in 148
113 previously disclosed.15−17 The structure of the resulting poly bis(α- organic samples. Molecular weight was determined by gel permeation 149
f1 114 naphthyl) terephthalate is shown in Figure 1. This polymer was chromatography (GPC) with tetrahydrofuran as a solvent, using a 150
115 supported on Al2O3 to obtain the SHTA; then, it was thermally column of mixed Pgel C 5 μm 300 × 7.5 mm2 and Easy Vial polystyrene 151
116 activated and characterized. The obtained SHTA was tested in standards (162−6 035 000 g/mol) for the calibration curve. BET 152
117 hydrovisbreaking experiments using a batch reactor, and the results specific surface area, total pore volume, and pore size distribution were 153
118 compared with those obtained in the presence of liquid hydrogen donor measured in a Micromeritics ASAP-2000 equipment, using ASTM 154
119 and in the absence of hydrogen donor. D3663-03, ASTM D4222-03, and ASTM D4641-94 methods, 155
respectively. Thermogravimetry-differential thermal analysis (TGA− 156
DTA) analyses were performed in a PerkinElmer TGA 7 equipment, 157
from room temperature up to 700 °C under a high-purity nitrogen flow 158
rate of 30 mL min−1. Physical integrity of the formed STHA must be 159
preserved during hydrovisbreaking reaction test to avoid powdering 160
and loss of active phase. Accordingly, the radial crush strength was 161
measured by the ASTM D 6175. 162
2.4. Characterization of Feeds and Products. The properties of 163
the heavy crude oil and its residua are shown in Table 1. Two residues 164 t1
(R274 and R343 °C+) were obtained by true boiling point (TBP) 165
distillation from the heavy crude oil by the ASTM D2892 method. 166
The characterization of the crude oil, residues, and hydrotreated oils 167
was performed by means of several analytical techniques. Liquid 168
Figure 1. Structure of poly bis(α-naphthyl) terephthalate. products were analyzed by simulated distillation gas chromatography 169

