Name: in situ visualization of the phase behavior of oil samples under refinery process conditions
Uploaded: 2017-02-21T15:00:00.000+00:00
Duration: 11 min 20 s
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.

注意:在进行高温高压条件下的实验时，包括利用工程控制（H 2限流器，压力调节器和破裂盘总成）和个人防护设备（安全眼镜，耐高温手套使用所有适当安全守则，实验室外套，全长裤，封闭趾鞋）。使用前咨询的所有相关材料安全数据表（MSDS）。进行微反应器装载和清理在通风橱中，因为这些步骤涉及使用有害的挥发性有机溶剂（甲苯和二氯甲烷）。 注意:安装说明（见补充文件）。 1.微反应器加载<ol><li> 垂直和颠倒夹紧微反应器，与底面密封（从而定位在顶部）开放。 注:在此阶段，蓝宝石窗口，定制加工的磁体，该1/16"套圈，黄铜垫和底螺母不应还装配。 <ol><li>确保所使用的微反应器连接到气体管道接头被关闭。 </li></ol></li><li> 加载约0.6克样品进入通过开放面密封用薄刮刀反应器中。 <ol><li>如果样品最初保存在一个大容器，装在微反应器之前使一个子样本。 </li><li>来估算样品的反应器内装入量，前和负荷后称重所述容器和刮刀，并计算质量差。 </li></ol></li><li>滑动定制加工的磁铁到热电偶。 </li><li>从而使大圈朝上滑动1/16"前套圈。 </li><li> 确保密封表面（ 即，其中所述密封环位于嵌合槽）的底面密封嵌合的是干净和干燥。 注:鉴于最重的油样的高度粘稠性s时，极有可能是密封表面得到意外通过在装载过程中的样品被涂污。 <ol><li>浸在甲苯棉签的前端并将其应用到该密封表面来清洁它们。要小心，不要滴甲苯反应器腔体内，这会污染样品。 </li><li>如果需要，用甲苯清洗，确保密封表面是在继续下一步骤之前干燥。 </li></ol></li><li> 确保蓝宝石窗口是清洁和干燥。 <ol><li>如果蓝宝石窗口是脏的，用在合适的溶剂浸泡的棉签，然后用丙酮来清洁窗口表面进行最终洗涤;让它自然风干。 </li></ol></li><li>放置在密封表面上的密封环，然后在密封环的顶部的蓝宝石窗口，然后在蓝宝石窗口顶部黄铜垫;优选应用在黄铜衬垫润滑剂的微小的，针头大小的滴。 </li><li>螺纹机器人在底面密封而封装黄铜垫和蓝宝石窗嵌合汤姆螺母。调整底部螺母，直到达到手指拧紧的位置。 </li><li>按住反应器倒置，将其传送到副。用扳手由90°至手紧位置，拧紧底部螺母。 注:此步骤之后，将反应器并不需要进行任何不再保持颠倒。 </li><li> 检查微反应器在密封潜在缺陷。 注:窗口可能会出现一些芯片或破解，或有缺陷的密封件可被识别，如果窗口上的密封件的压缩面不会使连续的圆。 <ol><li>在缺陷的情况下，打开微反应器进行检查。 </li><li>采取补救措施后，试图重新密封反应器时使用全新的密封环。 </li></ol></li></ol> 2.微反应器安装<ol><li> 一旦微反应器被装入并密封，连接反应器气体管道并进行测试泄漏。 <ol><li>总是通过使用N 2在5MPa的最大压力开始泄漏测试。 注:泄漏试验的优选方法是在压力衰减试验中，那里的设置被加压，然后从气缸分离（闭阀V2和V3）。