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Deposition of Dispersed Nano-Particles in Porous Media Similar to Oil Sands. Effect of Temperature and Residence time Victor M Rodriguez-DeVecchis, Lante Antonio Carbognani Ortega, Carlos E. Scott, and Pedro Rafael Pereira-Almao Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b03484 • Publication Date (Web): 11 Jan 2018 Downloaded from http://pubs.acs.org on January 11, 2018

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Industrial & Engineering Chemistry Research

Deposition of Dispersed Nano-Particles in Porous Media Similar to Oil Sands. Effect of Temperature and Residence time Victor M. Rodriguez-DeVecchis*, Lante Carbognani Ortega, Carlos E. Scott, Pedro PereiraAlmao Schulich School of Engineering, University of Calgary, Calgary, Alberta, T2N 1N4, Canada. *[email protected] Abstract The use of nano-particles for a wide variety of purposes is attracting much interest among large oil producers. Technologies that intend to adsorb noxious components, or to modify flow patterns to enhance oil recovery or to upgrade the oil in place before pipelining are being subject to significant consideration with high potential to impact in the environmental and economic performance of this industry. A key aspect for chemical processes targeting the construction of adsorbers or reaction zones in the reservoir strides in the particles retention in the porous medium zone of interest, especially when a temperature above the one in the reservoir is applied. This work addresses the effect of different operation variables in the nano-particle deposition process. Of great importance is not only the amount of particles retained but also the profile, morphology, dispersion and penetration in the porous medium. A Ni-Mo-W dispersed nanoparticulate was evaluated. The deposition process was conducted at moderate conditions of temperature and residence time. During this process, retention of naturally occurring metals, mainly vanadium, in the bitumen was found to be in the low range of 25-70ppm wt. High particle retention, over 95%, was obtained in every case, with no observable effect on the sandpack’s oil permeability. The analysis of particle size distributions before and after passing through the sand pack was shown to have no significant variation. The concentration profiles along the porous media are similar for all experimental conditions investigated with around 30% of nanoparticles depositing at the entrance of the media. Correlations for the profile and cumulative concentration along the porous media core are proposed. Particles were identified and measured by Scanning Electron Microscopy- Energy Dispersion X-ray Analysis (SEMEDX) along the full length of the porous media core in each case. Low temperature deposition

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test runs showed particles deposited as large agglomerates all along the porous medium, while for high temperature deposition test runs, individually deposited particles were observed. Keywords: Nano-particle deposition, Porous media, Particle retention, oil reservoir 4.1. Introduction Industrial applications of particle transport processes in porous media include topics spanning from soil pollution and deep-bed filtration for water and waste-water treatment to geothermal energy and oil recovery1- 2. In some cases particles retention is to be avoided while in others it is the main objective of the process. For all the applications the phenomenon under evaluation involves fine solid particles suspended in the flowing liquid, eventually retained by the solid walls of the porous media. In cases such as waste-water treatment processes the objective is to retain those particles, while in others, like preventing soil pollution, retention of the solid particles is an undesired effect. The retention or deposition process is divided into two sequential steps: transport and attachment. The transport step involves particles being transported from the bulk of the fluid to the vicinity of the stationary surface. The second step is the capture of the particles by the stationary phase2-4. The transport of small submicron particles, falling within the Brownian domain, is dominated by convection and diffusion mechanisms, while the transport phenomenon of larger particles is controlled by hydrodynamic, gravitational and inertial effects. The transport of nanoparticles in porous media is affected not only by the conditions at which they interact with the media (temperature, pressure and flowrate), but also the nature of the particles and the suspension media can play a significant role on the retention and mobility of the particles in the media5-10. The nature and arrangement of the porous media can play an important role as well3. The attachment step involves several forces and mechanisms, depending on the nature of the solid particles as well as the stationary phase, including: double layer, van der Waals interactions, structural and steric interactions; also mechanisms such as inertial impaction, direct interception, sedimentation and electrostatic attraction can take place simultaneously1, 2. Based on the particular purpose of the application, the study of the particle transport phenomena can also take different approaches. In cases where the primary concern is the final destination of


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the particles after passing through the porous media, the breakthrough curves and effluent analysis are the most determining factors4, 11, 12. However, in cases where the principal focus is on the porous media, a detailed analysis of particle deposition over the surface, including placement and angle of attachment on the surface as well as particle arrangement, as single particles or agglomerates, will be of the highest importance1, 6, 11, 13, 14. The particle composition, concentration and dispersion medium are engineered depending on the process targeted and the type of reservoir15, 16. The particle injection and adsorption may affect a variety of parameters in the reservoir, the most common being altering the rock wettability and the catalytic properties of the rock surface for in reservoir upgrading17, 18. The use of organic fluids that are highly miscible with the oil in place, are currently proposed as the continuous media for the particle injection in some processes17, 18. The use of these types of fluids will minimize the impact of the injection on the reservoir formation and will also allow heating up the oil reducing its viscosity to improve productivity. The feasibility of introducing metallic nano-particles into the reservoir has been the subject of several studies19-23, where it has been proven that the particles attach to the sand with no significant reduction of the formation permeability19,20. The catalytic activity of these particles containing Ni, Mo, and W has also been proven, with promising results regarding upgrading levels and enhanced bitumen recovery21, 23-25. Metallic nano-particles deposition has been studied handling variables such as: permeability, temperature, flowrate and nature of the dispersion media19, 21, 24, 25. The success of the deposition process so far is based on high particles retention, as determined by a balance of the metals between the feed and the effluent liquid product. However, this criterion describes only partially the deposition process, not accounting for the particles size and morphology. To maximize the catalytic particles activity inside the reservoir, it is important to handle the deposition process in such a way that allows for a good distribution of these as well as the deposition of individual particles, avoiding as much as possible agglomeration in order to obtain the highest particle dispersion and thus activity. The focus of this work is on the latter aspect of the deposition process, assessing the differences on the particles deposition under various process conditions that can induce high retention of highly active particulates, widely dispersed