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Table 1. Properties of the Heavy Crude Oil and Residues In the hydrovisbreaking experiments including hydrogen donors, the 201
amount employed of both hydrogen donors was established based on 202
residue residue two criteria: using the same mass of hydrogen donor and an equivalent 203
property crude oil 274 °C+ 343 °C+ amount of hydrogen transferable by complete dehydrogenation. 204
specific gravity @ 60/60 °F 0.9910 1.0230 1.0391 Dehydrogenation of tetralin C10H12 to naphthalene C10H8 renders 2 205
API gravity 10.89 6.43 4.28 mol of H2, while based on the hydrogenated monomer C28H42O6, 13 206
kinematic viscosity, cSt mol of H2 may be transferred by complete dehydrogenation to form 207
37.8 °C 6110 458 079a 2,570 749a C28H16O6. Accordingly, 5.5 g of tetralin, with 97% purity represents 208
54.4 °C 1518 60 568a 873 888a 0.04 mol, which accounts for 0.08 mol of H2 transferable. On the other 209
hand, 5.5 g of ATHS with a polymer content of 50 wt % contains 2.8 g of 210
98.8 °C 120a 1480 86 152
the activated form of the monomer equivalent to 0.006 mol of 211
121.1 °C 51a 422 34 131 C28H42O6 that by complete dehydrogenation may donate 0.08 mol of 212
150.0 °C 22a 122 12 258 H2 . 213
Conradson carbon, wt % 17.58 19.73 21.40 The hydrovisbreaking experiments were performed in a 500 mL 214
a autoclave stainless steel reactor (Parr Instrument Company model
Estimated values. 215
4566). Reactor characteristics are maximum temperature, 500 °C; 216
170 (SIMDIS) to determine the boiling point distribution according to the maximum pressure, 13.8 MPa; equipped with a magnetic drive to 217
171 ASTM D7169 method, using an Agilent 7890 gas chromatograph with a provide a trouble-free linkage to an internal stirrer; internal cooling with 218
172 5-m length metallic column, 0.7 μm film diameter, and 0.53 mm inner temperature control; digital display of pressure and stirring speed; and 219
173 diameter; PAC software; and ultrahigh-purity helium (99.999%) as a equipped with a catalyst basket. The evaluated hydrogen transfer agents 220
174 carrier. API gravity was determined by the ASTM D287 method, were tetralin (97% purity), commercially available from Aldrich 221
175 specific gravity by the ASTM D70 method, and kinematic viscosity was Company, and the SHTA prepared from a polymer containing 222
176 measured using an Anton Paar Stabinger kinematic viscosimeter naphthalene units in its structure.15,17 223
177 according to the ASTM D445 method, with a measurement interval of 2 For hydrovisbreaking tests, components of the reaction system were 224
178 × 10−1 to 3 × 105 cSt. It is noteworthy to indicate that residua viscosity previously cleaned, inspected, and weighed. A typical experiment 225
179 cannot be experimentally measured at low temperatures, since it consisted of introducing 150 g of the heavy crude oil or residue into the 226
180 exceeds the measurement capabilities of the viscosimeter (3 × 105 cSt reactor. For the case of tetralin, 5.5 g of sample was mixed with the feed, 227
181 maximum); thus, some values included in Table 1 were estimated while for the SHTA, 5.5 g was placed into a fixed basket (annular- 228
182 according to the ASTM D341 method based on the experimental values shaped mesh basket). Then, the reactor was closed by means of a 229
183 measured at 90, 98.8, and 105 °C. standard procedure assisted by a torque wrench; subsequently, the 230
184 2.5. Evaluation of the SHTA. Three sets of hydrovisbreaking reactor was purged three times with nitrogen (UAP 99.999% inert 231
185 experiments in a batch reactor with each feed (12.1° API crude oil, atmosphere). Afterward, the reactor was pressurized up to 10.4 MPa 232
186 R274 and R343 °C+ residues) were performed: with nitrogen and leak test was performed by means of a hydrogen leak 233
detector. The reactor is depressurized and then pressurized with 234
187 (a) Hydrovisbreaking in the absence of hydrogen donor (HVB).
hydrogen up to 2.6 MPa at room temperature to obtain 6.2 MPa as 235
188 (b) Hydrovisbreaking using tetralin as a liquid hydrogen donor
initial reaction pressure by heating up to 430 °C. 236
189 (HVB+tetralin).
The reactor is immersed in a preheated sand bath to quickly reach a 237
190 (c) Hydrovisbreaking using SHTA as a heterogeneous hydrogen
temperature of 370 °C, and then placed inside specially manufactured 238
191 donor (HVB + SHTA).
electrical resistances to achieve rapid heating to reach the reaction 239
t2 192 A summary of the experiments is given in Table 2. For comparison temperature (430 °C) in approximately 3 min and stirring at 300 rpm. 240
193 purposes, in the experiments with residues, the hydrotreated product is Once the reaction temperature of 430 °C is reached, it is maintained for 241
10 min assisted by cooling air, stirring is continued, and pressure 242
Table 2. Experimental Tests with Heavy Crude Oil and buildup is recorded. After this period, the reactor is suddenly cooled to 243
Residuesa room temperature in an ice bath. The previous procedure is aimed to 244
avoid excessive coke formation during heating stages, and it was strictly 245
test H2 pressure tetralin SHTA temperature applied to all hydrovisbreaking experiments. 246
no. reactants (MPa) (g) (g) (°C) Once room temperature is reached, the reactor is weighed and the 247
1 crude oil 3.44 430 gas produced is subsequently exhausted, the reactor is reweighed, and 248
2 crude oil 3.44 5.5 430 the amount of gases produced is determined by weight difference. The 249
3 crude oil 3.44 5.5 430 reactor is opened to quantify the liquid product, also by weight 250
3.44 difference, since the exhaust gases are subtracted. Liquid samples are 251
recovered to perform product characterization. 252
4 R274 °C+ 3.44 430
In the case of experiments including SHTA, the metal mesh 253
5 R274 °C+ 3.44 5.5 430
containing the SHTA is removed, then immersed in a recipient 254
6 R274 °C+ 3.44 5.5 430 containing hot toluene, and various washing steps are executed until the 255
3.44 toluene became colorless. Finally, the recovered SHTA is dried and 256
7 R343 °C+ 3.44 430 weighed. It was found that the amount of spent SHTA was nearly the 257
8 R343 °C+ 3.44 5.5 430 same compared with the fresh SHTA loaded in all experiments, so 258
9 R343 °C+ 3.44 5.5 430 minimal adhesion of formed coke was detected. 259
10 crude oil 3.44 5.5* To determine the solid product yield (coke), the reaction product 260
a was decanted and a small sample (10 g) was diluted in hot toluene to 261
Reference test in the presence of pure Al2O3 support.
obtain the sediments content according to the ASTM D4807 method. 262
To determine the amount of coke, the liquid reaction products were 263
194 theoretically blended with the corresponding light fraction obtained by diluted in hot toluene and coke was separated and weighed. 264
195 TBP distillation, to determine the final properties of the upgraded oil. In
196 such a way, the effect of hydrogen donor can be evaluated by comparing 3. RESULTS AND DISCUSSION
197 changes in the properties of the heavy crude oil feed and the upgraded
198 oils. Crude oils obtained by blending the processed residues and their 3.1. Characterization of Polymer and SHTA. The 265
199 corresponding untreated light fraction are also referred to as compositions of polymer, fresh SHTA, and activated SHTA 266
f3 200 reconstituted oils. This approach is clearly illustrated in Figure 3. measured by elemental analysis are shown in Table 3. Polymer 267 t3

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Figure 3. Process schemes for comparison of hydrovisbreaking experiments with heavy crude oil and residues.

