Biomass conversion in
Brazil: main challenges in
heterogeneous Catalysis
Eduardo Falabella Sousa-Aguiar
Carla A. F. Melo, Cristina P. B.
Quitete, Jefferson R. Gomes, Márcio
Portilho, Nei Pereira Jr.
EQ/UFRJ and
Petrobras/CENPES/CB
Bai Juyi
Introduction
The pillow's low, the quilt is warm, the body smooth
and peaceful,
Sun shines on the door of the room, the curtain not
yet open.
Still the youthful taste of spring remains in the air,
Often it will come to you even in your sleep.
Spring Sleep
Bai Juyi, famous chinese poet
Introduction
 Brazil is the 10th largest energy consumer in the world
and the largest in South America. At the same time, it is
an important oil and gas producer in the region and the
world's second largest ethanol producer.
Petroleum and sugar
cane represent the
major components
of the Brazilian
energy matrix
Introduction.
The main segments of the Traditional Oil Industry
PRODUCTION
EXPLORATION
OIL
Traditional Oil
Industry
TRANSPORTATION
REFINING
DISTRIBUTION
Introduction
The survival of the oil industry will depend on
many factors . Indeed, the refiner of the future will
have to face multiple challenges.
E. Falabella et al. Catalysis Today (Print), v. 234, 13-23, 2014.
Introduction
The main challenges of the refinining industry in
the future are the following:
Increasing stringent environmental regulation
Growing demand for cleaner fuels
Globalisation
Increase in the production of derivatives from
declining quality oil
Uncertainty about the consumer’s choice
 Growing pressure of several segments of the
society aiming at the reduction of GHG
 Maintenance of its profitability
 Search for alternative raw materials such as
biomass and coal
Introduction
The refinery must search for
intelligent alternative solutions to
meet all those requirements.
Therefore, the search for alternative
feedstock such as biomass has become a
must in order to cope with more
stringent regulations. Also, alternative
refining routes such as synthetic fuels
are striking back.
Introduction
PRODUCTION
EXPLORATION
BIOMASS
OIL
NATURAL GAS
OIL Industry
of the Future
TRANSPORTATION
BIOFUELS/
BIOCHEMICALS
DISTRIBUTION
REFIN.
XTL PROCESSES
Introduction
Hence, the refining of the future will encompass
the concept of BIOREFINERIES.
According to the 2008 Farm Act, the term means a
facility (including equipment and processes) that
converts renewable biomass into biofuels and
biobased products, and may produce electricity.
www.ers.usda.gov/Briefing/bioenergy/glossary.htm
More recently, the term INTEGRATED BIOREFINERY
has been coined.
An integrated biorefinery is capable of efficiently
converting a broad range of biomass feedstocks
into affordable biofuels, biopower, and other
bioproducts. The integrated biorefinery must cope
with the problem of residues.
Introduction
Regarding biomass, Brazil is undoubtedly one of
the
greatest
world’s
biomass
producers.
Nevertheless, such agricultural production implies
an enormous generation of residues
Introduction
Brazilian agribusiness: increasing opportunities due to
low land occupancy
Surface already occupied by agriculture
Total available surface
MM hectares
394
400
350
300
250
220
188
176
169
169
132
138
116
66
96
76
71
ARGENTINA
Surface already occupied by agriculture
CANADA
CHINA
INDIA
27
EU
RUSSIA
USA
45
BRAZIL
200
150
100
50
0
269
Introduction
Production of Residues from the Main National Cultures
140
Bagasse and straw
Sugar Cane
Sugar
cane
Cotton
120
Oats
Corn
100
Wheat
80
Rice
Soya
60
Beans
Peanut
40
Sorghum
20
Barley
0
90
/9
1
91
/9
2
92
/9
3
93
/9
4
94
/9
5
95
/9
6
96
/9
7
97
/9
8
98
/9
9
99
/0
0
00
/0
1
01
/0
2
02
/0
3
03
/0
4
04
/0
5
05
/0
6
Agricultural Residue Generation
(million tons)
160
Havest season
Introduction
Biomass conversion is surely the solution not only
for the requirements of the refinery of the future,
but also to solve the problem of agricultural
residues.
