Caution: Use all appropriate safety practices when performing an experiment under high temperature and pressure conditions, including the use of engineering controls (H2 flow limiter, pressure regulators, and rupture disc assembly) and personal protective equipment (safety glasses, temperature-resistant gloves, lab coat, full-length pants, and closed-toe shoes). Consult all relevant material safety data sheets (MSDS) before use. Carry out micro-reactor loading and clean-up in a fume hood, as these steps involve the use of harmful volatile organic solvents (toluene and dichloromethane).
NOTE: Setup description (see supplemental file).
1. Micro-reactor Loading
2. Micro-reactor Installation
3. Regular Procedure for the Visualization of Cracking Reactions
4. Shutdown and Clean-up
5. Image Analysis9
Eq. 1
Eq. 2
Eq. 3
Eq. 4
Eq. 5
Eq. 6
The visual evolution of Athabasca Vacuum Residue is representative of the behavior of asphaltenic heavy crude oil samples and asphaltenic vacuum residue samples under thermal cracking conditions. However, using different samples and/or different temperature, pressure, or reaction conditions can give rise to a wide variety of phase behaviors. Micrographs corresponding to the thermal cracking experiment on an Athabasca Vacuum Residue sample at final set-point conditions of 435 °C and Patm (N2) are given in Figure 3, while Figure 4 shows the evolution of temperature during the experiment.
At room temperature, this sample is a pasty solid; thus, the sapphire window is mostly not wetted by the sample and is in contact with gas (in this case, N2). An air/sapphire interface yields a much brighter reflection than an oil/sapphire interface, so the appropriate illumination and exposure settings to image a liquid sample will always yield white regions if the sapphire surface is in contact with gas. At a higher temperature (> 150 °C), the sample becomes fluid enough to flow and wet the window surface. Small mineral solids inside the sample, which can be identified by small bright elements (Figure 3 A), can serve as an indicator of the stirring efficiency. As the sample is heated to higher temperatures, the images brighten correspondingly, with no color change as long as no significant reaction is taking place. Thermal cracking reactions in asphaltenic vacuum residues cause color and brightness changes that correspond to the chemical transformation of the sample. At extended reaction times, the formation of domains of anisotropic carbonaceous phase (mesophase) can be detected as stationary heterogeneities on the window (Figure 3 D).
An image analysis of the series of micrographs is shown in Figures 5 and 6, which show the evolution of brightness intensity and color with reaction time, respectively. At very early reaction times, the increase in image brightness follows the evolution of the temperature inside the reactor. As the temperature inside the reactor approaches the 435 °C set-point, thermal cracking reactions in the Athabasca Vacuum Residue become prevalent. Thermal cracking reactions in Athabasca Vacuum Residue induce a brightness change in the sample that follows a decreasing exponential trend. In the same period, the color of the sample remains stable in the first part of the reaction before undergoing a shift towards a blue color. The formation of mesophase has the effect of increasing the overall brightness intensity and enhancing the blue color shift9.
Figure 1: Photographs of the micro-reactor, held upside-down by a clamp. Pre-loading arrangement, with the bottom face opened (A). The loaded and sealed micro-reactor (B). Please click here to view a larger version of this figure.
Figure 2: Examples of preferable fields-of-view, as outlined by red rectangles, with respect to the inner surface of the sapphire window. Please click here to view a larger version of this figure.
Figure 3: Micrographs taken during a thermal cracking experiment on Athabasca Vacuum Residue with a condition set-point of 435 °C and Patm (N2) after 0 min (A), 25 min (B), 50 min (C), and 80 min (D). Scale bar = 100 µm. Please click here to view a larger version of this figure.
Figure 4: The temperature inside the reactor during a thermal cracking experiment on Athabasca Vacuum Residue with a set-point of 435 °C and Patm (N2). Please click here to view a larger version of this figure.
Figure 5: Evolution of the brightness intensity (I) of the micrographs taken during a thermal cracking experiment on Athabasca Vacuum Residue under 435 °C and Patm (N2), normalized by the brightness of the micrograph taken at 350 °C. Please click here to view a larger version of this figure.
Figure 6: Evolution of the hue and saturation (H and S in polar coordinates) of the micrographs taken during a thermal cracking experiment on Athabasca Vacuum Residue under 435 °C and Patm (N2). Please click here to view a larger version of this figure.
Figure 7: Evolution of the brightness intensity (I) of the micrographs taken during a thermal cracking experiment on Cold Lake bitumen under 435 °C and Patm (N2), normalized by the brightness of the micrograph taken at 350 °C. The data points outlined in red correspond to pictures taken with an overheated objective. Please click here to view a larger version of this figure.
Figure 8: The main incident rays (blue arrows) and reflected rays (red arrows) involved in the illumination of a sample through a window. Please click here to view a larger version of this figure.
