Bench-top Thermal and Steam Catalytic Cracking of Athabasca

Subscriber access provided by Nottingham Trent University

Process Engineering

Bench-top Thermal and Steam Catalytic Cracking of Athabasca Residual Fractions. Attainable Upgrading Levels Correlated with Fraction Properties. Lante Antonio Carbognani Ortega, Estrella Rogel, Maria J Perez-Zurita, Enzo Peluso, Josune Carbognani, Cesar Ovalles, Francisco A Lopez-Linares, Janie Vien, Ajit Pradhan, and Pedro Rafael Pereira-Almao Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b01890 • Publication Date (Web): 07 Aug 2019 Downloaded from pubs.acs.org on August 17, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 46 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

Bench-top Thermal and Steam Catalytic Cracking of Athabasca Residual Fractions. Attainable Upgrading Levels Correlated with Fraction Properties. Lante Carbognani Ortega,1* Estrella Rogel,2 Maria J. Perez-Zurita,1 Enzo Peluso,1 Josune Carbognani,1 Cesar Ovalles,2 Francisco Lopez-Linares,2 Janie Vien,2 Ajit Pradhan,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, Richmond, CA-USA

ABSTRACT Thermal cracking (TC) of Athabasca vacuum residue (ATVR) and its de-asphalted product (DAO) was studied. A comparison of conversion and products properties between TC and ultradispersed catalytic steam cracking (CSC) upgrading of both feedstocks is also reported, using K-Ni catalysts. Thermal conversions with stable products for the deasphalted fraction (DAO), reached 20% (w/w) higher values than the ATVR. DAO-CSC provided 8% (w/w) increased conversion compared to DAO TC, with stable products. Higher thermal conversions for the DAO compared to the VR were explained in term of the better properties determined for the asphaltenes produced in DAO upgrading, i.e., higher hydrogen content and better solubilization properties due to lower molecular sizes, solubility parameters and aromaticities. A definitive link between the nature of produced asphaltenes and products stabilities as measured via P-value, was found. Higher DAO-steam catalytic conversions with stable products were also obtained and rationalized based on the occurrence of water splitting into *H and *OH radicals and hydrogen production from steam reforming/steam cracking reactions occurring during

ACS Paragon Plus Environment

Energy & Fuels 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

CSC processing. Inhibition of hydrocarbon free radical recombination (coking) by *H capping and hydrogenation facilitated by Ni catalysts are believed key reactions occurring, leading to better DAO products properties. Exploratory evidence gathered with NiCeMo CSC-catalyst for whole bitumen processing added support to the later findings, i.e, olefin production inhibition was evidenced, indirect evidence of hydrogenation occurrence. A convenient field upgrading process that avoids distillation or separation (deasphalting) carried out at low T, P is thus envisaged. 1. INTRODUCTION In the early days of

petroleum refining for the production of useful products,

upgrading of heavy oil fractions was deemed necessary and thus, their conversion into lower distillation boiling cuts was first achieved by thermal cracking (TC).1 The advantage of solid materials (catalysts) to be able to lower the reaction’s activation energy and to better control products’ selectivity, was soon recognized and put into practice.2 The massive usage of liquid fuels during the two world wars in the 20th century, and the ensuing surge on economic development in the second half of that century, motivated the massive synthesis and application of heterogeneous-solid catalysts in refineries, particularly within hydroprocessing units.3,4 Very high pressures of expensive hydrogen gas were necessary for entering the pore space of such catalysts, thus guaranteeing successful processing. The use of water as a reagent participating in the dealkylation of aromatic compounds was investigated during the 1970-1980s.5 Monitoring the isotopes of O- and H proved useful for understanding the mechanisms involved in such reactions.6 Alkali or earthalkali metals, in particular the binary and even ternary combinations of these, proved


Page 2 of 46

Page 3 of 46 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

very interesting for the steam gasification of coals and petroleum cokes via edge recession of the solids.7 Metal pairs forming eutectic mixtures like K-Ni and K-Ca proved very efficient for steam catalysis, showing a capacity for water dissociation, and thus producing the hydrogen for further upgrading reactions using water as a reagent able to substitute relatively expensive hydrogen produced from methane reforming.7 Catalytic Steam Cracking (CSC) upgrading processing for heavy oil feedstocks has been recently the subject of an important review by Eletskii and coworkers.8 Complex occurring parallel reactions for CSC carried out under “low temperature”, i.e, 0.2 moles, of the order of hydrocarbons


Energy & Fuels 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 4 of 46

present having MW~ 600 g/mol) and, more importantly, improving reactors fluidodynamics thanks to the steam microbubbles co-flowing through these units.

.

.

.

.

R – Rn  R + R’

H2O -- CAT--> H + OH

.

.

-- CAT--> RH + Rn’H

R + Rn

.

(6)

(7) (8)

.

Rn’ + 2 OH -- CAT--> Rn-1’ + CO2 + H2 (9)

.

.

R + Rn’

 R - R + Rn’- Rn’

(10)

The importance of catalytic metals regeneration participating in CSC was covered in Eletskii et.al. review for Fe, Ce and Zr, particularly for the pair ZrCe, discussing on how these metallic species change their oxidation states and act like oxygen pumps, regenerating their oxidized states by taking oxygen back from water.8 Catalysts with water scission and hydrogen transfer capability were advantageously used decades ago for improving vacuum residue (VR) thermal cracking in the presence of steam (CSC) by a consortium integrated by PDVSA, UOP and Foster Wheeler in a 18,000 barrels per day (bpd) vacuum residue visbreaker train located at the Curazao Refinery.9-12 Metal sulfided K-Ni particles were employed in these tests, ultradispersed within the VR using an Skid unit able to generate these sulfided forms from decomposition of metal precursor transient emulsions.9-12 Better dispersion control,13,14 due to the development of improved measurement of metal particle size distributions provided what can be termed a second generation of ultradispersed K-Ni catalysts family. The successful CSC upgrading using K-Ni catalyst initially applied to Maracaibo Lake’s