如果压力的时间（超过30分钟）延长的量保持稳定，不泄漏是观察。 </li><li>进行在较高的压力附加泄漏测试是否为即将到来的实验目标压力小于5兆帕以上。 注意:这些附加的泄漏测试可以与6MPa的最大压力增量直到用于实验所需的压力条件匹配来执行。考虑16兆帕作为压力为泄漏测试和设置操作的上限。 注意:如果使用加压在即将到来的实验设置气不惰性的（如易燃气体），进行另一系列采用t泄漏测试他在一个成功的系列泄漏测试，N 2目标气体队伍。 </li></ol></li><li>成功泄漏测试之后，进行接下来的安装步骤前减压的设置。 </li><li>放置在微反应器中的不锈钢加热块，其本身在线圈加热器插入。位于上方的显微镜物镜的平台上的装配位置。 </li><li>包住反应器，加热器，和填充有陶瓷纤维的外壳的两个半体的加热块。夹在一起使用软管夹在壳体的两半。 </li><li> 微调电抗器的过显微镜物镜的位置。 <ol><li>打开采用交叉偏振光显微镜。调整使用最低放大率以便集中在蓝宝石窗口的内表面上的物镜的垂直位置。 </li><li>这样的观点在最低的放大倍率（通常为50X）领域涵盖的Radia反应器的位置窗口表面，其中所述内边界包括1/16"前套圈的边缘，如在图1中描述l的一部分。 注:通过软件获得的实际显微照片应居中本场来看，这将避免显示套圈本身的子集。 </li></ol></li><li>连接微反应器（TT1）到温度控制器（TIC1）的热电偶。 </li><li>转动马达驱动的外部磁体120 rpm的速度上。 </li><li>加压设置到所需的设定点。 注:大气压力运行通过打开所有出口阀在排气进行。间歇实验可以通过关闭阀V4来执行。的压力（优选为高压条件下）的恒定头下实验可以通过使用回压调节器PV2进行。 </li></ol> 3.裂化反应的可视化正常程序<ol><li>在整个实验中，可视化样品或拍摄快照，只有当放置显微镜物镜反应器下。避免离开反应器下的显微镜物镜不需要时它。 注意:在高温下的反应器下离开显微镜物镜将导致图像的人工增亮，导致差的数据，并可能导致物镜的恶化。 </li><li>打开温度控制器和应用200℃的温度设定点。一旦样品温度达到200℃，进行了一轮核查。 注:A轮验证，就会引起核实的显微镜物镜的压力，温度，反应器的位置，焦距和搅拌。随着温度的变化，该平台支撑在反应器和加热组件轻微变形，所以显微镜物镜的垂直位置必须调整为蓝宝石/样品界面保持在焦点。搅拌可由电机来检测的1/16"套圈的或在样品中的小的异质性（如小矿物固体）的离子。 </li><li>如果一切正常的样品到达200℃，执行一个设定点变化至300℃。一旦样品温度达到300℃，进行新一轮核查。 </li><li>重复上述步骤，以350℃作为新的温度设定点。 注:350℃通常可被认为是较高的温度下限值，其中的裂化反应是不显著（在分钟的时间尺度）。 </li><li>设定点温度变化所需的反应温度，一般在400-450℃的范围内。 </li><li> 使得最终温度设定点变化后，开始以规则的时间间隔监测反应和记录数据时，最好是每分钟。 <ol><li>进行数据记录的每一步骤如下:旋转显微镜的物镜转换器放置在反应器下的目标。调整焦点。拍摄快照。旋转物镜转换器，以从反应器中下方移开的目标。注意温度。 注:对于未来的量化的图像进行分析，快照应该一致的设置可采取整个实验，即在放大率，照明条件和照相机采集设置（光敏性响应和曝光时间）的条款。作为指导原则，在该手稿提交的显微照片拍摄的100X放大率，最大的照明条件（使用卤素灯泡）时，照相机的线性灵敏度响应，和暴露时间范围为200-400毫秒。 </li><li>反复进行数据记录的步骤，只要必要的。 注意:通常情况下，在观察的持续时间是由在样品中的视觉变化（颜色，亮度，和异质）或通过反应转化的估计引导。 注意:最好避免大量的中间相形成积炭后继续实验（这使得该反应器更难以清洗）。 </li></ol></li></ol> 4.关闭和清理<ol><li> 通过旋转温度控制器和搅拌器关闭和减压的设置终止实验。让反应堆冷却。 注:冷却该反应器可以由从壳体和流出加热组件的除去微反应器来促进。施加冷空气流至微反应器也可以使该过程更快和更容易。 <ol><li>一旦微反应器被冷却到室温，从设置的气体管线断开连接，将其放置在一个副松开底部螺母，并且启封的微反应器。 </li></ol></li><li> 在通风橱中，通过除去底部螺母，黄铜垫，蓝宝石窗口，该1/16"套圈，磁铁采取的微反应器分开。取下密封圈。 注:焦炭可能已经在实验过程中形成的，因此可能导致1/16";套圈和磁铁被卡住的热电偶。 <ol><li>用镊子拔1/16"套圈和磁铁了。用铲子撬密封环从密封槽的，但注意不要划伤的过程中密封槽。 </li></ol></li><li>以除去大部分粘附于微反应器壁的材料的，擦洗的微反应器与溶剂浸泡（甲苯或二氯甲烷）纸巾片的内部空腔。重复用砂布，最好是粗砂砾（＃100）件的过程。 注意:在此过程中，不划伤密封表面。在此步骤的结束，的微反应器腔内不锈钢的金属光泽应当是显而易见的。 </li><li> 除去用一块砂布的粘到定制加工磁体的平坦表面的材料，优选粗砂砾（＃100）。 <ol><li>使用溶剂浸泡1/16"线，除去粘在豪内的物料定制加工的磁铁乐。 </li></ol></li><li>用溶剂浸泡（甲苯，二氯甲烷，或丙酮）棉签除去粘在蓝宝石窗口的材料。 </li><li>以除去粘附于反应器壁，包括密封表面的材料的其余部分，可使用溶剂浸泡（甲苯或二氯甲烷）棉签。 注意:当在使用的溶剂浸泡的棉签擦洗后，棉签出来以在其上可忽略不计的痕迹的清理过程完成。 注:然而乏味这个过程可能是，这一步重要的是要避免实验之间的交叉污染。 </li><li>让微反应器风干。 </li></ol> 5.图像分析9 <ol><li>提取关于红，绿，蓝（RGB）通道的平均值，以及在色调，饱和度和强度（HSI）色彩空间中的相应的信息显微照片信息。 注:恒指合作LOR空间由圆柱坐标，其中，色调，饱和度和强度对应的角度，径向和垂直坐标分别描述。相应HSI值的像素的RGB值之间的关系由下面的等式12，13，其中m是RGB值的最小值定，而α和β是一对色度坐标: </li></ol><img alt="式（1）" src="/files/ftp_upload/55246/55246eq1.jpg" />式。 1 <img alt="公式（2）" src="/files/ftp_upload/55246/55246eq2.jpg" />式。 2 <img alt="公式3" src="/files/ftp_upload/55246/55246eq3.jpg" />式。 3 <img alt="公式4" src="/files/ftp_upload/55246/55246eq4.jpg" />式。 4 <img alt="公式5" src="/files/ftp_upload/55246/55246eq5.jpg" />式。 5 &lt;/ P&gt; <img alt="公式6" src="/files/ftp_upload/55246/55246eq6.jpg" />式。 6

