Article Cite This: Energy Fuels XXXX, XXX, XXX−XXX
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Study on Atmospheric Distillation of Some Plain and Chemically Dispersed Crude Oils: Comparison of Yields and Fuel Quality of Distillate Fractions Imtiaz Ahmad,*,† Sayed Muhammad Sohail,† Hizbullah Khan,‡ Waqas Ahmad,† Kashif Gul,† Razia Khan,† and Aftab Yasin§ †
Institute of Chemical Sciences, and ‡Department of Environmental Sciences, University of Peshawar, Peshawar, 25120, Pakistan Hydrocarbon Development Institute of Pakistan, Peshawar Operation, Hayatabad, Peshawar, 25120, Pakistan
§
ABSTRACT: This paper discusses the distillation behavior of the plain (control) and chemically dispersed crude oils. The oils used were paraffinic (denoted as P-RCP-I), naphthenic (denoted as P-RCN-II), and aromatic (denoted as P-RCA-III) crudes. The chemical dispersants used were anionic, cationic, and neutral surfactants including sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), and Triton X-100 (a branched p-octylphenol with an average of 9−10 ethylene oxide units). The effect of Dispersant-to-Oil ratio on the yields of distillate fractions (gasoline and diesel) was investigated. Looking at the results, we conclude that using chemically dispersed crudes enabled us to obtain better yields of light distillate fractions (F1 and F2) in comparison with the control. Among the dispersants used, the SDS was more effective in RCA-III crude where the yield of F1 increased significantly to 58% and that of residue decreased to 6%. The CTAB was found to be more effective in RCN-II crude, which gave a significant increase in yields of F1 to 49% with corresponding decrease in R yield, while the Triton X-100 also proved to be more effective in RCN-II crude which gave 48% and 6% yields of F1 and R fractions, respectively. The fuel properties of the resultant fractions derived from chemically dispersed crudes did not disturb and remained within the ranges prescribed for petrofuels. dispersed catalytic upgradation,11 etc. However, these methods alter the chemical composition of the derived light fractions and disturb the physico-chemical properties which create difficulties in using them as premier fuels in the energy sector. Further, most of these methods are tedious, costly, and require severe reaction conditions, i.e., high temperature, high hydrogen partial pressure, and catalysts. To avoid these problems, new technologies in oil refining like hydrogen addition and carbon rejection, deasphalting, gasification, delayed coking, residue fluid catalytic cracking (RFCC), ebullated-bed hydrocracking, slurry-phase hydrocracking, fixed-bed hydro-treating, microwave extraction, treatment with ionic liquids, etc.,12−16 are being sought aimed at increasing yields of light distillate fractions with desired fuel properties.17,18 However, integrated schemes are still needed focusing on product yields, composition, quality of products, elimination of low-value byproducts, reduction in impurities/ coking, etc. Thus, there is a dire need to develop new costeffective and feasible methods so as to get the last drop of distillable oil. The main factors responsible for high amount of residual fractions during atmospheric distillation of petroleum crudes are the heavy molecular weight constituents of crude oil like asphaltenes and resins.19−21 Under ordinary atmospheric pressure distillation, the giant asphaltic and resinous molecules are not suffered from thermal scissions, remain intact, and
1. INTRODUCTION Crude oil after preliminary treatments is subjected to refining so as to get marketable products like naphtha, gasoline, kerosene, diesel fuel, lubricating oil feed stock, furnace oil, etc., and a large amount of asphalt/bitumen is left over as residue (10−35%).1 Owing to its high viscosity, density, and contamination by sediments as well as high asphaltene and resin contents, the residue cannot be directly used as a boiler fuel and instead used for nonfuel purposes.2,3 The global demand for energy continues and will increase over the next few decades as the world’s energy consumption will increase phenomenally in the next few decades. Alternative energy sources like nuclear and renewable energy have attracted much attention in the recent years; however, the main role of these sources will be to supplant, rather than to substitute the fossil fuels. Therefore, major breakthroughs in the oil industry’s core science and engineering are needed so as to meet with the World’s growing energy demand for petrofuels. Most of the research is devoted to explore challenges like poor/profitable yields of premium fuels and high amount of less or nonprofitable residual fuels, being faced in oil refining.4−6The high yields of residue/residuum is an ongoing challenge at a refinery, and economic and strategic reasons demand the exploitation of residual streams. Accordingly, the selection of proper processes may play a key role so as to cope with this challenge. Ample research is underway on upgrading crude oil and processing of heavy residues so as to get high yields of low molecular weight fraction(s) through delayed coking,2 thermal cracking,7 catalytic cracking,8 hydrocracking,9 steam cracking,10 © XXXX American Chemical Society
Received: September 26, 2017 Revised: November 30, 2017
A
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
Article
Energy & Fuels thereby concentrate in residues. Further, these constituents tend to form stable aggregates, hence keeping some hydrocarbons including sterane biomarkers, polyaromatic hydrocarbons, C27−C31 hopanes, and resins caged/occluded within asphaltenes via strong intermolecular forces.22 Modifications in the conventional atmospheric distillation to increase the yields without reducing the quality of the derived premium fuels could be a better solution. Among the modified distillation processes, thermally coupled distillation, reactive distillation, and molecular distillation are being researched at bench scale with greater success.23,24 However, further research for pilot plant exploitation is needed. Asphaltenes have an island architecture, which provides space/rooms for the occluded hydrocarbons. Such occluded compounds are protected from thermal degradation during distillation and even during petroleum formation by diagenesis.25 It is possible to release occluded components, using heat treatment, in a process similar to the way biomarkers are released from the kerogen during crude oil generation.26 However, this is possible only if the interaction between the adjoined asphaltene molecules is disrupted so as to open up caged hydrocarbons. Surfactant-assisted distillation has been reported elsewhere27,28 with greater success in this regard. However, research on the role of surfactants particularly chemical surfactants in petroleum refining/distillation is still rare. The idea of the present work is to explore the efficacy of chemical surfactants as dispersants so as to release the oil occluded/caged within the asphaltenes framework by exposing to distillation conditions to increase the yield of light distillate fractions, i.e., gasoline and diesel fuels, from crude oils under study without disturbing key fuel properties.
