Name: laboratory production of biofuels and biochemicals from a rapeseed oil through catalytic cracking conversion
Uploaded: 2016-09-02T15:00:00
Description: Watch this Scientific Journal Video about Laboratory Production of Biofuels and Biochemicals from a Rapeseed Oil through Catalytic Cracking Conversion at JoVE.com

The authors wish to thank the analytical laboratory of the CanmetENERGY Technology Centre for its technical support, and Suncor Energy Inc. for supplying the synthetic crude oil. Partial funding for this study was provided by Natural Resources Canada and government of Canada&#39;s interdepartmental Program of Energy Research and Development (PERD) with project ID A22.015. Yi Zhang would like to acknowledge his Natural Sciences and Engineering Research Council (NSERC) of Canada Visiting Fellowship from January 2015 to January 2016.

Caution: Please consult all relevant material safety data sheets (MSDS) before using the materials. Work with crude oil samples should only be done while wearing proper personal protective equipment (safety glasses, gloves, pants, closed-toe shoes, lab coat), and the opening, transfer and handling of crude samples should occur in a vented fumehood. Heated hydrocarbons can be flammable in air, and the reaction system should be carefully leak-checked prior to use with crude oil mixtures. The reactor can reach temperatures as high as 750 &#176;...

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The protocol described here utilizes cyclic operation of a single reactor containing a batch of fluidized catalyst particles to simulate feed oil cracking and catalyst regeneration. The oil to be cracked is preheated and fed from the top through an injector tube with its tip close to the bottom of the fluid bed. The vapor generated after catalytic cracking is condensed and collected in a receiver, and the liquid product collected is subsequently analyzed for simulated distillation to determine yields of fractions in diff...

There is strong global interest in both the private and public sectors to find efficient and economic means to produce transportation fuels from biomass-derived feedstocks. This interest is driven by a general concern over the substantial contribution of burning petroleum fossil fuels to greenhouse gas (GHG) emissions and its associated contribution to global warming. Also, there is strong political will in North America and Europe to displace foreign-produced petroleum with renewable domestic liquid fuels. In 2008, biofuels provided 1.8% of the world&#39;s transportation fuels1. In many developed countries, it is required that biofuels replace from 6% to 10% of petroleum fuels in the near future2. In Canada, regulations require an average renewable fuel content of 5% in gasoline starting December 15, 20103. The Renewable Energy Directive (RED) in Europe has also mandated a 10% renewable energy target for the European Union transport sector by 20204.
The challenge has been to develop and demonstrate a viable economic pathway to produce fungible transportation fuels from biomass. Biological sources include triglyceride-based biomass such as vegetable oils and animal fats, as well as waste cooking oil and cellulosic biomass such as wood chips, forest wastes, and agriculture residues. Over the past two decades, research has focused on the evaluation of biomass-derived oil processing using conventional fluid catalytic cracking (FCC)5-12, a technology responsible for producing most of the gasoline in a petroleum refinery. Our novel approach in this study is to co-process canola oil mixed with oil sands bitumen-derived feedstock. Normally, bitumen must be upgraded prior to refining, producing refinery feedstocks such as synthetic crude oil (SCO)&#8212;this processing route is particularly energy intensive, accounting for 68-78% of the GHG emissions from the SCO production13 and, in 2011, constituting 2.6% of Canada&#39;s total GHG emissions14. Replacing a portion of upgraded HGO with biofeed would reduce GHG emissions, since biofuel production involves a much smaller carbon footprint. Canola oil is chosen in this work because it is abundant in Canada and the US. This feedstock possesses a density and viscosity similar to those of HGOs while the contents of sulfur, nitrogen, and metals that could affect FCC performance or product quality are negligible. Moreover, this co-processing option offers significant technological and economic advantages as it would allow utilization of the existing refinery infrastructure and, hence, would require little additional hardware or modification of the refinery. In addition, there may be potential synergy that could result in product quality improvement when co-processing a highly aromatic bitumen feed with its straight-chain biomass counterpart. However, co-processing involves important technical challenges. These include the unique physical and chemical characteristics of bio-feeds: high oxygen content, paraffinic-rich composition, compatibility with petroleum feedstocks, fouling potential, etc.
This study provides a detailed protocol for the production of biofuels at laboratory scale from canola oil through catalytic cracking. A fully automated reaction system&#160;&#8211; referred to in this work as the laboratory test unit (LTU)15 &#8211; is used for this work. Figure 1 shows schematically how this unit operates. This LTU has become the industry standard for laboratory FCC studies. The objective of this study is to test the suitability of the LTU for cracking canola oil to produce fuels and chemicals with the goal of mitigating GHG emissions.
<img alt="Figure 1" src="/files/ftp_upload/54390/54390fig1.jpg" /> 
Figure 1: Conceptual illustration of the reactor. Illustration showing flow lines of the catalyst, feed, product, and diluent. <a href="https://www.jove.com/files/ftp_upload/54390/54390fig1large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>