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The authors have nothing to disclose.

该议定书中的关键步骤在协议中的第一个关键步骤是确保金属对蓝宝石密封的完整性，特别是当试验是在压力下进行。因此，并行性，光滑度，和密封表面的清洁度应该仔细检查，以及渗漏试验应彻底。由于蓝宝石的断裂模量是温度14的递减函数，加厚蓝宝石窗口应该在高压和高温下使用工作。作为一个指导原则，8个毫米厚蓝宝石窗口都在我们的实验旨在模拟...

油样在一个宽的温度范围，压力和反应条件的相位行为的研究可以产生非常有用的信息，其处理各种饲料炼油厂的操作者。特别地，处理单元和线路由不受控制的形成焦炭或沉积物的结垢会严重影响生产（吞吐量的损失）和能量效率（在传热阻力增加）1，2，3。可能堵塞结垢物质可能需要清理的目的，这将具有高度的负面经济影响4关机的积累造成的。导电饲料的结垢倾向的评估可以是工艺条件5的优化和精炼流的配合非常有价值的。 我们已经制定了一个在原地在我们的实验室石油稳定性的分析器，以允许油样受炼油厂工艺条件的可视化。该装置依赖于由不锈钢制成的管件和装备有在底部密封的蓝宝石窗口一个专门设计的反应器中。该装置的主要原理是在温度和压力的期望范围的反应器内的样品，将所得交叉偏振反射的摄像的照明。虽然以前的相对于这种设置集中在热裂解过程模拟减粘裂化条件6，7，8，9（其不需要高压力），反应器的设计被翻修调查加氢下样品的行为（公布工作下催化裂化高H 2压力）和水热10（热在高预裂ssure蒸汽）的条件。因此，该设备，以便在20-450℃的温度范围和0.1-16兆帕压力范围内进行操作，以维持这两个450°C和16兆帕最长为6小时的反应时间的能力进行了修订。 分析在样品的下温度，压力和反应条件的特定范围的可视信息的第一级是确定样品是否为单相或多相。这个系统是独特的，因为它允许不透明各向同性材料的可视化，并且不限于在其他工作中11所描述的各向异性材料的可视化。而样品的结垢倾向的主要指标是滴沉积出大量液体的倾向;气 - 液，液 - 液，液 - 固和更复杂的相行为可以观察到。然而，有价值的信息，也可以从液体的视觉演化，因为它仍然坎萃取ogeneous（单相）。特别是，图像的亮度是相关的折射率和样品的消光系数，而样品的颜色是在可见光范围内的光谱信息（380-700纳米）的子集，其可以是用作其化学9的描述符。

<table><tbody><tr><td>Sapphire window, C-plane, 3 mm 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 &amp;amp; Engineering</td><td>31005</td><td></td></tr><tr><td>Type-K thermocouple</td><td>Omega</td><td>KMQXL-062U-9&amp;nbsp;</td><td></td></tr><tr><td>Ferrule (1/16&quot;)</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.

阿萨巴斯卡减压渣油的视觉进化代表沥青质的重质原油样品和沥青减压渣油样品的热裂解条件下的行为的。然而，使用不同的样品和/或不同温度，压力，或反应条件可以产生各种各样的相行为。对应于热裂解实验上在435℃下和P 个大气压 （N 2）中给出在图3中，而图4示出了温度的实验过程中的演化的最终设定点条件的阿萨巴斯卡?...

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.

在油样品的相行为在炼油工艺条件的原位可视化

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 ...

in-situ-visualization-phase-behavior-oil-samples-under-refinery

Universidad de Cartagena UDEC

Research

JoVE Journal

Engineering

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

6.6K 次观看.  University of Alberta. 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.

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

Biomass Conversion to Produce Hydrocarbon Liquid Fuel Via Hot-vapor Filtered Fast Pyrolysis and Catalytic Hydrotreating

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.

Experimental methods for fast pyrolysis of lignocellulosic biomass to produce bio-oils and for the catalytic hydrotreating of bio-oils to produce fuel range hydrocarbons are presented. Hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil was also assessed.

生物质转化为油气生产液体燃料通过热蒸汽过滤快速热解和催化加氢

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among ...

科研

生物化学

High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems

The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. Specifically, the sapphire cell enables visual data collection from multiple loadings to solve a set of material balances to precisely determine phase composition. Ternary phase diagrams can then be established to determine the proportion of each component in each phase at a given condition. In principle, any ternary system can be studied although ternary systems (gas-liquid-liquid) are the specific examples discussed herein. For instance, the ternary THF-Water-CO2 system was studied at 25 and 40&#160;&#176;C and is described herein. Of key importance, this technique does not require sampling. Circumventing the possible disturbance of the system equilibrium upon sampling, inherent measurement errors, and technical difficulties of physically sampling under pressure is a significant benefit of this technique. Perhaps as important, the sapphire cell also enables the direct visual observation of the phase behavior. In fact, as the CO2 pressure is increased, the homogeneous THF-Water solution phase splits at about 2 MPa. With this technique, it was possible to easily and clearly observe the cloud point and determine the composition of the newly formed phases as a function of pressure.
The data acquired with the sapphire cell technique can be used for many applications. In our case, we measured swelling and composition for tunable solvents, like gas-expanded liquids, gas-expanded ionic liquids and Organic Aqueous Tunable Systems (OATS)1-4. For the latest system, OATS, the high-pressure sapphire cell enabled the study of (1) phase behavior as a function of pressure and temperature, (2) composition of each phase (gas-liquid-liquid) as a function of pressure and temperature and (3) catalyst partitioning in the two liquid phases as a function of pressure and composition. Finally, the sapphire cell is an especially effective tool to gather accurate and reproducible measurements in a timely fashion.

