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

The lecture is designed for 4th Chemical Engineering Students, UAM

Biofuel Industry Introduction, Production Processing

& Characterization of Product

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: 3rd 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

• Hiking of crude oil prices

• Diesel fuel shortage

• Excessive greenhouse gases emissions of fossil fuels

Introduction

Incentives for Bio-energy sources

• 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

Oil bearing plants

Agricultural crops and residues

Woody biomass

Industrial and

municipal waste

Biomass resources

Harvesting,

collection,

handling,

and storage

Supply systems Conversion

Biochemical (fermentation)

Thermochemical (gasification)

Chemical (transesterification)

End products

Transportation fuels (biodiesel, bioethanol)

Heat Electricity

Solid fuels (wood pellets, charcoal)

High added-value chemicals

(pharmaceuticals, polymers)

Physical chemical (extraction)

byproducts

WORLD expertise

UNIDO and FAO FAO WORLD

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 bio-ethanol

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 First Generation of Biofuels

Biofuel type Specific name Feedstock Conversion Technologies

Bioethanol Cellulosic bioethanol Lignocellulosic biomass and biowaste

Advanced hydrolysis & fermentaion

Biogas SNG (Synthetic Natural Gas) Lignocellulosic biomass

and residues

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

Overview of Biofuel Production Technologies Second/Third* Generation Biofuels

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

Glycerol

Sugar fermentation

Thermochemical conversion

• Ethanol • Lactic acid

Chemicals

• Proteins • Vitamins • Fragrances • Pharmaceuticals

Bio-SNG

Chemicals 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 (CO2 , CO, NOx, SO2, 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.

Glycerol

O O O Me Me Me

O = O = O =

HO

HO

HO

Biodiesel (Methyl Ester Alcohol)

3 ester alcohol + 1 glycerine

O = O O

O = O

O =

Triglyceride

1 triglyceride + 3 alcohol

3 MeOH

KOH Catalyst

catalyst

Transesterification Reaction

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.

Molecular Structure

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 K-OR + H2O

Acid + KOH Soap + water

It results in loss of catalyst and reduction in yield

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

Feedstock Issues

Process Issues

• 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.

Type of Alcohol

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

• Base Catalysts: NaOH, KOH, NaMeO

• Acid Catalysts: H2SO4, PTSA, MSA, H3PO4, CaCO3

• Typical base concentrations are : NaOH/KOH – 0.3 to 1.5 % Na MeO – 0.5 % or less

• Sulfated Zeolites & Clays • Hetro-poly acids • Metal Oxides, Sulfates • Composite materials

Homogenous

Heterogeneous 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.

Batch, Base Catalyzed Process

TG

Alcohol

Catalyst

Batch Reactor

Ester

Crude Glycerol

Alcohol

Alcohol

Wat

er

Water

Neutralized Glycerol

Wash Water

Dryer

Biodiesel

Water

Acid

0.5MT/DAY BIODIESEL UNIT

Vacuum Drier Separating Vessel Reaction Vessel

Washing Vessel

Control Panel

Oil Tank

Methaoxide Vessel

Skid

Motor & Gear Box

Motor& Gear Pump Development Cost : US $ 7000

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

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.

Preferred method for High FFA feeds: Acid Catalysis followed by base catalysis

Methanol +

KOH

Vegetable Oil Storage

Tank 1500 Kg

Methanol +

H2SO4

Motor

Storage Tank

500 Ltrs.

Motor

Biodiesel Storage

Tank 1000 Ltrs.

P2

SV2

Rea

cto

r 6

00

Ltr

s.

SV2

Air

SVO

P1

SV3

P3

Sett

lin

g T

ank

1

00

0 L

trs.

Vaccum Drier

Separating Column 500 Ltrs./ Charge

Washing Column 500 Ltrs./ Charge

Vaccum

Drier

Glycerol Storage Tank 500 Ltrs.

Transesterification Reactor, 500Lts./Charge

P4

P5 P6 P7 P8

Biodiesel Unit

1tpd Capacity

Experimental set-up

Methanol recovery

Heterogeneous Catalysis of Biodiesel Production

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 65oC and 350 rpm were sufficient to obtain 96.7% FAME conversion. The catalyst was uncalcined Sodium orthosilicate (Na4SiO4).

SCO Tank

Acid Tank

Catalyst

Storage

Methanol Tank

Mixer

E-10P-2

P-3

Esterification

Reactor

P-5

P-6

P-7

P-10

P-11

P-12

Decanter

Transesterification

Reactor

P-14

Treated SCO

P-16

Decanter

Crude

Glycerol

layerP-6

FiltrationSCO Drying

Distillation I

Methanol

(for recycling)

E-25

P-29

Extraction

Column

HeaterWater

P-30

P-31

P-32

Biodiesel

Drying

P-33

P-34

Biodiesel

Tank

Extraction

Column

DryerP-35

P-36

Glycerol

Tank

Water

Hydrocyclone

P-41

Recovered

catalyst

Product

mixture

P-44

FAME layer

V-3

P-47

P-48

Biodiesel production process using heterogeneous catalysts (i.e. Na4SiO4)

Catalyst Preparation

rocks fine particles

Glycerin

Biodiesel

Operating conditions: 9/1 M/O, 2h reaction time, 5.0%wt. PR concentration at 65oC and

350 rpm

Operating conditions: 6/1 M/O, 2h reaction time, 1.5%wt. KOH concentration at 65oC and

350 rpm

Generation of biodiesel and glycerol layers

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.

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)

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

International prices of feedstocks in 2018

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 @ 15oC g/ml 0.86 0.88 0.864 0.86-0.90 0.85 0.86-0.90

Kinematic viscosity @ 40oC

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 oC 167 162 189 120 >60 >101

Cloud point oC 9 -1 -3 31 13 -3 to14

Pour point oC 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 stability @110oC

h 1.2 3.95 11 min. 10 min. - 3 min.

Qualifications of biodiesel produced from various feedstock’s

Oleo chemicals Production

It is the time…

Oleo chemical Industry

24 million tons in 2016, and will grow with a rate of 7% in 2017

Malaysia and Thailand represent 70% of global market

Fatty Acids

Fatty Alcohols

Fatty Amines

Fatty Acids Methyl Esters “Biodiesel”

Glycerol

Fatty alcohols

(Detergents) 55%

Fatty acids (Soaps)

30%

Biodiesel and

Lubricants 15%

Oleo chemical is the sum of the transesterification and hydrolysis processes to convert the natural oils into sustainable products.

NA

TU

RA

L O

ILS

Fatty Alcohols

Glycerin

Fatty Acid Methyl Esters “Biodiesel”

Fatty Acids

Transesterification

Splittin

g E

sterification

Direct

hy

dro

genatio

n

Am

inatio

n

Hyd

rogen

ation

Neutralization

Esterification

Ethoxylation

Esterification

Amination Fatty Amines

F.A. ethoxylates

F.A. esters

F.A. liquid soap

Triacetine

Partial glycerides

Non-ionic surfactant

Esters

F. O

H su

lfates

F. O

H eth

oxylates

Alk

yl chlo

rides

Alk

yl ether su

lfate

Alk

yl etho

xylate

Alk

yl ether

carbo

xylate

Am

ine o

xide

F.A

. Alk

ano

lamid

es

Hyd

rogen

ated lan

olin

Plant Source Seed oil content

(% oil by wt in

biomass)

Oil yield

(L oil/ha year)

Land use

(m2 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

• 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.

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.

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

Any questions?