<table border="0" cellpadding="0" cellspacing="0" width="818">
	<tbody>
		<tr height="168">
			<td height="168" style="height:168px;width:231px;">Advanced Cracking Evaluation (ACE) Unit</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;">ACE R+ 46</td>
			<td dir="LTR" style="width:309px;">Assembled by Zeton Inc. SN:505-46;&#160; consisting of (1) a reactor; (2) catalyst addition system; (3) feed delivery system;&#160; (4) liquid collection system; (5) gas collection system; (6) gas analyzing system; (7) catalyst regeneration system; (8) CO catalytic convertor; (9) coke analyzing system</td>
		</tr>
		<tr height="126">
			<td height="126" style="height:126px;width:231px;">Reactor (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;">V-105</td>
			<td style="width:309px;">A 1.6 cm ID stainless steel tube having a tapered conical bottom and with a diluent (nitrogen) flowing from the bottom to fluidize the catalyst and also serve as the stripping gas at the end of the run</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Catalyst Addition System (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Six hoppers (V-120F, with respective valves) for addition of catalyst for up to 6 runs</td>
		</tr>
		<tr height="126">
			<td height="126" style="height:126px;width:231px;">Feed Delivery System (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Consisting of feed bottle (V-100), syringe (FS-115), pump (P-100), and injector (with 1.125 inch injector height, i.e., the distance from the lowest point of the conical reactor bottom to the bottom end of the feed injector)</td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:231px;">Liquid Collection System (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Six liquid receivers (V-110F) immersed in a common coolant bath (Ethylene glycol/water mixture in 50:50 mass ratio) at about &#8211;15 &#176;C in a large tank (V-145)</td>
		</tr>
		<tr height="127">
			<td height="127" style="height:127px;width:231px;">Gas Collection System (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Based on water displacement principle; consisting of gas collection vessel (V-150) with a motor-driven stirrer (MTR-100), and a weight scale (WT-100) for weighing the displaced water collected in a beaker (V100)&#160;</td>
		</tr>
		<tr height="101">
			<td height="101" style="height:101px;width:231px;">Gas Analyzing System (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Key element being Agilent micro GC (model 3000A) with four capillary columns equipped with respective thermal conductivity detectors (TCDs)&#160;</td>
		</tr>
		<tr height="101">
			<td height="101" style="height:101px;width:231px;">Catalyst Regeneration System (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;">V-105</td>
			<td style="width:309px;">Spent catalyst in reactor being burned in situ in air at +700 &#176;C to ensure complete removal of carbon deposited on the catalyst</td>
		</tr>
		<tr height="109">
			<td height="109" style="height:109px;width:231px;">CO Catalytic Convertor&#160; (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">A reactor (V-140) with CuO as catalyst to oxidize any CO and hydrocarbons in exhausted flue gas to CO2 (to be analyzed by IR gas analyzer) and H2O (to be absorbed by a dryer)</td>
		</tr>
		<tr height="46">
			<td height="46" style="height:46px;width:231px;">Coke Analyzing System (ACE)</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Servomex (Model 1440C) IR analyzer for measuring CO2 in exhausted flue gas</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">R+MM Software Suite</td>
			<td style="width:168px;">Kayser Technology Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Including iFIX 3.5&#160;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Agilent Micro GC</td>
			<td style="width:168px;">Agilent Technologies</td>
			<td style="width:111px;">3000A</td>
			<td style="width:309px;">For gas analysis after cracking</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Cerity Networked Data System</td>
			<td style="width:168px;">Agilent Technologies</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Software for Agilent Micro GC</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:231px;">CO2 Gas Analyser</td>
			<td style="width:168px;">Servomex Inc.</td>
			<td style="width:111px;">1440C</td>
			<td style="width:309px;">SN: 01440C1C02/2900</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">NESLAB Refrigerated Bath</td>
			<td style="width:168px;">Themo Electron Corporation</td>
			<td style="width:111px;">RTE 740</td>
			<td style="width:309px;">SN: 104300061</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Orion&#160; Sage Syringe Pump</td>
			<td style="width:168px;">Themo Electron Corporation</td>
			<td style="width:111px;">M362</td>
			<td style="width:309px;">For delivering feed oil to injector tube</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Synthetic Crude Oil (SCO)&#160;</td>
			<td style="width:168px;">Suncor Energy Inc.</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Identified as Suncor OSA 10-4.1</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Catalyst P</td>
			<td style="width:168px;">Petro-Canada Refinery</td>
			<td style="width:111px;"></td>
			<td style="width:309px;">Equilibrium catalyst</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Balance</td>
			<td style="width:168px;">Mettler Toledo</td>
			<td style="width:111px;">AB304-S</td>
			<td style="width:309px;">For weighing liquid product receivers</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Balance</td>
			<td style="width:168px;">Mettler Toledo</td>
			<td style="width:111px;">XS8001S</td>
			<td style="width:309px;">For weighing water displaced by gas product</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Ethylene Glycol</td>
			<td style="width:168px;">Fisher Scientifc Inc.</td>
			<td style="width:111px;">CAS 107-21-1</td>
			<td style="width:309px;">Mixed with distilled water as coolant (50 v% )</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Drierite</td>
			<td style="width:168px;">W.A. Hammond Drierite Co. Ltd.</td>
			<td style="width:111px;">24001</td>
			<td style="width:309px;">For water absorption after CO catalytic converter</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:231px;">Copper Oxide</td>
			<td style="width:168px;">LECO Corporation</td>
			<td style="width:111px;">501-170</td>
