Processability of Oils and Residua - Energy

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Thermal Crackability/Processability of Oils and Residua Lante A Carbognani Ortega, Josune Carbognani, Estrella Rogel, Cesar Ovalles, Janie Vien, Harris Morazan, Francisco A Lopez-Linares, and Pedro Rafael Pereira-Almao Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.5b02355 • Publication Date (Web): 05 Jan 2016 Downloaded from http://pubs.acs.org on January 10, 2016

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Thermal Crackability/Processability of Oils and Residua Lante Carbognani Ortega,1 Josune Carbognani,1 Estrella Rogel,2 Cesar Ovalles,2 Janie Vien,2 Harris Morazan,2 Francisco Lopez-Linares,2 Pedro Pereira-Almao1 1. Schulich School of Engineering, University of Calgary, Calgary, Alberta, T2N 1N4, Canada. 2. Petroleum and Materials Characterization Unit, Chevron Energy Technology Company, 100 Chevron Way, Richmond, CA 94801, USA.

Abstract The maximum potential for producing light ends under a set of operational parameters for oil feedstocks is termed “crackability”. When constrained by the appearance of undesirable solid phases, the term “processability” applies to the potential of light ends production. These parameters were correlated with samples thermal maturity. Thermal maturity was inferred from two proposed indicators, the first one based on “delta solubility parameter” (∆PS) and the second on differential heavy hydrocarbon abundances determined by high temperature simulated distillation (∆% (C44-C100). A set of 36 samples comprising oils, distillation residua and thermally cracked residua was studied. Samples with increased thermal maturity were found to decrease their crackability/processability. Samples with high solubility parameter (∆PS), low ∆% (C44C100) and low molecular weight were found to have increased thermal maturity. Attempts to correlate SARA group-type distributions with thermal maturity were not successful. Highly paraffinic samples were found to deviate from the determined behavior of studied samples. Application of the proposed crackability/processability indicators to thermal processing under batch, semi batch and continuous setup conditions, was found to describe most of the experimentally determined results.

1. Introduction Thermal cracking (TC) is the oldest and simplest upgrading process to breaking up large hydrocarbon molecules into smaller ones. The parameters for controlling TC conversion are set up temperature and residence time. Using heat, kinetic energy induces

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bond breakage over oil molecules which gives rise to products with smaller molecular weight (MW). Distribution of products depend on the feedstock characteristics, normally giving origin to unsaturated components (olefins) since most oil components lack hydrogen in comparison to their carbon contents.1 The maximum potential for producing valuable light products under a set of operational parameters for oil feedstocks is termed “crackability”. The term “processability” is related to the former concept however includes one important constraint that is the limit at which production of valuable products is reached, limit defined by the production of undesirable solid phases. The nature of these solid phases is multiple, i.e., solids can be either insolubilized “asphaltenes” or else, refractory materials known as “petroleum coke”. Both are operationally defined solubility hydrocarbon classes, the first one comprising components insoluble in alkanes but soluble in aromatics, the second pertains to insoluble species in any organic solvent.2 As a rule of thumb, it has been proposed that the relative reactivity (Crackability) of petroleum samples follows the decreasing order: 2 Paraffinic/Naphtheno-paraffinics > Naphthenic/Aromatic-naphthenics > Aromatics (1) With increasing usage of gasoline cars, TC was replaced by catalytic cracking for better design for production of gasoline components. With different types of catalytic cracking, fluid catalytic cracking (FCC) is widely used because it produces higher value products-providing higher revenues. From the preceding, it is not a surprise that important efforts have been made to optimize the operation of FCC units by both improving catalysts or by generating models that predict “crackability” and products distributions based on selected FCC feedstock properties.


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A general correlation for FCC feed crackability is based on the determination of the K-UOP factor, determination of average molal boiling point and specific gravity of the sample. Thus, FCC feeds crackability was indicated to follow the order:3 Paraffinics > Naphthenics > Aromatics (2) (K>12) (11.5≈ K≈ 11.6) ( K 1.1, see Table 1). Results comparing the five oils TC conversions versus ∆% (C44-C100) parameter, are presented on Figure 11. Decrease of ∆% (C44-C100) was observed for TC products from four oils, in line with all that was discussed in the preceding. South America oil SA6 proved otherwise, worth mentioning that this is a crude oil related to SA7 from a reservoir (geochemical) point of view. It seems that oils like SA6 and SA7 initially presenting very low content of crackable materials as determined via HTSD (∆% (C44-C100)), behave differently from most studied materials in the present work. Worth mentioning again that the samples arising from the lightparaffinic Arab Light oil behave differently, having in common their paraffinic nature. Based on the experiment it becomes evident that the proposed “maturity” parameters ∆PS and ∆% (C44-C100) seem to provide expected behaviors in thermal cracking for most samples, except for highly paraffinic materials like those initially depleted of “crackable” fractions, as indicated by HTSD and illustrated with samples SA6 and SA7.

