Biofuel Industry Introduction, Production Processing & Characterization of Product

Biofuel Industry Introduction, Production Processing & Characterization of Product The lecture is designed for 4 th Chemical Engineering Students, UAM Presented by Dr. Eng. Hassan I. El- Shimi Assistant Professor, Chemical Engineering Department, Cairo University, Egypt Phone: +2 01024497780 E-mail: hassan.ibrahim@eng1.cu.edu.eg Madrid, Spain in 18 March 2019

Professor biography Hassan I. El Shimi is a Ph.D. Holder. Assistant Professor at Chemical Engineering Department, Faculty of Engineering, Cairo University, Giza, Egypt. B.Sc. in 2010, M.Sc. in 2013 and Ph.D. in 2016 from Cairo University, Egypt. Researcher: Published more than 25 papers in reputed journals and conferences. For citations and copies of some of El Shimi' papers, please visit my Cairo Scholar and ORCID pages. The research area includes Renewable Energy Production, Wastewater Treatment, Desalination, Recycling, Oleochemicals Production, Feasibility Studies, and Plant and Process Design. Member in the federation of Arab Engineers. Certified Environmental Expert by Ministry of Environmental Affairs, Egypt. Dr. Eng. Hassan I. El Shimi Assistant Professor Department of Chemical Engineering, Cairo University, Egypt Address: 3 rd Floor Chemical Building, Faculty of Engineering, Gamaa Str., Giza Square, Giza, Egypt E-mail: hassan.ibrahim@eng1.cu.edu.eg E-mail: hassanshimi@gmail.com Tel./Fax.: +201024497780

Introduction

Introduction Incentives for Bio-energy sources Hiking of crude oil prices Diesel fuel shortage Excessive greenhouse gases emissions of fossil fuels Now, the world consumption of petroleum-based fuels is 1,062 million tons, and it is expected to rise to an estimated 2,053 million tons in 2030. Renewable energy represents 20% of total electricity production worldwide. Bioethanol (88mt/y) and Biodiesel (20mt/y) are the main biofuels.

Biofuel value chain and WORLD radius of attention Biomass resources Supply systems Conversion End products Oil bearing plants Agricultural crops and residues Harvesting, collection, Chemical (transesterification) Physical chemical (extraction) Transportation fuels (biodiesel, bioethanol) Solid fuels (wood pellets, charcoal) Woody biomass Industrial and municipal waste handling, and storage Biochemical (fermentation) Thermochemical (gasification) Heat Electricity High added-value chemicals (pharmaceuticals, polymers) byproducts FAO UNIDO and FAO WORLD expertise WORLD

Overview of Biofuel Production Technologies First Generation of Biofuels Biofuel type Specific name Feedstock Conversion Technologies Pure vegetable oil Pure plant oil (PPO), Straight vegetable oil (SVO) Oil crops (e.g. rapeseed, oil palm, soy, canola, jatropha, castor, ) Cold pressing extraction Biodiesel - Biodiesel from energy crops: methyl and ethyl esters of fatty acids - Biodiesel from waste - Oil crops (e.g. rapeseed, oil palm, soy, canola, jatropha, castor, ) - Waste cooking/frying oil - Cold and warm pressing extraction, purification, and transesterification - Hydrogenation Bioethanol Conventional bioethanol Sugar beet, sugar cane, grain Hydrolysis and fermentation Biogas Upgraded biogas Biomass (wet) Anaerobic digestion Bio-ETBE Bioethanol Chemical Synthesis

Overview of Biofuel Production Technologies Second/Third* Generation Biofuels Biofuel type Specific name Feedstock Conversion Technologies Bioethanol Cellulosic bioethanol Lignocellulosic biomass and biowaste Biogas SNG (Synthetic Natural Gas) Lignocellulosic biomass and residues Advanced hydrolysis & fermentaion Pyrolysis/Gasification Biodiesel Biomass to Liquid (BTL), Fischer-Tropsch (FT) diesel, synthetic (bio)diesel Lignocellulosic biomass and residues Pyrolysis/Gasification & synthesis Other biofuels Biomethanol, heavier (mixed) alcohols, biodimethylether (Bio-DME) Lignocellulosic biomass and residues Gasification & synthesis Biohydrogen Lignocellulosic biomass and biowaste Gasification & synthesis or biological process

Overall biorefinery concept - a new chemical industry sector - equivalent to the petrochemistry concept

Biomass to high added value chemicals, an emerging chemistry Biomass Extraction of chemicals Biodiesel production Sugar fermentation Thermochemical conversion Proteins Vitamins Fragrances Pharmaceuticals Glycerol Chemicals Ethanol Lactic acid Chemicals Bio-SNG Chemicals Biodiesel is the fastest growing sub-sector of the Oleochemicals industry.