over porous media that closely resembles the oil sands that can be found in Canada, Venezuela and other parts of the world. The objective of this work is to increase understanding of the impact of operating variables in the injection of nano-particles suspended in an oil media on the retention, distribution and morphology of retained metal nanoparticles over porous media that resemble oil sands. 4.2. Methods and Materials 4.2.1 Nano-particle Feed Preparation. Particles evaluated in this research were composed of Ni, Mo and W, prepared by a transient emulsion method 26-27 applied to Athabasca bitumen (ATH) with aqueous solutions of transitionmetal salts: nickel acetate (98%, Aldrich), ammonium metatungstate (98%, Aldrich) and ammonium heptamolybdate (99%, Stream Chemicals)

28

. Galarraga has presented a detailed

description of the transient emulsions production and the nanoparticles obtained29. The preparation of the nano-particle feed employed a continuous mode of in line compact preparation (manufacturing) unit (CMU), consisting of water solution pumps, bitumen pumps, an additives pump to drive the synthesis in terms of chemical composition of the nano-particles, and a mixing zone, with static mixers, followed by a decomposition zone, from which the dispersed metal sulfides are obtained. The final products were a bitumen with incorporated nano-particles and the resulting water stream from solutions. A general schematic of the CMU is shown in Figure 1. In this work the nano-particles had a final target concentration of 1200ppmw of metals with respect to the bitumen, distributed as follows: 211ppm of Ni, 604ppm of Mo and 385ppm of W. 4.2.2 Sand pack particles deposition. The sand pack was prepared following the guidelines of Coy25 and Zamani20, using AGSCO Silica Sand 70-100 US Sieve and synthetic brine (1%wt NaCl). The water used in the sand pack preparation is later completely removed by flowing bitumen (without nanoparticles) at 100˚C at atmospheric pressure. The sand chemical composition is presented in Table 1. This preparation allows obtaining permeabilities close to the ones found in real oil sands reservoirs21. The packed bed obtained in all cases presented porosities between 28 and 35%, while obtained oil permeabilitites ranged from 11 to 15 Darcy’s values not far from average of oil sands permeability reported. The pore size and channel structure are thus similar to the ones in oil


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sands with the former being much larger than the particle size, thus not having significant impact on the studied phenomena.

The particle deposition over a sand pack was performed in a reactivity test unit using a vertical reactor in up flow configuration (35 cm long and 2.26 cm ID). The particle deposition consists of flowing the nano-particle feedstock (bitumen plus nano-particles, see Figure 1) through the sand pack at a moderate temperature such that the viscosity is reduced enough for the particles to move and attach to the sand, producing none or very little conversion on the bitumen. Afterwards, aliquots of the sand at different lengths along the reactor where taken and calcined in a muffled furnace at 500 ˚C for 12 h, for later analysis by SEM-EDX. A total of 5 different operating conditions were evaluated, covering three different temperatures (300 ˚C, 200˚C and 150 ˚C) and three residence times (24 h, 6 h and 3 h). In order to have a base line for comparison, two “blank” depositions (oil with no added particles) were performed at conditions of 300 ˚C -24 h and 150 ˚C-24 h to account for the removal of naturally present metals in the bitumen. All experiments were conducted for a total of 9 Pore Volumes (PV), i.e. empty volume or non-occupied space by the packed sand grains, each one to have the same amount of particles percolated through the sand pack, in every case. 4.2.3 Simulated Distillation. The liquid products were analyzed through High Temperature Simulated Distillation (HTSD) following standard method ASTM D7169, to observe their composition and detect any level of change in the feedstock. The results are reported in terms of typical cuts for the oil industry according to their boiling points: Naphtha (IBP-216˚C), Distillates (216-343 ˚C), Vacuum Gas Oil (VGO) (343-550 ˚C) and Vacuum Residue (VR) (550+ ˚C). Errors derived from SimDist are typically 1% relative for lighter fractions (Naphta, Distillates and VGO) and 4% relative for VR. 4.2.4 Inductively Coupled Plasma-Atomic Emission Spectroscopy. An Inductively Coupled Plasma (ICP) with Atomic Emission Spectroscopy emission (AES) (IRIS Intrepid II Optical Emission Spectrometer-ICP Spectrometer, Thermo Electron Corporation) was used to determine the amount of metals present in the bitumen before and after the incorporation of the metals as well as the amount of metals remaining in the sand pack after