Page 5 of 46 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

heavy oils9-12 was further successfully demonstrated with catalysts from the second family developed by this research group, applied to vacuum gasoil (VGO),15 deasphalted oil (DAO),16-17 Canadian bitumen,18 and also to the more refractory Arab VR.19 Some of these previous works further investigated the use of

18O

labelled water,17,19 thus

unequivocally demonstrating the participation of water as one of the reagents in the occurring CSC reactions. Higher conversions than those obtained in TC were achieved, noticing that CSC products stability as determined by the determination of P-value were higher than those measured for the TC products.19 Better catalytic formulations containing NiCe in addition to other metals (third catalysts family developed within this research group) were studied for CSC carried out at much lower temperatures, i.e., instead of working within the 430-445ºC range, successful results were obtained in the 350-380ºC.20,21 Dispersed particles removal after processing was avoided by using fixed bed reactors, with the active phases dispersed on solid supports for this catalyst family. Fundamental research has been produced based on this third catalyst family, involving DAO22 as well as whole bitumen.23 Isotopically 18O marked water was again used for providing evidence of the water splitting capability of the studied catalysts formulations.22 Work is currently being carried out in our laboratory to further investigate different upgrading schematics based on Ni-Ce plus other active metallic species, by developing robust solid supports conceived for real industrial applications (fourth catalysts family, public information not disclosed at present). The present article focuses on a comparison of TC versus CSC for VR and DAO isolated fractions from Athabasca (AT) vacuum residue, where K-Ni ultradispersed solid particles from the second family were used for CSC. Physicochemical characterization of


Energy & Fuels 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

products and their asphaltenes provided the basis for ranking the upgrading levels achieved under the studied process schematics. Simultaneous tests carried out with supported NiCeMo catalysts for process upgrading of whole Athabasca bitumen (third family), investigated the feasible occurrence of hydrogenation reactions by monitoring the inhibition of olefins production. 2. EXPERIMENTAL 2.1 Fractions isolation. Athabasca bitumen was distilled following routine ASTM standard methods for producing its VR, whose content (>545ºC) was 50 ±1w%.24,25 In order to run the continuous unit with DAO feedstock, the whole ATVR was separated at preparative scale in order to produce the DAO. Exploratory deasphalting experiments were ran at two scales (230 ± 30 g and 13 ± 2 g), varying solvent/VR ratios spanning a range from 10-50. Isolation of asphaltenes from the VR (Preparative DAO separation) was carried out using n-pentane (nC5) in a 13:1/vol:wt ratio. Routinely, 250-260 g of VR melted at 150 ºC were poured into a 5L round-bottomed flask followed by the addition of 3.5L solvent. The mixture was refluxed for two hours, cooled down to ambient temperature and the asphaltenes were isolated by filtration (Whatman paper #2). The solvent from the filtrate was reclaimed by distillation. Both the DAO and the asphaltenes were brought to constant weight inside a vacuum oven, kept at 80ºC and 130 mmHg vacuum. 2.2 VR thermal cracking. The Athabasca VR was thermally cracked inside a 3-neck glass reactor (Figure 1A), at a temperature of 380 ºC and varying residence times spanning from 0.5-3.5 hours. Details can be found elsewhere.26


Page 6 of 46

Page 7 of 46 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

2.3 Deasphalted oil (DAO) TC and CSC. The most important premise of the study is that the processing whole residua or their derived DAO fractions yield different results. Figure 2 presents the schematic for these options. The same set up was used for continuous processing DAO TC and CSC. A schematic representation of the bench top unit is presented on Figure 1B. An upflow reactor (10 mL volume) was used, having an L/D ratio of 12. Operating pressure was set to 400 psig. The liquid hourly space velocity (LHSV) was determined as shown by Equation (11). Reaction temperatures for TC were set in the 416-429 ºC range and LHSV in the 2-3.2 h-1 range. Reaction temperatures used for CSC were set in the 429-443 ºC range and LHSV in the 2.5-3.2h-1 range. DAO catalytic runs incorporated catalytic metal particles into the feedstock (300 ppm by weight Ni and 400 ppm by weight K), dispersed into the feed by means of laboratory scale SKID unit,27 which decomposes the metal precursors present within microdroplets existing in transient formed microemulsions. Steam co-flow ranging form 2-6 wt%, mostly 4wt% based on the amount of pumped DAO, was set up both for the DAO and the DAO-catalyst feedstocks. LHSV [h-1] = DAO volumetric flow (@ T, P) [mL/h]/ Reactor volume [mL]

(11)

(T=140ºC (DAO fluidization); P = 400 psig) 2.4 Whole bitumen CSC with supported catalysts. Exploratory tests were carried out using the bench unit presented on Figure 1B; however, the DAO pump was filled with bitumen in the present instance. For these experiments, the reactor was packed with NiCeMo supported catalyst like those described before.20,21 Set up conditions spanned 355-375ºC and 400 psig., with fixed Weight Hourly Space velocity (WHSV) of 0.25.