Figure 12: Evolution of the brightness intensity (I) of the micrographs taken during a hydroconversion experiment, normalized by the brightness of the micrograph taken at 350 °C. The hydroconversion experiment was carried out on a heavy vacuum gasoil sample under 420 °C and 15 MPa (H2), with 12.3 wt.% Ni/Mo catalyst. Please click here to view a larger version of this figure.
Sapphire window, C-plane, 3mm thick – 20 mm diam., Scratch/Dig: 80/50 | Guild Optical Associates | ||
C-seal | American Seal & Engineering | 31005 | |
Type-K thermocouple | Omega | KMQXL-062U-9 | |
Ferrule (1/16") | Swagelok | SS-103-1 | Inserted for creating a clearance gap between the magnet and the window surface |
Coil Heater | OEM Heaters | K002441 | |
Temperature controller | Omron | E5CK | |
Inverted microscope | Zeiss | Axio Observer.D1m | Require cross-polarizer module |
Toluene, 99.9% HPLC Grade | Fisher | Catalog # T290-4 | Harmful, to be handled in fume hood |
Methylene chloride, 99.9% HPLC Grade | Fisher | Catalog # D143-4 | Harmful, to be handled in fume hood |
Acetone, 99.7 Certified ACS Grade | Fisher | Catalog # A18P-4 |
To help address production issues in refineries caused by the fouling of process units and lines, we have developed a setup as well as a method to visualize the behavior of petroleum samples under process conditions. The experimental setup relies on a custom-built micro-reactor fitted with a sapphire window at the bottom, which is placed over the objective of an inverted microscope equipped with a cross-polarizer module. Using reflection microscopy enables the visualization of opaque samples, such as petroleum vacuum residues, or asphaltenes. The combination of the sapphire window from the micro-reactor with the cross-polarizer module of the microscope on the light path allows high-contrast imaging of isotropic and anisotropic media. While observations are carried out, the micro-reactor can be heated to the temperature range of cracking reactions (up to 450 °C), can be subjected to H2 pressure relevant to hydroconversion reactions (up to 16 MPa), and can stir the sample by magnetic coupling.
Observations are typically carried out by taking snapshots of the sample under cross-polarized light at regular time intervals. Image analyses may not only provide information on the temperature, pressure, and reactive conditions yielding phase separation, but may also give an estimate of the evolution of the chemical (absorption/reflection spectra) and physical (refractive index) properties of the sample before the onset of phase separation.
To help address production issues in refineries caused by the fouling of process units and lines, we have developed a setup as well as a method to visualize the behavior of petroleum samples under process conditions. The experimental setup relies on a custom-built micro-reactor fitted with a sapphire window at the bottom, which is placed over the objective of an inverted microscope equipped with a cross-polarizer module. Using reflection microscopy enables the visualization of opaque samples, such as petroleum vacuum residues, or asphaltenes. The combination of the sapphire window from the micro-reactor with the cross-polarizer module of the microscope on the light path allows high-contrast imaging of isotropic and anisotropic media. While observations are carried out, the micro-reactor can be heated to the temperature range of cracking reactions (up to 450 °C), can be subjected to H2 pressure relevant to hydroconversion reactions (up to 16 MPa), and can stir the sample by magnetic coupling.
Observations are typically carried out by taking snapshots of the sample under cross-polarized light at regular time intervals. Image analyses may not only provide information on the temperature, pressure, and reactive conditions yielding phase separation, but may also give an estimate of the evolution of the chemical (absorption/reflection spectra) and physical (refractive index) properties of the sample before the onset of phase separation.
To help address production issues in refineries caused by the fouling of process units and lines, we have developed a setup as well as a method to visualize the behavior of petroleum samples under process conditions. The experimental setup relies on a custom-built micro-reactor fitted with a sapphire window at the bottom, which is placed over the objective of an inverted microscope equipped with a cross-polarizer module. Using reflection microscopy enables the visualization of opaque samples, such as petroleum vacuum residues, or asphaltenes. The combination of the sapphire window from the micro-reactor with the cross-polarizer module of the microscope on the light path allows high-contrast imaging of isotropic and anisotropic media. While observations are carried out, the micro-reactor can be heated to the temperature range of cracking reactions (up to 450 °C), can be subjected to H2 pressure relevant to hydroconversion reactions (up to 16 MPa), and can stir the sample by magnetic coupling.
Observations are typically carried out by taking snapshots of the sample under cross-polarized light at regular time intervals. Image analyses may not only provide information on the temperature, pressure, and reactive conditions yielding phase separation, but may also give an estimate of the evolution of the chemical (absorption/reflection spectra) and physical (refractive index) properties of the sample before the onset of phase separation.