processing. In order to transform the samples into aqueous solutions, phosphoric acid and nitric acid were added to an aliquot of the bitumen and placed into a microwave digestor (CEM model Mars 6) before dilution to an appropriate concentration for ICP-AES. The error of the technique is typically 5% for determined concentrations of each of the metals. 4.2.5 Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy. In order to analyze the surface of the sand and observe the deposited particles, the sand samples collected at different heights along the reactor were analyzed with a Scanning Electron Microscope (FEI QUANTA FED 250), after been calcined to remove the hydrocarbon phase covering them. The SEM was coupled with an Energy Dispersive X-ray Spectrometer (EDX or EDS, BRUKER X FLASH 5030) that performs an elemental analysis over different zones (particles and background). This protocol guarantees only particles of interest are measured, containing Ni, Mo and W, while other artifacts are not considered. 4.2.6 Nanoparticle Tracking Analysis (NTA). A sample produced during the nano-particle feed preparation was set aside and taken for Nanoparticle Tracking Analysis (NTA) using a NanoSight NS300 equipment and NTA 3.0 software for data analysis in order to obtain the diameter of particles suspended in the feed and in reactor effluents, when possible. The procedure followed was presented by RodriguezDeVecchis et al.30. 4.3. Results and Discussion 4.3.1 Blank Depositions The Athabasca Bitumen used contains 100 ppm of the same metals that compose the particles under study (89 ppm of Ni, 10 ppm of Mo and 1 ppm of W), therefore blank depositions were performed in order to know the extent of de-metallization that can occur during the process. Athabasca Bitumen with no incorporation of additional metals was flown through a sand pack and metals were measured in the effluent. Blank depositions were performed at two different temperatures (150 ˚C and 300 ˚C) that were the extreme temperatures at which the nano-particles deposition was performed; both tests were carried out at 24 h residence time, the most severe condition set up for depositions evaluation.


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The metal content profiles for both experiments are shown in Figure 2 and Figure 3, evidencing very low degree of metal removal in both cases. In average 12 ppm (12.6%) of metals are removed at 150 ˚C and 10 ppm (9.7%) at 300 ˚C. The average values are shown in the first part of Table 2.

The amount of natural occurring metals removed from the feed is very low specially when compared to the amount of particles defined for incorporation so, for practical effects it will be considered that these naturally existing metals are not extracted and their concentration is constant. This concentration is subtracted to obtain the amount of metals actually incorporated and deposited. 4.3.2 Nano-particle Feed Preparation The ultradispersed nano-particles were prepared in the CMU (see Figure 1). During this process there was no significant change in the bitumen composition as it can be deducted from the SimDist results shown in Table S1, as evidenced by the low residue conversion and very little variation in the cut distribution for all experiments. The metal incorporation results in the CMU are presented in Table S2, were the achieved concentration of metals is very close to the target, with less than 4% error. All depositions were carried out with the same feedstock. 4.3.3 Retention of nano-particles by the porous media. For each of the deposition experiments a new sand pack was prepared with fresh sand and the process was carried along for the equivalent of 9 Pore Volumes (PV), sampling the liquid effluent at the end of each PV. The liquid products distribution showed very little variation compared to the feedstock (see Table S1), with conversion levels between 2 and 11% of the residue fraction following the expected trend, of higher conversion at the more severe conditions. Low levels of conversion were desirable in this case in order to focus on the deposition of the particles when passing through a porous medium, minimizing the effect that changes in the flowing fluid carrier propertiescould have over the particle deposition. The metal content in the liquid effluent at different times is presented in Figures 4 to 6. Determined metal contents are based on the metal added to the feed, disregarding the natural



metals present in the bitumen, since the blank deposition demonstrated very small removal from the bitumen. All cases show a small difference for the 1st and 2nd PV, where metal retention is slightly smaller, and from the 3rd PV on the effluent profile is flat with no significant variations. In all effluents absolute metal levels come back to values very close to bitumen initial metal content, which is in agreement with the results obtained with blank depositions. Therefore the retention of metals of interest can be attributed to the nano-particles, disregarding the deposition of indigenous metals present in the feedstock. For all conditions tested particle retention levels from the beginning up to the end of the deposition experiment were 95% or higher. As targeted all experiments resulted in high retention percentage. The average values of metals in the effluent and percentual retentions are shown in Table 3. When looking at the individual metal profiles, Mo and W exhibit the same trend, i.e., metal trends showed almost total retention at 300-24 and less for the remainder of the studied conditions; however, without significant variation. On the other hand, Ni is the metal that presents the lowest retention in all cases, with decreased retention as the operating conditions become less severe (see Figure 4). Temperature was found to have bigger effect on the Ni retention compared to the residence time, since experiments performed at 200 ˚C and 150 ˚C show the lowest retention (Figure 4). Oil permeabilities were measured for each sandpack before and after the nano-particle deposition, with no significant change observed in any case, ranging between 11 and 15 Darcys. 4.3.4 Retention of other metals during the sand pack deposition process The deposition of nano-particles over the sand pack has as final target, the creation of a particlesrich zone as an enabler for bitumen upgrading, therefore it is also important to look at other metals present in the bitumen that may be depositing over the porous media. The main focus of this section is to monitor the vanadium and iron deposition, since both have an important presence in the original bitumen. Figures 7 and 8 show the profile of each metal in each of the performed experiments including all 5 nano-particle depositions and 2 blank depositions, compared to the initial bitumen content.


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Figure 7 presents the vanadium profile during all studied depositions. There was not a clear trend of deposition for this metal at the different operating conditions. In general between 15 to 40 ppm of V were removed, and retention seems to decrease slightly after the 3rd PV injected. After the 6th PV was injected, values presented little variation reaching a plateau. Special cases occurred for the blank deposition at 150-24 and nano-particle deposition carried out at 300-24, where during the first 3 PVs, higher uptake of Vanadium was reached with values spanning ~(50-60) ppm; however, deposition of this metal decreased significantly along the next PV reaching similar levels as the rest of the other conditions by the 6th PV. An opposite situation occurred with iron retention, i.e., in no case the natural occurring iron on the bitumen was removed (Figure 8). In all studied cases Fe concentrations for the first 4 PVs was found higher than the natural one (up to 40 ppm more); this was possibly due to the transfer of this metal from the processing units; however, this has no impact in the experiments. After the 5th PV, determined Fe concentrations were found similar to the natural one for bitumen. Based on the previous results, total retention of natural occurring metals can range between 2572 ppm that is, between 7-20%, however, the most typical range is around 10-15%, mostly V retention that accounts for half or more of the total metals retained. 4.3.8 Particles size distributions The high retention levels obtained for all experimental conditions implies that the remaining concentration of metals in the effluent is very low, making difficult the particle size determination for comparison with the nano-particle feed. The samples with enough particles after the deposition process were analyzed. Table 4 presents the particle size measurement for the initial nano-particles present in the feed and two of the liquid products obtained under different conditions (200-24 and 300-6). The results showed that the particle sizes that exit the porous medium are very similar in both cases to the size obtained for the feed, within the reported error. The mode value for 300-6 is somewhat smaller than the other two samples but still in the same size range. When comparing the values of D10 and D90, in order to analyze the size of 80% of the particles measured, sizes spanned between 85nm (D10) to 270nm (D90) and the range presents no significant difference among all samples.



The NTA results point out that particles retention over the porous media occurs for the whole range of particles sizes in a similar way and there is no discrimination in the retention by particles size. Sections 4.3.5 through 4.3.7 will address the quantity, morphology and dispersion nature of metal particles over the studied sand packs. 4.3.5 Concentration of nanoparticles along the porous media length Of particular interest is not only the total retention of the particles by the porous media but also the location of the nanoparticles within the porous media, since the effect of the particles will be limited to the zones where these can be found. The agreement of the metal balance performed over the sand and liquid samples has been addressed in detail by Zamani et al.19-20 with similar nanoparticles, with an excellent metal balance agreement, in average 97%. For this work several aliquots of the sandpacks were taken at approximately every 5cm along the axial length of the porous media and analyzed for metal content. The results are presented as percentage of retained particles (based on the total metal retained) for every section of the porous media and are presented in Figure 9. Nanoparticles were found along the full length of the sand pack for every condition studied and in general all show a similar behavior. About 30% of the deposited particles are found at the entrance of the porous media and the concentration decreases rapidly at the beginning to later flatten towards the last 10cm of the sand pack at 5-10% of the retention. The concentration profiles obtained resemble to those previously reported in the literature 19-20. The low temperature runs (200 ˚C and 150 ˚C) show a monotonic behavior while the high temperature (300 ˚C) have some irregularities with zones of increase concentration in the middle of the porous media, occurring at 25 cm for low residence times (6 h and 3 h) and at 15 cm for 24 h residence time. Also the high temperature and low residence times (6 h and 3 h) do not show such a sharp decrease in concentration at the beginning of the sand pack. However, these differences are in general small compared to the general trend observed for all cases. Figure 10 shows the cumulative percentage retention throughout the porous media length where similar behavior for all experimental conditions are observed. The low temperature depositions increase monotonically while the high temperature ones (300 ˚C) have a larger slope at the


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beginning (first 10 cm) and then converge with the low temperature behavior. For the case of high residence time and high temperature (300 ˚C – 24 h) the cumulative profile shows a change of slope after 25 cm in the sand pack. Although some differences in the profile of retention in the porous media are noticed depending on the experimental conditions the general trend is very similar in every case, therefore average values are used to find a correlation that predicts this profile (see Figure 11). The correlations for both the percentage retention and the cumulative percentage retention were presented as a function of dimensionless length. The fitting of the data requires a polynomial of order 2 in order to account for the sharp decrease of concentration after the inlet of the sand pack but a flattening of the profile towards the end. If instead of the average values the entire data is used for developing the correlation the fitting function is exactly the same but presents a lower degree of data correlation as it would be expected (lower R2). The determined correlations are deemed very important for prediction of metal particles retention on porous media, like the studied sandpacks of the present work 4.3.6 Qualitative morphology of nanoparticles retained along the porous media length Once the deposition experiments were completed the used sand pack was carefully removed from the core-holder. Samples of the sand were taken at approximately every 5cm along the axial length starting from the bottom, since the reactor was operated in an up-flow configuration. Sand samples where labelled “Bottom 1” (B1) through 8 (B8), top section. The sand calcination was performed at 500 ˚C in an air atmosphere for 12 h, to guarantee all hydrocarbons were burnt and removed from the sand. During the SEM analysis the sands visually appeared clean and no presence of hydrocarbons was observed in any case. The approach taken for the SEM analysis was to measure as many particles in each of the samples as it could be reasonably performed during the equipment time allocated (a few hours). All measured particles were confirmed as particles of interest by EDX analysis on each single focused particle. The presence of W or Mo was used as a definitive indicator of the presence of incorporated particles, since the natural amount of these metals in the bitumen is very small. A sample of the clean sand was analyzed together with sands from the sand pack containing