temperature sensor. A thermometer was inserted into the flask at the proper location, not submerged into the fluid and positioned at the low point of distillate takeoff. The assembly was mounted on a temperature controlled heater. The flask was connected to a built-in condenser and heated so as to maintain a distillation rate of 4−5 mL min−1. The volume measurements were made in a level-stabilized receiver with an illuminated screen at the background. In order to determine the yields of gasoline, diesel, heavy fractions, and residue, each crude oil was distilled into three fractions and residue, i.e., light fraction designated as F1 [initial boiling point (IBP) to 160 °C], medium fraction designated as F2 (160−250−380 °C), heavy faction designated as F3 (250−340 °C), and residue designated as R (>340 °C) in distillation of plain as well as chemically dispersed crudes. The plain crudes were designated as light crude (P-RCP-I), medium crude (P-RCN-II), and heavy crude (P-RCA-III), while the chemically dispersed crudes were designated as SDS-dispersed crudes (CD1-RCP-I, CD1-RCN-II, and CD1-RCA-III), the CTAB-dispersed crudes (CD2-RCP-I, CD2-RCN-II, and CD2-RCA-III), and the Triton X-100-dispersed crudes (CD3-RCP-I, CD3-RCN-II, and CD3-RCAIII). All experiments were performed twice so as to ensure reproducibility. 2.4. Characterization. 2.4.1. Characterization of Crude Oils. The crude oils were characterized by determining their physicochemical properties as described by ASTM methods. Properties like density (ASTM D1480), specific gravity and American Petroleum Institute (API) gravity (ASTM D4052), Conradson carbon residue (ASTM D189-05), ash (ASTM D189-05), kinematic viscosity (ASTM 445), pour point (ASTM D97-05), flash point (ASTM D93), aniline point (ASTM D611-04), total acid number and total base number (ASTM D974-14e1) and asphaltenes content (ASTM D6560-12), Watson characterization factor (K) (ASTM D86), and the Correlation Index (C.I.)29 were determined. K and C.I. were determined according to eqs 1 and 2 as
2. EXPERIMENTAL SECTION
where Tb (K) is the average boiling point in Rankine (°R) and SG is the specific gravity determined at 15.6/15.6 °C. C.I. was determined as
K=
2.1. Chemicals and Reagents. Three oils, i.e., paraffinic crude, naphthenic crude, and aromatic-based crude, denoted as RCP-I, RCN-II, and RCA-III, respectively, and distinguished by their physico-chemical properties were used in this work. The preliminary characterizations were carried out by standard ASTM/IP methods. Anionic surfactant (SDS), cationic surfactant (CTAB), and nonionic surfactant (Triton X-100) were obtained from commercial sources. Ethyl alcohol (AR-grade) was procured from Merck. Other chemicals/solvents used were of analytical grade and used without further purification. 2.2. Preparation of Solutions. The stock solution (30%) of each surfactant was prepared by weighing 30 g of the reagent and dissolving in ethanol (Merck), making a total volume up to 100 mL in a volumetric flask. The solution was homogenized by constant stirring using a magnetic stirrer for 15 min. The different working solutions were then prepared within the concentration range of 5−30% by pipetting out an adequate amount from the stock solution and consequently diluting with the solvent. Each flask was then labeled and stored for further use. The as received crude oils were homogenized by mild heating using a magnetic stirrer for 20 min. The chemically dispersed samples were then prepared in different DORs of 5:100, 10:100, 15:100, 20:100, 25:100, and 30:100 by stirring and mild heating. The samples were subsequently subjected to atmospheric pressure distillation studies. 2.3. Atmospheric Pressure Distillation. The plain as well as the chemically dispersed crude oils were subjected to atmospheric pressure distillation using an automatic distillation apparatus (Stanhope-SETA) according to the American Society for Testing and Material standard method (ASTM D86). The apparatus was calibrated prior to experiments. In a typical run, a 100 mL aliquot of the prewarmed crude oil was trickled into a distillation flask, a 500 mL round-bottom flask provided with a side arm, coupled to a
1.216 3 Tb SG
C.I. = 87552/TB + 473.7G − 456.8
(1)
(2)
where TB is the average boiling point in Rankine (°R) and G is the specific gravity determined at 15.6/15.6 °C. 2.4.2. Characterization of Surfactants. The thermal stability of each surfactant was determined by a Thermo-gravimetric analyzer (Diamond TG/DTA, PerkinElmer, USA). The experimental conditions used were: heating rate, 10 °C min−1; O2 atmosphere, 50 mL min−1; and temperature, from ambient to 300 °C. 2.4.3. Fuel Properties of Distillate Fractions. The distillate fractions (F1, F2, and F3) derived from each crude oil were characterized by physico-chemical methods. The key fuel properties including density, specific gravity, and American Petroleum Institute (API) gravity, Conradson carbon residue, ash, kinematic viscosity, pour point, flash point, aniline point, calorific value (ASTM D480913/IP 12), diesel index, octane number (ASTM D2699-16e1), and cetane number (ASTM D613-16a) were determined.