Energy & Fuels 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 8 of 46

2.5 Fractions analysis. Distillation properties were determined by High Temperature Simulated Distillation (HTSD), following ASTM D7169.28 One Agilent model 6890N chromatograph was used for the analysis, provided with Simdist Expert V8 software from Separation Systems.29 Sample solutions were prepared in CS2 (150mg/20mL) and 1 L injected with the cold on-column injector from Separation Systems.29 HTSD provided the results used for conversion yields calculation at 545ºC, as shown by Equation 12: wt% conversion (@545ºC) = (wt% >545ºC in feedstock) – (wt% > 545ºC in product) x 100 (wt% > 545ºC in feedstock)

(12)

Several analytical parameters were determined following methodologies recently published in greater detail,30 herein briefly described. Average Molecular Weight (MW) was determined via Size Exclusion Liquid Chromatography (SEC), run with an Agilent model 1100 liquid chromatograph, using highly dilute samples for minimizing aggregation of the analytes. Solubility profile was performed using High Performance Liquid Chromatography (HPLC) equipment (Agilent model 1100); however, it does not involve chromatography but a technique able to provide samples solubility fraction distributions as conceived and described before.31 Fluorescence spectroscopy is a technique able to probe intermolecular association and was carried out by using diluted samples in toluene solvent (5 ppm wt/vol). Synchronous excitation-emission FL spectra were taken with a Hitachi model F-4500 spectrometer, setting the excitation wavelength of 310 nm and emission determined within the 200-900 nm range. Elemental (C, H, N) analysis was carried out following standard combustion method, using a Carlo Erba model 1108 analyzer. Saturates, Aromatics, Resins and Asphaltenes (SARA) analysis was achieved combining solvent microdeasphalting plus Thin Layer Chromatography (TLC) of the


Page 9 of 46 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

deasphalted sample, as reported before.32 One Iatroscan model MK-6 chromatograph was used for SAR analysis of the maltenes fractions. For upgraded products, Asphaltenes were precipitated from the cracked heavy bottoms, their amounts then corrected by the abundance of light end (about *H + *OH

(21) Decarboxylation (22) Water splitting

The existence of H2 and H-radicals addressed in the preceding paragraph, is believed the key for the production of the DAO CSC stable products discussed in the present section. *H and *OH free radicals existence under the discussed reaction conditions


Page 23 of 46 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

(reaction (22)) is feasible thanks to the adsorption of water over solid catalysts, phenomenon that decreases dissociation energies for the adsorbed molecules. The previous water scission has not been reported in the open literature for low temperature ranges; however, has been addressed by others in general ways.8,55,56 The use of asterisks instead of dots identifies these free radicals as originating from adsorbed molecules. H2 presence derives from the occurrence of reactions (17-21) described in the preceding. The two-important species *H and H2 participate as reagents in reactions (23) and (24). Reaction (23), i.e., catalytic hydrogenation favored by the presence of Ni-hydrogenating catalyst plus H2 avoids the undesirable olefin addition reactions, claimed deleterious by others.54 Existence of H-radicals from reaction (22) allows the direct capping of thermal produced free radicals (Reaction (24)), thus avoiding their unwanted reactions that lead to coke formation. R1-CH=CH-R2 + H2 R1-CH2-CH2-R2 R-CH.2 + *H  R-CH3

(23) Catalytic hydrogenation (24) Free radicals capping

Preceding discussion about the parallel and/or sequential complex reactions participating in CSC could be confusing, since mutually exclusive reactions like dehydrogenation (16) and catalytic hydrogenation (23) are simultaneously included. The feasibility for their simultaneous occurrence is due to the fact that dehydrogenation is always happening as soon as the critical thermal cracking temperature (350°C) is reached,57 phenomenon that noticeably increases with increasing operation temperature. Catalytic hydrogenation (23) on the other hand is not necessarily occurring under all circumstances, i.e., it requires the adsorption of present H2 over active metals (like Ni) and thus depends both on the availability of H2 and metal surface active sites. Catalysts


Energy & Fuels 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

high dispersion efficiency and activity are fundamental parameters for successful H2 incorporation. Regenerating catalysts oxidized state by taking oxygen from water is a key aspect for the expected extended long life of the solids.8 Changing in processing parameters and/or catalysts activity could explain different success achieved when applying CSC to real feedstocks, like successfully described by others before,15,19 or not in other instances.17 From the preceding discussion, the present work gathered circumstantial evidence that suggests hydrogen incorporation both via hydrogen radicals capping as well as hydrogenation with Ni catalyst presence, for the samples derived from CSC. Enhanced determined solubility properties are believed derive from higher H/C ratios for hydrogenated CSC products, following similar patterns as discussed before in section 3.3. These circumstantial findings also support the existence of water splitting, focusing on the possibility of radical capping occurrence with *H species, thus complementing the simultaneous oxidation reactions carried out by the *OH species. The existence of oxidation reactions taking place with *18OH, which led to increased levels of marked 18O

2C

derived from the splitting of marked H2O18 and oxidation of carbon moieties in

sample molecules by reaction with *18OH has been previously confirmed 17,19,22 Further evidence on the existence of hydrogenation reactions occurring during CSC was determined from comparison of olefins production during thermal or CSC processing. Olefin contents determined via proton Nuclear Magnetic Resonance spectroscopy (1H-NMR) following an in-house methodology,36 have been determined for the thermal cracked products from ATVR; at the time the discussed experiments with KNi catalysts were carried out, this was not attempted; however, olefin analysis was


Page 24 of 46

Page 25 of 46 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

carried out for CSC products generated from whole Athabasca bitumen, using supported catalysts selected from the third catalyst family that comprises Ni, Ce and Mo species.20,21,23 Olefins contents (Figure 14) were plotted as a function of vacuum residue conversion at 545ºC. Results indicate that olefins increase in a systematic way as a function of residue conversion for both studied feedstocks and both processing schematics. However, it is important to note that olefin contents for bitumen CSC were kept under 1.4 wt%, a much lower value than that obtained for VR TC which spanned the 2-8 wt% range. For similar VR conversion values of 18wt%, 40 wt% lower olefin content (1wt% absolute) was determined for bitumen CSC processing compared to VR TC processing. Despite not many experimental points were compared and despite olefin results at the 1-2 wt% level are affected by 20% relative errors,36 CSC olefin levels from CSC experiments were observed to reach a plateau while TC results were observed to exponentially increase, findings believed to provide evidence for the occurrence of the hydrogenation reaction (23) during CSC upgrading of heavy hydrocarbons involving the presence of Ni, Ce, Mo catalytic species. In addition to better samples stabilities provided by CSC as discussed above, important viscosity reductions have been determined in these studies. Viscosities for CSC bitumen products are shown in Figure 14. Findings indicate that viscosities in the 11,0001,100 cP@12ºC were attained, which is considered outstanding, i.e., with up to 18% w/w residue conversion, viscosity values decreased from about 1.5 million cP (12ºC) for the bitumen feedstock to as low as 1,100 cP (12ºC) for the most converted product. The preceding findings imply that relatively small diluent additions will be required for pipelining the produced bitumen CSC products compared with the unconverted oil.


