Prepared by :

Supervisors :

Nihal REMEK CENGZ

Prof. Dr. Mithat YKSEL
Prof. Dr. Levent BALLCE
Prof. Dr. Mehmet SALAM

Submission Date: 27.05.2010

Contents

World Energy Prospects

Energy resources and renewable

alternatives

Biofuel Production Technologies

Biomass to high added value chemicals

Recent Studies on Glycerol

2

Contents-2

Biodiesel & Glycerol potential

Processes to produce hydrogen from glycerol

Supercritical water

Project materials (including analytical &

instrumental equipments)

Experimental Results
3

World Energy Prospects

Increase in
Population

60%

Energy demand

63160%

Source:
CIA's The World Factbook
World POPClock Projection, U.S. Census Bureau
Energy Sources, 26:1119-1129,2004

Other concerns
Pollution , Resource depletion, Climate Change

Energy Sources
* Fossil energy sources like petroleum,
natural gas and coal which have limited reserves .
* The first energy crisis emerged in 1973 was
seriously showed that these nonrenewable
energy sources will not meet the energy demand
of the world.
6

Energy Sources-2

Renewable Energy

Renewable energy sources like

solar energy, hydropower, and
biomass attract interest of many
researchers. These can provide
the source of renewable liquid,
gaseous and solid fuels.

Renewable energy sources

Summary of energy resources consumption in United States, 2004

By 2030, bio-energy, 15-20% energy consumption
Source:
USDA-DOE, 2005, http://www.eere.energy.gov/biomass/publications.html.

Overview of Biofuel Production

Technologies
Biofuel type

Specific name

Feedstock

Conversion Technologies

Pure vegetable oil

Pure plant oil (PPO), Oil crops (e.g. rapeseed, oil Cold pressing extraction
Straight vegetable oil palm, soy, canola, jatropha,
castor, )
(SVO)

Biodiesel

Bioethanol
Biogas
Bio-ETBE

- Oil crops (e.g. rapeseed, oil - Cold and warm pressing

Biodiesel from
energy crops: methyl palm, soy, canola, jatropha, extraction, purification,
and ethyl esters of
castor, )
and transesterification
fatty acids
- Waste cooking/frying oil
- Hydrogenation
- Biodiesel from
waste
Conventional bioSugar beet, sugar cane,
Hydrolysis and
ethanol
grain
fermentation

Upgraded biogas

Biomass (wet)

Anaerobic digestion

Bioethanol

Chemical Synthesis

First-High Level Biofuel Conference in Africa

Addis Ababa, Ethiopia
30th July - 1st August 2007

10

Biomass to high added value chemicals

Biomass

Extraction
of chemicals
Proteins
Vitamins
Fragrances
Pharmaceuticals

Biodiesel
production

Sugar
fermentation

Thermochemical
conversion

Glycerol

Ethanol
Lactic acid

Bio-SNG

Chemicals

Chemicals

Chemicals

11

Recent Studies on Glycerol

Catalytic and Non-catalytic Supercritical Water Gasification of Microalgae and

Glycerol, Anand G. Chakinala,* Derk W. F. (Wim) Brilman, Wim P.M. van
Swaaij, and Sascha R. A. Kersten, Institute, UniVersity of Twente, PO Box 217,
7500 AE Enschede, The Netherlands, Ind. Eng. Chem. Res. 2010, 49, 11131122

Catalytic gasification of glycine and glycerol in supercritical water, Donghai Xu,

Shuzhong Wang*, Xin Hu, Chongming Chen, Qingming Zhang,Yanmeng Gong,
State Key Laboratory of Multiphase Flow in Power Engineering, Xian Jiaotong
University, Xian, Shaanxi Province 710049, China , International Journal of
Hydrogen Energy, 3 4 ( 2 0 0 9 ) 5 3 5 7 5 3 6 4

Ionic reactions and pyrolysis of glycerol as competing reaction pathways in nearand supercritical water, W. Bu hler, E. Dinjus, H.J. Ederer *, A. Kruse *, C.
Mas, Institut fur Technische Chemie CPV, Forschungszentrum Karlsruhe, PO Box 3640, 76021
Karlsruhe, Germany, Received 9 February 2001; received in revised form 20 July 2001;
accepted 23 August 2001
12