High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems

The high pressure sapphire cell apparatus is a unique tool to study, without sampling, phase behavior under a wide range of pressures. Using a cathetometer, very precise volume measurements can be recorded to measure liquid expansion and phase composition. Thus, this synthetic method enables the study of (1) phase equilibria of multi-component mixtures and (2) the partition behavior of catalyst or model compounds as a function of pressure.

高压蓝宝石细胞对CO的相平衡测量<sub&gt; 2</sub&gt; /有机/水系统

The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. ...

化学

Chemical Analysis of Water-accommodated Fractions of Crude Oil Spills Using TIMS-FT-ICR MS

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system requires the careful preparation of the sample in order to accurately replicate the natural formation of the water-accommodated fraction that occurs in nature. Low-energy water-accommodated fractions (LEWAF) are carefully prepared by mixing crude oil and water at a set ratio. Aspirator bottles are then irradiated, and at set time points, the water is sampled and extracted using standard techniques. A second challenge is the representative characterization of the sample, which must take into consideration the chemical changes that occur over time. A targeted analysis of the aromatic fraction of the LEWAF can be performed using an atmospheric-pressure laser ionization source coupled to a custom-built trapped ion mobility spectrometry&#8211;Fourier transform&#8211;ion cyclotron resonance mass spectrometer (TIMS-FT-ICR MS). The TIMS-FT-ICR MS analysis provides high-resolution ion mobility and ultrahigh-resolution MS analysis, which further allow the identification of isomeric components by their collision cross-sections (CCS) and chemical formula. Results show that as the oil-water mixture is exposed to light, there is significant photo-solubilization of the surface oil into the water. Over time, the chemical transformation of the solubilized molecules takes place, with a decrease in the number of identifications of nitrogen- and sulfur-bearing species in favor of those with a greater oxygen content than were typically observed in the base oil.

The low-energy water-accommodated fraction (LEWAF) of crude oil is a challenging system to analyze, because over time, this complex mixture undergoes chemical transformations. This protocol illustrates methods for the preparation of the LEWAF sample and for performing photo-irradiation and chemical analysis by trapped ion mobility spectrometry&#8211;FT-ICR MS.

原油水容纳组分的化学分析泄漏使用TIMS-FT-ICR MS

Multiple chemical processes control how crude oil is incorporated into seawater and also the chemical reactions that occur overtime. Studying this system ...

环境科学

Phase Diagram Characterization Using Magnetic Beads as Liquid Carriers

Magnetic beads with ~1.9 &#181;m average diameter were used to transport microliter volumes of liquids between contiguous liquid segments with a tube for the purpose of investigating phase change of those liquid segments. The magnetic beads were externally controlled using a magnet, allowing for the beads to bridge the air valve between the adjacent liquid segments. A hydrophobic coating was applied to the inner surface of the tube to enhance the separation between two liquid segments. The applied magnetic field formed an aggregate cluster of magnetic beads, capturing a certain liquid amount within the cluster that is referred to as carry-over volume. A fluorescent dye was added to one liquid segment, followed by a series of liquid transfers, which then changed the fluorescence intensity in the neighboring liquid segment. Based on the numerical analysis of the measured fluorescence intensity change, the carry-over volume per mass of magnetic beads has been found to be ~2 to 3 &#181;l/mg. This small amount of liquid allowed for the use of comparatively small liquid segments of a couple hundred microliters, enhancing the feasibility of the device for a lab-in-tube approach. This technique of applying small compositional variation in a liquid volume was applied to analyzing the binary phase diagram between water and the surfactant C12E5 (pentaethylene glycol monododecyl ether), leading to quicker analysis with smaller sample volumes than conventional methods.

