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Summary

Abstract

Introduction

Protocol

Representative Results

Discussion

Acknowledgements

Materials

References

Chemistry

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

Published: September 2nd, 2016

DOI:

10.3791/54390

1CanmetENERGY, Natural Resources Canada

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 (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 °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 °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 °C (gasoline), 221-343 °C (light cycle oil), and 343 °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 °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.

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's transportation fuels1. In many developed countries, it is required that biofuels replace from 6% to 1....

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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 °.......

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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 °C and 8.0 hr.......

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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.......

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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'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.

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Name Company Catalog Number Comments
Advanced Cracking Evaluation (ACE) Unit Kayser Technology Inc. ACE R+ 46 Assembled by Zeton Inc. SN:505-46;  consisting of (1) a reactor; (2) catalyst addition system; (3) feed delivery system;  (4) liquid collection system; (5) gas collection system; (6) gas analyzing system; (7) catalyst regeneration system; (8) CO catalytic convertor; (9) coke analyzing system
Reactor (ACE) Kayser Technology Inc. V-105 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
Catalyst Addition System (ACE) Kayser Technology Inc. Six hoppers (V-120F, with respective valves) for addition of catalyst for up to 6 runs
Feed Delivery System (ACE) Kayser Technology Inc. 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)
Liquid Collection System (ACE) Kayser Technology Inc. Six liquid receivers (V-110F) immersed in a common coolant bath (Ethylene glycol/water mixture in 50:50 mass ratio) at about –15 °C in a large tank (V-145)
Gas Collection System (ACE) Kayser Technology Inc. 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) 
Gas Analyzing System (ACE) Kayser Technology Inc. Key element being Agilent micro GC (model 3000A) with four capillary columns equipped with respective thermal conductivity detectors (TCDs) 
Catalyst Regeneration System (ACE) Kayser Technology Inc. V-105 Spent catalyst in reactor being burned in situ in air at +700 °C to ensure complete removal of carbon deposited on the catalyst
CO Catalytic Convertor  (ACE) Kayser Technology Inc. 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)
Coke Analyzing System (ACE) Kayser Technology Inc. Servomex (Model 1440C) IR analyzer for measuring CO2 in exhausted flue gas
R+MM Software Suite Kayser Technology Inc. Including iFIX 3.5 
Agilent Micro GC Agilent Technologies 3000A For gas analysis after cracking
Cerity Networked Data System Agilent Technologies Software for Agilent Micro GC
CO2 Gas Analyser Servomex Inc. 1440C SN: 01440C1C02/2900
NESLAB Refrigerated Bath Themo Electron Corporation RTE 740 SN: 104300061
Orion  Sage Syringe Pump Themo Electron Corporation M362 For delivering feed oil to injector tube
Synthetic Crude Oil (SCO)  Suncor Energy Inc. Identified as Suncor OSA 10-4.1
Catalyst P Petro-Canada Refinery Equilibrium catalyst
Balance Mettler Toledo AB304-S For weighing liquid product receivers
Balance Mettler Toledo XS8001S For weighing water displaced by gas product
Ethylene Glycol Fisher Scientifc Inc. CAS 107-21-1 Mixed with distilled water as coolant (50 v% )
Drierite W.A. Hammond Drierite Co. Ltd. 24001 For water absorption after CO catalytic converter
Copper Oxide LECO Corporation 501-170 Catalyst for conversion of CO to CO2
Toluene Fisher Scientific Co.  CAS 108-88-3 For cleaning liquid receivers
Acetone Fisher Scientific Co.  CAS 67-64-1 For cleaning liquid receivers
Micro GC Calibration Gas Air Liquid Canada Inc. SPG-25MX0015306 Multicomponent standard gas
19.8% CO2 Standard Gas BOC Canada Ltd. 24069890 For calibration of IR analyzer
Argon Gas Linde Canada ltd. 24001306 Grade 5.0 Purity
Helium Gas Linde Canada ltd. 24001333 Grade 5.0 Purity
Gas analyzer GC Module Inficon GCMOD-15 Channel A
Gas analyzer GC Module Inficon GCMOD-03 Channel B
Gas analyzer GC Module Inficon GCMOD-04 Channel C
Gas analyzer GC Module Inficon GCMOD-73 Channel D
HP 6890 GC Hewlett-Packard Co.  G1530A For simulated distillation
ASTM 2887 Standard Sample PAC L.P. 26650.150 For quality control in simulated distillation
ASTM 2887 Standard Sample PAC L.P. 25950.200 For calibration in simulated distillation
Column for GC 6890 (simulated distillation) Agilent Technologies CP7562 10m x 0.53mm x 1.2µm, HP 6890 GC column
Liquid Nitrogen Air Liquid Canada Inc. SPG-NIT1AC240LC For use in simulated distillation 
Nitrogen Air Liquid Canada Inc. Bulk (building N2) For use in ACE unit operation
Isotemp Programmable Furnace Thermo Fisher Scientifc Inc. 10-750-126 For calcination of catalyst
GC Vials, Crimp Top Chromatograghic Specialties Inc C223682C 2ml, for liquid product
Seals, Crimp Top Chromatograghic Specialties Inc C221150 11 mm, for use with GC vials
4 oz clear Boston round bottles Fisher Scientific Co.  02-911-784 With PE cone lined caps, for use in feed system
Sieve Endecotts Ltd. 6140269 Aperture 38 micron
Sieve Endecotts Ltd. 6146265 Aperture 250 micron
Shaker Endecotts Ltd. MIN 2737-11 Minor-Meinzer 2 Sieve Shaker for catalyst screening
V20 Volumetric KF Titrator Mettler Toledo 5131025056 For water content analysis of the liquid product
Hydranal Composite 5 Sigma-Aldrich 34805-1L-R Reagent for Karl Fischer titration
Methanol (extremely low water grade) Fisher Scientific Co.  A413-4 Mixed with toluene (40:60 w/w) for KF titration: also used to recover water in receiver
Glass Wool Fisher Scientific Co.  11-388 Placed inside the top of receiver outlet arm 