Table 3. Results of Elemental Analysis • The polymer structure in the fresh SHTA and SHTA after 304
hydrogenation is maintained into the support matrix 305
sample C, wt % H, wt % O, wt %
polymer 75 4 21
To know the thermal stability of the SHTA after hydro- 306

fresh SHTA 37 2 34
genation, it was evaluated by thermogravimetric analysis from 307

activated SHTA 36 5 33
the room temperature to 800 °C interval using 2.5 °C/min as a 308
heating rate and dry air or nitrogen as a carrier gas (Figure 6). 309 f6
The thermogram shows: 310

268 data correspond to the dehydrogenated form of the monomer • A mass loss of 8 wt % from 50 at 110 °C, which is ascribed 311
269 C28H16O6, and the fresh SHTA corresponds to this monomer to water evaporation (dehydration step). 312
270 supported on Al2O3 with a 50 wt % loading. Activated SHTA • A thermally stable material between 110 and 300 °C. 313
271 matches with the hydrogenated form of the monomer C28H42O6 • A gradual mass loss from 300 to 600 °C, which 314
272 supported on Al2O3. corresponds to the polymer decomposition and the 315
273 The FTIR spectra of fresh and hydrogenated SHTA are structural change from boehmite to aluminum oxide 316
f4 274 shown in Figure 4, from which the following observations can be (2AlOOH → Al2O3 + H2O). 317
275 made: • The SHTA after hydrogenation at 400 °C in a nitrogen 318
276 Fresh polymer (Figure 4a): atmosphere shows a stability interval from room temper- 319
277 • An important, intense band appears at 1735 cm−1, ature to near 450 °C. 320
278 characteristic of the ester CO group, and at 3067 • At temperatures from 450 to 585 °C, 50% mass loss is due 321
279 cm−1, the C−H aromatic rings stretching band; h to polymer decomposition and to the structural change of 322
280 ydrogenated polymer (Figure 4b): boehmite to aluminum oxide. 323
281 • The ester CO group disappears due to the hydro- • The results indicate that the SHTA after hydrogenation 324
282 genation of the carbonyl group, and a C−H stretching will be thermally stable at the reaction temperature (430 325
283 band appears at 2920 cm−1, showing a partial hydro- °C). 326
284 genation of the benzene ring The textural properties of boehmite support, polymer, and 327
285 ; both spectra (Figure 4a,b): SHTA after hydrogenation are listed in Table 4. The following 328 t4
286 • Combination bands are observed near 1900 cm−1, comments can be made from these results: 329
287 indicating that the benzene terephthalate is not hydro-
288 genated and only the naphthalene ring is hydrogenated, • The boehmite has an average pore size of 23 Å that is in 330

289 leading to the tetralin structure, which favors the the range of mesoporosity according to the IUPAC 331

290 hydrogen transfer from the polymer structure in the classification. Boehmite provides unique properties that 332

291 SHTA; enhance the manufacturing of the catalyst. The important 333

292 X-ray diffractograms of the support (boehmite), the attributes of catalysts such as surface area and porosity are 334

293 polymer, the fresh SHTA, and the SHTA after hydro- modified by incorporating boehmite into the catalyst raw 335

f5 294 genation are shown in Figure 5. These results indicate materials. 336

295 that: • The polymer shows poor textural properties, since it is not 337
296 • A crystalline structure with signals at 14, 28, 38, 49, and a porous material. 338
297 65° in the 2θ scale corresponds to boehmite AlO(OH) • The polymer has an average pore diameter of 122.8 Å, 339
298 used as a support which must be ascribed to void spaces between solid 340
299 • The polymer shows a broad peak at 26° in the 2θ scale due particles. 341
300 to their ordered structure • The SHTA after hydrogenation shows textural properties 342
301 • The diffractograms of the fresh SHTA and SHTA after relatively lower than most of the Al2O3 industrial 343
302 hydrogenation show signals due to both the boehmite supported catalysts. For instance, the specific surface 344
303 support and the organic polymer area is 128 m2/g in SHTA compared with 150−250 m2/g 345

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Figure 4. FTIR spectra of (a) fresh SHTA and (b) SHTA after hydrogenation.

346 in hydrotreating catalysts supported on Al2O3.18,19 This • The interaction between the organic polymer and the 360
347 effect is the result of the high loading of organic polymer inorganic matrix hinders the extraction of the whole 361
348 employed in the SHTA formulation (50 wt %). organic polymer structures, yielding the extraction of 362

349 The molecular weight distribution of the organic polymer and small fractions of the organic polymer using tetrahy- 363

f7 350 SHTA is shown in Figure 7. The following values were obtained: drofuran as a solvent. 364

351 • The weight-average molecular mass of the organic The radial crush strengths of the synthesized materials 365

352 polymer is 48 212 g/mol with the average number of obtained were 366

353 units in the polymer of around 102. • 4.9 N/mm for the fresh SHTA 367
354 • The weight-average molecular mass of the SHTA is 635 • 6.0 N/mm for the SHTA after hydrogenation 368
355 g/mol, which is 1.3 times the molecular mass of the 3.2. Evaluation of SHTA. Three feedstocks with API 369
356 hydrogenated monomer. ranging from 4.3 to 10.9° were used to evaluate the performance 370
357 • The lower molecular mass of the SHTA compared with of the proposed SHTA as a hydrogen donor. The hydro- 371
358 the organic polymer is due to the extraction of a fraction of visbreaking experiments were carried out in a batch reactor in 372
359 the organic polymer contained in the inorganic matrix. the absence of a hydrogen donor (HVB), using tetralin as a 373