			<td style="width:309px;">Catalyst for conversion of CO to CO2</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Toluene</td>
			<td style="width:168px;">Fisher Scientific Co.&#160;</td>
			<td style="width:111px;">CAS 108-88-3</td>
			<td style="width:309px;">For cleaning liquid receivers</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Acetone</td>
			<td style="width:168px;">Fisher Scientific Co.&#160;</td>
			<td style="width:111px;">CAS 67-64-1</td>
			<td style="width:309px;">For cleaning liquid receivers</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Micro GC Calibration Gas</td>
			<td style="width:168px;">Air Liquid Canada Inc.</td>
			<td style="width:111px;">SPG-25MX0015306</td>
			<td style="width:309px;">Multicomponent standard gas</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:231px;">19.8% CO2 Standard Gas</td>
			<td style="width:168px;">BOC Canada Ltd.</td>
			<td style="width:111px;">24069890</td>
			<td style="width:309px;">For calibration of IR analyzer</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Argon Gas</td>
			<td style="width:168px;">Linde Canada ltd.</td>
			<td style="width:111px;">24001306</td>
			<td style="width:309px;">Grade 5.0 Purity</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Helium Gas</td>
			<td style="width:168px;">Linde Canada ltd.</td>
			<td style="width:111px;">24001333</td>
			<td style="width:309px;">Grade 5.0 Purity</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Gas analyzer GC Module</td>
			<td style="width:168px;">Inficon</td>
			<td style="width:111px;">GCMOD-15</td>
			<td style="width:309px;">Channel A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Gas analyzer GC Module</td>
			<td style="width:168px;">Inficon</td>
			<td style="width:111px;">GCMOD-03</td>
			<td style="width:309px;">Channel B</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Gas analyzer GC Module</td>
			<td style="width:168px;">Inficon</td>
			<td style="width:111px;">GCMOD-04</td>
			<td style="width:309px;">Channel C</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Gas analyzer GC Module</td>
			<td style="width:168px;">Inficon</td>
			<td style="width:111px;">GCMOD-73</td>
			<td style="width:309px;">Channel D</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">HP 6890 GC</td>
			<td style="width:168px;">Hewlett-Packard Co.&#160;</td>
			<td style="width:111px;">G1530A</td>
			<td style="width:309px;">For simulated distillation</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">ASTM 2887 Standard Sample</td>
			<td style="width:168px;">PAC L.P.</td>
			<td style="width:111px;">26650.150</td>
			<td style="width:309px;">For quality control in simulated distillation</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">ASTM 2887 Standard Sample</td>
			<td style="width:168px;">PAC L.P.</td>
			<td style="width:111px;">25950.200</td>
			<td style="width:309px;">For calibration in simulated distillation</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Column for GC 6890 (simulated distillation)</td>
			<td style="width:168px;">Agilent Technologies</td>
			<td style="width:111px;">CP7562</td>
			<td style="width:309px;">10m x 0.53mm x 1.2&#181;m, HP 6890 GC column</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Liquid Nitrogen</td>
			<td style="width:168px;">Air Liquid Canada Inc.</td>
			<td style="width:111px;">SPG-NIT1AC240LC</td>
			<td style="width:309px;">For use in simulated distillation&#160;</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Nitrogen</td>
			<td style="width:168px;">Air Liquid Canada Inc.</td>
			<td style="width:111px;">Bulk (building N2)</td>
			<td style="width:309px;">For use in ACE unit operation</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Isotemp Programmable Furnace</td>
			<td style="width:168px;">Thermo Fisher Scientifc Inc.</td>
			<td style="width:111px;">10-750-126</td>
			<td style="width:309px;">For calcination of catalyst</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">GC Vials, Crimp Top</td>
			<td style="width:168px;">Chromatograghic Specialties Inc</td>
			<td style="width:111px;">C223682C</td>
			<td style="width:309px;">2ml, for liquid product</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Seals, Crimp Top</td>
			<td style="width:168px;">Chromatograghic Specialties Inc</td>
			<td style="width:111px;">C221150</td>
			<td style="width:309px;">11 mm, for use with GC vials</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">4 oz clear Boston round bottles</td>
			<td style="width:168px;">Fisher Scientific Co.&#160;</td>
			<td style="width:111px;">02-911-784</td>
			<td style="width:309px;">With PE cone lined caps, for use in feed system</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Sieve</td>
			<td style="width:168px;">Endecotts Ltd.</td>
			<td style="width:111px;">6140269</td>
			<td style="width:309px;">Aperture 38 micron</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Sieve</td>
			<td style="width:168px;">Endecotts Ltd.</td>
			<td style="width:111px;">6146265</td>
			<td style="width:309px;">Aperture 250 micron</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">Shaker</td>
			<td style="width:168px;">Endecotts Ltd.</td>
			<td style="width:111px;">MIN 2737-11</td>
			<td style="width:309px;">Minor-Meinzer 2 Sieve Shaker for catalyst screening</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:231px;">V20 Volumetric KF Titrator</td>
			<td style="width:168px;">Mettler Toledo</td>
			<td style="width:111px;">5131025056</td>
			<td style="width:309px;">For water content analysis of the liquid product</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Hydranal Composite 5</td>
			<td style="width:168px;">Sigma-Aldrich</td>
			<td style="width:111px;">34805-1L-R</td>
			<td style="width:309px;">Reagent for Karl Fischer titration</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:231px;">Methanol (extremely low water grade)</td>
			<td style="width:168px;">Fisher Scientific Co.&#160;</td>
			<td style="width:111px;">A413-4</td>
			<td style="width:309px;">Mixed with toluene (40:60 w/w) for KF titration: also used to recover water in receiver</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:231px;">Glass Wool</td>
			<td style="width:168px;">Fisher Scientific Co.&#160;</td>
			<td style="width:111px;">11-388</td>
			<td style="width:309px;">Placed inside the top of receiver outlet arm&#160;</td>
		</tr>
	</tbody>
</table>

