More Efficient Biodiesel Production Adam Harvey Process Intensification Group [PIG] School of Chemical Engineering & Advanced Materials Newcastle University

What is Biodiesel?? Methyl ester produced by reacting vegetable oils (triglycerides) with methanol. This requires a basic catalyst (usually NaOH). + 3 MeOH CH 2 CH CH 2 COO Triglyceride (vegetable oil) + CH 2 CH CH 2 HO Glycerol COOCH 3 Biodiesel (FAME) x 3 Lower Viscosity Cleaner Burning Catalyst

Why should/will biodiesel be used? 1.RENEWABLE 2.REDUCED LIFECYCLE CARBON DIOXIDE EMISSION 3.REDUCED POLLUTION: 1.Particulates!! 2.Carbon monoxide 3.Hydrocarbons 4.Sulphur compounds 4.Immediate effect: distribution network and engines are already in place 5.As a use for waste oils 6.Security of supply 7.Increased lubricity: increases engine lifetime 8.Non-toxic 9.Biodegradable

Project 1: Design of Intensified Biodiesel Plants Based on an “intensified” continuous reactor, known as the oscillatory flow reactor [OFR] Commercial project: development of a portable biodiesel plant: Use in developing countries where supply of transport fuels can be unreliable: Farmers producing their own transport fuel: an example of “distributed production” Demonstrator currently being fabricated. Further development of OFR for biodiesel to start soon.

Intensified, Portable Biodiesel Plant Vegetable Oil Methanol + Catalyst REACTORSETTLER Glycerol Tank Flash DRYPOLISH BIODIESEL TANK Portable Unit glycerol

Process Intensification: The Oscillatory Flow Reactor 15 minutes < 2h

Niche Application of the OFR length/diameter ratio much smaller than equivalent conventional PFR length/diameter ratio much smaller than equivalent conventional PFR plug flow RTD plug flow RTD effective two phase mixing of liquids effective two phase mixing of liquids Conversion of long residence time batch processes to continuous processes

Initial Dispersion Injection point Net flow

Net Flow In Net Flow Out Reaction’s Progress along Reactor

Commercial Demonstration Plant

Project 2: Solid Catalysts for Biodiesel 1.Reduce capital costs of biodiesel plants 2.Reduced running costs 3.Reduced waste (soap) 4.Reduce glycerol purification costs waste water, soap Oil Methanol Catalyst glycerol & methanol Reactor water washing, dry, polish etc Flash biodiesel Methanol recycle Neutralisation saltglycerol Current Process

Oil Methanol Flash biodiesel Methanol recycle glycerol Separation of catalyst from product via simple - filter Reactor Biodiesel Process using Solid Catalyst

Solid Catalysts (requirements) Robust (long lifetime) Active (2h reaction time or less) Inexpensive Available in bulk quantities Easy to manufacture Stable

Solid Catalysts Alkaline earth metal oxide substrates, doped with alkali metals, e.g.: – –LiCaO – –LiMgO – –KCaO – –KMgO Problem 1 i. i.Solubility of substrate ii. ii.Leaching of catalyst

Project 3: Biodiesel Directly from Seed: “Combined Extraction and Reaction” Would facilitate distributed production Successful demonstration for rapeseed solvent extraction + reaction Alcohols + Catalyst Biodiesel Glycerol Meal Oilseeds

Conventional Biodiesel Production 1. Farm 2. Oil Extraction 3. Conversion to Biodiesel Oilseed Growing Crushing Oilseeds Solvent Extraction Vegetable Oil Hexane Meal Reactor Methanol + Catalyst Downstream Processing Glycerol Biodiesel

Distributed Biodiesel Production 1. Farm Oilseed Growing Reactor Methanol + Catalyst Downstream Processing Glycerol Biodiesel Oilseed Cracking Meal

Reactive Extraction Successfully produced biodiesel directly from rapeseeds and jatropha nuts Successfully produced biodiesel directly from rapeseeds and jatropha nuts Now optimising the process Now optimising the process Downstream separation studies have begun Downstream separation studies have begun

Other Biodiesel Projects 1. Biodiesel from Algae: design of photobioreactors and whole process 2. Triglyceride cracking to produce biodiesel 3. Biodiesel from jatropha (reactive extraction using solid catalysts) 4. Study of cold flow properties

Acknowledgments Dr Jonathan Lee, CEAM, Newcastle Dr Jonathan Lee, CEAM, Newcastle PhD Students PhD Students Research exchange students Research exchange students Masters research students Masters research students

What about the Glycerol? ~15% (volume) of the total output of a biodiesel reaction is (impure) glycerol. What should be done with it? Cosmetics industry? Energy? “Renewable chemicals”: Propylene glycol, methanol, lactic acid, propane-1,3-diol, epichlorohydrin etc “Glycerochemistry”

1.Flow 2.Burning characteristics: 1.Trumpet Formation 2.Lacquer Formation 3.Pollution: acrolein formation (a.k.a. 2-propenal) “Acrolein is such a severe pulmonary irritant and lacrimating agent that it has been used as a chemical weapon during World War I.” & “suspected human carcinogen.”World War Ihumancarcinogen Why not burn the fats/oils directly ?