Introduction
Fuels/Chemicals
Biomass feedstock
Lignocellulosic
biomass
Hydrolysis/
fermentation
Pyrolysis
Gasification
Ethanol
Bio-oil
Hydro treating
Syngas
Fischer-Tropsch
SUCROCHEMISTRY
Diesel
Modified
Fischer-Tropsch
THERMOCHEMICAL ROUTES
Methanol synthesis
OLEOCHEMISTRY
Sugar/starch
crops
Hydrolysis/
fermentation
Vegetable oils
and fats
Transesterification
Paraffin,
Lubricants,
Naphtha, LPG
Mixed alcohols
Methanol/
DME
Ethanol, Butanol,
Hydrocarbons
Biodiesel
Esterification
Hydro treating
H-Bio(greendiesel)
Introduction
Actually,
biofuels
and biobased
products
may
replace
several
fuels
obtained
via
traditional
oil refining.
Main Types of Biofuels
Petroleum derivatives
Methanol
Gasoline
Ethanol
Kerosene
Butanol
Naphtha
Mixed alcohols
Paraffin/Lubricant
Fischer-Tropsch products
LPG
Fatty acid methyl esters
H-Bio
Bio-DME
Biocrude
Diesel
Crude Oil
Lignocellulosic biomass
The lignocellulosic materials are the most abundant
organic compounds in the biosphere, participating in
approximately 50% of the terrestrial biomass;
The term lignocellulose structure is related to the part of
the plant which forms the cell wall, basically constituted
of polysaccharides [cellulose (40-60%) and hemicellulose
(20-40%)].
These components are associated to a macromolecular
structure containing aromatic substances, denominated
lignin (15-25%)
Those materials possess in their compositions
approximately, 50-70% of polysaccharides (in a dry basis),
which contain in their monomeric units valuable
glycosides (sugars).
Lignocellulosic biomass
Cellulose and hemicellulose have different compositions,
hence distinct potentials for chemical transformation
CELLULOSE
HEMICELLULOSE
Consists of glucose units
Consists of various units of
pentoses and hexoses
High degree of polymerization
(2,000 a 18,000)
Low degree of polymerization
(50 a 300)
Forms fibrous arrangement
Does not form fibrous
arrangement
Presents crystalline and amorphous
regions
Presents only amorphous regions
Slowly attacked by diluted
inorganic acid in hot conditions
Rapidly attacked by inorganic
acid diluted in hot conditions
Insoluble in alkalis
Soluble in alkalis
Lignocellulosic biomass
Composition (%)
Material
Cellulose
Hemicellulose
Lignin
Other
Cane Bagasse
36
28
20
NR
Cane Straw
36
21
16
27
Maize Straw
36
28
29
NR
Corncob
36
28
NR
NR
Corn Straw
39
36
10
NR
Barley Straw
44
27
7
NR
Rice Straw
33
26
7
NR
Oat Straw
41
16
11
NR
Cotton Straw
42
12
15
NR
Peanut Shell
38
36
16
NR
Rice Shell
36.1
19.7
19.4
20.1
Barley Bran
23
32.7
21.4
NR
Pine Tree
44
26
29
NR
Different raw materials
present different
compositions and different
potential utilisation
In Brazil, sugar cane
bagasse and sugar cane
straw are the most
promising raw materials
Lignocellulosic biomass
 Several processes have been developed aiming at
using lignocellulosic biomass;
Most use biochemical transformations (enzimes) to
produce sugars from lignocellulosic materials;
Petrobras is developing, together with BIOeCON BV
and TU-Delft, the BICHEM technology, which uses
heterogeneous catalysis.
Lignocellulosic biomass
BICHEM
- Production of isosorbide from bagasse
STEPS
1 – Separation of lignin
and hemicellulose
2 – Hydrolysis (molten
salt as catalyst)
3 – Hydrogenation
4 - Dehydration
R. Menegassi, J. Moulijn et al.
ChemSusChem Volume 3(3), 325–328,
2010
Lignocellulosic biomass
BICHEM
- Production of isosorbide from bagasse
Reactions involved
glucose
cellulose
isosorbide
sorbitol
Lignocellulosic biomass
BICHEM
- Production of isosorbide from bagasse
Main catalytic challenges
1 – Increase the acidity of the molten salt used as
catalysts in the hydrolysis step;
2 – Carry out hydrogenation and dehydration in a
single step, using a bi-functional catalyst (ex. Metal
containing zeolite).
Thermochemical route
Thermochemical route
Biomass is converted thermo-chemically into
intermediates
The processing technologies can be categorised as
gasification, pyrolysis, or hydrothermal processing.
Intermediate products include clean syngas (CO + H2), biooil (pyrolysis or hydrothermal product), and gases rich in
methane or hydrogen.
These intermediates can further be converted into
gasoline, diesel, alcohols, ethers, synthetic natural gas etc.
and also high-purity hydrogen, which can be used as fuels
and electric power generation.
Thermochemical route
Thermochemical route
The main thermochemical routes involving heterogeneous
catalysts are the following:
- H-BIO (also called green diesel);
-BTL (comprising gasification, Fischer-Tropsch and
hydrotreating);
-Bio dimethylether (DME)/Bio methanol;
- Pyrolysis
Thermochemical route
H-BIO
 H-BIO
is a technology developed by Petrobras which
allows the production of diesel from renewable feedstock
such as vegetable oils by processing them in the existing
refining scheme ;
In the H-BIO technology vegetable oils are co-processed
with petroleum in hydro treating units; ;
The converted product contributes to improve the diesel
pool quality in the refinery, increasing the cetane number,
reducing the sulphur content.
Thermochemical route
H-BIO
Vegetable
Oil
Petroleum
Untreated
Diesel
Fraction
Straight Run Diesel
Atmospheric
Distillation
Existing
HDT
Atmospheric
Residue
Vacuum
Distillation
Gasoil
LCO
FCC
Vacuum
Residue
Delayed
Coking
Coker Gasoil
H-BIO
Process
Diesel
Pool
Thermochemical route
H-BIO
YIELDS
100 litres
Soybean oil
35 NM3 H2
Soybean
Oil
96 litres
of Diesel
Diesel
+
2.2 NM3 of Propane
Very high yield ( at least 95% v/v to diesel) without
residue generation and a small propane production
as a by-product
Thermochemical route
H-BIO
Main catalytic challenges
Biomass conversion in HDT units generates CO and
CO2 which are hydrogenated to methane, increasing
hydrogen consumption and reducing catalytic activity;
The main challenge is to develop a catalyst with high
HDT activity which, notwithstanding, produces less CO
and CO2 from biomass conversion;
Petrobras has developed such catalyst (PI 0900789-0).
Thermochemical route
BTL
Biomass-to-liquids
Slurry (Co) or
Tubular (Fe)
reactor
Waxes (>C20)
Low T FTS
BIOMASS
Hydrocracking
Gasifier
Air or oxygen
stream
Gas cleaning
&
conditioning
Clean syngas
(CO + H2)
DIESEL
High T FTS
CFB or FFB
(Fe)
reactor
Particulate Removal
Wet Scrubbing
Catalytic Conversion of Tar
Sulphur Scrubbing
Water Gas Shift
BTL
comprises:
a) Gasification
b) Gas cleaning
c) Fischer-Tropsh
d) Upgrade
Olefins (C3 – C11)
Oligomerisation
Isomerisation
Hydrogenation
GASOLINE
All those
steps have
catalytic
challenges
Thermochemical route
BTL
Gas Cleaning
Primary
methods
-Selection
of
convenient
operational conditions
- Convenient gasifier design.
- Addition of minerals (olivine,
dolomite, magnesite, etc.)
-Less expensive
- Low tar levels when catalysts
are used
However
- Produced gas is not suitable
for derivatives production.
Secondary
methods
- Physical processes
Wet gas cleaning
- Lower efficiency.