Energy & Fuels 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

Rough estimates for cold countries like Canada indicate 50-70% diluent savings; for hot countries saving figures could reach nearby 100% diluent savings. The low olefin contents for bitumen CSC products are considered a preliminary indication for the occurrence of hydrogenation reaction (23) during bitumen catalytic steam cracking process. Finally, the later discussed results brought a shift on the research focus by considering CSC catalysts able to successfully perform in the 350-380 ºC range and pressures 400psig,20,21,23 topic that will be covered in upcoming contributions from the group, carrying out accelerated tests confirming catalyst lifetimes beyond those currently determined (3 months still active) and testing higher severities than those described in the present work, where activation of steam reforming reactions will compete favorably versus hydrogenation reactions. One further attractive feature of this later alternative is the processing of whole bitumen, thus avoiding any of the initial separation steps (distillation and deasphalting) already discussed in relation to the schematics presented on Figure 2. Whole bitumen processing following a simple process schematic is thus deemed a very convenient possibility for field upgrading processing.

4. CONCLUSIONS Thermal and ultradispersed catalytic steam cracking upgrading with K-Ni formulations for Athabasca vacuum residue was studied in the present work. Thermal conversions with stable products for the whole residue or its deasphalted fraction (DAO), respectively reached 28 wt% and 48 wt%. Further comparison between the thermal or catalytic steam cracking of the DAO fraction showed 8 wt% increased conversion for the latter, attaining a conversion of 48 and 56 wt% respectively, both with stable products.


Page 26 of 46

Page 27 of 46 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

Higher attainable thermal conversions for the DAO were explained in terms of the better properties of the produced asphaltenes: higher hydrogen content and better solubilization properties due to lower molecular sizes, lower solubility parameters and lower aromaticities.

A definitive link was found between the nature of produced

asphaltenes and products stabilities measured by P-value. Adding processing complexity, i.e., a further deasphalting step, could be expected to be offset by two advantages: I) Amelioration of processing routes for DAO feedstocks, II) Further use of separated asphaltenes. Higher determined DAO steam catalytic conversions with stable products were rationalized based on: 1. The feasible occurrence of catalytic hydrogenation reactions driven by the existence of H2 from reforming reactions, presumably transferred with the aid of hydrogenating Ni catalysts; 2. Production of *H-radicals by K-catalytic water activation, species able to cap thermal produced hydrocarbon free radicals, thus avoiding coke-forming reactions. Exploratory whole bitumen upgrading determined with supported NiCeMo catalysts provides evidence for the occurrence of hydrogenation reactions during CSC, as indicated by the inhibition of olefins production. Products from these exploratory studies showed three orders of magnitude viscosity reductions, practically reaching pipelining values. Process of whole bitumen at low T, P, i. e., 350-380°C and 400 psig, is deemed a very attractive alternative for field upgrading.


Energy & Fuels 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

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. ORCID: Lante Carbognani Ortega, 0000-0002-8817-5715 Notes: The authors declare no competing financial interest.

ACKNOWLEDGEMENTS Funding from AICISE (Alberta Ingenuity Centre for In Situ Energy), joint initiative carried out from 2004-2010, sponsored by Shell, Total, Repsol, Conoco-Philips and Nexen, made possible the initial related research that brought to the present study. In the same way, funding from NSERC/NEXEN/AIEES Industrial Research Chair in Catalysis for Bitumen Upgrading (2010-2015), Canada Foundation for Innovation (CFI), the Institute for Sustainable Energy, Environment and Economy (ISEE) and, Schulich School of Engineering is acknowledged. Cenovus Energy support allowed the development of catalysts and process schematics using solids selected from the third family. Dr. Michael Moir from Chevron-ETC is thanked for helpful discussions that enriched the article. MSc. Eng. Manuel F. Gonzales in acknowledged for his early involvement in experiments carried out with vacuum residue. Dr. Azfar Hassan is acknowledged for MCR analyses. MSc Marianna Trujillo is acknowledged for NMR olefin analysis. Chevron ETC is thanked for permission to publish this work. REFERENCES 1. Burton, W. M. Manufacture of Gasoline. US 1,049,667 (1913). 2. Houdry, E.; Burt, W. E.; Pew Jr., A. E.; Peters Jr. W. A. Oil&Gas J., Engineering and Operating Section, 1938, 37, 40-45.