4. Conclusions The maximum potential for producing light ends under a set of operational parameters for oil feedstocks is termed “crackability”. When constrained by the appearance of


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undesirable solid phases, the term “processability” applies to the potential of light ends production. These parameters were correlated with samples thermal maturity Thermal maturity was inferred from two proposed indicators, asphaltenes delta solubility parameter (∆PS) and (∆% (C44-C100) which provides differential contents of heavy hydrocarbon fractions via high temperature simulated distillation. A set of 36 samples comprising oils, distillation residua and thermal cracked residua was studied. Samples increased thermal maturity was found to decrease their crackability/processability. Samples with high solubility parameter, low ∆% (C44-C100) and low molecular weight were found to have increased thermal maturity. Attempts to correlate SARA group-type distributions with thermal maturity were not successful. Paraffinic samples like Arab Light and several South America’s oils were found to deviate from the determined trends for the other studied samples. Applicability of the proposed crackability/processability indicators to thermal processing under batch, semi batch and continuous set up conditions, was found to describe most of the experimentally determined results.

Acknowledgements Funding from CHEVRON-ETC, NSERC/Nexen/AIEES Industrial Research Chair in Catalysis for Bitumen Upgrading, Canada Foundation for Innovation (CFI), the Institute for Sustainable Energy, Environment and Economy (ISEE) and, Schulich School of Engineering is acknowledged. Chevron ETC is thanked for permission to publish this work. Manuel Gonzales is acknowledged for running semibatch visbreaking experiments. Lante Carbognani Arambarri, Redescal Gomez and Dr. Fathi Mazim are thanked for running the continuous reactor thermal cracking experiments. Catalysis for Bitumen


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Upgrading group (CBU) from University of Calgary is thanked for providing studied samples.

Definitions and acronyms. AEBP: Atmospheric Equivalent Boiling Point. Crackability: Maximum potential for producing light ends under a set of operational parameters for oil feedstocks. ∆%(C44-C100): “thermal crackability index” determined via high temperature simulated distillation. ∆PS: Delta Solubility Parameter determined as the difference in time between the maximum of the low solubility parameter peak and 75 % of the solubility profile distribution. Referred also as “Solubility profile”. FCC: Fluid Catalytic Cracking. HDN: Hydrodenitrogenation. HTSD: High Temperature Simulated Distillation. MCR: Microcarbon Residue. MW: Molecular Weight. Processability: Same as crackability, constrained to the appearance of solids (asphaltenes and/or coke). SARA: Distribution of hydrocarbon group-types determined by solvent deasphalting plus thin layer chromatography (Saturates, Aromatics, Resins, Asphaltenes). SEC: Size Exclusion Chromatography.


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SX (P-value): Sample stability index determined by titration with n-hexadecane (also know as P-value or Peptization value). TC: Thermal Cracking. TGA: Thermogravimetric analysis. VR: Vacuum Residue.

References.