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heavy crude oil that was separated before the hydrovisbreaking 379
experiment. 380
3.2.1. Products Distribution. Table 5 shows the distribution 381 t5
of products for different hydrovisbreaking experiments. The 382
expected effect of hydrogen donor is a reduction of the extent of 383
mild cracking reactions through capping free radicals so that its 384
effectiveness can be measured by the degree of diminishing of 385
the production of gases and/or coke. Prior to the tests, we 386
carried out a control experiment in triplicate, from which it was 387
determined that the amount of coke and gases falls within a 5% 388
interval of error, which is within typical the experimental error in 389
this type of setup. Based on this result, it can be stated that the 390
amount of gases produced in a series of experiments is roughly 391
the same. On the contrary, coke formation is clearly inhibited in 392
Figure 5. X-ray diffraction for (a) SHTA after hydrogenation, (b) fresh the experiments including tetralin and SHTA as hydrogen 393
SHTA, (c) organic polymer, and (d) boehmite.
donor, except for the case of processing R274 °C+, where the 394
amount of coke is the same with and without the hydrogen 395
donor additive. The reductions in coke formation result in a 396
concomitant positive rise in liquid product yields. In the case of 397
tetralin, the values must be taken cautiously since liquid yield is 398
also enhanced by the addition of liquid tetralin. For this reason, a 399
second value for liquid yield is included in Table 5, where the 400
contribution for liquid tetralin addition was discounted. Liquid 401
yields toward different crude oil fractions are discussed in detail 402
below. 403
3.2.2. Properties of Upgraded Crude Oil and Residues. The 404
results of API gravity and viscosity of the hydrotreated products 405
and of the upgraded oils according to the process scheme given 406
in Figure 3 are listed in Table 6. The highest improvement in 407 t6
product quality through API gravity is achieved using tetralin as 408
Figure 6. Thermogravimetric analysis of the SHTA: (---) TGA in air, a hydrogen donor for all of the feeds employed. Nonetheless, 409
(―) TGA in nitrogen.
experiments with SHTA showed similar values to those obtained 410

Table 4. Textural Properties of Polymer, Boehmite, and with tetralin with differences lower than 1°API. Clearly, 411

SHTA after Hydrogenation hydrovisbreaking experiments in the absence of hydrogen 412

donor showed the lowest enhancement of API gravity. This 413
SHTA after behavior can be readily visualized in Figure 8, in which the 414 f8
polymer boehmite hydrogenation evolution of API gravity of the processed crude oil by three 415
BET specific surface area, 1.5 304 128 approaches: hydrovisbreaking of the whole crude oil, hydro- 416
m2/g
visbreaking of only its 274 °C+ residue, or hydrovisbreaking of 417
total pore volume, cm3/g 0.005 0.436 0.164
only its 343 °C+ residue. It is important to highlight that the 418
average pore diameter, Å 122.8 23 19
experiments where tetralin was added as a hydrogen donor 419
include a slight improvement in product quality due to a dilution 420
effect. For this reason, in experiments with tetralin, two values of 421
API increment are disclosed: ΔAPI, which refers to increase in 422
gravity due to hydrovisbreaking, and ΔglobalAPI, which is the 423
result of the sum of hydrovisbreaking plus tetralin dilution effect. 424
According to the API trend, similar reductions in viscosity were 425
achieved by HVB assisted with tetralin or SHTA, where tetralin 426
showed a slightly higher improvement. In contrast, HVB alone 427
showed the minor viscosity drop (Table 6). Hence, HVB 428
assisted by a hydrogen donor, either tetralin or SHTA, renders 429
roughly the same improvement in quality and decrease in 430
viscosity, and both are superior to the hydrogen donor-free 431
HVB. 432
3.2.3. Composition of Upgraded Oils. The results of GC- 433
Figure 7. Molecular weight distribution determined by GPC for the simulated distillation were used to determine the composition of 434
SHTA and polymer. the hydrotreated oils. In simulated distillation, initial boiling 435
point (IBP) is defined as the temperature corresponding to an 436
374 liquid hydrogen donor (HVB + tetralin) and SHTA as a accumulated 0.5% of the total area of the eluted sample after 437
375 hydrogen donor (HVB + SHTA). The purpose of using two correcting for the percent of sample recovery. The following 438
376 residues derived from the same heavy crude oils is to determine fractions were considered: naphtha (IBP-204 °C), middle 439
377 the hydrogen capability of the developed material in the distillates (204−343 °C), gas oil (343−538 °C), and vacuum 440
378 presence of heavy hydrocarbons, i.e., the light fraction of the residue (538 °C+). The hydrotreated oils were integrated with 441

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Table 5. Product Distribution for the Hydrovisbreaking Experiments at 430 °C

gases coke liquid product
test reactants g g/g fed, % g g/g fed, % g g/g fed, %
1 crude oil + H2 3.6 2.4 7.4 4.9 139.4 92.9
2 crude oil + H2+ tetralin 3.8 2.5 4.5 3.0 147.5 98.3
142.0a 94.7a
3 crude oil + H2 + SHTA 3.5 2.3 5.6 3.7 141.3 94.2
4 R 274 °C+ H2 4.4 2.9 6.5 4.4 139.4 92.9
5 R 274 °C+ H2 + tetralin 5.2 3.5 6.8 4.5 143.8 95.9
138.3a 92.2a
6 R 274 °C+ H2 + SHTA 5.0 3.3 6.5 4.4 138.8 92.5
7 R 343 °C+ H2 4.8 3.2 8.2 5.5 137.3 91.5
8 R 343 °C+ H2 + tetralin 5.4 3.6 5.7 3.8 144.7 96.5
139.2a 92.8a
9 R 343 °C+ H2 + SHTA 5.0 3.3 6.4 4.3 138.9 92.6
10 crude oil + H2 + Al2O3 3.7 2.5 7.5 5.0 139.1 92.7
a
Data obtained by discounting the tetralin dilution effect.