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.

The established protocol has been successfully applied to an oil blend of 15:85 volume ratio (i.e., 14.73:85.27 mass ratio) between canola oil and an SCO-derived HGO20. For practical reasons (cost, availability of canola oil, and possible challenges in commercial operation), the study was focused on feedstock containing 15 v% canola oil addition, although feeds with higher concentrations were also tried. The blend was catalytically cracked at 490-530 &#176;C and 8.0 hr...

Watch this Scientific Journal Video about Laboratory Production of Biofuels and Biochemicals from a Rapeseed Oil through Catalytic Cracking Conversion at JoVE.com

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

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.

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 ...

The overall goal of this laboratory method is to produce biofuels and biochemicals from co-processing of canola oil with fossil-based feeds. This method can help answer key questions in chemical engineering, really, into catalytic cracking of heavy oils, fuel chemistry, catalysis, and reaction mechanisms. The main advantage of this technique is that the method is fast and cost effective, enabling full control over the test parameters and the reduction of human error.The implications of this technique extend towards catalyst development, as the equipment used is simple, reliable, and productive for testing new formulas. Although this study focus on product distribution and the quality, the main study can also be applied to other fields such as predictive modelling and simulations. I'm pleased to introduce my teammates.Research Scientist, Nicole Heshka, Yi Zhang, and R&D program advisor Edward Little. They will demonstrate the procedure and/or discuss the method. To begin this procedure, disconnect the oil feed line below the purge valve of a laboratory test unit, or LTU, and attach a short temporary tube to the bottom of the valve.Following this, preheat a previously prepared feedstock to 85 degrees celsius to enable the heavy gas oil, or HGO, blend to flow easily. Place a tared beaker at the discharge of the short temporary tube connected to the oil feed pump. Then start the preset pump cal user program in the reaction unit software.After the pump cal program is complete, remove and weigh the beaker containing the feed. Divide the mass of the feed delivered into the beaker by the injection time. Next, adjust the pump speed using the three digit dial on the pump, and repeat the previous steps until the desired feed rate of 1.2 grams per minute is attained.Then remove the short temporary tube and reconnect the feed line. Through the reaction unit software, switch the valve to the position that enables the zero gas to flow to the IR analyzer. Turn the knob in association with the flow control valve to get about 250 standard cubic centimeters per minute on the flow indicator.Following this, zero the analyzer using the zero adjustment screw on the front panel with a flat-bladed screw driver. Switch the hand valve to supply the carbon dioxide standard gas to the analyzer. Then adjust the manual valve to obtain a flow of approximately 250 standard cubic centimeters per minute.Adjust the analyzer reading to match the concentration of the standard span gas using the span screw on the front panel. Place a small plug of glass wool inside the top of each receiver outlet arm. Following this, place the receiver in a flask of suitable size to keep it upright.Then weigh the receiver in an analytical balance covered by a cubic plastic shield to ensure a draft-free environment. Now install and connect the weighed receiver to the product line. Install an oil feed line in the reactor with a length that allows for 1.125 inch injector height.Place a filter at the exit of the reactor to prevent any catalyst dust from entering the product line, changing the filter after 50 to 100 runs. It is critical to maintain consistency between runs. For example, always use an on size and coke-free equilibrium catalyst, oil feed line in the reactor with the same injector height, and constant molecular weight for the C5 plus unresolved gas lump.After feed pump calibration and receiver installation, perform a pressure test on the reactor system by running the program PTEST1. Close the gas vent and pressurize the reactor system with 150 millimeters mercury of nitrogen followed by isolation of the system. Observe the pressure reading for a few minutes to ensure the pressure drop is no more than 0.4 millimeters of mercury per minute, indicating that no leaks are present.On the LTU setup screen, input the relevant information for the experiment. Then place the system into run mode by clicking the Run button on the process flow screen. Observe as fresh catalyst from the specified hopper is discharged into the reactor.At this point, monitor the reaction system to ensure it reaches the correct conditions previously specified in the software. When the reaction conditions are met, watch to see that the syringe pump delivers