Recent Studies on Glycerol-2

Catalytic dehydration of glycerol in sub- and supercritical water: a new

chemical process for acrolein production, L. Ott, M. Bicker and H. Vogel*,
Received 5th May 2005, Accepted 14th November 2005, First published as an
Advance Article on the web 5th December 2005 DOI: 10.1039/b506285c

Catalytic gasification of glycerol in supercritical water , Anna Maya, Joan

Salvada,b, Carles Torrasb, Daniel Montana,b,a Department dEnginyeria
Qumica, Universitat Rovira i Virgili (URV), Av. Pasos Catalans 26, 43007
Tarragona, Spain, b Bioenergy and Biofuels Division, Catalonia Institute for
Energy Research (IREC), Av. Pasos Catalans 16, 43007 Tarragona, Spain,
Received in revised form 24 March 2010, Chemical Engineering Journal

13

Recent Studies on Glycerol-3

Value-added Utilization of Crude Glycerol from Biodiesel Production: A

Survey of Current Research Activities, Naresh Pachauri, Brian He, Biological
and Agricultural Engineering, University of Idaho, Moscow, Idaho 83844-2060 , An
ASABE Meeting Presentation, Paper Number: 066223, Portland, Oregon, 9 - 12
July 2006

Chemoselective catalytic conversion of glycerol as a biorenewable source to

valuable commodity chemicals, Chun-Hui (Clayton) Zhou,*ab Jorge N.
Beltramini,b Yong-Xian Fana and G. Q. (Max) Lu*b, Received 8th October
2007, First published as an Advance Article on the web 22nd November 2007

14

Biodiesel

Environmental benefits, lower

emission of carbon monoxide
and carbon dioxide compared to
regular diesel (National
Biodiesel Board, 2004).

From vegetable sources

(soybean, sunflower, canola,
cotton seed, rapeseed and palm
oil) and animal fats.
15

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

16

Biodiesel Production

Depending on the feedstock and process

design, biodiesel production results in several
by-products:
Crude glycerol
Washwater
Press cake
Crop residues

18

TRANSESTERIFICATION
METHANOL + KOH

WASTE
OIL

CRUDE
BIODIESEL
BIODIESEL

OIL CROPS
ALGAE

Oil
pressing

PRESS
CAKE

VIRGIN
OIL

Washing

CRUDE
GLYCEROL

WASHWATER

19

Glycerol Potential
Glycerol ;
is a polyalcohol ,
clear, colorless liquid
hygroscopic
odorless
used in food and cosmetics
synthesized chemically from
epichlorohydrin, derived from
propylene or biochemically by
microbial fermentation
20

Glycerol Potential
600 000 tones in Europe in 2006

Molecular
formula

Molar mass
glycerol market price has
Density
decreased tofrom $ 1/L to $ 0.7/L by
2010

C3H5(OH)3
92.09382 g/mol
1.261 g/cm

cannot be used in cosmetics or

food unless a costly refining process
glycerol represents around 10
wt% of the plant product
21

Processes to produce Hydrogen

from Glycerol
To improve the economics of biodiesel
production and also to improve the glycerol
market, it is important to process glycerol into
value-added products.
Pyrolysis
Steam Gasification
SCWG
22

23

Supercritical Water, SCW

The water which is at above the critical pressure
and temperature of water (Tc: 374C and Pc: 221 bar)
is called as supercritical water.
Under these conditions,
dielectric constant,
viscosity,
density
ion product of water

24

In such conditions, water undergoes significant variations of its physical properties,

like decreasing of the dielectric constant, thermal conductivity, ion product and
viscosity
while the density only decreases slowly.

25

Supercritical Water, SCW-2

A supercritical fluid possesses the
characteristics of both fluid and gaseous
substances: the fluid behavior of dissolving
soluble materials, and the gaseous behavior
of excellent diffusibility.