Table 6. API Gravity and Viscosity of Hydrotreated Oils and Upgraded Oils at 430 °C
kinematic viscosity kinematic viscosity
test reactants API 37.8 °C 54.4 °C CCR wt %
feed crude oil 10.9 6110 1518 17.58
1 crude oil + H2 13.5 353 279 13.60
2 crude oil + H2 + tetralin 17.0 240 195 14.75
3 crude oil + H2 + SHTA 16.1 260 201 14.68
feed R 274 °C 6.4 458 079a 60 568a 19.73
4 R 274 °C+ H2 9.8 1392 1120 16.50
5 R 274 °C+ H2 + tetralin 17.1 723 478 15.79
6 R 274 °C+ H2 + SHTA 16.5 781 562 16.54
feed R 343 °C 4.3 2 570 749a 873 888a 21.40
7 R 343 °C+ H2 10.8 1296 950 17.23
8 R 343 °C+ tetralin 19.1 536 204 18.17
9 R 343 °C+ H2 + SHTA 18.2 625 335 20.05
Calculated Values by Blending According to Figure 2
crude from R 274 °C+ H2 15.67 252.5 144.1 14.58
crude from R 274 °C+ H2 + tetralin 22.11 180 122 14.00
crude from R 274 °C+ H2 + SHTA 21.67 178 114 14.61
crude from R 343 °C+ H2 18.15 113 75 14.00
crude from R 343 °C+ H2 + tetralin 24.76 83 47 14.84
crude from R 343 °C+ H2 + SHTA 24.15 80 37 14.90
10 crude oil + H2 + Al2O3 13.5 324 261 not determined
a
Estimated values.

442 the corresponding light fractions to obtain the upgraded oils, dehydrogenated derivatives also contribute to the product 460
443 which can be compared directly with the crude oil feedstock distribution. Since tetralin, naphthalene, cis-decalin, trans- 461
t7 444 (Table 7). To better identify changes in the distribution of decalin have normal boiling points of 207.6, 218, 196, and 187 462
445 fractions, the crude oil feedstock and the upgraded crude oils are °C, respectively, it is expected that these compounds would 463
f9 446 included in Figure 9. appear in the naphtha (IBP-204 °C) and middle distillate (204− 464
447 Figure 9a shows the case of hydrovisbreaking of the complete 343 °C) fractions. When SHTA is used, the amount of remnant 465
448 crude oil. In the HVB alone, the vacuum residue (VR) is cracked VR is roughly the same as in the case of HVB + tetralin, but the 466
449 to produce naphtha and middle distillates, but the gas oil fraction amount of gas oil is lower, while middle distillates and naphtha 467
450 remains practically unchanged. When the crude oil is processed are similar to the HVB alone. Hence, although both the 468
451 by HVB + tetralin, the VR reaction rate is faster yielding mainly performances of tetralin and SHTA are similar as hydrogen 469
452 gas oil, which is due to the change in reaction selectivity being donors, their effect on reaction selectivity may be different and 470
453 more hydrogenation-dominated than thermal cracking as a can be partially attributed to the fact that liquid hydrogen donor 471
454 consequence of the incorporation of the liquid hydrogen donor. remains in the upgraded oil while SHTA is not present in the 472
455 It is expected that upgraded oil fractions by thermal cracking composition of the product; thus, SHTA acts in a similar manner 473
456 evolve from heavy to light fractions in a cascade-type of reaction to a solid catalyst. Nonetheless, it is important to highlight that 474
457 mechanism: VR→gas oil→middle distillates→naphtha→gases. hydrogen provided by the SHTA comes from dehydrogenation 475
458 It is important to consider that as a consequence of reactions and not from an H−H bond scission by a metallic 476
459 incorporating a liquid hydrogen donor, tetralin and its catalytic site. Hence, SHTA is a macromolecule capable of 477

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Figure 8. Changes in API gravity of crude oil by three process schemes: hydrovisbreaking (HVB), hydrovisbreaking with tetralin incorporation, and
hydrovisbreaking with SHTA incorporation. (a) Crude oil hydrotreated directly, (b) hydrovisbreaking of R274 °C+ residue and incorporation of a
light fraction, and (c) hydrovisbreaking of R343 °C+ residue and incorporation of a light fraction.

