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

Summary

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.

Abstract

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.

Introduction

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....

Protocol

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 °C, and high-temperature safety gloves should be used when working near hot surfaces.

1. General Considerations

Results

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.......

Discussion

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.......

Materials

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