the oil feed into the reactor. Following feed injection, observe vapor products flowing through the liquid receivers into the water displacement system for gas collection.Check to see that the high boiling products are condensing in the liquid receivers. At the end of the catalyst's stripping cycle, watch to ensure that the air flow begins and the reactor temperature is raised to approximately 715 degrees celsius. Monitor the IR analyzer which should show a sharp increase in carbon dioxide concentration followed by a decrease to below 0.3%At the end of the catalyst regeneration, ensure that the computer software records the mass of displaced water along with the pressure and temperature of the gas in the collection vessel.After mixing and warming to approximately 30 degrees celsius, observe delivery of the gas to the GC for analysis. Observe the reactor cooling down to skin temperatures, 50 degrees celsius below the reaction set points. Save all the data for the run.If it is the last run, discharge the spent catalyst to the waste vessel. Using the computer, attach to a gas chromatograph, or GC, integrate the peaks, and process the data using the calibration established. Input the final GC data into the LTU program through the LTU computer.For good material balance, it is critical to accurately determine the mass of liquid product, including water if present. The following steps include the methodology to recover the liquid product, in a way the long liquid product receiver, in a draft-free environment. After removing the clamp from the liquid product receiver, tilt the receiver and collect any liquid product droplets on the beveled metal tip below the product valve.Immediately seal the receiver with labeled rubber stoppers and carefully remove it from the ethylene glycol bath. Rinse off the ethylene glycol with cold water, and dry the receiver with a paper towel. Following this, place the liquid product receiver on a rack at room temperature for 20 minutes, allowing any frozen product to thaw and run down into a GC vial placed at the bottom of the receiver.Collect the liquid holdup around the metal joint of the receiver with a teared cotton wool swab. Determine the mass of the liquid holdup. Open the liquid product receiver to atmosphere in a vented fume hood for pressure equalization by momentarily removing the stopper from the top outlet.After replacing the stopper, obtain the receiver mass. Next, remove the GC vial with the sample from the condenser. Close and store the vial in a refrigerator at four degrees celsius for later analysis.If a water droplet is observed in the bottom of the GC vial, use a clean syringe to transfer as much water-free oil product as possible to another vial and close it immediately. Rinse the inner walls of the receiver condenser thoroughly with a small quantity of methanol, and collect all of the methanol wash into the original GC vial containing the water droplet. Finally, close the vial and obtain the mass of the liquid for water analysis.The yield and conversion data show qualitatively that upon cracking, canola oil in the HGO blend contributes substantially to the yields of biofuels and biochemicals. The presence of water and carbon monoxide plus carbon dioxide as cracked products from the blend but not from HGO alone, indicates that canola oil participates in reactions. The hydrogen and carbon monoxide yields are not very sensitive to catalyst to oil ratio changes for a feed at a given temperature.However, for a feed at a given catalyst to oil ratio, both hydrogen and carbon monoxide yields increase with increasing temperature, which is the driving force for cracking. Comparing the two feeds, the blend gives higher carbon monoxide yields but lower hydrogen yields than the base oil. After injection of an oil, the reactor temperature drops, reaching a minimum and then rising towards the initial temperature of 530 degrees celsius.As the catalyst to oil ratio increases, the temperature drop decreases since less oil is injected. Comparing the two feeds, the blend consistently exhibits a smaller drop of temperature due to heat release from the exothermic reaction. While attempting this procedure, it is important to carefully follow the instructions accompanying the laboratory test unit, and to maintain consistent operation between tests.Demonstration of this procedure is useful because the steps for recovery of liquid product are critical to test quality but are difficult to describe in writing. Following this procedure, other feeds like light tight oil can be co-processed with heavy crudes in order to answer questions about their suitability for refinery operations. Don't forget that crude oil can be hazardous and should only be handled while wearing proper protective equipment.Additionally, toxic hydrogen sulfide may be present in products and exhaust gas. They should only be handled under good ventilation. After watching this video, you should have a good understanding of how to operate a laboratory test unit for quality results and how to properly collect products for further analysis.