Here, we present a protocol to investigate multi-component phase diagrams using externally controlled magnetic beads as liquid carriers in a lab-in-tube approach. This approach can aid in applications that seek to gather further information on phase change in complex liquid systems.

相图表征使用磁珠用作液体载体

Magnetic beads with ~1.9 &#181;m average diameter were used to transport microliter volumes of liquids between contiguous liquid segments with a tube for ...

工程学

Measurement of the Rheology of Crude Oil in Equilibrium with CO2 at Reservoir Conditions

A rheometer system to measure the rheology of crude oil in equilibrium with carbon dioxide (CO2) at high temperatures and pressures is described. The system comprises a high-pressure rheometer which is connected to a circulation loop. The rheometer has a rotational flow-through measurement cell with two alternative geometries: coaxial cylinder and double gap. The circulation loop contains a mixer, to bring the crude oil sample into equilibrium with CO2, and a gear pump that transports the mixture from the mixer to the rheometer and recycles it back to the mixer. The CO2 and crude oil are brought to equilibrium by stirring and circulation and the rheology of the saturated mixture is measured by the rheometer. The system is used to measure the rheological properties of Zuata crude oil (and its toluene dilution) in equilibrium with CO2 at elevated pressures up to 220 bar and a temperature of 50 &#176;C. The results show that CO2 addition changes the oil rheology significantly, initially reducing the viscosity as the CO2 pressure is increased and then increasing the viscosity above a threshold pressure. The non-Newtonian response of the crude is also seen to change with the addition of CO2.

Measurement of the Rheology of Crude Oil in Equilibrium with CO2 at Reservoir Conditions

A method for measuring the rheology of crude oil in equilibrium with carbon dioxide at reservoir conditions is presented.

与CO平衡的原油流变学测量<sub&gt; 2</sub&gt;在水库条件

A rheometer system to measure the rheology of crude oil in equilibrium with carbon dioxide (CO2) at high temperatures and pressures is described. The ...

Microfluidic Devices for Characterizing Pore-scale Event Processes in Porous Media for Oil Recovery Applications

Microfluidic devices are versatile tools for studying transport processes at a microscopic scale. A demand exists for microfluidic devices that are resistant to low molecular-weight oil components, unlike traditional polydimethylsiloxane (PDMS) devices. Here, we demonstrate a facile method for making a device with this property, and we use the product of this protocol for examining the pore-scale mechanisms by which foam recovers crude oil. A pattern is first designed using computer-aided design (CAD) software and printed on a transparency with a high-resolution printer. This pattern is then transferred to a photoresist via a lithography procedure. PDMS is cast on the pattern, cured in an oven, and removed to obtain a mold. A thiol-ene crosslinking polymer, commonly used as an optical adhesive (OA), is then poured onto the mold and cured under UV light. The PDMS mold is peeled away from the optical adhesive cast. A glass substrate is then prepared, and the two halves of the device are bonded together. Optical adhesive-based devices are more robust than traditional PDMS microfluidic devices. The epoxy structure is resistant to swelling by many organic solvents, which opens new possibilities for experiments involving light organic liquids. Additionally, the surface wettability behavior of these devices is more stable than that of PDMS. The construction of optical adhesive microfluidic devices is simple, yet requires incrementally more effort than the making of PDMS-based devices. Also, though optical adhesive devices are stable in organic liquids, they may exhibit reduced bond-strength after a long time. Optical adhesive microfluidic devices can be made in geometries that act as 2-D micromodels for porous media. These devices are applied in the study of oil displacement to improve our understanding of the pore-scale mechanisms involved in enhanced oil recovery and aquifer remediation.

The goal of this procedure is to easily and rapidly produce a microfluidic device with customizable geometry and resistance to swelling by organic fluids for oil recovery studies. A polydimethylsiloxane mold is first generated, and then used to cast the epoxy-based device. A representative displacement study is reported.

微流体器件用于表征多孔介质中的孔隙尺度事件过程, 用于采油应用

Microfluidic devices are versatile tools for studying transport processes at a microscopic scale. A demand exists for microfluidic devices that are ...

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The composition of heavy crude oils and shale oils varies substantially depending on the origin of the mixture. In particular they contain an increased amount of nitrogen containing compounds compared to the conventionally used sweet crude oils. As nitrogen compounds have an influence on the operation of thermal processes occurring in coker units and steam crackers, and as some species are considered as environmentally hazardous, a detailed analysis of the reactions involving nitrogen containing compounds under pyrolysis conditions provides valuable information. Therefore a novel method has been developed and validated with a feedstock containing a high nitrogen content, i.e., a shale oil. First, the feed was characterized offline by comprehensive two-dimensional gas chromatography (GC &#215; GC) coupled with a nitrogen chemiluminescence detector (NCD). In a second step the on-line analysis method was developed and tested on a steam cracking pilot plant by feeding pyridine dissolved in heptane. The former being a representative compound for one of the most abundant classes of compounds present in shale oil. The composition of the reactor effluent was determined via an in-house developed automated sampling system followed by immediate injection of the sample on a GC &#215; GC coupled with a time-of-flight mass spectrometer (TOF-MS), flame ionization detector (FID) and NCD. A novel method for quantitative analysis of nitrogen containing compounds using NCD and 2-chloropyridine as an internal standard has been developed and demonstrated.

A method combining comprehensive two-dimensional gas chromatography with nitrogen chemiluminescence detection has been developed and applied to on-line analysis of nitrogen containing compounds in a complex hydrocarbon matrix.

在线含硫化合物在复杂油气矩阵氮分析

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The ...

Laboratory Production of Biofuels and Biochemicals from a Rapeseed Oil through Catalytic Cracking Conversion

The work is based on a reported study which investigates the processability of canola oil (bio-feed) in the presence of bitumen-derived heavy gas oil (HGO) for production of transportation fuels through a fluid catalytic cracking (FCC) route. Cracking experiments are performed with a fully automated reaction unit at a fixed weight hourly space velocity (WHSV) of 8 hr-1, 490-530 &#176;C, and catalyst/oil ratios of 4-12 g/g. When a feed is in contact with catalyst in the fluid-bed reactor, cracking takes place generating gaseous, liquid, and solid products. The vapor produced is condensed and collected in a liquid receiver at -15 &#176;C. The non-condensable effluent is first directed to a vessel and is sent, after homogenization, to an on-line gas chromatograph (GC) for refinery gas analysis. The coke deposited on the catalyst is determined in situ by burning the spent catalyst in air at high temperatures. Levels of CO2 are measured quantitatively via an infrared (IR) cell, and are converted to coke yield. Liquid samples in the receivers are analyzed by GC for simulated distillation to determine the amounts in different boiling ranges, i.e., IBP-221 &#176;C (gasoline), 221-343 &#176;C (light cycle oil), and 343 &#176;C+ (heavy cycle oil). Cracking of a feed containing canola oil generates water, which appears at the bottom of a liquid receiver and on its inner wall. Recovery of water on the wall is achieved through washing with methanol followed by Karl Fischer titration for water content. Basic results reported include conversion (the portion of the feed converted to gas and liquid product with a boiling point below 221 &#176;C, coke, and water, if present) and yields of dry gas (H2-C2's, CO, and CO2), liquefied petroleum gas (C3-C4), gasoline, light cycle oil, heavy cycle oil, coke, and water, if present.

This paper presents an experimental method to produce biofuels and biochemicals from canola oil mixed with a fossil-based feed in the presence of a catalyst at mild temperatures. Gaseous, liquid, and solid products from a reaction unit are quantified and characterized. Conversion and individual product yields are calculated and reported.

通过催化裂化转换从菜籽油生物燃料和生物化学实验室生产

The work is based on a reported study which investigates the processability of canola oil (bio-feed) in the presence of bitumen-derived heavy gas oil ...