Table 7. Volumetric Composition of Hydrotreated Oils and Upgraded Oils, % volume

test reactants naphtha IBP-240 °C middle distillates 204−343 °C gas oil 343−538 °C vacuum residue 538 °C+
crude 6.9 15.6 27.5 50.0
1 crude + H2 12.5 21.9 27.2 38.4
2 crude + H2 + tetralin 14.3 22.1 31.2 32.4
3 crude + H2 + SHTA 14.5 21.9 31.1 32.5
R 274 °C 0 9.4 29.1 61.5
4 R 274 °C +H2 6.1 18.7 28.5 46.7
5 R 274 °C + H2 + tetralin 8.1 19.5 36.8 35.6
6 R 274 °C + H2 + SHTA 5.9 19.7 37.9 36.5
R 343 °C 0 0 32.1 67.9
7 R 343 °C + H2 6.0 14.9 45.4 33.7
8 R 343 °C + H2+tetralin 5.8 16.5 52.2 25.5
9 R 343 °C + H2+SHTA 5.0 15.6 54.6 24.8
Calculated Values by Blending According to Figure 3
crude from HDT R 274 °C+ H2 9.8 27.2 27.3 35.7
crude from HDT R 274 °C+ tetralin 7.0 27.0 36.9 29.1
crude from HDT R 274 °C+ SHTA 9.6 26.5 34.4 29.5
crude from HDT R 343 °C+ H2 7.1 30.5 28.0 34.4
crude from HDT R 343 °C+ tetralin 7.3 30.8 36.0 25.9
crude from HDT R 343 °C+ SHTA 7.2 30.5 35.6 26.7
10 crude + H2 + Al2O3 13.7 21.1 25.9 39.3

478 donating hydrogen and rehydrogenating by molecular H2, but a composition is HVB + tetralin > HVB + SHTA > HVB; for 485
479 specific catalytic site cannot be identified. In that sense, SHTA is middle distillate, it is the same in all cases; and naphtha exhibited 486
480 different from a solid catalyst. the lowest values in the case of HVB + tetralin. 487
481 Figure 9b shows the composition of upgraded oil by The results of hydrovisbreaking the R343 °C+ are shown in 488
482 hydrovisbreaking the R274 °C+. Again, the VR composition is Figure 9c. The compositions of naphtha and middle distillates 489
483 similar in the two cases of HVB assisted by hydrogen donor and are the same for the three processed products. Both cases of 490
484 is higher than HVB alone. Interestingly, the trend in gas oil HVB + hydrogen donors show similar values in all fractions. The 491

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Figure 9. Volumetric composition of upgraded oils measured by GC-simulated distillation. (a) Crude oil processed directly, (b) hydrovisbreaking of
R274 °C+ residue and incorporation of light fraction, and (c) hydrovisbreaking of R343 °C+ residue and incorporation of light fraction. Vacuum
residue, gas oil, middle distillates, naphtha.

492 differences in product composition compared with HVB alone sample was recovered and the hydrogen content was measured 523
493 are evident. by gas refinery analysis in a gas chromatograph. The unreacted 524
494 To better visualize the effect of hydrogen donor additives, the hydrogen is computed by multiplying the hydrogen weight 525
495 volumes of the liquid fractions in the product for the different fraction by the total mass of gases experimentally measured. 526
f10 496 experiments is shown in Figure 10. In all of the set of Finally, the hydrogen consumption was calculated by the 527
497 experiments, the reference is the volume of the fractions difference between fed hydrogen and the content of hydrogen in 528
498 contained in 150 mL of the crude oil. Figure 10a−c shows the the gas product according to the following equation: 529
499 volume yields of the different fractions by processing the
500 complete crude oil, the reconstituted oil by processing only the H 2consumption = H 2feed − Wgas × YH2 product (1)
wt % 530
501 R274 °C+, and the reconstituted oil by processing the R343 °C
502 +. The numbers included in these figures as labels account for Conversion was calculated based on the volume of R538 °C+ 531
503 the difference between the volume of the fraction in the fed residue in the feed and the volume of R538 °C+ residue in the 532
504 crude oil and the volume of the fractions in the upgraded oil. For product. The said volumes were obtained from the correspond- 533
505 instance, the −27 label of the HVB + SHTA experiment for ing distillation plots. The conversion is calculated using the 534
506 vacuum residue (VR) in Figure 10a means that the difference following equation: 535

507 between the volume of VR in the fed crude oil and the volume of VR538 °C + feed + VR538 °C + product
508 VR in the upgraded oil corresponds to a decrease in volume of conversion(vol %) =
509 27 mL. A clear trend of higher production of gas oil and middle VR 538 °C + feed
510 distillates by hydrogen donor incorporation is evident in Figure × 100 (2) 536
511 10.
512 Figure 10 also shows higher volumetric yields of gas oil and The volumetric expansion on feed basis is calculated by the 537
513 middle distillates as the hydrocarbon feed becomes heavier, quotient of the volume of the liquid products obtained from the 538
514 which confirm the idea that processing heavier molecules HVB process divided by the volume of the feed expressed as a 539
515 resulted in improved quality. percentage, as indicated in the following expression: 540
516 3.2.4. Significant Data Processing. In this section, data
517 processing is described to obtain the following parameters: volumetric expansion, %
518 hydrogen consumption, conversion, volumetric yield, Con- volume of the HVB product
519 radson carbon residue (CCR) removal. = × 100
volume of the feed (3) 541
520 Feed hydrogen was computed by means of ideal gas law at
521 reactor startup conditions: room temperature, loading pressure, Removal of Conradson carbon residue content was calculated by 542
522 and gas volume (0.35 L). At the end of each reaction, a gas means of the next equation 543

