Name: in situ visualization of the phase behavior of oil samples under refinery process conditions
Uploaded: 2017-02-21T15:00:00
Description: Watch this Scientific Journal Video about In Situ Visualization of the Phase Behavior of Oil Samples Under Refinery Process Conditions at JoVE.com

The authors acknowledge Daniel Palys for supplying Figure 12 and for his assistance in managing laboratory supplies.

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 involv...

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Critical Steps within the Protocol
The first critical step in the protocol is ensuring the integrity of the metal-to-sapphire seal, especially if the experiment is to be carried out under pressure. Thus, the parallelism, the smoothness, and the cleanliness of the sealing surfaces should be carefully inspected, and the leak tests should be thorough. Since the modulus of rupture of sapphire is a decreasing function of temperature14, thicker sapphire windows should be used fo...

The study of the phase behavior of oil samples in a wide range of temperatures, pressures, and reactive conditions can yield very useful information for the operator of a refinery that processes a variety of feeds. In particular, the fouling of process units and lines by an uncontrolled formation of coke or sediments can severely affect production (loss of throughput) and energy efficiency (increase in heat transfer resistance)1,2,3. Possible plugging caused by the accumulation of fouling material may require a shutdown for clean-up purposes, which would have a highly negative economic impact4. Conducting an assessment of the fouling propensities of feeds can be highly valuable for the optimization of process conditions5 and the blending of refinery streams.
We have developed an in situ analyzer of petroleum stability in our laboratory to allow the visualization of oil samples subject to refinery process conditions. This apparatus relies on a specifically designed reactor made of stainless steel fittings and equipped with a sealed sapphire window at the bottom. The main principle of the device is the illumination of the sample inside the reactor at the desired range of temperature and pressure and the imaging of the resulting cross-polarized reflection. While previous published work relative to this setup focused on thermal cracking processes to emulate visbreaking conditions6,7,8,9 (which do not require high pressure), the reactor design was overhauled to investigate the behavior of samples under hydroconversion (catalytic cracking under high H2 pressure) and aquathermal10 (thermal cracking under high-pressure steam) conditions. Thus, the device was revised in order to operate in the 20-450 &#176;C temperature range and the 0.1-16 MPa pressure range, with the ability to sustain both 450 &#176;C and 16 MPa for reaction times of up to 6 h.
The first level of analysis on the visual information of the samples under a particular range of temperature, pressure, and reactive conditions is to determine whether the sample is single-phase or multiphase. This system is unique in that it allows for the visualization of opaque isotropic material and is not limited to the visualization of anisotropic material described in other work11. While the main indicator of the fouling propensity of samples is the tendency to drop sediments out of the bulk liquid; gas-liquid, liquid-liquid, liquid-solid, and more complex phase behaviors can be observed. However, valuable information can also be extracted from the visual evolution of a liquid as it remains homogeneous (single-phase). In particular, the brightness of the images is related to the refractive index and the extinction coefficient of the sample, while the color of the sample is a subset of its spectral information in the visible light range (380-700 nm), which can be used as a descriptor of its chemistry9.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>Sapphire window, C-plane, 3mm thick - 20 mm diam., Scratch/Dig: 80/50</td>
			<td>Guild Optical Associates</td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>C-seal</td>
			<td>American Seal &#38; Engineering</td>
			<td>31005</td>
			<td></td>
		</tr>
		<tr>
			<td>Type-K thermocouple</td>
			<td>Omega</td>
			<td>KMQXL-062U-9&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>Ferrule (1/16&#34;)</td>
			<td>Swagelok</td>
			<td>SS-103-1</td>
			<td>Inserted for creating a clearance gap between the magnet and the window surface</td>
		</tr>
		<tr>
			<td>Coil Heater</td>
			<td>OEM Heaters</td>
			<td>K002441</td>
			<td></td>
		</tr>
		<tr>
			<td>Temperature controller</td>
			<td>Omron</td>
			<td>E5CK</td>
			<td></td>
		</tr>
		<tr>
			<td>Inverted microscope</td>
			<td>Zeiss</td>
			<td>Axio Observer.D1m</td>
			<td>Require cross-polarizer module</td>
		</tr>
		<tr>
			<td>Toluene, 99.9% HPLC Grade</td>
			<td>Fisher</td>
			<td>Catalog # T290-4</td>
			<td>Harmful, to be handled in fume hood</td>
		</tr>
		<tr>
			<td>Methylene chloride, 99.9% HPLC Grade</td>
			<td>Fisher</td>
			<td>Catalog # D143-4</td>
			<td>Harmful, to be handled in fume hood</td>
		</tr>
		<tr>
			<td>Acetone, 99.7 Certified ACS Grade</td>
			<td>Fisher</td>
			<td>Catalog # A18P-4</td>
			<td></td>
		</tr>
	</tbody>
</table>

in situ visualization of the phase behavior of oil samples under refinery process conditions

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 &#176;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.

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 &#176;C and P...

Watch this Scientific Journal Video about In Situ Visualization of the Phase Behavior of Oil Samples Under Refinery Process Conditions at JoVE.com

In Situ Visualization of the Phase Behavior of Oil Samples Under Refinery Process Conditions

This article describes a setup and method for the in situ visualization of oil samples under a variety of temperature and pressure conditions that aim to emulate refining and upgrading processes. It is primarily used for studying isotropic and anisotropic media involved in the fouling behavior of petroleum feeds.

In Situ Visualization of the Phase Behavior of Oil Samples Under Refinery Process Conditions

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 ...

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