-T<100°C - washing
-200<T<500°C – adsorption
processes
- Chemical processes
Hot gas cleaning
-Thermal cracking
900<T<1200°C
- Catalytic conversion of tars
600<T<900°C
Thermochemical route
BTL
Gas Cleaning – Catalytic conversion
Main reactions
CnHm + n CO2 → (m/2) H2 + (2n) CO
CnHm + n H2O → (m/2 + n) H2 + n CO
Dry reforming
Steam reforming
Main catalytic features
- High tar conversion
- Deactivation resistance
- Easy regeneration
-Low cost
-Capable of promoting methane reforming
Main catalysts tested
-Non-metallic oxides
-Ni-containing catalysts
-Noble metal-containing catalysts
BTL
Thermochemical route
Gas Cleaning – Catalytic conversion
Many
catalysts,
promoters
and
supports
have already
been tested
(Yung, 2009)
BTL
Thermochemical route
Gas Cleaning – Catalytic conversion
Catalysts
Dolomite
CaMg(CO3)2
Olivine
(Fe, Mg)2SiO4
Magnesite
(MgCO3)
Ni-olivine
Noble metals
M/CeO2/SiO2,
where M=(Rh, Pd,
Pt, Ru, Ni)
Advantages
Cheap and abundant
High conversions (>90%)
Cheap
High mechanical
resistance
Cheap
High mechanical
resistance
High conversions (>97%)
High mechanical
resistance
Highest stability and
activity
Rh/CeO2/SiO2 is the best
High resistance to coke
and sulphur deactivation
Disadvantages
Friable material
Low catalytic conversion when
compared to dolomite
Low catalytic conversion when
compared to dolomite
Coke deactivation has to be
improved
Expensive
BTL
Thermochemical route
Fischer-Tropsch synthesis
-Activity correlates well with
the increase in Co surface
area;
-For particles smaller than
6nm, activity drops suddenly;
K. P. de Jong et al.
J. AM. CHEM. SOC. 9 ,128, 12, 2006
Challenge – small Co
particles with narrow PSD
Optimum  6 to 8 nm
average particle size
Thermochemical route
BTL
Co nanoparticles with a narrow PSD can be
stabilised by Ionic liquids via thermal
decomposition of Co(CO)8 .
Co nanoparticules dispersed
in BMI.BF4
E. Falabella, J. Dupont et al.
ChemSusChem, Vol.1 (4), 291–294, 2008
BTL
Thermochemical route
Fischer-Tropsch
Also, the use of new reactor technology such
as microractors has been proposed.
Challenge
Microreactors with a
homogeneous
distribution on the
walls and a
convenient width of
the catalyst layer
L. Almeida, F. Echave, O. Sanz, M. Centeno, G. Arzamendi, L. Gandia,
E. Falabella, J. Odriozola, M. Montes
Chemical Engineering Journal, Volume 167 (2-3), 536-544, 2011
Thermochemical route
Bio-DME
PROPERTIES
High cetane number (60)