  1. Bringezu, S., et al. Towards Sustainable Production and Use of Resources - Assessing Biofuels. United Nations Environment Programme. , (2009).
  2. Sheehan, J., Camobresco, V., Duffield, J., Graboski, M., Shapouri, H. Life cycle inventory for biodiesel and petroleum diesel for use in an urban bus. National Renewable Energy Laboratory Report. , (1998).
  3. . Renewable Fuels Regulations. Canada Gazette Part II. 144 (18), 1614-1740 (2010).
  4. . Directive 2009/28/EC of the European Parliament and of the Council of 23 April 2009 on the promotion of the use of energy from renewable sources and amending and subsequently repealing Directives 2001/77/EC and 2003/30/EC (Text with EEA relevance). Official Journal of the European Union. 140, 16-62 (2009).
  5. Al-Sabawi, M., Chen, J., Ng, S. Fluid catalytic cracking of biomass-derived oils and their blends with petroleum feedstocks: A Review. Energy Fuels. 26 (9), 5355-5372 (2012).
  6. Dupain, X., Costa, D. J., Schaverien, C. J., Makkee, M., Moulijn, J. A. Cracking of a rapeseed vegetable oil under realistic FCC conditions. Appl. Catal. B: Environ. 72 (1-2), 44-61 (2007).
  7. Tian, H., Li, C., Yang, C., Shan, H. Alternative processing technology for converting vegetable oils and animal fats to clean fuels and light olefins. Chin J Chem Eng. 16 (3), 394-400 (2008).
  8. Melero, J. A., Clavero, M. M., Calleja, G., Garcia, A., Miravalles, R., Galindo, T. Production of bio-fuels via the catalytic cracking of mixtures of crude vegetable oils and nonedible animal fats with vacuum gas oil. Energy Fuels. 24 (1), 707-717 (2010).
  9. Bielansky, P., Reichhold, A., Schönberger, C. Catalytic cracking of rapeseed oil to high octane gasoline and olefins. Chem Eng Process. 49 (8), 873-880 (2010).
  10. Ng, S. H., Shi, Y., Ding, L., Chen, S. Catalytic cracking of a rapeseed oil for production of transportation fuels and chemicals: Yield structure. 2010 AIChE Annual Meeting. , (2010).
  11. Bielansky, P., Weinert, A., Schönberger, C., Reichhold, A. Catalytic conversion of vegetable oils in a continuous FCC pilot plant. Fuel Process Technol. 92 (12), 2305-2311 (2011).
  12. Ng, S. H., Lay, C., Bhatt, S., Freel, B., Graham, R. Upgrading of biomass-derived liquid to clean fuels. 2012 AIChE Annual Meeting. , (2012).
  13. Ordorica-Garcia, G., Croiset, E., Douglas, P., Elkamel, A., Gupta, M. Modeling the energy demands and greenhouse gas emissions of the Canadian oil sands industry. Energy Fuels. 21 (4), 2098-2111 (2007).
  14. . . Canada's Emission Trends. , (2013).
  15. Kayser, J. C. Versatile fluidized bed reactor. US Patent. , (2000).
  16. . . ACE Operating Manual: PID Drawing No. R+ 101 and 102. , (2007).
  17. . . System Manual: ACE - Model R+. , (2007).