deposited particles; also a blank experiment (sand exposed to bitumen with no incorporated particles) was compared. Figure 12 shows a visual comparison of single grains at the entrance, for each of the sand packs after the deposition process. Clean sand shows no bright spots, observed to appear in all of the other cases. The blank deposition (11-B) showed significant fewer amounts of these bright spots in comparison with the ones from the nano-particle depositions. However, it is important to clarify that by no means are all of these bright spots particles of interest, in fact most of them are not, thus this characterization cannot be used as a qualitative assessment of the deposition process. SEM-EDX photograms for the analyzed particles were shown in a recent publication (Rodriguez-DeVecchis et al. 2015)30, where the difference between the sand grains (background) and nano-particles are addressed. Figures 13 through 18 show a selection of the most representative images of sand aliquots after deposition in different sections of the porous media with examples of particles measured in every case. Measurement of single particles is favored over the measurement of agglomerates, this is, whenever possible individual particles were measured even if they are part of a bigger agglomerate; only in cases where it was not possible to measure single particles within the agglomerate, the agglomerate size was reported. The scale in the images was varied with the sole purpose to show as many particles as possible in an individual image. The particle sizing is done with a software feature of the SEM-EDX using higher magnifications. Although from a visual comparison the sand from the blank deposition looked similar to others in terms of the presence of bright spots, these are in lower concentration, as expected from the much lower metal amount in the feed. Presence of particles with the targeted metals is very scarce and usually related to large particle sizes. However, identification of Ni, Mo and W incorporated particles was possible in every sand sample. On all studied samples after deposition, particle identification was successful and showed that depending on the operating conditions and the distance from the entrance of the sand pack the dispersion of particles over the sand grain surface can change considerably despite the similar overall retention levels achieved. 4.3.7 Nano-particles dispersion over the sand pack


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Based on the SEM-EDX imaging it was observed that the dispersion of particles attached to the sand is influenced by the operating conditions of the deposition and the distance along the porous media. For the low temperatures tested (150 ˚C and 200 ˚C), deposition of particles as large agglomerates was determined. The presence of particles at these conditions is found along the whole reactor but particles could not be observed as individual particles over the surface of the sand grains (Figures 15-16). At 300 ˚C the deposition of the metallic-particles as single entities over the sand depends on the distance from the entrance. Close to the reactor’s entrance, single particles are observed, but further from the entrance metallic particles showed again in form of large agglomerates (Figures 14, 17-18). The depth of the nano-particles dispersion as individual particles seems highly influenced by the residence time. At lower residence times (higher flowrates), the penetration of the particles dispersion was reduced considerably. At 3 h residence time, dispersed particles could only be found at the entrance of the reactor (0cm, Figure 18-A), while at 6h the dispersed particles could be found even at 5cm from the entrance (Figure 17-A and 17-B). Lastly, at 24 h well dispersed particles were found up to 10cm from the sand pack’s entrance (Figure 14-C). Figure 19 shows the determined data correlation for well dispersed particles at 300 ˚C. A second degree polynomial correlation between the residence time and the achieved depth of dispersed particles at 300 ˚C can be proposed based on the results. This correlation can also be used to predict the desired conditions of the deposition process based on the desired depth set for achievement; particles retention also was found to follow a second order polynomic behavior (Figure 11). Error bars in Figure 19 represent the uncertainty on the specific length at which the sample was collected during the extraction process of the sand samples. Table 5 presents a summary of particles and agglomerate sizes measured in each deposition as well as the nano-particles presence along the reactor. Based on the morphology observed in the deposition process the mechanism for the agglomerate formation requires further research to establish if the agglomerates are being formed in the fluid phase and later retained by the porous media or if the process occurs over the solid mineral pack or both, or which one is the dominant effect under lower or higher severity conditions such as Temperature, Pressure, particles concentration and porous media surface and nature.



4.4. Conclusions The effect of Temperature and residence time on the deposition of nano-particles of Ni, Mo, and W dispersed in an oil media over porous media representative of permeable oil sand reservoirs was investigated. High particle retention (over 95% for all experimental conditions) was obtained in the range of temperature and residence time evaluated, these ranges are representative of thermal enhanced oil recovery methods such as in the in situ upgrading technology (ISUT) and in situ combustion. The particles of interest were successfully identified and measured, although unevenly distributed, and were found in every section of the sandpack in all cases. Incorporation of metallic nanoparticles in the sand pack had no observable effect on the bed permeability. The studied deposition process showed a very small effect on the liquid product distribution, as intended, to avoid the effect that drastic changes in viscosity could have on the process. Removal of natural occurring metals (Fe and V) in the bitumen was found to be very low (around 10 ppm), in the temperature range evaluated. Overall, natural metals removal was in the range of 10-15%, most of it being Vanadium. Deposited particle sizes before and after passing through the porous medium, were measured in order to study the possibility of agglomeration in the fluid phase. It was found that 80% of the particles were in the range of 85 nm (D10) to 260 nm (D90) in all samples analyzed, similar to the particle size in the original feed, thus indicating no agglomeration in the fluid dispersion. The deposition profiles are similar for all the studied combination of operating variables, with around 30% of the nanoparticles being retained at the entrance of the porous media. For shorter residence times (3 and 6 h) slightly higher retention values close to the entrance and exit of the sand pack were observed while 24 h showed a more monotonic decrease in the profile. Correlations for the concentration and cumulative profile were proposed based on a second order polynomic that properly described all the experimental conditions investigated in this work. The high retention values together with the deposition profile demonstrates the feasibility of controllably creating a particle rich zone around the injection well bore without damage to the reservoir and to efficiently maximize the impact of the injected nano-particles under processes of thermal enhanced oil recovery and upgrading.


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The morphology of deposited particles shows significant differences based on the deposition conditions. At low temperatures (150 ˚C and 200 ˚C) the incorporated particles were found in the form of large agglomerates throughout the full length of the sand pack. For high temperature (300 ˚C) it was evidenced that near the reactor entrance particles deposited as individual entities. The depths of well dispersed deposited nano-particles were strongly related to the residence time, i.e., as residence time increased so did the depth of the dispersed nano-particles, increasing from 0 cm at 3 h up to 10 cm at 24 h. That behavior can be correlated with a second degree polynomic expression in all cases then suggesting the inter-particular collisions may be responsible for most of the behavior’s observed. The retention of smaller (individual) particles at the beginning of the porous media together with the high amount deposited in this section calls for phenomenological models different than deep bed filtration, which has been used to describe this process. The agglomeration process that generated the visualized nano-particles aggregated deposits over the sand surface requires further investigation to unravel the predominant mechanisms, which should include not only particle-particle interaction but also the interaction of the particle with the oil media, in particular with the largest and most polar fractions that may play a role in the agglomeration and deposition process. Author Information Corresponding Author *E-mail: [email protected] Notes The authors declare no competing financial interest

Acknowledgements The authors are grateful to the Natural Sciences and Engineering Research Council of Canada (NSERC), Nexen-CNOOC Ltd, and Alberta Innovates-Energy and Environment Solutions (AIEES) for the financial support provided through the NSERC/NEXEN/AIEES Industrial Research Chair in Catalysis for Bitumen Upgrading. Also, the contribution of facilities from the Canada Foundation for Innovation, the Institute for Sustainable Energy, Environment and



Economy, the Schulich School of Engineering at the University of Calgary are greatly appreciated. The authors specially thank Dr. Chris DeBuhr (Department of Geoscience) and Dr. Argenis Aguero (Schulich School of Engineering) at University of Calgary, for valuable help with the SEM-EDX data acquisition, imaging and analysis and, with ICP-AES analysis, respectively.

Supporting Information Contains Table for Liquid product Distribution (Table S1) and Nanoparticle Feed metal analysis (Table S2). Contains additional SEM imaging for the morphology studies for blank deposition (Figure S1), Deposition 300-24 (Figure S2), Deposition 200-24 (Figure S3), Deposition 150-24 (Figure S4), Deposition 300-6 (Figure S5) and Deposition 300-3 (Figure S6). This information is available free of charge via the Internet at http://pubs.acs.orgh/.

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(7) Lecoanet, H.F.; Bottero, J.Y.; Wiesner, M.R. Laboratory Assessment of the Mobility of Nanomaterials in Porous Media. Environ. Sci. Technol. 2004, 38, 5164. (8) McDowell-Boyer, L.M. Chemical Mobilization of Micron-Sized Particles in Saturated Porous Media under Steady Flow Conditions. Environ. Sci. Technol. 1992, 26, 586. (9) Pelley, A.J.; Tufenkji, N. Effect of Particle Size and Natural Organic Matter on the Migration of Nano- and Microsacle Latex Particles in Saturated Porous Media. J. Colloid Interface Sci. 2008, 321, 74. (10) Tian, Y.; Gao, B.; Silvera-Batista, C.; Ziegler, K. Transport of Engineered Nanoparticles in Saturated Porous Media. J. Nanopart. Res. 2010, 12, 2371. (11) Liu, X.; Wazne, M.; Christodoulatos, C.; Jasinkiewicz, K.L. Aggregation and Deposition Behavior of Boron Nanoparticles in Porous Media. J. Colloid Interface Sci. 2009, 330, 90. (12) Tiraferri, A.; Sethi, R. Enhanced Transport of Zerovalent Iron Nanoparticles in Saturated Porous Media by Guar Gum. J. Nanopart. Res. 2009, 11, 635. (13) Solovitch, N.; Labille, J.; Rose, J.; Chaurand, P.; Borschneck, D.; Wiesner,R.; Bottero, J.Y. Concurrent Aggregation and Deposition of TiO2 Nanoparticles in Sandy Porous Media. Environ. Sci. Technol. 2010, 44, 4897. (14) Song, L.; Elimelech, M. Dynamics of Colloid Deposition in Porous Media: Modeling the Role of Retained Particles. Colloids Surf., A. 1993, 73, 49. (15) Esfandyari Bayat, A.; Junin, R.; Samsuri, A.; Piroozian, A.; Hokmabadi, M. Impact of Metal Oxide Nanoparticles on Enhanced Oil Recovery from Limestone Media at Several Temperatures. Energy Fuels. 2014, 28, 6255. (16) Moghadasi, J.; Müler-Steinhagen, H.; Jamialahmadi, M.; Sharif, A. Theoretical and experimental study of Particle Movement and Deposition in Porous Media during Water Injection. J. Pet. Sci. Eng. 2004, 43, 163. (17) Pereira-Almao, P.; Chen, Z.; Maini, B.; Scott-Algara, C. In Situ Upgrading via Hot Fluid Injection. CA Patent CA 2810022, 2014. (18) Pereira-Almao, P.; Chen, Z.; Maini, B.; Scott-Algara, C. In Situ Upgrading via Hot Fluid Injection. Patent WO 2013/177683 A1, 2013. (19) Zamani, A.; Maini, B.; Pereira-Almao, P. Experimental Study on Transport of UltraDispersed Catalyst Particles in Porous Media. Energy Fuels. 2010, 24, 4980.



(20) Zamani, A.; Maini, B.; Pereira-Almao, P. Flow of Nanodispersed Catalyst Particles through Porous Media: Effect of Permeability and Temperature. Can. J. Chem. Eng. 2012, 90, 304. (21) Rendon, V.S. Catalytic Heavy Oil upgrading with Injection of Ultra-Dispersed Particles and Hydrogen in Porous Media. M.S. Thesis, University of Calgary, Canada, 2012. (22) Hashemi, R.; Nassar, N. N.; Pereira-Almao, P. Transport Behavior of Multimetallic Ultradispersed Nanoparticles in an Oil-Sands-Packed Bed Column at High Temperature and Pressure. Energy Fuels. 2012, 26, 1645. (23) Hashemi, R.; Nassar, N. N.; Pereira-Almao, P. In situ Upgrading of Athabasca Bitumen Using Multimetalic Ultradispersed Nanocatalysts in an Oil Sands Packed-Bed Column: Part 1. Produced Liquid Quality Enhancement. Energy Fuels. 2013, 28, 1338. (24) Hovsepian, C.N.; Carbognani Ortega, L.; Pereira-Almao, P. Laboratory Two-Dimensional Experiment Simulation of Catalytic In Situ Upgrading. Energy Fuels. 2016, 30, 3652. (25) Coy, L.A. Experimental simulation of a Hot Fluid Injection Process for In-reservoir Upgrading. M.S. Thesis, University of Calgary, 2012. (26) Contreras Lapeira, C. Development of a New Methodology for Preparing Nanometric Nickel, Molybdenum and Nickel Molybdate Catalytic Particles using Transient Emulsions. M.S. Thesis, University of Calgary, 2010. (27) Contreras, C.; Scott, C. E.; Pereira-Almao, P. Preparation of Ni, Mo and NiMo nanoparticles from transient w/o emulsions. Prepr. Pap.-Am. Chem. Soc., Div. Petr. Chem. 2009, 54, 56. (28) Pereira-Almao, P.; Ali-Marcano, V.A.; Lopez-Linares, F.; Vasquez, A. Ultradispersed Catalyst Composition and Methods of Preparation. U.S. Patent 7,897,537, 2011. (29) Galarraga, C.E. Upgrading Athabasca Bitumen using Submicronic Nickel Tungsten Molybdate Catalyst at conditions near to In-reservoir Operation. Ph.D. Dissertation, University of Calgary, 2011. (30) Rodriguez-DeVecchis, V.M.; Carbognani Ortega, L.; Scott, C.E.; Pereira-Almao, P. Use of Nanoparticle Tracking Analysis for Particle Size Determination of Dispersed Catalyst in Bitumen and Heavy Oil Fractions. Ind. Eng. Chem. Res. 2015, 54, 9877.


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Table Captions Table 1. Chemical Composition AGSCO Silica Sand. Table 2. Average metals in liquid effluents from blank depositions. Table 3. Average metals in liquid effluents from nano-particle depositions over sand pack. Table 4. Particle size measurement for feed and products (NTA). Discussion on parameters significate were addressed elsewhere 30. Table 5. Summary of nano-particle presence, dispersion and size for each deposition particles containing Mo and W.



Figure captions

Figure 1. Compact Manufacturing Unit (CMU) schematic. Figure 2. Metal profile for blank deposition carried out at 150 ˚C and 24h. Figure 3. Metal profile for blank deposition carried out at 300 ˚C and 24h. Figure 4. Ni content in the effluent for all experimental conditions. Figure 5. Mo content in the effluent for all experimental conditions. Figure 6. W content in the effluent for all experimental conditions. Figure 7. Vanadium profiles on liquid products from all sand pack deposition experiments. Figure 8. Iron profiles on liquid products from all sand pack deposition experiments. Figure 9. Percentage retention (%wt) along the length of the porous media. Figure 10. Cumulative percentage retention (%wt) along porous media. Figure 11. Correlations for retention profile and cumulative retention vs dimensionless length. Figure 12. Visual comparison of a single grain at the entrance of each of the decorated sand. A) Clean sand. B) Blank deposition. C) 300-24. D) 200-24. E) 150-24. F) 300-6. G) 300-3. Figure 13. Particle identification and sizing for the blank deposition. A) B1 (0cm). B) B2 (5cm). C) B4 (15cm). Figure 14. Particle identification and sizing for the deposition carried out at 300-24. A) B1 (0cm). B) B2 (5cm). C) B6 (25cm). Figure 15. Particle identification and sizing for the deposition carried out at 200-24. A) B2 (5cm). B) B6 (25cm). C) B8 (35cm). Figure 16. Particle identification and sizing for the deposition carried out at 150-24. A) B3 (10cm). B) B5 (20cm). C) B8 (35cm). Figure 17. Particle identification and sizing for the deposition carried out at 300-6. A) B1 (0cm). B) B2 (5cm). C) B5 (20cm). Figure 18. Particle identification and sizing for the deposition carried out at 300-3. A) B1 (0cm). B) B2 (5cm). C) B8 (35cm). Figure 19. Data correlation between residence time (h) and achieved depth for well dispersed particles dispersion (experiments run at 300˚C).