Biofuel/biofuel production technology selection criteria Technological criteria (energy content, non renewable energy consumed, availability, carbon residue, sulfur content, viscosity, density, efficiency, scale up, ) Financial criteria (static, dynamic, risk) Environmental criteria (CO 2, CO, NO x, SO 2, etc.) Socio-economic criteria

Comparison of technologies Economic versus environmental aspects Source: IEE Leipzig, 2007

Biodiesel

What is Biodiesel? Biodiesel, a fuel composed of mono-alkyl esters of long chain fatty acids derived from variety of vegetable oils or animal fats, designated as B100, and confirming to different quality standards e.g. ASTM D 6751, EN14214 or IS 15607.

Transesterification Reaction 1 triglyceride + 3 alcohol catalys t 3 ester alcohol + 1 glycerine O = O O = O O = O 3 MeOH HO Me Me Me O = O O = O O = O HO KOH Catalyst HO Triglyceride Glycerol Biodiesel (Methyl Ester Alcohol)

Molecular Structure Fats and oils have quite big molecules with a spinal of glycerol on which are bond three fatty acid rests. By the transesterification, the fatty acid rests are removed from the glycerol and each is bond with methanol. The products are one mole glycerol and three mole of fatty acid methyl ester.

Issues Related to Base Catalyzed Transesterification Process Feedstock Issues FFA Water Process Issues Type of Alcohol Molar Ratio Catalyst Reaction time & temperature Agitation

Feedstock Issues 1. Free Fatty Acids (FFA) Free Fatty acids in the oils react with alkaline catalyst to form soaps. R-OH + KOH Acid + KOH K-OR + H2O Soap + water It results in loss of catalyst and reduction in yield

Feedstock Issues 2. Water Water deactivates the catalysts. Drying of oil is required. Water hydrolyses fats to form free fatty acids. Free fatty acids react with alkali catalysts forms soaps Soaps semi solid mixture glycerol separation

Process Issues Type of Alcohol Methanol, Ethanol, Butanol etc Methanol commercially used In methanolysis, emulsion forms and separated into lower glycerol portion and upper ester portion. Reaction time is small In ethanolysis, emulsions are stable and requires more complicated separation and purification process. Reaction time is large Typical alcohol: TG ratio is 6:1 for base catalyzed reactions.

Catalyst? Chemical marriage brokers The presence of a catalyst facilitates reactions that would be kinetically impossible or very slow without a catalyst

Various Catalysts used in Biodiesel Production Homogenous Base Catalysts: NaOH, KOH, NaMeO Acid Catalysts: H 2 SO 4, PTSA, MSA, H 3 PO 4, CaCO 3 Typical base concentrations are : NaOH/KOH 0.3 to 1.5 % Na MeO 0.5 % or less Heterogeneous Sulfated Zeolites & Clays Hetro-poly acids Metal Oxides, Sulfates Composite materials El Shimi investigated Na4SiO4 and Phosphate Rock as optimum catalysts in biodiesel manufacture (Oct. 2016)

Reaction time, Temperature & Agitation Transesterification reaction will proceed at ambient (30 C) temperatures but needs 4-8 hours to reach completion. Reaction time can be shortened to 2-4 hours at 40 C and 1-2 hours at 60 C. Higher temperatures will decrease reaction times but require pressure vessels because methanol boils at 65 C. Better agitation should be adopted to accelerate reaction.

Water Batch, Base Catalyzed Process Alcohol Water Water TG Ester Alcohol Catalyst Batch Reactor Crude Glycerol Alcohol Wash Water Dryer Acid Biodiesel Neutralized Glycerol

0.5MT/DAY BIODIESEL UNIT Control Panel Motor & Gear Box Oil Tank Skid Methaoxide Vessel Washing Vessel Reaction Vessel Separating Vessel Vacuum Drier Development Cost : US $ 7000 Motor& Gear Pump

High FFA Feed Stocks Biodiesel feed stocks are classified by the amount of free fatty acids they contain: Refined vegetable oils < 0.05% Crude vegetable oil 0.5-5% Used Cooking Oil 2-7% Animal fat 10-30% Price decreases as FFAs increase but processing cost also increase Base Catalyzed Reaction not suitable for high FFA feeds because of soap formation. Most of the non-edible oils available Worldwide contains high FFA (2-12%) & to decrease the cost of biodiesel, it is imperative to utilize high FFA oil or fatty acids

Acid Catalyzed Processes Acid catalyzed processes are used for direct esterification of free fatty acids in a high FFA feedstock Limitations: Water formation by FFA + methanol ==> methyl ester + water High alcohol: FFA ratio required about 40:1 Large amounts (5 to 25 %) catalyst may be required

Preferred method for High FFA feeds: Acid Catalysis followed by base catalysis 1. Use acid catalysis for conversion of FFAs to methyl esters, until FFA < 0.5%. Acid esterification of FFA is fast (1 hour) but acid catalyzed transesterification is slow (2 days at 60 C). 2. Then, add additional methanol and base catalyst to transesterify the triglycerides.

Settling Tank 1000 Ltrs. Reactor 600 Ltrs. Biodiesel Unit 1tpd Capacity Vegetable Oil Storage Tank 1500 Kg Motor SV2 Air Methanol + H2SO4 SVO P1 SV2 P3 Vaccum Drier P2 SV3 Methanol + KOH Motor Biodiesel Storage Tank 1000 Ltrs. P8 P7 Vaccum Drier P6 P5 Storage Tank 500 Ltrs. Glycerol Storage Tank 500 Ltrs. Washing Column 500 Ltrs./ Charge Separating Column 500 Ltrs./ Charge P4 Transesterification Reactor, 500Lts./Charge

Heterogeneous Catalysis of Biodiesel Production Experimental set-up The optimum conditions detected by El Shimi et al. (2016): 6/1 M/O molar ratio, 3h reaction time, 5.87%wt. Catalyst amount at 65 o C and 350 rpm were sufficient to obtain 96.7% FAME conversion. The catalyst was uncalcined Sodium orthosilicate (Na4SiO4). Methanol recovery

rocks Catalyst Preparation fine particles P-7 Methanol (for recycling) Water P-30 Heater P-31 Catalyst Storage P-11 FAME layer P-33 Biodiesel Drying Distillation I Methanol Tank Filtration SCO Tank P-6 P-6 SCO Drying P-3 Mixer P-10 Esterification Reactor P-5 P-14 Decanter Treated SCO P-16 P-41 Transesterification Reactor Hydrocyclone Product mixture Recovered catalyst P-44 P-29 E-25 P-47 V-3 Decanter Crude Glycerol layer Extraction Column P-32 P-34 Biodiesel Tank P-12 P-48 Acid Tank P-2 E-10 Water P-35 Dryer Extraction Column P-36 Glycerol Tank Biodiesel production process using heterogeneous catalysts (i.e. Na4SiO4)

Biodiesel Glycerin Operating conditions: 9/1 M/O, 2h reaction time, 5.0%wt. PR concentration at 65 o C and 350 rpm Generation of biodiesel and glycerol layers Operating conditions: 6/1 M/O, 2h reaction time, 1.5%wt. KOH concentration at 65 o C and 350 rpm

Qualifications of Product Physico-chemical Properties of Biofuel

Sustainable Feedstock of Biodiesel Industry Sustainable Feedstock for Biodiesel Industry: is the feedstock that meets the needs of the biodiesel industry with environment, economic and social benefits. International prices of feedstocks in 2018 Feedstock Price US$/ton Waste Frying Oils (WFOs) 330 Crude Palm Oil 870 Jatropha Oil 500 Crude Soybean Oil 370 Castor Oil 1400 Rapeseed Oil 750 Jojoba oil 600 Algal Oils 2000 Fish oil 850 Yellow Grease (YG) <600 Animal Fats (AF) 1000 Spent Bleaching Clay (SBC) 300 Biodegradable Non-edible (non-conflict with food crisis) Non-expensive Available Obtaining a qualified biofuel Waste Fried Oil (WFO) Algae Oil (Oilgae) Jatropha Oil (JO)

Product Quality Product quality is important modern diesel engines are very sensitive to fuel. It is not biodiesel until it meets Quality Standards. Reaction must be >98% complete. Acid number for degrading, oxidized fuel Flashpoint for residual methanol Water & sediment fuel fouling, deposits Sulfated ash for residual catalyst Total glycerin for incomplete conversion, detects residual mono, di and tri glycerides Free glycerin inadequate fuel washing

Property Unit WCO Biodiesel Jatropha Biodiesel Algal Biodiesel Palm Biodiesel Petro-diesel standards Biodiesel ASTM-D 6751 Density @ 15 o C g/ml 0.86 0.88 0.864 0.86-0.90 0.85 0.86-0.90 Kinematic viscosity @ 40 o C cst 4.3 4.84 12.4 3.5-5.0 1.6-7.0 1.9-6.0 Esters content %wt. 98.3 96.7 98.1 96.5 min. - >96.5 Flash point o C 167 162 189 120 >60 >101 Cloud point o C 9-1 -3 31 13-3 to14 Pour point o C 5-6 -9 23-40 8-15 to 6 Diesel index - - 67 - >48 - Cetane index 60 51.6 70 38-40 40-55 48-65 Calorific value MJ/kg 43.4 37.2 45.63 36.9 >40.8 38-45 Total sulfur %wt. 0.003 Nil Nil 0.02 0.57 <0.05 Water content %wt. 0.04 Nil 39 (ppm) <0.065 0.00 <0.1 Ash content %wt. 0.001 0.025 Nil 0.01 0.02 <0.02 Acid index mg KOH/g oil 0.12 0.24 0.75 0.5 max. - <0.8 Free glycerol %wt. 0.005 Nil Nil 0.02 - <0.02 Total glycerol %wt. 0.17 0.17 Nil <0.25 - <0.24 Oxidation @110 o C Qualifications of biodiesel produced from various feedstock s stability h 1.2 3.95 11 min. 10 min. - 3 min.

Oleo chemicals Production It is the time

Oleo chemical Industry Oleo chemical is the sum of the transesterification and hydrolysis processes to convert the natural oils into sustainable products. Fatty Acids Methyl Esters Biodiesel Fatty Alcohols Fatty Amines Fatty Acids Glycerol Biodiesel and Lubricants 15% Fatty acids (Soaps) 30% Fatty alcohols (Detergents) 55% 24 million tons in 2016, and will grow with a rate of 7% in 2017 Malaysia and Thailand represent 70% of global market

Glycerin Esterification Non-ionic surfactant Partial glycerides Triacetine Splitting Fatty Acids Esterification Ethoxylation Neutralization Amination F.A. esters F.A. ethoxylates F.A. liquid soap Fatty Amines NATURAL OILS Esterification Transesterification F.A. Alkanolamides Amination Hydrogenated lanolin Direct hydrogenation Fatty Acid Methyl Esters Biodiesel Amine oxide Alkyl ether carboxylate Alkyl ethoxylate Alkyl ether sulfate Hydrogenation Fatty Alcohols F. OH ethoxylates Alkyl chlorides Esters F. OH sulfates

Oleochemicals industry is still a new business, growing throughout the world and only survives by being a part of the government policy. Feedstock is the controlling factor of biodiesel and oleochemical industry. Plant Source Seed oil content (% oil by wt in biomass) Oil yield (L oil/ha year) Land use (m 2 year/kg biodiesel) Biodiesel productivity (kg biodiesel/ha year) Corn 44 172 66 152 Soybean 18 636 18 562 Jatropha C. 28 741 15 656 Sunflower 40 1070 11 946 Castor 48 1307 9 1156 Palm oil 36 5366 2 4747 Microalgae (medium oil content) 50 97 800 0.1 86 515

Oleochemical Business Environment Considerably new business. Growing throughout the world. Environment / Energy security / Self sufficient. Only survive by government policy. Capacity way over demand. Availability of feedstock. Food vs. Fuel. FAME has its limitations. Sustainability.

Any questions? Hassan El Shimi http://scholar.cu.edu.eg/?q=hassanelshimi/