26

Supercritical Water, SCW-3

Thus, supercritical water;
acts as a homogeneous non-polar
solvent of high diffusivity and high
transport properties,
able to dissolve any organic compounds
and gases.
acts a good solvent also for gases and
nonpolar organic materials,
also serves as a reactant apart from
being a solvent in many reactions,
behaves as a catalyst in many acid or
base catalyzed organic reactions,
can start the radical reactions at above
critical pressure and critical temperature.
27

Phase Change of Water in a Vicinity of

its critical point

28

Biofuel Applications: Gases

Hydrogen: can be used in fuel

cells for generating electricity

Methane: can be combusted

directly or converted to ethanol

29

Hydrogen; Energy Carrier

Hydrogen is not an energy source and not a

primary energy existing freely in nature.
It is a secondary form of energy that has to be
manufactured like electricity. It is an energy
carrier.
Combustion product of hydrogen is clean,
which consists of water and a little amount of
nitrogen oxides.
30

SCW reaction pathways

Figure 6 : Simplified free radical reaction pathway

High T, low-density range free radical

reactions are preferred, (gas phase rxns)

31

SCW reaction pathways-2

At low T and high P, polar and ionic
reaction pathways dominate (liquid phase rxns)

32

Components Formation Pathways

Methanol is formed only by the radical
Allyl alcohol, which is the second frequent product at high temperatures, is also formed
only by the free radical mechanism
Acetaldehyde is the main product at nearly all conditions. It is formed by an ionic and
a free radical pathway
Acrolein again is formed by ionic and by radical reaction steps
Formaldehyde in the ionic mechanism is formed by the same reactions as
acetaldehyde.
Carbon monoxide, Carbon dioxide, Hydrogen is formed by the reaction of radicals
Propionaldehyde The radical pathway which is very complicated. One of the paths
starts from allyl alcohol

33

Supercritical Water Gasification

Advantages:

High gasification efficiency

High hydrogen yield
Formation of char and tar is suppressed
Carbon monoxide formation is negligible
or (CO + H2O
CO2 + H2)

Complete conversion
Clean product gas
34

Materials
Feedstock:

Pure glycerol, 50g/L

Crude glycerol

Content of Crude Glycerol

Glycerol

wt %

Methanol

25

Sodium Hydroxide

1.00

Stearic Acid

0.125

50

35

Catalysts Used in the Experiments

In this study, walnut and hazelnut activated
carbon catalysts were used as primary catalysts.
Also, Cobalt impregnated forms of these active
carbons of hazelnut and walnut shells were used as
secondary catalysts for comparison.

Figure 1: SEM photo of activated carbon

36

Preparation of Co Impregnated
Activated Carbons
The hazelnut, walnut or another
raw material is mixed with ZnCl2
and waited 24 h.
It is placed into a special furnace
with a retort. Retort is heated up
to 750 oC step by step. After it is
cooled down, it is waited in a
%10 HCl solution, and washed
with pure water.
These preparation is done by our
research group

37

38

Equipments Used for Analysis of SCWG

Products
Products
Gaseous

Compounds

Equipment

CO, CO2, H2, CH4 and C2-C4

Gas Chromatography with

hydrocarbons

FID-TCD detectors

Aldehydes

Aqueous

HPLC with UV-VIS

detector

Total organic carbon

TOC

Phenol and its derivatives

Colorimeter

Qualitative liquid phase analysis

GC-MS
39

Gas Chromatography
HP Molesieve
(30 m long x 0.53 mm inside diameter x 50
Column

mm film thickness)
HP Plot Q
(30 m long x 0.53 mm inside diameter x 40
mm film thickness)

Stationary Phase

Impregnated silica

Mobile Phase

Argon

Detectors

Detector Temperature
Injection Temperature
Temperature
Program

Flame Ionization Detector (FID)

C2H6

Thermal Conductivity Detector (TCD)

FID: 280 C

C2H4

C3H6

C3 H 8

CH4

C4s

TCD: 250 C
100 C
45 C isothermal 2 min.
40 C/min 60 C isothermal 14 min.
10 C/min 250 C isothermal 10.5 min.