1. The Petroleum Handbook (by SHELL). Elsevier Science Publishers B.V., AmsterdamThe Netherlands. 1983 (6th edition), 2. Speight, J. G. “The Chemistry and Technology of Petroleum”, 4th edition. CRC Press, Taylor & Francis Group Boca Raton, FLA. 2006. 3. www.KBRS.co.uk/CatalyticCrackingReferenceMaterial.pdf (downloaded March 25, 2015). 4. Ng, S. H.; Wang, J.; Fairbridge, C.; Zhu, Y.; Yang, L.; Ding, F.; Yui, S. Energy Fuels 2004, 18, 160-171. 5. Ng, S. H.; Wang, J.; Fairbridge, C.; Zhu, Y.; Yang, L.; Ding, F.; Yui, S. Energy Fuels, 2004, 18, 172-187. 6. Bollas, G. M.; Vasalos, I. A.; Lappas, A. A.; Iatridis, D. K.; Tsioni, G. K. Ind. Eng. Chem. Res. 2004, 43, 3270-3281. 7. Martinez-Crus, F. L.;, Navas-Guzman, G.; Osorio-Suarez, J. P. CT&F, Ciencia, Tecnologia y Futuro 2009, 3(5), 1-19. 8. Xu, Z.; van der Berg, F. G. A.; Sun, X.; Xu, C.; Zhao, S. Energy Fuels 2014, 28, 16641673. 9. Nilsson, P.; Massoth, F. E.; Ottersted, J. E. Applied Catalysis 1986, 26, 175-189. 10. Hsu, C. S.; Robinson, P. R. Practical Advances in Petroleum Processing, Vol.1. Springer, N.Y.-USA. 2006. 11. Carbognani, L.; Garcia, C.; Izquierdo, A.; DiMarco, M. P.; Perez, C.; Rangel, A.; Sanchez,V. Prep. Pap. Am. Chem. Soc. Div. Pet. Chem. 1987, 32, 406-412.


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12. Izquierdo, A.; Carbognani, L.; Leon, V.; Parisi, A. Fuel. Sci. Technol. Int’l. 1989, 7(5&6), 561-570. 13. van der Berg, F. G. A.; Heijnis, R. M. A.; Stamps, P. A.; Kramer, P. A. Pet. Sci. Technol. 2003, 21 (3&4), 449-460. 14. Carbognani, L. Pet. Sci. Technol. 2006, 24, 1161-1173. 15. Ovalles, C.; Rogel, E.; Lopez, J.; Pradhan, A.; Moir, M. Energy Fuels 2013, 27, 6552-6559. 16. Castellanos, E.; Neumann, H. J.; Prieto, J. Fuel Sci. Technol. Int’l. 1993, 11(12), 1731-1758. 17. Fixari, B.; LePerchec, P.; Bigois, M. Fuel Sci. Technol. Int’l. 1991, 9(3), 321-335. 18. Kopsch, H. Thermal Methods in Petroleum Analysis. VCH Publishers Inc. N. Y.USA. 1995. 19. Di Carlo, S.; Janis, B. Chemical Engineering Science 1992, 47(9-11), 2695-2700. 20. Carbognani, L.; Lubkowitz, J.; Gonzalez, M. F.; Pereira-Almao, P. Energy Fuels 2007, 21, 2831-2839. 21. Carbognani, L.; Carbognani, J.; Molero, H.; Pereira-Almao, P. Energy Fuels 2013, 27, 2033-2041. 22. Rogel, E.; Ovalles, C.; Moir, M. Energy Fuels 2010, 24, 4369-4374. 23. ASTM D2892. Standard Test Method for Distillation of Crude Petroleum (15Theoretical Plate Column). American Society for Testing and Materials (ASTM): West Conshohocken, PA, 2011. 24. ASTM D5236. Standard Test Method for Distillation of Heavy Hydrocarbon Mixtures (Vacuum Potstill Method). American Society for Testing and Materials (ASTM): West Conshohocken, PA, 2011. 25. Rogel, E.; Ovalles, C.; Moir, M. Energy Fuels 2012, 26, 2655-2662. 26. Yau, W. W.; Kirkland, J. J.; Bly, D. D. Modern Size Exclusion Chromatography. Wiley-Interscience, N.Y.-USA. 1979. 27. Carbognani, L.; Roa-Fuentes, L. C.; Diaz, L.; Lopez-Linares, F.; Vasquez, A.; Pereira-Almao, P.; Haghigat, P.; Maini, B.B.; Spencer, R. J. Pet. Sci. Technol. 2010, 28, 632-645.


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28. Carbognani, L.; Gonzalez, M. F.; Pereira-Almao, P. Energy Fuels 2007, 21, 16311639. 29. Fathi, M. M.; Pereira-Almao, P. Energy Fuels 2011, 25, 4867-4877. 30. Bennett, B.; Larter, S. R.; Carbognani, L.; Pereira-Almao, P. Energy Fuels 2008, 22, 440-448. 31. Schwartz, H. E.; Brownlee, R. G.; Boduszynski. M. M.; Su, F. Analytical Chemistry 1987, 59, 1393-1401. 32. Hassan, A.; Carbognani, L.; Pereira-Almao, P. Fuel 2008, 87, 3631-3639. 33. Ovalles, C.; Rogel, E.; Moir, M.; Thomas, L.; Pradhan, A. Energy Fuels 2012, 26, 549-556. 34. Rogel, E. Energy Fuel, 1997, 11, 920-925. 35. Peluso, E.

Hydroprocessing full-range of heavy oils and bitumen using

ultradispersed catalysts at low severity. PhD Dissertation, University of Calgary, Canada. 2011. 36. Tissot, B. P.; Welte, D. H. Petroleum Formation and Occurrence. Springer-Verlag. Berlin, Heidelberg, New York. 1978. 37. Jamaluddin, A. K. M.; Nazarko, T. W.; Sills, S.; Fuhr, B.J. SPE Production & Facilities, 1996 (10), 161-165. (SPE 28994). 38. Gaestel, Ch.; Smadia, R.; Lamminan, K. A. Rev. Gen. Routes Aerod. 1971, 488, 9598. 39. Rogel, E.; Leon, O.; Contreras, E.; Carbognani, L.; Torres, E.; Espidel, J.; Zambrano, A. Energy Fuels 2003, 17, 1583-1590. 40. Stratiev, D.; Shiskova, I.; Dinkov, R.; Nikolova, R.; Mitkova, M.; Stanulov, K.; Sharpe, R.; Russell, C. A.; Obryvalina, A.; Telyashedv, R. Fuel 2014, 123, 133-142. 41. Stankievicz, A. B.; Flannery, M. D.; Fuex, N. A.; Broze, G., Couch, J. L.; Dubey, S. T.; Iyer, S. D.; Ratulowski, J.; Westerich, J. T. Proceeds. 3rd Int’l. Symp. Mechanisms Mitigation Fouling Petr. Natur. Gas Prod. AIChE 2002 Spring Nat’l. Mtg. New OrleansUSA, March 10-14, paper 47C, pp. 410-416. 42.www.etc-cte.ec.gc.ca/databasesoilproperties/pdf/WEB_Arabian_Light.pdf (Downloaded on september 9th, 2015).


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Table 1. Samples and determined properties Nature

Oil

Residua

Conv.VR

Sample ID (1)

∆PS (2)

Mn (3)

Mw (3)

%off (4)

wt% >545º (4)

∆% (C44 -100) (5)

Sat. (6)

Aro. (6)

Res. (6)

(C7) Asph. (6)