laboratory-production-biofuels-biochemicals-from-rapeseed-oil-through

Research

JoVE Journal

Chemistry

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Unsymmetrical 1,2-diols are hardly accessible by reductive pinacol coupling processes. A successful execution of such a transformation is bound to a clear recognition and strict differentiation of two similar carbonyl compounds (aldehydes &#8594; secondary 1,2-diols or ketones &#8594; tertiary 1,2-diols). This fine-tuning is still a challenge and an unsolved problem for an organic chemist. There exist several reports on successful execution of this transformation but they cannot be generalized. Herein we describe a catalytic direct pinacol coupling process which proceeds via a retropinacol/cross-pinacol coupling sequence. Thus, unsymmetrical substituted 1,2-diols can be accessed with almost quantitative yields by means of an&#160;operationally simple performance under very mild conditions. Artificial techniques, such as syringe-pump techniques or delayed additions of reactants are not necessary. The procedure we describe provides a very rapid access to cross-pinacol products (1,2-diols, vicinal diols). A further extension of this new process, e.g. an enantioselective performance could provide a very useful tool for the synthesis of unsymmetrical chiral 1,2-diols.

A novel account for the synthesis of unsymmetrical 1,2-diols based on a retropinacol/cross-pinacol coupling mechanism is described. Due to the catalytic execution of this reaction a considerable improvement compared to conventional cross-pinacol couplings is achieved.

Unsymmetrical 1,2-diols are hardly accessible by reductive pinacol coupling processes. A successful execution of such a transformation is bound to a clear ...

Thin-layer Chromatographic (TLC) Separations and Bioassays of Plant Extracts to Identify Antimicrobial Compounds

A common screen for plant antimicrobial compounds consists of separating plant extracts by paper or thin-layer chromatography (PC or TLC), exposing the chromatograms to microbial suspensions (e.g. fungi or bacteria in broth or agar), allowing time for the microbes to grow in a humid environment, and visualizing zones with no microbial growth.&#160;The effectiveness of this screening method, known as bioautography, depends on both the quality of the chromatographic separation and the care taken with microbial culture conditions.&#160;This paper describes standard protocols for TLC and contact bioautography&#160;with a novel application to amino acid-fermenting bacteria. The extract is separated on flexible (aluminum-backed) silica TLC plates, and bands are visualized under ultraviolet (UV) light.&#160;Zones are cut out and incubated face down onto agar inoculated with the test microorganism.&#160;Inhibitory bands are visualized by staining the agar plates with tetrazolium red.&#160;The method is applied to the separation of red clover (Trifolium pratense cv. Kenland) phenolic compounds and their screening for activity against Clostridium sticklandii, a hyper ammonia-producing bacterium (HAB) that is native to the bovine rumen.&#160;The TLC methods apply to many types of plant extracts&#160;and other bacterial species (aerobic or anaerobic), as well as fungi, can be used as test organisms if culture conditions are modified to fit the growth requirements of the species.