Net heating value 6,900 kcal/kg
Physicochemical properties similar to those of propane
and butane, main LPG components
Neither particulate nor sulphur oxides
emissions upon burning
No greenhouse effect or
harm to ozone layer
Non-toxic substance
DME – the fuel of the 21st century
Bio-DME
Thermochemical route
Routes to produce DME from biomass
BIOMASS
RESIDUES
E. Falabella, L. Appel et al. Catalysis Today
Volume 101 (1), 39-44, 2005
Bio-DME
Thermochemical route
2CO + 4H2  2CH3OH
2CH3OH  CH3OCH3 + H2O
Reactions
involved in one
step DME
production
CO + H2O  CO2 + H2
methanol catalyst + solid acid catalyst
Bifunctional catalyst
Thermochemical route
Bio-DME
CH3OCH3
CH3OCH3
H2
H2O
CH3OH
H2
CO
H2O
CH3OH
CO
CO2
methanol catalyst
acid sites
E. Falabella, L. Appel, C. Mota. Catalysis Today
Volume 101 (1), 3-7, 2005
Thermochemical route
Bio-DME
DME direct synthesis
DME
MeOH 100
CO2
E. Falabella, L.
Appel et al. Fuel
Processing
Technology
Volume 91 (5), 469475, 2010
75
Selectivity %
The addition of
acidic oxides to a
methanol catalyst
promotes DME
formation, but also
CO2 yield
50
25
0
HZSM-5 S-ZrO2
Porous
alumina
Non Methanol
porous catalyst
alumina
Bio-DME
Thermochemical route
Main Catalytic Challenges
 Decrease catalyst deactivation
 Improve CO2 hydrogenation
 Real bifunctional catalyst (not a mixture)
 The role of acidic sites (is a conjugated
pair Bronsted-Lewis really required?)
Oleochemistry
Oleochemistry refers to the transformation
of fats and vegetable oils through different
processes;
The
main
basic
products
of
the
oleochemical complex are Fatty Acids, Fatty
Esters, Fatty Alcohols, Glycerine;
Several important commercial products
may be obtained via oleochemistry.
Oleochemistry
Palm oil
Fatty acids
Fatty Esters
Fatty Alcohols
Glycerol
Candles
Colored Pencils
Cosmetics
Soap
Liquid Soap
Detergents
Emulsifier
Soap
Surfactants
Food preservation
Substitutes
Diesel
Fabrics
Cosmetics
Plastics
Detergents
Surfactants
Shampoos
Foaming agents
Cosmetics
Pharmaceutics
Tooth paste
Antifreeze
Emulsifiers
Fatty Nitrogen
compounds
Fabric softener
Anti-brittle agents
Surfactants
Anti-corrosives
Oleochemistry
In Brazil, the first oleochemical plant has been
working since 2008, with capacity to produce
about 100 tons of fatty alcohols;
Using coconut oil and palm kernel oil, the main
products are:
-lauryl alcohol, keto-stearyl alcohol and its
fractions, cetyl alcohol and stearyl alcohol;
- caprylic-capric acid.
Also, highly pure, thermally stable USP / Kosher
glycerine is produced.
Oleochemistry
FAME
I – Hydroesterification, comprising two steps:
HYDROLYSIS
ESTERIFICATION
Brazil has three plants in operation, where
conversions above 99% are reached
FAME
Oleochemistry
I – Transesterification:
In the process of transesterification, oils or fats
react with short chain alcohols producing esters
(methyl or ethyl) and glycerol;
Currently, there are 64 biodiesel industrial plants in
Brazil running with transesterification processes.
Total capacity of production is about 5 billion
liters/year
Main catalytic challenges
- Development of acidic and basic solid catalysts;
- Development of new catalysts/new reaction systems
(microreactors) for glycerol upgrade via reforming.
D. Hufschmidt, L. Bobadilla, F. Romero-Saria, M. Centeno, J. Odriozola,
M. Montes, E. Falabella. Catalysis Today, 149 (3-4), 394-400, 2010.
Final Conclusions
 In
Brazil biomass is widely available from agrobased industry. Therefore, biomass conversion
technologies seem to be an attractive alternative to
recycle biomass residues and produce high added
value fuels and chemicals in a environmentally
friendly way.
 Biomass conversion processes can enhance the
agriculture economy and reinforce other industries
(ex.: sugar, alcohol, paper industry, etc).
Furthermore, the process integration could allow
more efficient biomass utilisation (cost reduction,
energy production and parallel production of fuel
and chemicals).
GREEN IS THE SOLUTION !
Final Conclusions
Haizi (1964-1989)
Brilliant Chinese poet
From tomorrow on,
I will be a happy man;
Grooming, chopping,
and traveling all over the world.
From tomorrow on,
I will care foodstuff and vegetable,
Living in a house towards the sea,
with spring blossoms.
From tomorrow on,
write to each of my dear ones,
Telling them of my happiness,
What the lightening of happiness has told me,
I will spread it to each of them.
Give a warm name for every river and every mountain,
Strangers, I will also wish you happy.
May you have a brilliant future!
May you lovers eventually become spouse!
May you enjoy happiness in this earthly world!
I only wish to face the sea, with spring flowers blossoming