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Table 1. Chemical composition of AGSCO Silica Sand. Specie Wt. (%) SiO2 98.2 Fe2O3 0.14 Al2O3 0.49 TiO2 0.02 CaO 0.02 MgO 0.01 K2O 0.21 Na2O 0.06 Table 2. Average metals in liquid effluents from blank depositions. Condition

Original BIT [ppm]

T (˚C) – τ (h) Mo Blank 300-24 10 Blank 150-24

Ni

W

Total

88

1

99

Metals in liquid effluent [ppm] (average of 9 PV eluted) Mo Ni W Total (%) 4 82 3 89 90 6 78 3 87 87

Table 3. Average metals in liquid effluents from nano-particle depositions over a sand pack. Condition

Nano-particle Feed (CMU)

T (˚C) – τ (h) 300-24 200-24 150-24 300-6 300-3

Mo

627

Ni

228

W

390

Total

1245

Metals in liquid effluent [ppm] Mo Ni W Total (%) 4 15 15 14 17

2 46 38 17 25

2 5 2 7 7

8 66 56 38 49


0.64 5.26 4.47 3.03 3.92

Nano-particle retention (%) 99 95 96 97 96


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Table 4.Particle size measurement for feed and products (NTA). Discussion on parameters signification were addressed elsewhere 30. Sample Parameter Mean Mode SD D10 D50 D90

Nano-particle Feed Average Error (nm) (±) 184.7 12.4 172.9 23.3 69.7 8.4 92.1 14.5 177.6 11.9 266.3 23.5

200-24 PV 6 Average Error (nm) (±) 192.1 12.5 186.7 27.5 82.9 12.6 81.3 6.9 175.2 9.1 282.7 29.5

300-6 PV 6 Average Error (±) (nm) 181.7 5 132.5 11.9 71.8 2.9 93.8 4.6 177.8 9.6 265.6 3.8

Table 5. Summary of particle presence, dispersion and size for deposited particles containing Mo and W. Condition T (˚C) – τ (h)

300-24

300-60

300-3

200-24

150-24

Total

Num. of particles analyzed

127

67

35

31

39

209

Average part. Diam. (nm)

142

136

150

190

169

157

Num. of agglomerates

8

6

6

15

51

86

Average agg. diam. (nm)

2257

1150

724

1003

2046

1436

Particles presence

All

All

All

All

All

Dispersion depth

B1-B3

B1-B2

B1

-

-

Agglomerate presence

B4-B8

B3-B8

B2-B8

B1-B8

B1-B8

Figure 1. Compact Manufacturing Unit (CMU) schematic


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Figure 2. Metal profile for blank deposition carried out at 150 ˚C and 24h.

Figure 3. Metal profile for blank deposition carried out at 300 ˚C and 24h.

Ni content (ppm)

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


200.0

300-6

300-3

150.0

200-24

150-24

300-24

100.0 50.0 0.0 0

2

4 PV

6


8


Figure 4. Ni content in the effluent for all experimental conditions.

Mo content (ppm)

600.0 500.0

300-24

300-6

400.0

300-3

200-24

300.0

150-24

200.0 100.0 0.0 0

2

4

PV

6

8

Figure 5. Mo content in the effluent for all experimental conditions.

400.0 350.0 W content (ppm)

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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300.0

300-24

300-6

250.0

300-3

200-24

200.0

150-24

150.0 100.0 50.0 0.0 0

2

4

6 PV

Figure 6. W content in the effluent for all experimental conditions.


8

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Figure 7. Vanadium profile on liquid products from all sand pack deposition experiments.

Figure 8. Iron profiles on liquid products from all sand pack deposition experiments.



Percentage retention (%wt)

35 300-24 200-24

30

300-6 150-24

300-3

25 20 15 10 5 0 0

5

10 15 20 25 Distance from entrance (cm)

30

35

Figure 9. Percentage retention (%wt) along the length of the porous media. 100 90 80 70 60 50 40 30 20 10 0

Cumulative Percentage retention (%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

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300-24 200-24 150-24 300-6 300-3 0

5

10 15 20 25 Distance from entrance (cm)

30

35

Figure 10. Cumulative percentage retention (%wt) along the porous media.


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100 Retention percentage (%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


y = -33.7x2 + 99.9x + 32.7 R² = 0.9962

80 60

% Concentration % Cumulative

40

y = 40.7x2 - 59.9x + 27.9 R² = 0.9244

20 0 0.0

0.2

0.4 0.6 Dimensionless length (z/L)

0.8

1.0

Figure 11. Correlations for retention profile and cumulative retention vs dimensionless length



Figure 12. Visual comparison of single grains at the entrance of each of the decorated sand. A) Clean sand. B) Blank deposition. C) 300-24. D) 200-24. E) 150-24. F) 300-6. G) 300-3.

Figure 13. Particle identification and sizing for the blank deposition. A) B1 (0cm). B) B2 (5cm). C) B4 (15cm).

Figure 14. Particle identification and sizing for the deposition carried out at 300-24. A) B1 (0cm). B) B2 (5cm). C) B3 (10cm) D) B6 (25cm).


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Figure 15. Particle identification and sizing for the deposition carried out at 200-24. A) B2 (5cm). B) B6 (25cm). C) B8 (35cm).






Figure 19. Data correlation between residence time (h) and achieved depth of well dispersed particles (experiments carried at 300˚C).


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