Page 28 of 46

Page 29 of 46 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

3. Meyers, R.A. Handbook of Petroleum Refining Processes. 4th ed. Mac Graw Hill Education. New York, Chicago, San Francisco, Athens, London, Madrid, Mexico City, Milan, New Delhi, Singapur, Sidney, Toronto. 2016. 4. Speight, R. G. The Chemistry and Technology of Petroleum. 4th ed. CRC Press, Taylor&Francis Group. Boca Raton, FLA-USA. 2007. 5. Duprez, D.; Pereira, P.; Miloudi, A.; Maurel, R. J. Catalysis, 1982, 75, 151-163. 6. Duprez, D. Catalysis Today, 2006, 112, 17-22. 7. Heinemann, H.; Somorjai, G. A. Fundamental and Exploratory Studies of Catalytic Steam Gasification of Carbonaceous Materials. Final report 1985-1994. LBL-35374(UC 109). Lawrence Berkeley Laboratory-University of California, pp 1-70. 1994. 8. Eletskii, P. M.; Mironenko, O. O.; Kukushkin, R. G.; Sosnin, G. A.; Yakovlev, V.A. Catalysis in Industry, 2018, 10(3), 185-201. 9. Pereira, P.; Marzin, R.; Zacarias, L.; Lopez Trosell, I.; Hernandez, F.; Cordova, J.; Szeoke, J.; Flores, C.; Duque, J.; Solari, R. B. Vision Tecnologica, 1998, 6(1), 5-14. 10. Marzin, R.; Pereira, P.; McGrath, M. J.; Feintuch, H. M.; Thompson, G.; Houde, E. Oil&Gas J., 1998, 77(44), 79-86. 11. Pereira, P.; Flores, C.; Zbinden, H.; Guitian, J.; Solari, R. B.; Feintuch, H.; Gillis, D.; Oil&Gas J., 2001, 99(20), 79-85 12.Higuerey, I.; Pereira, P.; Leon, V. Prep. Am. Chem. Soc. Div. Pet. Chem, 2001, 46, 64-65. 13. Pereira-Almao, P.; Marcano, V. A.; Lopez-Linares. F; Vasquez, A. Ultradispersed catalyst compositions and methods of preparation. US Patents: US 7,897,537 B2 (2010), US 8,283,279(2012), US 8,298,982 (2012). 14. Rodriguez-DeVecchis,V. M.; Carbognani Ortega, L.; Scott, C. E.; Pereira- Almao, P.


Energy & Fuels 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 30 of 46

Ind. Eng. Chem. Res, 2015, 54 (40), 9877–9886. 15. Trujillo-Ferrer, G. Thermal and Catalytic Steam Reactivity Evaluation of Athabasca Vacuum Gasoil. MSc Thesis, University of Calgary, Calgary, 2008. 16. Pereira-Almao, P.; Trujillo, G. L.; Peluso, E.; Galarraga,C.; Sosa, C.; Scott Algara, C.; Lopez-Linares, F.; Carbognani Ortega, L. A.: Zerpa Reques, N. G. Systems and methods for catalytic steam cracking of non-asphaltene containing heavy hydrocarbons. US 9562199B2 (2017). 17. Cabrales-Navarro, F. A.; Pereira-Almao, P. Energy Fuels, 2017, 31, 3121-3131. 18. Rhigi, T. M. Evaluation of Catalytic Steam Cracking Process for Total Acid Number Reduction of Heavy Oils. MSc Thesis, University of Calgary, Calgary, 2016. 19. Fathi, M. M.; Pereira-Almao, P. Energy Fuels, 2011, 25, 4867-4877. 20. Pereira-Almao, P.; Vitale-Rojas, G. V.; Perez Zurita. M. J.; Carbognani, L. A.; Smith, S. H.; Sosa, C.

Metallo Silicate Catalyst (MSC) Compositions, Methods of

Preparation and Methods of use in Partial Upgrading of Hydrocarbon Feedstocks. US Patent 10,265,685 B2 (Apr.23, 2019). 21. Pereira-Almao, P.; Vitale-Rojas, G. V.; Perez Zurita. M. J.; Carbognani, L. A.; Smith, S. H.; Sosa, C. Metallo Silicate Catalyst (MSC) Compositions, Methods of Preparation and Methods of use in Partial Upgrading of Hydrocarbon Feedstocks.

US Patent

10,272,417 B2 (Apr.30, 2019). 22. Garcia-Hubner, E. A. Catalysts for Catalytic Steam Cracking of De-asphalted Oil in a Fixed Bed Reactor. MSc Thesis, University of Calgary, Calgary, 2015. 23. Bernal Sardi, L. V. Evaluation of a Ni-Ce-Mo catalytic system for Steam Cracking of Bitumen. MSc Thesis, University of Calgary, Calgary, 2017.


Page 31 of 46 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

24. ASTM D2892. Standard Test Method for Distillation of Crude Petroleum (15Theoretical Plate Column). American Society for Testing and Materials (ASTM): West Conshohocken, PA, 2011. 25. 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. 26. Gonzalez, M. F. Stability Improvement of Thermal Treated Oil. MSc Thesis, University of Calgary, Calgary, 2006. 27. Pereira-Almao, P.; Pereira Cota, A. S.; Coy Plazas, A.; Scott, C. E. Catalytic Preparation Unit for use in Processing of Heavy Hydrocarbons. Patent Application 20180086990 (March 29, 2018). 28. ASTM D7169. Test Method for Boiling Point Distribution of Samples with Residues Such as Crude Oils and Atmospheric and Vacuum Residues by High Temperature Gas Chromatography. American Society for Testing and Materials (ASTM): West Conshohocken, PA, 2011. 29. Separation Systems, Gulf Breeze, FL. 32561,USA ([email protected]). 30. Carbognani Ortega, L.; Rogel, E.; Vien, J.; Ovalles, C.; Guzman, H.; Lopez-Linares, F.; Pereira-Almao, P. Energy Fuels, 2015, 29, 3664-3674. 31. Rogel, E.; Ovalles, C.; Moir, M. . Energy Fuels, 2010, 24, 4369-4374. 32. 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.


Energy & Fuels 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

33. ASTM D5186. Standard Test Method for Determination of Aromatic Content and Polynuclear Aromatic Content of Diesel Fuel and Aviation Turbine Fuels by Supercritical Fluid Chromatography; American Society for Testing and Materials (ASTM): West Conshohocken, PA, 2011. 34. Lopez-Linares, F.; Carbognani, L.; Hassan, A.; Pereira-Almao, P.; Rogel, E.; Ovalles, C.; Pradhan, A.; Zintsmaster, J. Energy Fuels, 2011, 25, 4049-4054. 35. Hassan, A.; Carbognani, L.; Pereira-Almao, P. Fuel, 2008, 87, 3631-3639. 36. Carbognani, L.; Lopez-Linares, F.; Wu, Q.; Trujillo, M.; Carbognani, J.; PereiraAlmao, P. Analysis of Olefins in Heavy Oil, Bitumen and their Upgraded Products. Chapter 5 in “Analytical Methods in Petroleum Upstream Applications”, Ovalles, C.; Rechsteiner, C. E. Jr. (Eds.), CRC Press, Taylor&Francis, Boca Raton, FL-USA, 2015, pp.81-109. 37. ASTM D6550. Standard Test Method for Determination of Olefin Contents of Gasolines by Supercritical-Fluid Chromatography. American Society for Testing and Materials (ASTM): West Conshohocken, PA, 2011. 38. Gillis, D. B.; VanTine, F. M. UOP/FW USA Solvent Deasphalting Process. Chapter 10.4 in “Handbook of Petroleum Refining Processes” Meyer, R. A. (editor). Mc GrawHill Education, 3rd Edition, Columbus, OH-USA. 2003. 39. Rogel, E.; Vien, J.; Morazan, H.; Lopez-Linares, F.; Lang, J.; Benson, I.; Carbognani Ortega, L. A.; Ovalles, C. Energy Fuels, 2017, 31, 9213-9222. 40. ASTM D6560. Standard Test Method for Determination of Asphaltenes (Heptane Insolubles) in Crude Petroleum and Petroleum Products; American Society for Testing and Materials (ASTM): West Conshohocken, PA, 2011.


Page 32 of 46

Page 33 of 46 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

41. Marimoto, M.; Sugimoto, Y.; Sato, S.; Takanohashi, T. Energy Fuels, 2014, 28, 6322-6325. 42. Strausz, O. P.; Lown, E. M. Composition and Properties of Bitumen. Chapter 5 in “The Chemistry of Alberta Oil Sands, Bitumens and Heavy Oils”. Alberta Energy Research Institute, Calgary, Alberta, Canada, 2003, pp. 89-103. 43. Isquierdo, F.; Pereira-Almao, P.; Vitale, G.; Scott, C. E. Prep. Pap. Am .Chem. Soc. Div. Energy Fuels, 2014, 59, 599-600. 44. Guzman, H. J.; Isquierdo, F.; Carbognani, L.; Vitale, G.; Scott, C. E.; Pereira-Almao, P. Energy Fuels, 2017, 31, 10706-10717. 45. Ashtari, M.; Carbognani Ortega, L.; Lopez-Linares, F.; Eldood, A.; Pereira-Almao, P. Energy Fuels, 2016, 30, 4596-4608. 46. Asthari, M.; Carbognani, L.; Pereira-Almao, P. Energy Fuels, 2016, 30, 5470-5482. 47. Carbognani, L. Energy Fuels, 2001, 15, 1013-1020. 48. Moir, M. E. Asphaltenes, What art thou? Chapter 1 in “The Boduszynski Continuum: Contributions to the Understanding of the Molecular Composition of Petroleum”, Ovalles, C.; Moir, M. E. (eds), American Chemical Society Symposium Series #1282, Washington, D.C. 2018. 49.Wasserfallen, D.; Kastler, M.; Pisula, W.; Hofer, W. A.; Fogel, Y.; Wang, Z.; Mullen, K. J. Am. Chem. Soc., 2006, 128, 1334-1339. 50. Rieger, R.; Mullen, K. J. Phys. Org. Chem., 2010, 23, 315-325. 51. Doltz, F.; Brand, J. D.; Ito, S.; Gherghel, L.; Mullen, K. J. Am. Chem. Soc., 2006, 128, 9526-9534. 52. Andersen, S. I. J. Liq. Chrom. Relat. Technol., 1994, 17, 4065-4079.


Energy & Fuels 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

53. Xu, Z.; van der Berg, F. G. A.; Sun, X.; Hu, C.; Zhao, S. Energy Fuels, 2014, 28, 1664-1673. 54. Gray, M. R.; McCaffrey, W. C. Energy Fuels, 2002, 16, 756-766. 55. Thomas, J. M.; Thomas, W. J. Fundamentals of Adsorption, Chapter 2 in “Principles and Practice of Heterogeneous Catalysis.” VCH eds, Weinheim, New York, 1996, pp 65-69. 56. Armentrout, P. B.; Simmons, J. J. Am. Chem. Soc., 1992, 114, 8627-8633. 57. Carbognani Ortega, L. A.; Carbognani, J.; Pereira-Almao, P. Correlation of Thermogravimetry and High Temperature Simulaled Distillation for Oil Analysis: Thermal Cracking Influence over both Methodologies. Chapter 10 in “The Boduszynski Continuum: Contributions to the Understanding of the Molecular Composition of Petroleum”. ACS Symposium Series 1282, Ovalles, C.; Moir, M.E. (eds). American Chemical Society, Washington D.C. 2018, pp. 223-239.


Page 34 of 46

Page 35 of 46 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

Table 1. Set-up operational conditions and samples determined properties. Process

Sample ID*

Catalyst+

T (°C)

LHSV (h-1)

P (psig)

Water (wt%)

Conversion C5C7@545C++ Asp. Asp. (wt%) (wt%) (wt%) VR 0.0 21.4 15.5 (60min) VRTC VB1 --380 atm** --18.3 24.7 16.6 (90min)  VRTC VB2 --380 atm** --24.8 26.8 19.3 VRTC VB3 --380 (180min)  atm** --31.8 36.5 25.0 VRTC VB4 --380 (210min)  atm** --33.2 36.9 28.9 DAO --0.0 1.5 nd DAOTC TC1 --416 2.0 400 2 39.9 10.3 nd DAOTC TC2 --420 2.0 400 2 47.5 11.3 nd DAOTC TC3 --423 2.0 400 2 49.1 13.3 nd DAOTC TC4 --423 2.0 400 4 47.1 12.4 nd DAOTC TC5 --423 2.0 400 6 49.0 14.0 nd DAOTC TC6 --423 2.5 400 4 45.0 11.9 nd DAOTC TC7 --426 2.5 400 4 49.3 14.7 nd DAOTC TC8 --426 3.0 400 4 44.8 11.7 nd DAOTC TC9 --429 3.0 400 4 49.3 17.9 nd DAOCSC CSC1 KNi D 429 3.0 400 4 50.6 14.6 nd DAOCSC CSC2 KNi D 432 3.0 400 4 52.6 15.3 nd DAOCSC CSC3 KNi D 435 3.2 400 4 53.3 15.8 nd DAOCSC CSC4 KNi D 435 3.0 400 4 53.0 16.5 nd DAOCSC CSC5 KNi D 438 3.0 400 4 56.2 16.8 nd DAOCSC CSC6 KNi D 438 2.5 400 4 56.0 17.0 nd DAOCSC CSC7 KNi D 440 3.2 400 4 57.9 17.7 nd DAOCSC CSC8 KNi D 443 3.2 400 4 61.5 18.0 nd Bitumen 0.0 17.0 12.0 BitCSC CSCB1 NiCeMo S 355 0.25 400 5 14.8 nd nd BitCSC CSCB2 NiCeMo S 360 0.25 400 5 13.0 nd nd BitCSC CSCB3 NiCeMo S 365 0.25 400 5 17.8 nd nd BitCSC CSCB4 NiCeMo S 370 0.25 400 5 13.8 nd nd BitCSC CSCB5 NiCeMo S 375 0.25 400 5 14.9 nd nd *Samples in red selected for more detailed characterization (see text); + D, S : Dispersed, Supported catalysts; Residence time for batch reactions; **Laboratory pressure (~660 mmHg); ++ Conversion repeatability at 545°C: ±1 wt%; n.d: not determined

Figure captions Figure 1. Experimental set up schematics. A. Batch system used for VR TC. B. Continuous bench plant used for DAO TC and CSC experiments. Figure 2. Upgrading feasible pathways explored in the present study.


MCR (wt%)

P-value

22.4 24.6 27.0 28.3 30.7 11.6 16.0 17.0 17.3 16.3 16.5 15.8 17.6 16.0 17.9 17.5 17.2 17.0 17.2 17.5 19.0 18.0 22.0 nd nd nd nd nd nd

2.7 1.7 1.5 1.1 1 >3 1.3 1.2 1.1 1.15 1.15 1.25 1.1 1.2 1.1 1.2 1.2 1.25 1.2 1.2 1.1 1.2 1.1 2.8 nd nd nd nd nd

Energy & Fuels 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

Figure 3. Laboratory scale ATVR deasphalting with nC5 precipitant. Two sample scales and different solvent/sample ratios studied. Figure 4. nC5 Asphaltenes and MCR determined increases as a function of thermal conversion severity for ATVR and DAO samples. Figure 5. Products stabilities (P-value) determined for thermal or catalytic steam cracked ATVR and/or DAO, as a function of residua conversions. Figure 6. Fraction separation schematic and identification of studied fractions for the discussion of the present article. Both numeric/color attributes used for samples IDs. Figure 7. Hydrogen/carbon atomic ratios for asphaltenes isolated form ATVR and/or DAO thermal cracked products, plotted as a function of residua conversions. Figure 8. Molecular weights (SEC) determined for fractions produced via thermal cracking of ATVR and/or DAO, plotted as a function of residua conversions. Figure 9. Solubility parameters for asphaltenes isolated from thermal products obtained from ATVR and/or DAO, plotted as a function of residua conversions. Figure 10. Average molecular parameters (NMR) determined for fractions isolated from thermal cracked products obtained from ATVR and/or DAO. Reported parameters: #AromRings/molecule (Aromatic rings present in the average molecular representation); fa: Carbon aromaticity determined via 13CNMR (fa = #Arom C / (#Arom C + Paraffinic C); #C/chain: average number of carbon atoms present in average alkyl appendages from average molecular representations. nC5 asphaltenes exclusively studied; Selected analyzed samples (See Table 1): VR and DAO, VB3 and TC1. Figure 11. Synchronous fluorescence spectroscopy for asphaltenes and maltenes fractions obtained from thermal cracking ATVR and/or DAO. nC5 asphaltenes and


Page 36 of 46

Page 37 of 46 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

maltenes exclusively studied. Inset values described the vacuum residua attained conversion yields. The sharp signals appearing at ~350 and ~650 nm were caused by the solvent (and/or unknown species present in this medium). Figure 12. Hydrocarbon SARA analysis for selected thermal/catalytic cracked products obtained from DAO processing. A. SARA distributions. B. nC5 asphaltenes increases determined as a function of vacuum residua conversions. Selected analyzed samples (See Table 1): DAO; TC1; TC6; CSC3; CSC6; CSC8. Figure 13. Solubility profiles determined for selected thermal/catalytic steam cracked products obtained from DAO processing. A. Solubility profile traces with appended residua conversion levels and products stabilities (P-values). B. Increase of high solubility components (maxima at ~17 min on Figure 13A), as a function of residua attained conversions. Circled samples indicate unstable products (P-value = 1.1). Figure 14. Olefin contents for thermal cracked bitumen distillation residue and catalytic steam cracked whole bitumen. 1H-NMR method used for olefins analysis.36 Low temperature dynamic viscosity reported for CSC bitumen products.Viscosity value for unconverted bitumen (not included): 1.5 x106 cP.