  18. . . ASTM D2887-15 Standard test method for boiling range distribution of petroleum fractions by gas chromatography. , (2015).
  19. . . AASTM D4377-00 Standard test method for water in crude oils by potentiometric Karl Fischer titration. , (2015).
  20. Ng, S. H., et al. FCC coprocessing oil sands heavy gas oil and canola oil. 1. Yield structure. Fuel. 156, 163-176 (2015).
  21. Cox, J. D., Wagman, D. D., Medvedev, V. A. . CODATA Key values for thermodynamics. , (1984).
  22. Ng, S. H., et al. FCC study of Canadian oil-sands derived vacuum gas oils. 1. Feed and catalyst effects on yield structure. Energy Fuels. 16 (5), 1196-1208 (2002).
  23. Ng, S. H., Dabros, T., Humphries, A. Fluid catalytic cracking quality improvement of bitumen after paraffinic froth treatment. Energy Fuels. 21 (3), 1432-1441 (2007).
  24. Scherzer, J., Magee, J. S., Mitchell, M. M. Chapter 5, Correlation between catalyst formulation and catalytic properties. Fluid Catalytic Cracking: Science and Technology. , 145-182 (1993).
  25. Fisher, I. P. Effect of feedstock variability on catalytic cracking yields. Appl. Catal. 65 (2), 189-210 (1990).
  26. Ng, S. H., et al. Study of Canadian FCC feeds from various origins and treatments. 1. Ranking of feedstocks based on feed quality and product distribution. Energy Fuels. 18 (1), 160-171 (2004).
  27. Ng, S. H., et al. Study of Canadian FCC feeds from various origins and treatments. 2. Some specific cracking characteristics and comparisons of product yields and qualities between a riser reactor and a MAT unit. Energy Fuels. 18 (1), 172-187 (2004).
  28. Ng, S. H., et al. Key observations from a comprehensive FCC study on Canadian heavy gas oils from various origins. 1. Yield profiles in batch reactors. Fuel Process Technol. 87 (6), 475-485 (2006).
  29. Scherzer, J. Octane-enhancing zeolitic FCC catalysts: Scientific and technical aspects. Catalysis Reviews: Science and Engineering. 31 (3), 215-354 (1989).
  30. . . ASTM D7964/D7964M-14 Standard test method for determining activity of fluid catalytic cracking (FCC) catalysts in a fluidized bed. , (2014).
  31. . . ASTM D5154-10 Standard test method for determining activity and selectivity of fluid catalytic cracking (FCC) catalysts by Microactivity test. , (2010).
  32. Moorehead, E. L., McLean, J. B., Cronkright, W. A., Magee, J. S., Mitchell, M. M. Chapter 7, Microactivity evaluation of FCC catalysts in the laboratory: Principles, approaches and applications. Fluid Catalytic Cracking: Science and Technology. , 223-255 (1993).
  33. Rawlence, D. J., Gosling, K. FCC catalyst performance evaluation. Appl. Catal. 43 (2), 213-237 (1988).

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