Biomass conversion in Brazil: main challenges in heterogeneous Catalysis Eduardo Falabella...

Biomass conversion in Brazil: main challenges in heterogeneous Catalysis

Biomass conversion in Brazil: main challenges in heterogeneous Catalysis

Eduardo Falabella Sousa-AguiarCarla A. F. Melo, Cristina P. B. Quitete, Jefferson R. Gomes, Márcio Portilho, Nei Pereira Jr.

EQ/UFRJ andPetrobras/CENPES/CB

Introduction Introduction

Spring SleepBai Juyi

Spring SleepBai Juyi

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 SleepBai Juyi, famous chinese poet

IntroductionIntroduction

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. Introduction.

Traditional Oil Industry

EXPLORATION PRODUCTION

REFINING

TRANSPORTATION DISTRIBUTION

The main segments of the Traditional Oil Industry

OILOIL


The survival of the oil industry will depend on many factors . Indeed, the refiner of the future will have to face multiple challenges.

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.


The main challenges of the refinining industry in the future are the following:Increasing stringent environmental regulation Growing demand for cleaner fuelsGlobalisationIncrease in the production of derivatives from declining quality oilUncertainty 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


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.

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.


OIL Industry of the Future

EXPLORATION PRODUCTION

REFIN.

TRANSPORTATION DISTRIBUTION

BIOMASS NATURAL GAS

BIOFUELS/BIOCHEMICALSBIOFUELS/BIOCHEMICALS XTL PROCESSESXTL PROCESSES

OILOIL


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.

http://www.ers.usda.gov/Briefing/bioenergy/glossary.htm


Regarding biomass, Brazil is undoubtedly one of the greatest world’s biomass producers. Nevertheless, such agricultural production implies an enormous generation of residues

Brazilian agribusiness: increasing opportunities due to low land occupancy

Brazilian agribusiness: increasing opportunities due to low land occupancy

BR

AZ

IL

US

A

RU

SS

IA

EU

IND

IA

CH

INA

CA

NA

DA

AR

GE

NT

INA

Surface already occupied by agriculture

394

269

220

176 169138

76 7166

188

132116

169

96

4527

050

100

150

200

250

300

350

400

MM hectaresSurface already occupied by agriculture

Total available surface



0

20

40

60

80

100

120

140

160

Havest season

Ag

ricu

ltu

ral R

esi

du

e G

en

era

tion

(m

illion

ton

s)

Sugar Cane

Cotton

Oats

Corn

Wheat

Rice

Soya

Beans

Peanut

Sorghum

Barley

Production of Residues from the Main National Cultures

Bagasse and strawSugar cane


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.

Biomass feedstock

Lignocellulosicbiomass

Sugar/starchcrops

Vegetable oilsand fats

Hydrolysis/fermentation

Fuels/Chemicals

Ethanol

PyrolysisBio-oil Hydro treating Diesel

GasificationSyngas Fischer-Tropsch Paraffin,

Lubricants, Naphtha, LPGModified

Fischer-Tropsch Mixed alcohols

Methanol synthesis Methanol/DME

Hydrolysis/fermentation

Ethanol, Butanol, Hydrocarbons

TransesterificationBiodiesel

Esterification

Hydro treating H-Bio(greendiesel)


SUCROCHEMISTRY

THERMOCHEMICAL ROUTES

OLEOCHEMISTRY


Main Types of Biofuels

Methanol

Ethanol

Butanol

Mixed alcohols

Fischer-Tropsch products

Fatty acid methyl esters

H-Bio

Bio-DME

Biocrude

Petroleum derivatives

Gasoline

Kerosene

Naphtha

Paraffin/Lubricant

LPG

Diesel

Crude Oil

Actually, biofuels and bio-based products may replace several fuels obtained via traditional oil refining.

Lignocellulosic biomassLignocellulosic 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).


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

Cellulose and hemicellulose have different compositions, hence distinct potentials for chemical transformation


Material

Composition (%)

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


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.


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



Reactions involvedReactions involved

cellulose

glucose

sorbitol

isosorbide



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

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), bio-oil (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 routeThermochemical 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


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.


H-BIO


H-BIO

AtmosphericDistillation

AtmosphericDistillation

VacuumDistillationVacuum

Distillation

DelayedCoking

DelayedCoking

FCCFCC

Petroleum

Gasoil

AtmosphericResidue

VacuumResidue

LCO

Straight Run Diesel

Coker Gasoil

ExistingHDT

H-BIOProcess

DieselPool

VegetableOilVegetableOil

UntreatedDieselFraction


H-BIO

SoybeanOil

Diesel + 2.2 NM3 of Propane35 NM3 H2

100 litres Soybean oil

96 litres of Diesel96 litres of Diesel

YIELDS

Very high yield ( at least 95% v/v to diesel) without residue generation and a small propane production as a by-product


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).