3. RESULTS AND DISCUSSION 3.1. Characterization of Raw Crudes and Surfactants. The physico-chemical properties of the raw crudes, i.e., PRCP-I, P-RCN-II, and P-RCA-III, were determined and are summarized in Table 1.The API gravities were determined to be 54, 35, and 19 °API, respectively. The light crude usually has an API gravity higher than 31.1 °API, the medium crude has 31.1−22.3 °API, while the heavy crude has 22.3−10 °API. The other properties determined were the total acid number as 0.41, 9.54, and 0.48 mgKOH/g; the total base number as 5, 10, B
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
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However, the thermal stabilities were less pronounced when the temperature was increased from 250 to 300 °C. The results inferred that the three surfactants used were found to be thermally stable in the temperature range selected for the distillation study of the crude oils. 3.2. Plain Crudes. The atmospheric distillation of the three plain crudes was carried out separately, and the product distribution of F1, F2, F3, and R was studied. The results are assembled in Figure 2. It can be seen that the P-RCN-II gave the highest amounts of F1 (IBP to 180 °C), the P-RCP-I gave the highest amount of F2 (180−250 °C), while the P-RCA-III gave the highest amount of F3 (250−350 °C). The amounts of the residue observed to be 27, 20, and 22% in the P-RCP-I, PRCN-II, and P-RCA-III, respectively. Overall, the P-RCP-I gave 32% F1, 25% F2, 16% F3, and 27% R, the P-RCN-II gave 40% F1, 25% F2, 15% F3, and 20% R, while the P-RCA-III gave 24% F1, 21% F2, 23% F3, and 32% R. The atmospheric residue describes the material at the bottom of the atmospheric distillation, which has an atmospheric equivalent temperature (AET) above 380 °C.30 It can be seen that all samples contained a high amount of residues, particularly the P-RCA-III. The reason for the diverse yields can be thought of as the differences in elemental/ chemical compositions of the three crudes which may be due to biotic source materials, source rocks, depositional environment, and diagenetic and thermal history. As reported earlier, more-aromatic, higher-boiling fractions and resides are dominated by polynuclear aromatics (e.g., multi-ring cycloalkane, aromatic, and polyaromatic structures) with minimal alkyl branching, are less reactive than fractions with higher H/ C ratios,31 and gave high yields of residue. The difference in aspahltenes, sulfur, and nitrogen containing compounds as well as occluded hydrocarbons °C32−34 which concentrate in residues can be the other obvious reason. 3.3. Chemically Dispersed Crudes. The results of the plain crudes confirmed that a significant amount of the residue is left over in all samples under study. The influence of various surfactants used in different DORs on the distillation behavior of the crude oils and the yields of the FI, F2, and F3 as a function of DOR was discussed. 3.3.1. SDS-Dispersed Crudes. In the first step, the SDS was used as a typical anionic surfactant in different DORs and the yields of the F1, F2, and F3 as a function of DOR were studied. Each of the three crudes was dispersed with SDS in different DORs, and the results are compiled in Figure 3 panels a−c. The optimum DOR was decided from the yields of light distillate fractions (gasoline and diesel). It can be observed that the yields increased with the increase in DOR in CD1-RCP-I crude (Figure 3 panel a) and CD1-RCN-II crude (Figure 3 panel b) where the optimum ratio was found to be 20:100, whereas the CD1-RCA-III crude (Figure 3 panel c) behaved differently, where 30:100 appeared to be the optimum ratio. As
Table 1. Physico-Chemical Properties of Plain Crudes property
unit
base/type of sample density API gravity @ 60 °F carbon residue kinematic viscosity @ 40 °C pour point flash point aniline point total acid number total base number asphaltenes Watson characterization constant correlation index
P-RCP-I
P-RCN-II
P-RCA-III
g/cm3
paraffinic 0.76 54
naphthenic 0.85 35
aromatic 0.94 19
% wt cSt
0.98 10.50
0.92 08.50
0.99 14.40
°C °C °C mgKOH/g mgKOH/g % wt
−12 96 86 0.41 5.00 10 12
−14 93 88 0.54 6.00 10 11
−16 96 90 0.48 7.00 12 10
8.74
54.08
90.82
and 12 mgKOH/g; and asphaltene contents as 10, 10, and 12 wt (%), respectively. The K factor is used to classify a crude oil based on its paraffinic, naphthenic, intermediate, or aromatic nature. A K value of 12.5 or higher indicates that a crude oil is predominantly paraffinic, whereas a 10 or lower value indicates its aromatic nature. For naphthenic crude, the K value varies from 10.5 to 12.9. The K values were found to be 12, 11, and 10, respectively. The C.I. values falling between 0 and 15 indicates a predominance of paraffinic hydrocarbons, 15−50 indicates predominance of either naphthenes or mixtures of paraffins, naphthenes, and aromatics, whereas values more than 50 indicate a predominance of aromatic species.29 The C.I. was found to be 8.74, 54.08, and 90.82, respectively. All characteristics are found to be typical to most crude oils. The overall results concluded that the P-RCP-1 is light crude, P-RCN-II is medium crude, while P-RCA-III is heavy crude. The properties of different surfactants as provided by the manufacturers are listed in Table-2. The TG study of the three surfactants was also carried out in the temperature range of 30−300 °C. The weight losses as a function of temperature were determined at a programmed heating rate of 10 °C/min, starting at 30 °C under air atmosphere. The thermograms are provided in Figure 1 panels a−c. It can be seen that all samples have almost similar curves with two stages of weight loss. For SDS, the weight losses were observed to be 2.5% and 66.5%, in the first and second stages, respectively. The weight loss observed for CTAB was 3% in the first stage, while 93% in the second stage. For Triton X-100, the weight losses were observed to be 10% and 90%, respectively. It can be seen that the weight loss is less significant in the first stage which is due to the large carbon chain framework of the surfactants and may be due to the decomposition of the functional groups. Table 2. Properties of Various Surfactants property chemical formulaa type/chargea molecular massa critical micelle concentrationa solubility in methanola
unit
Gm g/mol
CTAB
SDS
Triton X-100
C19H42BrN cationic 364.45 0.92−1.0 soluble
NaC12H25SO4 anionic 288.30 8.20 soluble
C14H22O(C2H4O)n neutral 647 0.2−0.9 soluble
a
The properties listed by the manufacturer(s) on the labels. C
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
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Figure 1. Thermograms of various dispersants: (a) SDS, (b) CTAB, and (c) Triton X-100.
26%, respectively. As the RCP-I crude was found to be light crude, hence the recovery of F1 was higher which further increased to a maximum of 56% in the chemically dispersed sample. Similar was the case of RCN-II crude, which was found to be a medium crude; the yield of F1 increased from 40% to 46% and the % R decreased from 20% to 7% in the dispersed sample. However, the differences in the % recovery of F2 and F3 were less pronounced. The effect of dispersant (SDS) on distribution of various fractions was very prominent in the RCA-III crude which was found to be heavy crude where the % recovery of F1 increased from 24% to 58%, while that of R decreased from 32% to about 6%. 3.3.2. CTAB-Dispersed Crudes. In the second step, all crudes were dispersed with a cationic surfactant separately and CTAB was used as a typical dispersant in different ratios so as to study the influence of DORs on the yields of different distillate fractions. Each of the three crudes was treated with this dispersant in different DORs, i.e., 0:100, 5:100, 10:100, 15:100, 20:100, 25:100, and 30:100, and subjected to fractional distillation under the same experimental conditions so as to investigate the optimum ratio of dispersant required for getting the distillate fractions in high yields. The results are displayed in Figure 4 panels a−c, which evidenced that the yield of light fractions linearly increased with the increase in DOR, in all of the three crudes. In RCP-I crude (Figure 4 panel a), a DOR of 20:100 caused a significant increase in the yield of F1 (from 32% to 39%), whereas the yield of R decreased (from 27% to 13%). The yields of F2 as well as F3 also increased slightly from 25% and 16% (plain crude) to 28% and 20% (in chemically dispersed crude). It can be seen that the yields of the distillate fractions increased at the expense of the residue, and almost 50% reduction can be noticed in the residue. The optimum DORs were also determined for RCN-II and RCA-III crudes. The results are compiled in Figure 4 panels b and c. It was observed that, under a DOR of 20:100, both crudes gave the high yields of distillate fractions. An increase can be observed in the yield of F1, from 40% (control) to 49%, whereas the yields of F3 slightly increased from 15% to 18%, respectively, in CD2-RCNII crude. The yield of F2 remained unaffected, whereas that of R exhibited a significant change (almost 3 fold) and reduced to
Figure 2. Yields of distillate fractions derived from P-RCP-I, P-RCNII, and P-RCA-III crudes.