Experimental Procedure for Laboratory Studies of In Situ Burning : Flammability and Burning Efficiency of Crude Oil

A new method for the simultaneous study of the flammability and burning efficiency of fresh and weathered crude oil through two experimental laboratory setups is presented. The experiments are easily repeatable compared to operational scale experiments (pool diameter &#8805;2 m), while still featuring quite realistic in situ burning conditions of crude oil on water. Experimental conditions include a flowing water sub-layer that cools the oil slick and an external heat flux (up to 50 kW/m2) that simulates the higher heat feedback to the fuel surface in operational scale crude oil pool fires. These conditions enable a controlled laboratory study of the burning efficiency of crude oil pool fires that are equivalent to operational scale experiments. The method also provides quantitative data on the requirements for igniting crude oils in terms of the critical heat flux, ignition delay time as a function of the incident heat flux, the surface temperature upon ignition, and the thermal inertia. This type of data can be used to determine the required strength and duration of an ignition source to ignite a certain type of fresh or weathered crude oil. The main limitation of the method is that the cooling effect of the flowing water sub-layer on the burning crude oil as a function of the external heat flux has not been fully quantified. Experimental results clearly showed that the flowing water sub-layer does improve how representative this setup is of in situ burning conditions, but to what extent this representation is accurate is currently uncertain. The method nevertheless features the most realistic in situ burning laboratory conditions currently available for simultaneously studying the flammability and burning efficiency of crude oil on water.

Experimental Procedure for Laboratory Studies of In Situ Burning : Flammability and Burning Efficiency of Crude Oil

Here, we present a protocol to simultaneously study the flammability and burning efficiency of fresh and weathered crude oil under conditions that simulate in situ burning operations on the sea.

原位燃烧试验方法: 原油可燃性和燃烧效率

A new method for the simultaneous study of the flammability and burning efficiency of fresh and weathered crude oil through two experimental laboratory ...

Combining Microfluidics and Microrheology to Determine Rheological Properties of Soft Matter during Repeated Phase Transitions

The microstructure of soft matter directly impacts macroscopic rheological properties and can be changed by factors including colloidal rearrangement during previous phase changes and applied shear. To determine the extent of these changes, we have developed a microfluidic device that enables repeated phase transitions induced by exchange of the surrounding fluid and microrheological characterization while limiting shear on the sample. This technique is &#181;2rheology, the combination of microfluidics and microrheology. The microfluidic device is a two-layer design with symmetric inlet streams entering a sample chamber that traps the gel sample in place during fluid exchange. Suction can be applied far away from the sample chamber to pull fluids into the sample chamber. Material rheological properties are characterized using multiple particle tracking microrheology (MPT). In MPT, fluorescent probe particles are embedded into the material and the Brownian motion of the probes is recorded using video microscopy. The movement of the particles is tracked and the mean-squared displacement (MSD) is calculated. The MSD is related to macroscopic rheological properties, using the Generalized Stokes-Einstein Relation. The phase of the material is identified by comparison to the critical relaxation exponent, determined using time-cure superposition. Measurements of a fibrous colloidal gel illustrate the utility of the technique. This gel has a delicate structure that can be irreversibly changed when shear is applied. &#181;2rheology data shows that the material repeatedly equilibrates to the same rheological properties after each phase transition, indicating that phase transitions do not play a role in microstructural changes. To determine the role of shear, samples can be sheared prior to injection into our microfluidic device. &#181;2rheology is a widely applicable technique for the characterization of soft matter enabling the determination of rheological properties of delicate microstructures in a single sample during phase transitions in response to repeated changes in the surrounding environmental conditions.

We demonstrate the fabrication and use of a microfluidic device that enables multiple particle tracking microrheology measurements to study the rheological effects of repeated phase transitions on soft matter.

微流体和 Microrheology 相结合测定软物质在重复相变过程中的流变特性

The microstructure of soft matter directly impacts macroscopic rheological properties and can be changed by factors including colloidal rearrangement ...

在油样品的相行为在炼油工艺条件的原位可视化

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