BTL

Gasifier

BIOMASS

Air or oxygenstream

Gas cleaning &

conditioning

CFB or FFB (Fe)

reactor

Slurry (Co) or Tubular (Fe) reactor

Low T FTS

High T FTS

Clean syngas(CO + H2)

Hydrocracking

Waxes (>C20)

DIESELDIESEL

Olefins (C3 – C11)

OligomerisationIsomerisationHydrogenation

GASOLINE

Particulate RemovalWet ScrubbingCatalytic Conversion of TarSulphur ScrubbingWater Gas Shift

Biomass-to-liquidsBTLcomprises:a) Gasificationb) Gas cleaningc) Fischer-Tropshd) Upgrade

All those steps have catalytic challenges

Thermochemical routeThermochemical routeBTL

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


Gas Cleaning – Catalytic conversion

Main reactions

CnHm + n CO2 → (m/2) H2 + (2n) CO Dry reformingCnHm + n H2O → (m/2 + n) H2 + n CO 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



Many catalysts, promoters and supports have already been tested (Yung, 2009)



Catalysts Advantages DisadvantagesDolomite CaMg(CO3)2

Cheap and abundantHigh conversions (>90%)

Friable material

Olivine (Fe, Mg)2SiO4

CheapHigh mechanical resistance

Low catalytic conversion when compared to dolomite

Magnesite (MgCO3)

CheapHigh mechanical resistance

Low catalytic conversion when compared to dolomite

Ni-olivine High conversions (>97%)High mechanical resistance

Coke deactivation has to be improved

Noble metalsM/CeO2/SiO2, where M=(Rh, Pd, Pt, Ru, Ni)

Highest stability and activityRh/CeO2/SiO2 is the bestHigh resistance to coke and sulphur deactivation

Expensive

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


Optimum 6 to 8 nmaverage particle size

Challenge – small Co particles with narrow PSD

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



ChallengeMicroreactors with a homogeneous distribution on the walls and a convenient width of the catalyst layer

Fischer-TropschAlso, the use of new reactor technology such as microractors has been proposed.

L. Almeida, F. Echave, O. Sanz, M. Centeno, G. Arzamendi, L. Gandia, E. Falabella, J. Odriozola, M. MontesChemical Engineering Journal, Volume 167 (2-3), 536-544, 2011

Thermochemical routeThermochemical routeBio-DME

PROPERTIESPROPERTIES

High cetane number (60)High cetane number (60)

Net heating value 6,900 kcal/kgNet heating value 6,900 kcal/kg

Physicochemical properties similar to those of propaneand butane, main LPG componentsPhysicochemical properties similar to those of propaneand butane, main LPG components

Neither particulate nor sulphur oxides emissions upon burningNeither particulate nor sulphur oxides emissions upon burning

No greenhouse effect orharm to ozone layerNo greenhouse effect orharm to ozone layer

Non-toxic substanceNon-toxic substance

DME – the fuel of the 21st centuryDME – the fuel of the 21st century


Routes to produce DME from biomassRoutes to produce DME from biomass

BIOMASSRESIDUES

E. Falabella, L. Appel et al. Catalysis TodayVolume 101 (1), 39-44, 2005


methanol catalyst + solid acid catalystmethanol catalyst + solid acid catalyst

2CO + 4H2 2CH3OH

2CH3OH CH3OCH3 + H2O

CO + H2O CO2 + H2

Bifunctional catalystBifunctional catalyst

Reactions involved in one

step DME production

CO

H2

CH3OH

CH3OCH3

H2OCO

CO2

H2

CH3OCH3

H2OCH3OH

acid sites

methanol catalyst


E. Falabella, L. Appel, C. Mota. Catalysis TodayVolume 101 (1), 3-7, 2005


0

25

50

75

100

HZSM-5 S-ZrO2 Porousalumina

Nonporousalumina

Methanolcatalyst

DME

MeOH

CO2

Se

lect

ivity

%

DME direct synthesisDME direct synthesis

The addition of acidic oxides to a methanol catalyst

promotes DME formation, but also

CO2 yield

E. Falabella, L. Appel et al. Fuel

Processing Technology

Volume 91 (5), 469-475, 2010


Decrease catalyst deactivation Decrease catalyst deactivation

Improve CO2 hydrogenation Improve CO2 hydrogenation

Real bifunctional catalyst (not a mixture) Real bifunctional catalyst (not a mixture)

The role of acidic sites (is a conjugated pair Bronsted-Lewis really required?)

The role of acidic sites (is a conjugated pair Bronsted-Lewis really required?)

Main Catalytic ChallengesMain Catalytic Challenges

OleochemistryOleochemistry

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.


Palm oil

Fatty acids Fatty Esters Fatty Alcohols Glycerol Fatty Nitrogen compounds

Candles Soap Detergents Cosmetics Fabric softenerColored Pencils Surfactants Surfactants Pharmaceutics Anti-brittle agentsCosmetics Food preservation Shampoos Tooth paste SurfactantsSoap Substitutes Foaming agents Antifreeze Anti-corrosivesLiquid Soap Diesel EmulsifiersDetergents FabricsEmulsifier Cosmetics

Plastics


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.


Brazil has three plants in operation, where conversions above 99% are reached

FAME

I – Hydroesterification, comprising two steps:HYDROLYSIS

ESTERIFICATION


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

FAME

I – Transesterification:

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 agro-based 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).

In Brazil biomass is widely available from agro-based 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 ConclusionsFinal Conclusions

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

Haizi (1964-1989)Brilliant Chinese poet

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Biomass conversion in Brazil: main challenges in heterogeneous Catalysis Eduardo Falabella...

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