ATMN 0.90 641 683 293 54.7 8.35 11.4 36.8 37.8 14.0 ATSGD 1.14 642 683 244 49.0 12.2 15.1 52.3 20.1 12.5 PRB 1.10 646 686 257 52.6 9.27 31.0 45.0 16.0 8.0 Lloyd 1.24 630 664 219 43.3 8.22 18.0 47.2 25.5 9.3 ElkPt 1.26 637 673 249 49.3 7.44 16.6 38.9 35.2 9.3 SA1 0.56 600 623 189 36.8 3.25 29.9 41.4 25.7 3.0 SA2 1.18 668 706 273 58.0 11.07 15.3 57.0 17.2 10.5 SA3 0.50 677 735 324 66.3 15.17 15.9 17.4 66.0 0.7 SA4 1.34 662 693 272 56.6 9.31 9.8 33.1 40.3 16.8 SA5 1.04 659 704 313 61.2 11.02 10.9 29.5 41.2 18.4 SA6 3.53 554 570 250 33.5 0.44 42.4 39.3 9.1 9.3 SA7 3.17 556 572 258 37.0 0.99 39.6 40.1 7.7 12.6 MX1 1.46 656 691 165 53.8 9.87 14.5 43.5 28.6 13.5 MX2 1.68 651 684 188 55.4 9.74 10.8 49.9 27.8 11.6 MX3 2.23 676 718 183 48.3 7.16 21.0 20.6 45.3 13.4 MX4 1.75 650 692 187 57.6 10.14 8.8 41.5 33.7 16.0 RU320+ 1.21 606 622 316 50.3 3.73 18.4 39.4 33.5 8.7 ATGDT520+ 0.20 716 759 525 91.0 20.58 8.8 47.2 9.6 34.5 ATMN470+ 1.00 659 699 422 70.8 15.28 5.3 57.0 22.2 15.5 SA1 370+ 1.11 593 614 380 50.5 6.32 24.6 38.8 33.4 3.2 SA7VR 3.33 619 634 517 88.5 -6.87 9.9 36.5 13.3 40.3 MX3VR 2.34 702 739 517 90.5 21.68 2.6 30.8 27.1 39.4 ALVR 1.33 643 657 511 88.4 6.26 6.1 60.3 23.5 10.1 ATSGD DAO 0.22 649 669 521 90.0 11.28 1.9 57.0 34.1 7.0 ATSGD DAO37 0.50 607 623 402 75.0 10.54 6.1 75.3 13.4 5.2 ATSGD DAO56 3.01 549 567 332 62.3 3.52 4.6 62.6 13.1 18.9 ATMN470 1.5 2.71 578 599 293 57.0 6.37 7.5 49.0 21.7 21.8 ATMN470 1.2 4.14 553 574 325 57.0 1.71 8.8 47.2 9.6 34.5 ATMN VB9 2.26 709 753 338 55.9 13.14 8.3 62.0 13.2 16.6 ATMN VB14 3.04 665 703 329 52.0 10.50 8.9 59.9 11.9 19.3 ATMN VB23 2.97 693 734 331 50.9 9.48 10.7 54.1 10.3 25.0 ATMN VB29 4.03 634 670 352 53.4 8.84 11.6 49.9 9.6 28.9 ALTC400C 2.55 610 624 372 69.6 8.80 8.8 62.9 14.8 13.5 ALTC420C 2.41 616 630 359 70.2 9.90 8.0 63.1 16.1 12.8 ALTC425C 2.72 606 620 345 69.4 4.70 8.9 62.6 15.0 13.5 ALTC430C 3.03 598 611 350 68.5 6.50 9.4 61.9 13.6 15.1 Notes: 1). For samples ID purposes: SA (South American); MX (Mexican); AR/VR(Atmospheric/Vacuum residua); DAO: Deasphalted oil; VB: visbroken; MN: Mined bitumen; SGD: Steam Assisted Gravity drainage produced bitumen. Appended numerical temperature qualifiers in deg ºC; Appended numerical qualifiers: P-values or VRs conversions. 2). ∆ solubility parameter as described previously.22 3). SEC determined molecular weights.26 4). HTSD determined parameters; 5%off temperature reported in deg ºC. 5). Thermal Crackability Index (see Eq. (3)). 6). SARA reported in wt%.27 7). For P-value see Eq. (4). 8). For VR conversion see Eq. (5)


Pvalue (7)

wt% Conv. @T(ºC) (8)

2.7 2.6

>3 2.7 1.6 1.6 2.2 1.9

2.6 2.6 1.6 1.9 2.9

1.5 1.2 1.8 1.5 1.1 1.0 1.6 1.4 1.3 1.3

37.1 56.0 22.4 25.9 8.7 13.7 23.3 28.5 21.7 20.6 21.5 27.2

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Figure captions Figure 1. Study of Athabasca vacuum residue (ATMN470+) and its derived visbroken fractions. Visbreaking semi batch experiments described. A. HTSD chromatograms, B. Samples maturity indexes provided by ratios of triaromatic/monoaromatic steroidal biomarkers (TAS/MAS).30 Figure 2. TGA and HTSD analysis of Athabasca vacuum residue (ATMN470+). A. TGA plots presenting weight loss and differential weight loss curves as a function of temperature. B. HTSD chromatogram correlated to injector/oven temperatures set up for elution and, equivalent boiling points (AEBP) determined with standard n-paraffin calibration. Determinations of distillable portions from the sample are indicated in both panels. Figure 3. Correlation between the percentages of distillable components computed for different type of hydrocarbon samples, determined via HTSD vs. TGA. Figure 4. HTSD elution of Athabasca bitumen from standard column or stationary phase deprived column. Areas corresponding to components eluted via distillation or “secondary cracking” mechanism (∆% (C44-C100)), highlighted in the figure. Figure 5. Asphaltene solubility profiles for selected pair of studied samples. A. Athabasca vacuum residue and its thermal cracked product to a P-value of 1.2, B. Virgin SA7 oil and its 530C+ vacuum residue. Plots are normalized outputs from evaporative light scattering detector. Figure 6. Correlation between ∆PS and ∆% (C44-C100) for the studied samples. A. Detail for oils. B. All studied HCs groups; vacuum residua deviating the most were highlighted within the figure. Figure 7. Correlation between ∆PS and ∆% (C44-C100) for the whole oils and their respective distillation residua. Samples identified by IDs appended to the residua (following the identification presented in Table 1). Figure 8. Correlation between Mn (SEC) and ∆% (C44-C100) for the studied samples. Circled point not considered for correlation (sample SA7VR). Figure 9. Correlation between samples (Resins + Asphaltenes) contents versus proposed maturity parameters: A. ∆% (C44-C100), B. ∆PS. Correlations for each hydrocarbon group presented in panel B. Figure 10. Vacuum residua thermal cracking conversion correlated to maturity parameters: A. ∆PS, B. ∆% (C44-C100). Experiments carried out under continuous (reactor) mode. Athabasca residua conversion determined at 545ºC, Arab Light at 540ºC. Appended lines presented only as visual aids.


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Figure 11. Correlation between VR conversion and ∆% (C44-C100) for oils thermally cracked under batch conditions.

--------------------------------------

FID detector response

Feedstock (ATMN470+) 18.3% 24.8% VB conv.@545ºC 31.8% 33.2% Light HCs increase

A

VR fractions decrease

0

TAS / (MAS + TAS)

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8

16

time (min)

24

32

1.0

B

0.8

0.6 0

10

20

30

VB wt% conversion @ 545ºC

Figure 1.


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A

A

0.8

0.6

80

Distilled to 370ºC: 28.6 wt%

60

0.4 Thermal cracking signal

40

20

0.2

0.0

-0.2

0 200

0

400

600

Temperature (ºC)

B

GC “Hump” wt%

Figure 2


800

Derivative weight (wt %/º C)

100

Mass (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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HTSD wt% distilled to AEBP 550 ºC

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x-HOil Hoil VR Upg. residua 80

60 y = 1.0511x + 2.2801 R2= 0.9312

40

20

(y = x)

0

0

20

40

60

80

TGA wt% distilled (370 ºC)

Figure 3

Standard HTSD column eluted to 425 ºC Fuse silica tube eluted to 350 ºC

C44 (545 ºC)

∆ %(C44-C100)

C100 (720 ºC)

Distillation

0.0

7.5 10

15.0 20

22.5 Time (Min) 44

C#

30.0 100

Figure 4


37.5

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(- )

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(+)

Solubility parameter

A

ATMN470+ ATMN470 1.2

10

14

18

22

B

SA7 SA7VR

10

14

18

22

Elution time (min)

Figure 5


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25

A

∆ % (C44-C100)

20 15 10 5 0 y = - 4.1217x + 15.156

-5

2 R = 0.8048

-10 0

1

2

3

4

5

∆PS Oils

25

Residua

Conv. Residua

B

MX3VR

20

∆% (C44-C100)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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15 10 5 0 y = - 2.6475x + 13.7630

-5

2 R = 0.2887

SA7VR

-10 0

1

2

∆PS

3

4

Figure 6


5

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Solid forms: Oils ; Empty forms: Residua

25 ATSGD520+

MX3VR

20

∆ % (C44-C100)

ATMN470+

15 10 5

SA1 370+

G en er

0

al

tre

nd

-5 SA7VR

-10

0

1

2

3

4

∆PS Figure 7.

Oils

25

Vac.residua

Conv. VRs

20 y = 0.0883x - 47.042 R2= 0.6861

15

∆% (C44-C100)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 34 of 37

10 5 0 -5 -10 500

600

700

Mn (Daltons) Figure 8


800

Oils Virgin residua

Converted residua

80

A 60

40

20 y = 1.19x + 27.83 R 2= 0.20

0 -10

0

10

20

∆% (C44-C100) wt% (Resins + C7-asphaltenes)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

wt% (Resins + C7-asphaltenes)

Page 35 of 37

80

B 60

R 2= 0.38

40 R 2= 0.63

20 R2= 0.29

0

0

1

2

3

4

∆ PS

Figure 9


5

Energy & Fuels

ATMN

ALVR

ATSGD DAO

5

A 4

∆PS

3

2

1

0 0

20

40

60

wt% VR conversion 12

B 10

∆% (C44-C100)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 36 of 37

8 6 4 2 0 0

20

40

wt% VR conversion Figure 10


60

Page 37 of 37

16

∆ % (C44-C100)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

12

8

PRB

4

MX3

ATSGD SA6 SA3

0

0

20

40

wt% VR conversion

Figure 11


60

Processability of Oils and Residua - Energy

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