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obtained by blending the hydrotreated R274 °C+ and R343 °C+ 556
residua with the corresponding light fraction are also included in 557
Table 8. Clearly, fractionating the crude oil and only processing 558
the heavy fraction render higher conversion, which enhances the 559
formation of light hydrocarbons, with the consequently higher 560
hydrogen consumption. For the processing of residue, the 561
conversion of residue is focused on the heavier compounds 562
contained in the crude oil, which produces lighter compounds 563
such as middle distillates and naphtha. 564
Hydrovisbreaking of heavy oils and residua causes significant 565
molecular weight reduction and increase in the production of 566
distillate fractions, which can be ascribed to the cleavage of the 567
C−C bonds (bond dissociation energy ∼70 kcal/mol). The 568
cleavage of the C−C bond during upgrading is believed to 569
proceed through a free-radical chain mechanism. The 570
incorporation of hydrogen donors in such processes produces 571
an enhancement of active hydrogen, which in turn produces 572
capping of free radicals. Hence, hydrogen donors function by 573
slowing excessive thermal cracking reactions allowing for tuning 574
selectivity to gas oil and/or middle distillates depending on the 575
feedstock type. Additionally, diminishing of coke production by 576
the slowing of condensation reactions (polymerization) is also 577
achieved using hydrogen donors. 578
Surface covering of STHA may be produced by coke buildup, 579
which results in lower transferring hydrogen capability 580
(deactivation). In the present research, the amounts of coke 581
produced in the experiments including SHTA are similar, which 582
does not allow a reliable estimation of the deactivation degree. In 583
this sense, further long-term experiments to directly measure 584
activity decay are required. 585
3.2.6. Aspects Related to Reaction Mechanism. The usage 586
of hydrogen donors as an additive is directed to increase 587
hydrogen availability in the liquid reaction media. In the 588
hydrovisbreaking experiments described in the present research, 589
the cracking of hydrocarbons is assumed to proceed via thermal 590
cracking through a free-radical mechanism. The mechanism 591
encompasses the next steps: (1) initiation by homolytic scission 592
of C−C bond; (2) chain propagation steps by several reactions 593
including hydrogen transfer, radical addition, radical decom- 594
position, and radical isomerization; and (3) the termination step 595
is the opposite to initiation, and it occurs by addition between 596
Figure 10. Yield of fractions obtained by processing different two radicals forming stable products.20−22 A simplified scheme 597
feedstocks: (a) HVB of crude oil, (b) HVB of R274 °C+, and (c) of this mechanism is depicted in Figure 11. 598 f11
HVB of R343 °C+. Based on the free-radical mechanism, the function of 599
hydrogen donors is to reduce the concentration of free radicals 600
CCR feed − CCR product by capping them through hydrogen transfer steps, and such an
CCR removal, % = × 100 601

544
CCR feed (4) idea of hydrogen donor role is presented in Figure 12. In a 602 f12
simple way, free radicals react with the hydrogen donor agent by 603
545 Hydrogen transferred by hydrogen donors was calculated as the hydrogen transfer reaction, yielding a stable hydrocarbon 604
546 difference between the hydrogen consumption in the presence product and the corresponding dehydrogenated form of the 605
547 and absence of hydrogen donor agent. In this regard, a transfer of four atoms of hydrogen may be 606
with ATHS or tetralin without ATHS or tetralin achieved by complete dehydrogenation of a tetralin molecule 607
H 2transferred = H 2 consumption − H 2 consumption
(Figure 12a), while the complete dehydrogenation of the 608
548 (5) saturated form of the monomer in SHTA renders 26 atoms of 609
549 3.2.5. Other Reaction Parameters. The values of conversion, hydrogen (Figure 12b). In line with the function of hydrogen 610
550 hydrogen consumption, and Conradson carbon residue removal donor disclosed in the present study, various authors have 611
t8 551 are included in Table 8. The conversion of the three processing consistently observed lowering of the amount of coke in thermal 612
552 options follows the trend HVB + tetralin > HVB + SHTA > HVB cracking of hydrocarbons when using hydrogen donors,23−36 613
553 for the three feedstocks employed. Accordingly, hydrogen which is a consequence of the decrease of free-radical 614
554 consumption follows the same trend as conversion. To compare concentration yielding a slowdown of polymerization reactions 615
555 the three approaches employed, the values for the upgraded oils that produce coke. 616

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Table 8. Parameters of the Hydrovisbreaking of Crude Oil and Residues

