Reaney: Industrial Products From Vegetable Oils
Date: March 2017
Term: 3 years
Status: Completed
Researcher(s): Martin Reaney, Lipid Quality and Utilization Program, University of Saskatchewan, Saskatoon SK
SaskCanola Investment: n/a
Total Project Cost: n/a
Funding Partners: ADF
Project Summary
Researchers at the University of Saskatchewan’s Lipid Quality and Utilization (LQU) program conducted several projects from 2014 to 2017, focusing on the development of industrial projects from vegetable oils. In 2014 and 2015, LQU completed three main projects including: conversion of glycerol to monoglyceride; production of lithium catalysts, high quality glycerol and lithium grease; and production of Trans-vaccenic Acid (TVA) for clinical trials.
Researchers at the University of Saskatchewan’s Lipid Quality and Utilization (LQU) program conducted several projects from 2014 to 2017, focusing on the development of industrial projects from vegetable oils. The goal was to explore methods for improving both physical and chemical properties of vegetable oil based consumer and industrial non-food products and lower the cost of production of these products. From 2014-2015, a number of projects were completed including three major projects, all focused on pilot scale production.
1. Conversion of Glycerol to Monoglyceride
Currently, biodiesel is produced by transesterification of triglycerides found in plant oils and animal fats. Glycerol (Gly) is the main co-product in the biodiesel synthesis process, representing 10% of the biodiesel production mass. Therefore, the increasing production of biodiesel around the world generates a Gly surplus that is becoming a matter of economic and environmental concern since the decrease in Gly price has forced producers to burn or sell it without refining. New applications intended to convert Gly into value-added chemicals are highly desirable not only to improve the economics of biodiesel production but also for ecological reasons.
In this project, researchers want to demonstrate the additional value to glycerol by its conversion to monoglycerides, and to identify effective low-cost catalysts. Canola oil was the triglyceride used in this study, as well as the different forms of magnesium - magnesium powder, magnesium chip and magnesium grit, and calcium oxide as a catalyst mixture to produce monoacyl glycerol from biodiesel waste. Reaction progress was monitored by Nuclear Magnetic Resonance (NMR) spectrometry. Recycled glycerol from a local two-stage biodiesel production process was compared to commercial glycerol.
The results showed that magnesium and calcium oxide were used as an effective catalyst mixture to produce monoacyl glycerol from biodiesel waste. The study also showed that magnesium turnings were a superior catalyst for glycerolysis of triglycerides, producing a higher yield and faster reaction than magnesium powder, and that calcium oxide can be used as a promoter. The reaction with recycled glycerol proceeded at a rate similar to the one with commercial glycerol. As a result of the study, researchers have shown that glycerolysis of triglyceride under mild conditions is possible with inexpensive catalysts at a pilot scale. The low cost of the catalyst combined with selectivity and high yield should provide substantial benefits of this reaction over the current commercial processes.
2. Production of Lithium Catalysts, High Quality Glycerol and Lithium Grease
In biodiesel production plants, 10% of the raw oil mass is released as a glycerol product which is complex and expensive to utilize. The objective of this study was to produce low cost lithium glyceroxide base catalyst that is easily prepared from aqueous solutions of lithium hydroxides and glycerol. The proposed catalyst can be prepared on site and is less costly to transport. Glycerol produced by this reaction is free of both soap and catalyst.
The objective of this research was to develop a continuous process for the production of lithium glyceroxide at a pilot scale. The reaction with pure and crude glycerol, a coproduct from the transesterification of TG, was studied. The variables investigated included: reaction temperature, mixing intensity and reactant flow rates. The experiments were conducted in a Rototherm, a continuous thin film evaporator. Refined and bleached canola oil and recycled glycerol were locally sourced. Both Nuclear Magnetic Resonance (NMR) spectrometry and an Infrared Spectrometer were used for analysis.
In the study, the glycerol phase was separated after the transesterification reaction catalyzed by lithium glyceroxide/hydroxide. Stearic acid or 12-hydroxystearic acid was dissolved in distilled water and added to mixture of lithium glyceroxide/hydroxide and glycerol. The mixture was stirred at a constant speed (1,000 rpm) for 30 min. The white solid precipitation was filtered and washed several times with acetone to remove water and glycerol, then dehydrated under vacuum for 3 h at room temperature.
The results of the study showed the lithium glyceroxide/hydroxide catalyst is easy to prepare without involving complicated synthesis processes, safe to ship and comparable in activity with sodium methoxide in catalyzing the transesterification reactions. It can be prepared on site used as an alternative solution to lower the cost of biodiesel plant operation without compromising production efficiency. As a result of the project, researchers have scaled up the production of lithium catalysts, high quality glycerol and lithium grease. The resulting improved glycerol and lithium grease have substantially more value than the crude glycerol produced by a normal biodiesel reaction.
3. Trans-vaccenic Acid (TVA) for Clinical Trials
The major trans-fatty acid found in ruminant meat and milk is trans-vaccenic acid (TVA, trans-11 C18:1) which has been reported to alter lipid metabolism in mammals. Biosynthetic evidence indicates that TVA is readily converted into conjugated linoleic acid (CLA) by enzymes. Dietary TVA may affect metabolism after conversion to CLA or it may act directly. There are no stereoisomerically pure forms of TVA commercially available for nutritional studies of TVA. Canola is a potential source of cis-vaccenic acid and, in the future, should TVA prove to be an effective product researchers could devise processes to recover canola cis vaccenic and convert it to TVA.
In this study, researchers introduced a new methyl ester route to stereoselective preparation of trans-vaccenic acid. The key step involves a Wittig reaction of methyl ester yilid and heptanal. Due to the good solubility of this methyl ester yilid, this reaction was achieved without solvent and thus larger scale reactions are possible. Oleic acid was used as internal standard. Two kilograms of TVA (94.9% of TVA and 1.8% of cis-vaccenic acid) were prepared using this novel approach. Researchers also developed the Good Manufacturing Process (GMP) process for TVA production at a pilot scale.
As a result of the study, researchers completed the first GMP production run at the pilot plant, scaling up production of TVA. This marks an important step in the evolution of the Bioprocessing Pilot Plant as researchers have demonstrated the capability of conducting processes for human trials.
Scientific publications.
Sun, G, Y Li, Z Cai, Y Teng, Y Wang, MJT Reaney (2017) K2CO3-loaded hydrotalcite: A promising heterogeneous solid base catalyst for biolubricant base oil production from waste cooking oils. Applied Catalysis B: Environmental. 209, 118–127.
Pradhan, S, J Shen, S Emami, P Mohanty, SN Naik, AK Dalai, MJT Reaney (2017) Synthesis of potassium glyceroxide catalyst for sustainable green fuel (biodiesel) production. Journal of Industrial and Engineering Chemistry 46, 266–272.
Dhabhai, R, E Ahmadifeijani, AK Dalai, MJT Reaney (2016) Purification of crude glycerol using a sequential physico-chemical treatment, membrane filtration, and activated charcoal adsorption. Separation and Purification Technology 168, 101-106.
Jacome-Sosa, MM, C, Vacca, R Mangat, A Diane, RC Nelson, MJT Reaney, J Shen, JM Curtis, DF Vine, CJ Field, M Igarashi, D Piomelli, S Banni, SD Proctor (2016) Vaccenic acid suppresses intestinal inflammation by increasing anandamide and related N-acylethanolamines in the JCR:LA-cp rat. Journal of Lipid Research 57(4), 638–649.