confirmed from the characterization of the three crudes, the PRCA-III is a heavy crude and thus requires a high amount of the SDS so as to partition/solvate the high concentration of aromatic and polar constituents by decreasing its polarity and vanishing the interactions between them, thereby exposing the occluded/caged hydrocarbons within the asphaltene’s network to distillation compared to the P-RCP-I and P-RCN-II crudes which are paraffinic and naphthenic, respectively, containing lesser amounts of aromatic and polar constituents. As reported earlier, the solubility of hydrocarbons increases linearly with increasing surfactant concentration as a consequence of association between the PAH and micelles above the critical micellar concentration, CMC.35Heteroatom-containing compounds, especially polar molecules, which concentrate in heavy, high-viscosity crudes are responsible for difficulties in refining, and deposit formation of petroleum.36 As can be seen from the compiled results, under optimum DOR, the yields of F1 and F2 considerably increased, whereas those of F3 and R decreased in comparison with the plain counterparts. The results inferred that the yields of F1 and F2 increased at the expense of F3 and R. For CD1-RCP-I crude, the % yields of F1 and F2 increased from 32% and 25% (in PRCP-I) to 56% and 36%, respectively. On the other hand, the yields of F3 and R decreased to 12% and 9% from 16% and D
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
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Figure 3. Yields of distillate fractions derived from chemically dispersed crudes as a function of SDS-to-oil ratio: (a) CD1-RCP-I, (b) CD1-RCN-II, and (c) CD1-RCA-III.
7% compared to 20% in the plain crude. Similarly, in CD2RCA-III crude, the yield of F1 increased from 24% to 31% and that of F3 from 23% to 28%, while F2 remained the same. The R decreased from 32% to 19%. It is evident from the compiled results that, in all three crudes, under the optimum DORs, the yields of F1 significantly increased, F2 slightly increased, F3 was less influenced, while that of R decreased significantly. The results showed that CTAB was more effective in reducing the residue in all three crudes. The cationic surfactant was observed to be capable of solvating the hydrocarbons with boiling points close to F1 and F2 fractions. 3.3.3. Triton X-100-Dispersed Crudes. In the third step, the three crudes were dispersed with a typical neutral surfactant, i.e., Triton X-100 in different DORs. The distributions of F1, F2, F3, and R as a function of DOR are shown in Figure 5 panels a−c. In CD-RCP-I crude (Figure 5 panel a), the yield of light fractions increased, while that of the residue decreased with the increase in DOR. The optimum DOR was found to be 30:100, under which the yield of F1 increased to 39% (from initial of 32% in plain crude), and that of R decreased from
27% to 11%. At a 30:100 ratio, the yields of F2 and F3 increased from 25% and 16% (plain crude) to 27% and 23%, respectively. Like the other surfactants, the TTX-100 also decreased the yield of R almost >50%, with a corresponding increase in the yields of F2, F2, and F3. Similar was the case of CD3-RCN-II crude (Figure 4 panel b), where the optimum DOR was found to be 30:100. Under optimum ratio, the yield of F1 increased from 40% (plain crude) to 48%, whereas that of R decreased from 20% to about 06%. Likewise, the yield of F3 also increased from 15% to 21%, whereas that of F2 remained unchanged. In CD3-RCA-III crude (Figure 5 panel c), the maximum yields of F1 and F2 were obtained under DOR of 20:100. It can be observed that, under this optimum DOR, the yields of F1 and F2 increased from 24% and 21% to 32% and 34%, respectively, whereas that of R decreased from 32% to 13%. Similarly, the yield of F3 also decreased from 23% to 21%. Hence, in heavy crude, the TTX decreased the yield of not only the residue but also the F3 fraction, with corresponding increase in the yields of F1 and F2. This may be attributed to the nonpolar (neutral) nature of the surfactant, which may E
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
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Figure 4. Yields of distillate fractions derived from chemically dispersed crudes as a function of CTAB-to-oil ratio: (a) CD2-RCP-I, (b) CD2-RCNII, and (c) CD2-RCA-III.
(0.034, 0.003, and 0.018% wt), viscosity (1.22, 1.44, and 4 cSt), pour point (−20, −22, and −12 °C), flash point (46, 48, and 88 °C), aniline point (73, 74, and 71 °C), calorific value (46, 45, and 44 MJ/kg), calculated diesel index (39.91, 26.64, and 24.14), octane number (80, 72, and 65), and cetane number (40, 46, and 76), respectively. The results of distillate fractions derived from P-RCN-II crude are compiled in Table 4 and found to be as follows: density (0.75, 0.83, and 0.86 g/cm3), API gravity (54, 38, and 33 °API), CCR (0.97, 0.99, and 0.99% wt), ash (negligible), viscosity (0.7, 1.013, and 2.26 cSt), pour point (−20, −16, and −12 °C), flash point (42, 48, and 88 °C), aniline point (71, 72, and 70 °C), calorific value (45, 45, and 43 MJ/kg), calculated diesel index (38.34, 27.36, and 23.10), octane number (78, 58, and 61), and cetane number (42, 49, and 78)), respectively. The results of distillate fractions derived from P-RCA-III crude oil are displayed in Table 5 and found to be as follows: density (0.79, 0.83, and 0.86 g/cm3), API gravity (47, 39, and 33 °API), CCR (0.99, 0.99, and 0.99% wt), ash (negligible), viscosity (2.07, 2.23, and 2.50 cSt), pour point (−22, −20, and −15 °C), flash point (46, 48, and 75 °C), aniline point (69, 68, and 66 °C), calorific value (47, 46, and 46 MJ/kg), calculated
have experienced less hindrance during interaction with heavier molecules in the residue. 3.4. Key Fuel Properties of Distillate Fractions. All fuel standards have their own specifications that can be classified in line with their relation to the origin of the fuels (fossil or others), the process used to synthesize and or refine, and the type of application, i.e., stationary, marine, or transport diesel engine. The ASTM D396 called “Standard Specification for Fuel Oils” is the most widely used standard to qualify fuel oils.37,38 The distillate fractions, i.e., F1, F2, and F3, obtained from the atmospheric distillation of plain and chemically dispersed crudes were characterized in terms of key physicochemical parameters including density, specific gravity, API gravity, pour point, kinematic viscosity, carbon residue, ash, flash point, aniline point, heating value, diesel index, octane number, cetane number, antiknock index, etc., and the results were compared with the standard specifications. 3.4.1. Distillate Fractions from Distillation of Plain Crudes. The different key fuel properties of the distillate fractions derived from P-RCP-I crude were determined. The results are compiled in Table 3. The properties were found to be as follows: density (0.76, 0.84, and 0.85 g/cm3), API gravity (54.68, 36, and 34 °API), CCR (0.97, 0.99, and 0.99% wt), ash F
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
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Energy & Fuels
Figure 5. Yields of distillate fractions derived from chemically dispersed crudes as a function of Triton X-100-to-oil ratio: (a) CD3-RCP-I, (b) CD3RCN-II, and (c) CD3-RCA-III.
Table 3. Physico-Chemical Properties of Light, Middle, and Heavy Oil Fractions Derived from Distillation of Plain and Various Chemically Dispersed RCP-I Samples P-RCP-I
CD1- RCP-I
CD2- RCP-I
CD3- RCP-I
property
unit
F1
F2
F3
F1
F2
F3
F1
F2
F3
F1
F2
F3
density @ 15 °C API gravity @ 60 °F carbon residue ash kinematic viscosity @ 40 °C pour point flash point aniline point calorific value diesel index octane number cetane number
g/cm3
0.76 54.68 0.972 0.034 1.255 −20 46 73 46 39.91 80 40
0.84 36 0.996 0.003 1.448 −22 48 74 45 26.64 72 46
0.85 34 0.997 0.018 4.00 −12 88 71 44 24.14 65 76
0.76 54 0.89 0.11 2.268 −10 34 74 48 39.96 96 46
0.83 39 0.965 0.039 2.293 −12 36 76 46 29.64 88 58
0.90 26 0.989 0.016 2.316 −9 70 70 45 18.20 75 84
0.787 50 0.991 0.014 3.95 −20 38 73 48 36.50 94 45
0.870 31 0.995 0.011 4.15 −18 46 74 47 22.94 85 56
0.91 24 0.996 0.016 4.97 −9 95 72 46 17.28 72 82
0.76 54 0.89 0.11 2.268 −10 34 74 48 39.96 96 44
0.83 39 0.965 0.039 2.293 −12 36 76 47 29.64 83 58
0.90 26 0.989 0.016 2.316 −9 70 70 46 18.20 71 84
% wt % wt cSt °C °C °C MJ/kg min min
fuels.42The viscosity for unleaded gasoline is reported to be 0.7 cSt, that of kerosene as 2.7 cSt, and that of diesel as 2−4 cSt.43The flash point for gasoline has been reported as 43 °C,44 that of kersoine as 37−65 °C, while that of diesel as >55 °C.45The kinematic viscosity requirements of diesel fuel standard ASTM D396, which sets a limit value of 2−3.6 cSt and 5.8−26.4 cSt at 38 °C for grade No. 2-D (diesel) and grade No. 4-D (medium distillate), respectively. For low-speed stationary engines, manufacturers recommend an optimum
diesel index (32.34, 26.52, and 21.78), octane number (84, 75, and 70) and cetane number (45, 46, and 80), respectively. The density of gasoline is reported to be within the range of 720−775 kg/m3,39,40 that of kerosene as 780−810 kg/m3, while that of diesel as 820−860 kg/m3. The API gravity of gasoline is reported to be within the range of 51−66 °API, while the value for kerosene is 47 °API and that of diesel fuels in the range of 30−42 °API.41The Conradson carbon residue values are falling within the range of 0.01−0.02 for automotive G
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
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Table 4. Physico-Chemical Properties of Light, Middle, and Heavy Oil Fractions Derived from Distillation of Plain and Various Chemically Dispersed RCN-II Samples P-RCN-II
CD1- RCN-II
CD2- RCN-II
CD3- RCN-II
property
unit
F1
F2
F3
F1
F2
F3
F1
F2
F3
F1
F2
F3
density @ 15 °C API gravity @ 60 °F carbon residue ash kinematic viscosity @ 40 °C pour point flash point aniline point calorific value diesel index octane number cetane number
g/cm3
0.75 54 0.972 0.003 0.762 −20 42 71 45 38.34 78 42
0.83 38 0.996 0.003 1.013 −16 48 72 45 27.36 68 49
0.86 33 0.995 0.016 2.268 −12 88 70 43 23.10 61 78
0.78 50 0.988 0.011 1.216 −9 34 75 47 37.50 98.8 47
0.84 37 0.991 0.014 1.341 −20 44 72 46 26.64 83 72
0.85 35 0.999 0.005 1.737 −11 65 70 45 24.50 73 80
0.769 54 0.991 0.066 1.351 −20 36 73 46 39.42 88 46
0.897 27 0.995 0.012 1.448 −16 46 72 46 19.44 80 58
0.901 25.7 0.997 0.002 1.689 −14 92 70 45 17.99 71 82
0.781 50 0.988 0.011 1.216 −9 34 75 46 37.50 98.80 44
0.847 37 0.991 0.014 1.341 −20 44 72 46 26.64 78 72
0.857 35 0.999 0.005 1.737 −11 65 70 45 24.50 70 80
% wt % wt cSt °C °C °C MJ/kg min min
kinematic viscosity of between 13 and 17 cSt for fuel before entering the pump.46 The calorific values are within the range reported for distillate petrofuels.The octane rating of a fuel is a measure of the fuel’s ability to resist autoignition and knock in a spark-ignited engine. Higher octane-rated fuel is desirable as it enables improved engine efficiency. The cetane number reflects the ability of a fuel to self-ignite when compressed under standardized conditions.47 The knock-limited performance of gasoline in most modern engines now tends to be better correlated with octane number.48Octane rating recommendations for the U.S. are contained in an appendix to ASTM Specification D4814 for gasoline.49 The results inferred that the key properties are reasonably closer to the values of ASTM standard specifications reported for gasoline, kerosene, and diesel oils.50,51 3.4.2. Distillate Fractions from Distillation of Chemically Dispersed Crudes. SDS-Dispersed Crudes. The physicochemical parameters of the distillate fractions derived from SDS-dispersed crudes are assembled in Tables 3−5. The values for different key fuel properties of the distillate fractions F1, F2, and F3 derived from CD1-RCP-I crude (Table 3) were found to be as follows: density (0.76, 0.83, and 0.90 g/cm3), API gravity (54, 39, 26 °API), CCR (0.89, 0.96, and 0.98% wt), ash (negligible), viscosity (2.2, 2.3, and 2.314 cSt), pour point (−10, −12, and −9 °C), flash point (34, 36, and 70 °C), aniline point (74, 76, and 70), calorific value (48, 46, and 45
MJ/kg), calculated diesel index (39, 29, and 18), octane numbers (96, 88, and 75), and cetane numbers (46, 58, and 84), respectively. The values for different key fuel properties of the distillate fractions F1, F2, and F3 derived from CD1-RCN-II (Table 4) are as follows: density (0.78, 0.84, and 0.85 g/cm3), API gravity (50, 37, and 35 °API), CCR (0.98, 0.99, and 0.99% wt), ash (negligible), viscosity (1.2, 1.3, and 1.7 cSt), pour point (−9, −20, and −11 °C), flash point (34, 44, and 65 °C), aniline point (75, 72, and 70 °C), calorific value (47, 46, 45 MJ/kg), calculated diesel index (37.60, 26.64, and 24.50), octane number (98, 83, and 73), and cetane number (47, 72, and 80), respectively. The values for different key fuel properties of the distillate fractions F1 and F2 derived from CD1-RCA-III crude (Table 5) were as follows: density (0.81, 0.84, and 0.87 g/cm3), API gravity (42, 36, 31 °API), CCR (0.83, 0.86, and 0.98% wt), ash (negligible), viscosity (4, 5.6, and 5.8 cSt), pour point (−10, 18, and −12 °C), flash point (34, 30, and 55 °C), aniline point (69, 67, and 65 °C), calculated diesel index (28.98, 24.12, and 20.15), calorific value (48, 47, and 47 MJ/kg), octane numbers (94, 85, and 81), and cetane numbers (53, 58, and 86), respectively. The densities and API gravities of the corresponding test fuels remained in the gasoline, kerosene, and diesel ranges. A difference can be observed in F3 which indicated the recovery
Table 5. Physico-Chemical Properties of Light, Middle, and Heavy Oil Fractions Derived from Distillation of Plain and Various Chemically Dispersed RCA-III Samples P-RCA-III property density @ 15 °C API gravity @ 60 °F carbon residue ash kinematic viscosity @ 40 °C pour point flash point aniline point calorific value diesel index octane number cetane number
unit g/cm
3
% wt % wt cSt °C °C °C MJ/kg min min
CD1- RCA-III
CD2- RCA-III
CD3- RCA-III
F1
F2
F3
F1
F2
F3
F1
F2
F3
F1
F2
F3
0.795 47 0.998 0.008 2.075 −22 46 69 47 32.43 84 45
0.838 39 0.996 0.009 2.230 - 20 48 68 46 26.52 75 46
0.866 33 0.992 0.017 2.510 −15 75 66 46 21.78 70 80
0.815 42 0.833 0.172 4.006 −10 34 69 48 28.98 94.6 53
0.845 36 0.863 0.135 5.695 −18 30 67 47 24.12 85 58
0.871 31 0.984 0.028 5.840 −12 55 65 47 20.15 81 86
0.788 50 0.994 0.012 3.378 −22 42 72 47 36 98 52
0.823 41 0.996 0.009 3.755 −20 45 71 47 29.11 78 58
0.856 35 0.998 0.014 4.875 −19 75 69 46 24.15 73 89
0.815 42 0.833 0.172 4.006 −10 34 69 47 28.98 94.6 50
0.845 36 0.863 0.135 5.695 −18 30 67 48 24.12 77 58
0.871 31 0.984 0.028 5.840 −12 55 65 46 20.15 69 86
H
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
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such as long alkyl side chains, aromatics, or heteroaromatics, high values of viscosity, pour points, and flash points were observed. However, the aniline point of the F1 fractions was close to that of the plain fractions, which indicated that the aromatic contents of the fractions remained undisturbed. On the other hand, the high octane number of F1 and high cetane numbers of F2 and F3 fractions showed that these products could be superior in ignition properties than those of the fractions derived from plain crudes. TTX-Dispersed Crudes. The physico-chemical properties of the light, middle, and heavy oil fractions derived from TTXdispersed crudes are presented in Tables 3−5.The properties determined for F1, F2, and F3 fractions of CD3-RCP-I crude are summarized in Table 3. The results were found to be as follows: density (0.76, 0.83, and 0.90 g/cm3), API gravity (54, 39, and 26 °API), CCR (0.89, 0.96, and 0.98% wt), ash (negligible %), viscosity (2.26, 2.29, and 2.31 cSt), pour point (−10, −12, and −9 °C), flash point (34, 36, and 70 °C), aniline point (74, 76, and 70 °C), calorific value (48, 46, and 46 MJ/kg), calculated diesel index (39.96, 29.6, and 18.20), octane number (96, 83, and 71), and cetane number (44, 58, and 84), respectively. The properties determined for F1, F2, and F3 fractions of CD3-RCN-II crude are assembled in Table 4 and found to be as follows: density (0.78, 0.84, and 0.85 g/cm3), API gravity (50, 37, and 35 °API), CCR (0.98, 0.99, and 0.99% wt), ash (negligible %), viscosity (1.2, 1.3, and 1.7 cSt), pour point (−9, −20, and −11 °C), flash point (34, 44, and 65 °C), aniline point (75, 72, and 70 °C), calorific value (46, 46, and 45 MJ/ kg), calculated diesel index (37.50, 26.84, and 24.50), octane number (98.8, 78, and 70), and cetane number (44, 72, and 80, respectively. The properties determined for F1, F2, and F3 fractions of CD3-RCA-III crude are compiled in Table 5 and found to be as follows: density (0.81, 0.84, and 0.87 g/cm3), API gravity (42, 36, and 31 °API), CCR (0.83, 0.86, and 0.98% wt), ash (negligible %), viscosity (4.0, 5.6, and 5.8 cSt), pour point (−10, 18, and −12 °C), flash point (34, 30, and 55 °C), aniline point (69, 67, and 65 °C), calorific value (47, 48, and 46 MJ/ kg), calculated diesel index (28.98, 24.12, and 20.15), octane number (94.6, 77, and 69), and cetane number (50, 58, and 86), respectively. Most of the values are within the range described for distillate fuels.52The results indicated that the physico-chemical characteristics of the F1 fractions derived from the distillation of the chemically dispersed samples resembled those of gasoline and those of the F2 and F3 showed conformance to the kerosene and diesel oil, respectively. However, the F3 fractions exhibited higher values of some of the key properties. Overall, the physico-chemical characteristics of all F1, F2, and F3 fractions derived from chemically dispersed crudes as well as their counterparts occurred within the permissible range of standard gasoline, kerosene, and diesel oil.52
of lighter occluded hydrocarbons during distillation of SDSdispersed crudes. The Conradson carbon and ash values were negligible. The viscosity showed lower limits defined for distillate fuels in the case of CD1-RCP-I and CD1-RCN-II crudes while higher limits in CD1-RCA-III crude. The pour points were extremely low in all samples which indicated the absence of waxes and crystallites. In general, the key properties of distillate fractions derived from SDS-dispersed samples exhibited no significant change and showed conformance with the properties of the fractions derived from plain distillation. The results further inferred that SDS caused the yields of gasoline and diesel oil fractions to increase without disturbing their fuel properties, which indicated no harm to the chemical integrity of the resultant distillate fractions in terms of compositions. CTAB-Dispersed Crudes. The fuel properties of the fractions derived from CTAB-dispersed crudes are shown in Tables 3−5. The properties determined for CD2-RCP-I derived F1, F2, and F3 fractions are summarized in Table 3 which were as follows: density (0.78, 0.87, and 0.91 g/cm3), API gravity (50, 30, and 24 °API), CCR (0.99, 0.99, and 0.99% wt), ash (negligible %), viscosity (3.95, 4.15, and 4.97 cSt), pour point (−20, −18, and −19 °C), flash point (38, 46, and 95 °C), aniline point (73, 74, and 72 °C), calorific value (48, 47, and 46 MJ/kg), calculated diesel index (36.50, 22.94, and 17.28), octane number (94, 85, and 72), and cetane number (45, 56, and 82), respectively. Table 4 depicts the properties determined for distillate fractions derived from CD2-RCN-II crude, which are found to be as follows: density (0.76, 0.89, and 0.90 g/cm3), API gravity (54, 27, and 25 °API), CCR (0.99, 0.99, and 0.99% wt), ash (negligible %), viscosity (1.3, 1.4, and 1.6 cSt), pour point (−20, −16, and −14 °C), flash point (36, 46, and 92 °C), aniline point (73, 72, and 70 °C), calorific value (46, 46, and 45 MJ/kg), calculated diesel index (39.43, 19.44, and 17.99), octane number (88, 80, and 71), and cetane number (46, 58, and 82 for F2 and F3 fractions), respectively. The distillation fractions of CD2-RCA-III crude were also analyzed for the key fuel properties. The results are compiled in Table 5. The properties were as follows: density (0.78, 0.82, and 0.85 g/cm3), API gravity (50, 41, and 35 °API), CCR (0.99, 0.99, and 0.99% wt), ash (negligible %), viscosity (3.3, 3.7, and 4.8 cSt), pour point (−22, −20, and −19 °C), flash point (42, 45, and 75 °C), aniline point (72, 71, and 69 °C), calorific value (47, 47, and 46 MJ/kg), calculated diesel index (36, 29.11, and 24.15), octane number (98, 78, and 73), and cetane number (62, 58, and 89), respectively. It can be seen from the data that all of the physico-chemical properties occurred close to the distillates fractions of the plain crudes. The properties of all F1 fractions matched well with the standard gasoline and those of F2 and F3 fractions resembled with the kerosene and diesel range products. It can, however, be observed that some of the properties showed slightly higher values in the case of chemically dispersed crudes than those of the plain crudes. The density of the F1, F2, and F3 showed a linear increase, while the API gravities exhibited a decrease from 50° to 24°. The carbon residue and ash contents remained the same as in fractions of the plain oils. The kinematic viscosity of the fractions derived from CTABdispersed crude showed an increase. Similar were the results for the pour point and flash points, which indicated that the distillates contained hydrocarbons with BPt within the respective ranges, but owing to more complex structures
4. CONCLUSIONS The results indicated that the yields of distillate fractions particularly those of F1 and F2 increased in chemically dispersed crudes compared to plain samples. Among the dispersants used, the SDS was more effective in RCA-III crude where the yield of F1 increased significantly to 58% and that of residue decreased to 6%. The CTAB was found to be more effective in RCN-II crude, which gave a significant increase in yields of F1 to 49%, whereas the R yield decreased to 7%. The I
DOI: 10.1021/acs.energyfuels.7b02857 Energy Fuels XXXX, XXX, XXX−XXX
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(24) Chen, C. L.; Chung, Y. H.; Lee, H. Y. Ind. Eng. Chem. Res. 2016, 55, 1347. (25) Gray, M. R.; Tykwinski, R. R.; Stryker, J. M.; Tan, X. Energy Fuels 2011, 25, 3125. (26) Behar, F.; Pelet, R. J. Anal. Appl. Pyrolysis 1984, 7, 121. (27) Noh, N. A. M.; Abdullah, A. A. A.; Ibrahim, M. N. M.; Yahya, A. R. M. J. Gen. Appl. Microbiol. 2012, 58, 153−161. (28) Noh, N. A. M.; Salleh, S. M.; Ibrahim, M. N. M.; Yahya, A. R. M. Pseudomonas aeruginosa USM-AR2 culture containing biosurfactant facilitates crude oil distillation process. In Proceedings of 2011 International Conference on Biotechnology and Environment Management (ICBEM 2011), Singapore, Sept 16−18, 2011. (29) Speight, J. G. Handbook of Petroleum Product Analysis; John Willey and Sons: New York, 2015 (30) Sbaite, P.; Batistella, C. B.; Winter, A.; Vasconcelos, C. J. G.; Maciel, M. W.; Filho, R. M.; Gomes, A.; Medina, L.; Kunert, R. Pet. Sci. Technol. 2006, 24, 265. (31) Speight, J. G. Handbook of Petroleum Analysis; Wiley Interscience: New York, 2001; Vol. 158. (32) Tanaka, R.; Sato, E.; Hunt, J. E.; Winans, R. E.; Sato, S.; Takanohashi, T. Energy Fuels 2004, 18, 1118. (33) Peters, K. E.; Walters, C. C.; Moldowan, J. M. The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History; Cambridge University Press: Cambridge, U.K., 2005. (34) Mazaheri Assadi, M.; Tabatabaee, M. S. Inter. J. Environment. Res. 2010, 4, 549−572. (35) Kabir-ud-Din; Shafi, M.; Bhat, P. A.; Dar, A. A. J. Hazard. Mater. 2009, 167, 575. (36) McKenna, A. M.; Blakney, G.T.; Xian, F.; Glaser, P. B.; Rodgers, R. P.; Marshall, A. G. Energy Fuels 2010, 24, 2939. (37) ASTM D396-17: Standard Specification for Fuel Oils; ASTM International: West Conshohocken, PA, 2017. (38) Speight, J. G. Handbook of Petroleum Product Analysis; WileyInterscience: New York, 2002. (39) BS EN 228:2008: Automotive fuels. Unleaded petrol. Requirements and test methods; British Standards Institution (BSI): London, U.K., 2008. (40) Demirbas, A. Energy Sources, Part A 2008, 30, 1433. (41) Bacha, J.; Freel, J.; Gibbs, A.; Gibbs, L.; Hemighaus, G.; Hoekman, K.; Kohler, D. Diesel Fuels Technical Review; Chevron Global Marketing: San Ramon, CA, 2007. (42) Guibet, J.-C. Characteristics of Petroleum Products for Energy Use. J. Pet. Refin. 1995, 1, 177−269. (43) ASTM D975-11: Standard specification for diesel fuel oil; ASTM International: West Conshohocken, PA, 2011. (44) Arpa, O.; Yumrutas, Y. Fuel Process. Technol. 2010, 91, 197. (45) Arpa, O.; Yumrutas, R.; Argunhan, Z. Fuel Process. Technol. 2010, 91, 1241. (46) Blin, J.; Brunschwig, C.; Chapuis, A.; Changotade, O.; Sidibe, S. S.; Noumi, E. S.; Girard, P. Renewable Sustainable Energy Rev. 2013, 22, 580. (47) Kalgathgi, G. T.; Nakata, K.; Mogi, K. Octane Appetite Studies in Direct Injection Spark Ignition (DISI) Engines; SAE Technical Paper 2005-01-0244; SAE: Warrendale, PA, 2005. (48) Sidibé, S. S.; Blin, J.; Vaitilingom, G.; Azoumah, Y. Renewable Sustainable Energy Rev. 2010, 14, 2748. (49) ASTM D4814-11: Standard specification for automotive sparkignition engine fuel; ASTM International: West Conshohocken, PA, 2011. (50) ASTM D4814-11: Standard specification for automotive sparkignition engine fuel; ASTM International: West Conshohocken, PA, 2017. (51) ASTM D7467-17: Standard specification for diesel fuel oil, biodiesel blend (B6 to B20); ASTM International: West Conshohocken, PA, 2017. (52) Alptekin, E.; Canakci, M. Characterization of the key fuel properties of methyl ester−diesel fuel blends. Fuel 2009, 88, 75.
Triton X-100 also proved to be more effective in RCN-II crude, which gave 48% and 6% yields of F1 and R fractions. The fuel properties of the resultant fractions derived from chemically dispersed crudes did not disturb to a greater extent and remained within the ranges prescribed for petrofuels.
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Imtiaz Ahmad: 0000-0003-2056-3540 Notes
The authors declare no competing financial interest.
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REFERENCES
(1) Jones, D. S. Quality control of products in petroleum refining. In Handbook of Petroleum Processing; Springer: Cham, Switzerland, 2015; pp 649−683. (2) Presti, D. L. Construct. Build. Mater. 2013, 49, 863. (3) Mangiafico, S.; Di Benedetto, H.; Sauzéat, C.; Olard, F.; Pouget, S.; Planque, L. Road Mater. Pavement Des. 2014, 15 (2), 312−329. (4) Kong, X.; Ohadi, M. Applications of Micro and Nano Technologies in the Oil and Gas Industry - Overview of the Recent Progress. In Abu Dhabi International Petroleum Exhibition and Conference, Abu Dhabi, UAE, Nov 1−4, 2010; Society of Petroleum Engineers, 2010; SPE-138241-MS. (5) Shah, N. K.; Li, Z.; Ierapetritou, M. G. Petroleum refining operations: key issues, advances, and opportunities. Ind. Eng. Chem. Res. 2011, 50, 1161. (6) Bridjanian, H.; Samimi, A. K. Bottom of the Barrel, An important challenge of the petroleum refining industry. Petrol. Coal 2011, 53 (1), 13. (7) AlHumaidan, F.; Lababidi, H. M.; Al-Rabiah, H. Fuel 2013, 103, 923. (8) Karakhanov, E. A.; Glotov, A. P.; Nikiforova, A. G.; Vutolkina, A. V.; Ivanov, A. O.; Kardashev, S. V.; Maksimov, A.L.; Lysenko, S. V. Fuel Process. Technol. 2016, 153, 50. (9) Manek, E.; Haydary, J. Fuel Process. Technol. 2017, 159, 320. (10) Fumoto, E.; Tago, T.; Tsuji, T.; Masuda, T. Energy Fuels 2004, 18, 1770. (11) Hart, A.; Greaves, M.; Wood, J. Chem. Eng. J. 2015, 282, 213. (12) Atkins, L.; Higgins, T.; Barnes, C. Heavy Crude Oil: A Global Analysis and Outlook to 2030; Hart Energy Consulting: Houston, TX, 2010. (13) Mutyala, S.; Fairbridge, C.; Paré, J. J.; Bélanger, J. M.; Ng, S.; Hawkins, R. Fuel Process. Technol. 2010, 91, 127. (14) Soto, A. Ionic Liquids for Extraction Processes in RefineryRelated Applications. In Ionic Liquids for Better Separation Processes; Springer: Berlin, 2016; pp 39−65. (15) Izza, H.; Korichi, M. Arabian J. Sci. .Eng. 2016, 41, 2623. (16) Cui, M.; Li, C.; Wang, J.; Deng, W. Energy Fuels 2016, 30, 2941. (17) Castañeda, L. C.; Muñoz, J. A. D.; Ancheyta, J. Fuel 2012, 100, 110. (18) Bevilacqua, M.; Ciarapica, F. E.; Giacchetta, G.; Paciarotti, C.; Marchetti, B. Innovative Maintenance Management Methods in Oil Refineries. In Quality and Reliability Management and Its Applications; Springer: London, 2016; pp 197−226. (19) Bayat, M.; Aminian, J.; Bazmi, M.; Shahhosseini, S.; Sharifi, K. Energy Convers. Manage. 2012, 64, 344. (20) Silva, F. B.; Guimarães, M. J. O. C.; Seidl, P. R.; Garcia, M. E. F. Brazilian J. Petrol. Gas 2013, 7, 107. (21) Speight, J. G. Oil Gas Sci. Technol. 2004, 59, 479. (22) McKenna, A.M.; Donald, L.J.; Fitzsimmons, J. E.; Juyal, P.; Spicer, V.; Standing, K. G.; Marshall, A.G.; Rodgers, R. P. Energy Fuels 2013, 27, 1246. (23) Lopes, M. S.; Maciel Filho, R.; Maciel, M. W.; Medina, L. C. Procedia Eng. 2012, 42, 329. J
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