conversion H2 consumption volumetric expansion, CCR H2 transferred by donor,
test reactants vol % ft3/bbl vol % removal, % ft3/bbl
1 crude + H2 27.2 284 94.8 27.9 -
2 crude + H2 + tetralin 34.3 340 102.7 17.2 56
3 crude + H2 + SHTA 36.4 332 97.9 21.1 48
10 crude + H2 + Al2O3 29.4 291 95.2 27.5 58
4 R 274 °C+ H2 27.1 346 95.9 22.1 -
5 R 274 °C + H2 + tetralin 39.7 425 104.3 23.0 79
6 R 274 °C+ H2 + SHTA 40.5 417 100.2 22.1 71
7 R 343 °C+ H2 51.9 395 96.8 25.7 -
8 R 343 °C+ H2 + tetralin 59.4 493 108.0 17.8 98
9 R 343 °C+ H2 + SHTA 62.3 480 103.1 20.1 85
HDT R274 °C − [IBP-274 °C]a 31.1 297 96.0 22.1
HDT R274 °C+ tetralin [IBP-274 °C]a 39.7 365 103.7 23.0 68
HDT R274 °C+ SHTA - [IBP-274 °C]a 40.9 358 100.2 22.1 61
HDT R343 °C − [IBP-343 °C]b 32.9 308 97.5 25.7
HDT R343 °C+ tetralin [IBP-343 °C]b 44.9 384 103.2 17.8 76
HDT R343 °C+ SHTA - [IBP-343 °C]b 45.3 374 102.5 20.1 66
a
Reconstituted crude obtained by blending the hydrotreated R274 °C+ and the IBP-274 °C fraction. bReconstituted crude obtained by blending
the hydrotreated R343 °C+ and the IBP-343 °C fraction.

Figure 11. Thermal cracking by free-radical mechanism.

617 The thermal cracking of molecules contained in crude oil from hydrogen donors delays the cracking of bulky molecules, 638
618 heavy to light fractions is normally visualized according to the rendering higher selectivity to gas oil and intermediate distillates 639
619 following path: compared with the hydrovisbreaking without hydrogen donor. 640
Regarding gas production, since free radicals of small size are not 641
vacuum residue → gasoil → middle distillates → naphtha effective in capping either HVB or HVB assisted by hydrogen 642
→ gases donors, the amount of gas produced is practically the same in 643
both types of experiments. 644
620 Based on the proposed mechanism depicted in Figure 10, the It is important to highlight that not all of the steps included in 645
621 presence of hydrogen donor additives facilitates the hydrogen the proposed mechanism depicted in Figure 10 imply cracking 646
622 transfer reaction, thus resulting in diminishing the free-radical of molecules producing each time shorter ones. The radical 647
623 concentration. It may be expected that capping of free radicals
addition step involves the reaction between olefin and a free 648
624 slows down all of the propagation steps. By this consideration,
radical yielding a longer molecule. In fact, this is the path toward 649
625 experiments assisted with hydrogen donors should present
626 lower values of conversion and gas production than without gradual growth of molecules as to produce coke. 650

627 hydrogen donors, that is, only the HVB. However, the results Assuming that a free-radical mechanism is quite reasonable in 651

628 disclosed in the present research showed higher conversion and the case of experiments in the absence of solid additives 652

629 roughly the same gas production by including hydrogen donors. (experiments 1, 2, 4, 5, 7, and 9), in experiments including 653

630 The results in the trend of conversion and gas production SHTA, a contribution to conversion of residue by catalytic 654
631 found by adding hydrogen donors to HVB are explained by mechanism may arise if a contribution of acid sites in the support 655
632 hypothesizing that during the processing of bulky molecules of is important. In this sense, the possibility of existence of strong 656
633 heavy fractions, the initial bond-breaking step takes place at acid sites in the pure Al2O3 support is low. Moreover, SHTA was 657
634 outer or exposed branches, generating two radicals with different synthesized with a high loading of polymer (50 wt %), which is 658
635 sizes, big and small. The functioning of hydrogen donors at enough to completely cover the support surface. Hence, a 659
636 capping free radicals is more effective facing radicals of big size negligible contribution of hydrocracking includes breaking of 660
637 compared with small ones. Accordingly, the presence of hydrocarbon molecules into simpler molecules by the addition 661

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By processing only the heavy fraction of the crude oil, the 695
upgrading in product quality is higher than processing the whole 696
crude oil. This approach allows us to focus on the transformation 697
of the higher-molecular-weight hydrocarbons located in the 698
heavy fraction of the crude oil. The decision of processing the 699
whole crude oil or only the heavy fraction depends on 700
economical aspects. 701

■ AUTHOR INFORMATION
Corresponding Author
702

703
Jorge Ancheyta − Instituto Mexicano del Petróleo, México City 704
07730, México; orcid.org/0000-0001-9626-637X; 705
Email: jancheyt@imp.mx 706

Authors 707
Laura O. Alemán-Vázquez − Instituto Mexicano del Petróleo, 708
México City 07730, México 709
Pablo Torres-Mancera − Instituto Mexicano del Petróleo, 710
México City 07730, México 711
José A. D. Muñoz − Instituto Mexicano del Petróleo, México 712
City 07730, México 713

Complete contact information is available at: 714

https://pubs.acs.org/10.1021/acs.energyfuels.0c01680 715

Figure 12. Thermal cracking of hydrocarbons assisted by hydrogen

donors: (a) tetralin and (b) SHTA. Notes 716
The authors declare no competing financial interest. 717

662
663
of hydrogen under high pressure and in the presence of a catalyst
and occurring by carbonium ion mechanism. Coherently,
■ ACKNOWLEDGMENTS
The authors thank the Mexican Institute of Petroleum for
718

719
experiments of visbreaking using the pure Al2O3 support supporting this research project. 720

■
664
665 showed roughly the same results as the pure thermal
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M https://dx.doi.org/10.1021/acs.energyfuels.0c01680
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