Energy & Fuels 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 38 of 46

A N2

VR

Heating mantle (with Omega controller)

To GC

B

Gas Backpressure meter

Hot Sep. Reactor

DAO Pump

Cold Separator

Steam Generator

Water Pump

Figure 1

Products

g l crackin Therma

Vacuum residue De as ph alt ing

Asphaltenes

Maltenes (DAO) Steam Catalytic Cracking

Thermal cracking

Products

Products

Figure 2.


Further upgrading schematics

Page 39 of 46

66

% w/w DAO

64 62

Feed (g) 13 ± 2

60

230 ± 30

58 56 54 0

10

20

30

40

50

60

Ratio nC5 / sample (mL / g)

Figure 3

DAO

Whole VR Thermal Cracked VR Thermal Cracked DAO Catalytic Steam Cracked DAO

40

Solid symbols: nC5 Asphaltenes Empty symbols: MCR

30

% wt

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

20 10 0

0

10

20

30

40

50

VR conversion @545ºC Figure 4


60

70

Energy & Fuels

DAO:

Whole VR: Thermal Cracked Thermal Cracked Catalytic Steam Cracked

3.0 2.5

P-value

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 40 of 46

2.0 1.5 1.0

0

10

20

30

40

50

60

70

VR conversion @545ºC

Figure 5

Thermal Cracking

Light distillates Cracked bottoms

Asphaltenes Deasphalting

Maltenes

2

Athabasca VR (Deasphalting)

Asphaltenes

Thermal Cracking

Maltenes (DAO) 1

Catalytic Steam Cracking



Maltenes

3


Figure 6



Maltenes

4

Page 41 of 46

1.40

Filled symbols: nC7 asphaltenes

Virgin (1)

1.20

Open symbols: nC5 asphaltenes

DAO TC (3)

1.00 0.80 VR TC (2)

0.60

0

10

20

30

40

50

60

wt% Conversion @ 545°C Figure 7

Asphaltenes VR TC

Filled symbols: Malt.TC nC7 asphaltenes

Virgin (1)

Virgin

Molecular Weight (a.m.u)

1,000 900 800

Open symbols: nC5 asphaltenes

DAO TC (3)

700 600 500 400

VR TC (2)

0

10

20

30

40

50

60

wt% Conversion @ 545°C

Molecular Weight (a.m.u)

H/C atomic ratio

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

660

Maltenes Virgin (1) DAO TC (3)

620 580 VR TC (2)

540

Filled symbols: nC7 maltenes

500 0

Open symbols: nC5 maltenes

10

20

30

40

50

wt% Conversion @ 545°C Figure 8


60

Energy & Fuels

21.8 21.4 VR TC (2)

21.0

DAO TC (3)

20.6 20.4

Filled symbols: nC7 asphaltenes Open symbols: nC5 asphaltenes

20.0

0

10

20

30

40

50

wt% Conversion @ 545°C Figure 9 Solid bars: Asphaltenes Empty bars: Maltenes

10

#AromRings/molecule

Value

8 6 4 2 0 10

fa x 10

Value

8 6 4 2 0 10

#C/chain

8

Value

Solubility Parameter

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 42 of 46

6 4 2 0

Malt Asph Malt Asph Malt Asph

VR (1)

VR TC (2) DAO TC (3)

Figure 10


60

Asphaltenes

1200 1000

DAO TC(3)

A Conv. @545ºC

800 600 400

VR TC (2)

45.0 49.0 39.9 33.2 31.8 24.8 18.3 VR(0)

200 0

0

200

400

600

800

1000

Wavelenght(nm) Maltenes

1200

B

1000 800

Conv. @545ºC 45.0 49.0 39.9

600 400 200 0

DAO TC(3) VR TC (2)

Fluorescence signal

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

Fluorescence signal

Page 43 of 46

33.2 31.8 24.8 18.3 VR(0)

0

200

400

00

800

Wavelength (nm)

Figure 11


1000

Energy & Fuels

100

wt% hydrocarbon group

A

C5 -Asphaltenes

80

Resins

60 Aromatics

40 20

Saturates

0 0

39.9

45.0

53.3

DAO TC (3)

B wt% nC5 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

Page 44 of 46

56.0

61.5

DAO CSC (4)

wt% conversion@545ºC 20 16 12 y = 0.2747x + 1.3118 R2= 0.9385

8 4 0

DAO TC (3)

0

10

20

30

DAO CSC (4)

40

50

60

wt% conversion@545ºC Figure 12


70

A 12

14

16

18

20

22 (min)

61.5 %conv. P -v ~1.1 56.0 %conv. P -v = 1.1 53.3 %conv. P -v =1.25

DAO CSC (4)

50.6 %conv. P -v = 1.20 49.0 %conv. P-v = 1.1 45.0%conv. P -v = 1.25

DAO TC (3)

39.9%conv. P -v = 1.3 0 %conv. P -v > 3

12

14

16

18

20

22

24

26

28

30

Time (min)

B log (% High SP species)

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

ELSD detector signal

Page 45 of 46

DAO TC (3)

DAO CSC (4)

2.5 2

y = 0.0246x + 0.4072 R 2= 0.9769

1.5 1 0.5 0

0

10

20

30

40

50

60

wt% conversion@545ºC

Figure 13


70

Energy & Fuels

%wt olefins contents: VRTC

Bitumen CSC

12

12

8

8

4

4

0

0 0

10

20

30

% wt residue conversion @ 545ºC

Figure 14


Viscosity @ 12ºC x 10-3 (cP)

Viscosity (@12ºC)x 10-3 for Bitumen CSC products

% wt olefins

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 46 of 46

Bench-top Thermal and Steam Catalytic Cracking of Athabasca

Recommend Documents