H2
CO2

N2, O2, CH4, CO

40

Column

Intersil ODS-3 (250 mm L 4.6

I.D.

Mobile Phase

A: Water
B: Methanol

Flowrate

1 mL/min

Detector

UV

Wavelength

365 nm

High Performance
Liquid Chromatography

Column
Temperature

30 C

Detector
Temperature

40 C

Injection Volume

20 L

Low temperature gradient

0. min. 35% A and 65% B

program of mobile phase

5. min. 35% A and 65% B

15. min. 15% A and 85% B
30. min. 10% A and 90% B

41

Total Organic Carbon

Analyzer

Colorimeter

42

Column

GC-MS
(Gas Chromatography-Mass
Spectroscopy)

Stationary
Phase

HP-FFAP (19091F-105)
50 m x 200 m x 0.3 m
Polyethylene Glycol TP

Mobile Phase

Helium

Detectors

5975C VL MSD type Triple-Axis Detector

Detector
Temperature

205 C

Mode: Splitless
Heater: 260 C
Pressure: 26.874 psi
Front Injector

Total Flow: 53.638 mL/min

Septum Purge Flow: 3 mL/min
Gas Saver: 20 mL/min after 2 min
Purge Flow to Split Vent: 50 mL/min at 2 min
Initial Temperature: 80 C
Pressure: 26.874 psi

Column

Flow: 0.63841 mL/min

Average Velocity: 19.592 cm/sec
Hold-up Time: 4.2534 min

Oven
Temperature
Program

80 C isothermal 1 min.
20 C/min to 120 C isothermal for 5 min.
6.13 C/min to 205 C isothermal for 40 min.
Run Time: 61.866 min

43

Experimental

Feed: 15 mL feedstock solution

Reaction time: 1 hour
Temperatures: 300, 400, 500 and 600 C
Totally 40 experiments with two feedstock
solutions and 4 different catalysts.

44

PURE GLYCEROL PRODUCT YIELDS

45

CRUDE GLYCEROL PRODUCT YIELDS

46

PRODUCT YILEDS OF
PURE AND CRUDE GLYCEROL BY
THE CATALYSTS

47

PURE GLYCEROL WITH WALNUT

ACTIVATED CARBON CATALYSTS

48

CRUDE GLYCEROL WITH WALNUT

ACTIVATED CARBON CATALYSTS

49

PURE GLYCEROL WITH HAZELNUT

ACTIVATED CARBON CATALYST

50

CRUDE GLYCEROL, HAZELNUT

ACTIVATED-C PRODUCT YIELDS

51

PURE GLYCEROL CO-IMPREGNATED

HAZELNUT ACTIVATED CARBON CATALYST

52

CRUDE GLYCEROL CO-IMPREGNATED

HAZELNUT ACTIVATED CARBON CATALYST

53

PURE GLYCEROL WITHOUT CATALYST

54

PURE GLYCEROL WITH WALNUT ACTIVATED

CATALYST

55

PURE GLYCEROL HAZELNUT ACTIVATED CARBON

CATALYST

56

PURE GLYCEROL WITH COBALT IMPREGNATED

HAZELNUT ACTIVATED CARBON CATALYST

57

CRUDE GLYCEROL WITHOUT

CATALYST

58

CRUDE GLYCEROL WITH WALNUT

ACTIVATED CATALYSTS

59

CRUDE GLYCEROL WITH HAZELNUT

ACTIVATED CARBON CATALYST

60

CRUDE GLYCEROL WITH CO

IMPREGNATED HAZELNUT

61

CONCLUSION

The objective of this study was to investigate the effect

of the gasification temperature and type of catalyst
The gasification of glycerol leads to formation of gases
consisting of mainly hydrogen, carbon dioxide and
methane.
The gas yield is very sensitive to the reactor
temperature. At high T, gas yield increases and types
of organic compounds and their amounts in aqueous
phase decrease.
For higher H2 yields, Co-Impregnated Activated
Carbon sould be used. Walnut and Hazelnut ActivatedC catalysys showed similar gasification activity.

62

THANK YOU FOR YOUR

ATTENTION.
QUESTIONS?

63