Thin-layer Chromatographic TLC Separations and Bioassays of Plant Extracts to Identify Antimicrobial Compounds

Methods are described for thin-layer chromatographic (TLC) separation of plant extracts and contact bioautography to identify antibacterial metabolites. The methods are applied to the screening of red clover phenolic compounds inhibiting hyper&#160;ammonia-producing bacteria (HAB) native to the bovine rumen.

A common screen for plant antimicrobial compounds consists of separating plant extracts by paper or thin-layer chromatography (PC or TLC), exposing the ...

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic nature of the monomer is conserved. The resulting polymer, polynorbornene, has a very high glass transition temperature, Tg, and interesting optical and electrical properties. However, the polymerization of functional norbornenes by this mechanism is complicated by the fact that the endo substituted norbornene monomer has, in general, a very low reactivity. Furthermore, the separation of the endo substituted monomer from the exo monomer is a tedious task. Here, we present a simple protocol for the polymerization of substituted norbornenes (endo:exo ca. 80:20) bearing either a carboxylic acid or a pendant double bond. The process does not require that both isomers be separated, and proceeds with low catalyst loadings (0.01 to 0.02 mol%). The polymer bearing pendant double bonds can be further transformed in high yield, to afford a polymer bearing pendant epoxy groups. These simple procedures can be applied to prepare polynorbornenes with a variety of functional groups, such as esters, alcohols, imides, double bonds, carboxylic acids, bromo-alkyls, aldehydes and anhydrides.

We describe the catalytic insertion polymerization of 5-norbornene-2-carboxylic acid and 5-vinyl-2-norbornene to form functional polymers with a very high glass transition temperature.

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid crystals (ILCs). Taking advantages of the high specificity of XB for haloperfluorocarbons and the ability of anions to act as XB-acceptors, we obtained supramolecular complexes based on 1-alkyl-3-methylimidazolium iodides and iodoperfluorocarbons, overcoming the well-known immiscibility between hydrocarbons (HCs) and perfluorocarbons (PFCs). The high directionality of the XB combined with the fluorophobic effect, allowed us to obtain enantiotropic liquid crystals where a rigid, non-aromatic, XB supramolecular anion acts as mesogenic core.
X-ray structure analysis of the complex between 1-ethyl-3-methylimidazolium iodide and iodoperfluorooctane showed the presence of a layered structure, which is a manifestation of the well-known tendency to segregation of perfluoroalkyl chains. This is consistent with the observation of smectic mesophases. Moreover, all the reported complexes melt below 100 &#176;C, and most are mesomorphic even at room temperature, despite that the starting materials were non-mesomorphic in nature.
The supramolecular strategy reported here provides new design principles for mesogen design allowing a totally new class of functional materials.

A protocol for the synthesis of a new type of mesogens, based on the halogen-bonded supramolecular anion [CnF2n+1-I&#183;&#183;&#183;I&#183;&#183;&#183;I-CnF2n+1]&#8722;, is reported.

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid ...

One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate glycosyl donor. Following azido-nitration of a glycal, the product 2-azido-1-nitrate ester can be hydrolyzed under microwave-assisted irradiation. This transformation is usually achieved using strongly nucleophilic reagents and extended reaction times. Microwave irradiation induces hydrolysis, in the absence of reagents, with short reaction times. Following denitration, the intermediate anomeric alcohol is converted, in the same pot, to the corresponding 2-azido-1-trichloroacetimidate.

A 2-azido-1-nitrate-ester can be converted to the corresponding 2-azido-1-trichloroacetimidate in a one-pot procedure. The goal of the manuscript is to demonstrate utility of the microwave reactor in carbohydrate synthesis.

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate ...

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile N-(2-alkoxyvinyl)sulfonamides, which react under a variety of conditions to afford useful N- and O-containing compounds. Acid-catalyzed addition of alcohols or thiols to N-(2-alkoxyvinyl)sulfonamide-containing phthalans provides access to ketals and thioketals, respectively. Selective reduction of the vinyl group in N-(2-alkoxyvinyl)sulfonamide-containing phthalans via hydrogenation yields the corresponding phthalan in good yield, whereas reduction with sodium bis(2-methoxyethoxy)aluminumhydride generates a ring-opened phenethylamine analogue. Because the N-(2-alkoxyvinyl)sulfonamide functional group is synthetically versatile, but often hydrolytically unstable, this protocol emphasizes key techniques in preparing, handling, and reacting these pivotal substrates in several useful transformations.

Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Representative experimental procedures for the synthesis of N-(2-alkoxyvinyl)sulfonamides and subsequent conversion to phthalan and phenethylamine derivatives are presented in detail.

Decomposition of N-tosyl-1,2,3-triazoles with rhodium(II) acetate dimer in the presence of alcohols forms synthetically versatile ...

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area

We demonstrate a method for the synthesis of NixNb1-xO catalysts with sponge-like and fold-like nanostructures. By varying the Nb:Ni ratio, a series of NixNb1-xO nanoparticles with different atomic compositions (x = 0.03, 0.08, 0.15, and 0.20) have been prepared by chemical precipitation. These NixNb1-xO catalysts are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The study revealed the sponge-like and fold-like appearance of Ni0.97Nb0.03O and Ni0.92Nb0.08O on the NiO surface, and the larger surface area of these NixNb1-xO catalysts, compared with the bulk NiO. Maximum surface area of 173 m2/g can be obtained for Ni0.92Nb0.08O catalysts. In addition, the catalytic hydroconversion of lignin-derived compounds using the synthesized Ni0.92Nb0.08O catalysts have been investigated.

Chemical Precipitation Method for the Synthesis of Nb2O5 Modified Bulk Nickel Catalysts with High Specific Surface Area

A protocol for the synthesis of sponge-like and fold-like Ni1-xNbxO nanoparticles by chemical precipitation is presented.

We demonstrate a method for the synthesis of NixNb1-xO catalysts with sponge-like and fold-like nanostructures. By varying the Nb:Ni ratio, a series of ...

Fabrication and Testing of Catalytic Aerogels Prepared Via Rapid Supercritical Extraction

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three preparation methods are described: (a) the incorporation of metal salts into silica or alumina wet gels using an impregnation method; (b) the incorporation of metal salts into alumina wet gels using a co-precursor method; and (c) the addition of metal nanoparticles directly into a silica aerogel precursor mixture. The methods utilize a hydraulic hot press, which allows for rapid (&#60;6 h) supercritical extraction and results in aerogels of low density (0.10 g/mL) and high surface area (200-800 m2/g). While the work presented here focuses on the use of copper salts and copper nanoparticles, the approach can be implemented using other metal salts and nanoparticles. A protocol for testing the three-way catalytic ability of these aerogels for automotive pollution mitigation is also presented. This technique uses custom-built equipment, the Union Catalytic Testbed (UCAT), in which a simulated exhaust mixture is passed over an aerogel sample at a controlled temperature and flow rate. The system is capable of measuring the ability of the catalytic aerogels, under both oxidizing and reducing conditions, to convert CO, NO and unburned hydrocarbons (HCs) to less harmful species (CO2, H2O and N2). Example catalytic results are presented for the aerogels described.

Here we present protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms. Methods for preparing materials using copper salts and copper-containing nanoparticles are featured. Catalytic testing protocols demonstrate the effectiveness of these aerogels for three-way catalysis applications.

Protocols for preparing and testing catalytic aerogels by incorporating metal species into silica and alumina aerogel platforms are presented. Three ...

Tuning the Acidity of Pt/ CNTs Catalysts for Hydrodeoxygenation of Diphenyl Ether

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid nanosheets, a series of Pt/xHMNO6/CNTs with different solid acid compositions (x = 5, 20 wt%; M = Nb, Ta; N = Mo, W) have been prepared by carbon nanotube pretreatment, protonic exchange, solid acid exfoliation, aggregation and finally Pt particles impregnation. The Pt/xHMNO6/CNTs are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and NH3-temperature programmed desorption. The study revealed that HNbWO6 nanosheets were attached on CNTs, with some edges of the nanosheets being bent in shape. The acid strength of the supported Pt catalysts increases in the following order: Pt/CNTs &#60; Pt/5HNbWO6/CNTs &#60; Pt/20HNbMoO6/CNTs &#60; Pt/20HNbWO6/CNTs &#60; Pt/20HTaWO6/CNTs. In addition, the catalytic hydroconversion of lignin-derived model compound: diphenyl ether using the synthesized Pt/20HNbWO6 catalyst has been investigated.

A protocol for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs is presented.

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid ...