Presentation DS Castro Marina Eurobioref

82 Pages·2011·15.12 MB·English

Conversion of cellulose and hemicellulose
into platform molecules: Chemical routes

D.P. Serrano , J. M. Coronado and J. A. Melero

School on Utilizaion of Biomass for the Production of Chemicals or Fuels
« The concept of Biorefinery comes into operation »
Castro Marina, Lecce, Italy
Speaker: David P. Serrano
Rey Juan Carlos University
IMDEA Energy Institute
A European Project supported within the Seventh Framework Programme for Research and Technological DeCvoenlofpidmeenntti al
Rey Juan Carlos University
●  Public university founded in 1996 in Madrid.
●  At present it has 35,000 students distributed in 4 campus.
●  Energy-related studies offered at URJC:
- Energy Engineering degree.
- Chemical Engineering degree.
- Environmental Engineering degree.
- Environmental Sciences degree.
- Master on Energy Technologies and Resources.
●  Biomass related research topics:
- Biodiesel synthesis with novel catalytic systems.
- Glycerol valorization.
- Catalytic pyrolysis of biomass-derived products.
- Biofuels production with fungi.
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IMDEA Energy Institute
●  Research Institute founded in 2006 by the Regional Government of
Madrid.
●  At present it has about 50 researchers organized in 6 research
units.
●  Biomass related research topics:
- Biofuel synthesis by catalytic hydrodeoxygenation of bio-oils.
- Hydrogen production by catalytic decomposition of biogas.
- Development of enzymes for lignocellulose degradation.
- Lipids production with microalgae.
- Technical, economical and environmental assessment of the
biomass conversion routes.
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Fossil fuels versus biofuels
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S 3 We can consider three general classes of feedstocks derived Fig. 2 Chemical structure of biomass feedstocks.

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S feedstocks, and lignocellulosic feedstocks. In Fig. 2, represen- and waste from wood processing. Lignocellulose is comprised
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L r tative chemical structures for starches and triglycerides are of three different fractions: lignin, hemicellulose, and cellulose.
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A s compared to that of cellulose—the predominate component of In this review we consider various processes by which biomass
C r
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N b lignocellulosic biomass. Fig. 3 shows different biofuels that can can be transformed into biofuels, giving special attention to
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R n glycosidic linkages, such as amylase and amylopectin, which are this review will focus primarily upon upgrading strategies for
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V facilities. Trigylderide feedstocks are those comprised of fatty we hope to outline various alternatives for biomass processing,
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acids and glycerol derived from both plant and animal sources. providing options such that each feedstock can be processed in
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y 0 Sources of triglycerides for the production of biodiesel include the most efficient way possible.
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e various vegetable oils, waste oil products (e.g., yellow grease, trap
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o h grease), and algal sources.8 Lignocellulosic biomass is the most
nl lis 2. Lignocellulosic biomass
w b abundant class of biomass. While starch and triglycerides are
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only present in some crops, lignocellulose contributes structural While attractive as an inexpensive and abundant feedstock,
integrity to plants and is thus always present. In general, most lignocellulosic biomass must be broken into its constituent
energy crops and waste biomass considered for energy pro- parts to be efficiently processed by specific refining strategies.
duction are lignocellulosic feedstocks, with examples including Biomass fractionation is a difficult process and has contributed
Fig. 3 Biomass-derived feedstocks and platforms for conversion to biofuels.
1494 | Green Chem., 2010, 12, 1493–1513 This journal is © The Royal Society of Chemistry 2010
First generation biofuels
●  Use easily accessible edible biomass.
●  This may have a negative impact on the supply of food for humans
and animals.
●  Their extensive and continued production does not seem to be a
sustainable solution, causing deforestation problems in some
regions.
●  Therefore, new alternatives for a more sustainable production of
biofuels (and also of chemicals according to the bio-refinery
concept) must be developed.
●  They should be based on the use of widely available biomass
feedstocks not employed in the food production.
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Biomass feedstocks
●  Polymeric compounds.
●  High degree of
functionality.
●  High content in
heteroatoms such as N,
P and mainly O.
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r 5
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b 4 Fig. 1 CO cycles for petroleum- and biomass-derived fuels.
m 2
0
e 0
t C
p
e 9/
8 S 03 We can consider three general classes of feedstocks derived Fig. 2 Chemical structure of biomass feedstocks.
2 1
from biomass that are appropriate for the production of renew-
n 0.
o 1
: able fuels:8 starchy feedstocks (including sugars), triglyceride switchgrass, miscanthus, agricultural residues, municipal wastes,
i
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SI d feedstocks, and lignocellulosic feedstocks. In Fig. 2, represen- and waste from wood processing. Lignocellulose is comprised Confidential 6
O |
g
L r tative chemical structures for starches and triglycerides are of three different fractions: lignin, hemicellulose, and cellulose.
o
R
.
A sc compared to that of cellulose—the predominate component of In this review we consider various processes by which biomass
C r
.
N bs lignocellulosic biomass. Fig. 3 shows different biofuels that can can be transformed into biofuels, giving special attention to
u
A
p
U / be obtained with each of these feedstocks. Starchy feedstocks utilization of lignocellulosic biomass. Without underestimating
/
J p:

Y tt are those comprised of glucose polysaccharides joined by a- the contributions of other possible feedstocks and processes,
E h

R n glycosidic linkages, such as amylase and amylopectin, which are this review will focus primarily upon upgrading strategies for
o
Y
0
T 1 easily hydrolyzed into the constituent sugar monomers, making theproductionoffuelsfromaqueoussolutionsoflignocellulose-
I 0
S 2
R them easy to process such as in first generation bioethanol derivedcarbohydrates.Withtheexamplesdiscussedinthiswork,
t
E s
u
V g facilities. Trigylderide feedstocks are those comprised of fatty we hope to outline various alternatives for biomass processing,
I u
N A acids and glycerol derived from both plant and animal sources. providing options such that each feedstock can be processed in
U
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y 0 Sources of triglycerides for the production of biodiesel include the most efficient way possible.
b
n

d o
e variousvegetableoils,wasteoilproducts(e.g.,yellowgrease,trap
d
d
e
a
o h grease), and algal sources.8 Lignocellulosic biomass is the most
nl lis 2. Lignocellulosic biomass
w b abundant class of biomass. While starch and triglycerides are
u
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D
only present in some crops, lignocellulose contributes structural While attractive as an inexpensive and abundant feedstock,
integrity to plants and is thus always present. In general, most lignocellulosic biomass must be broken into its constituent
energy crops and waste biomass considered for energy pro- parts to be efficiently processed by specific refining strategies.
duction are lignocellulosic feedstocks, with examples including Biomass fractionation is a difficult process and has contributed
Fig. 3 Biomass-derived feedstocks and platforms for conversion to biofuels.
1494 | Green Chem., 2010, 12, 1493–1513 This journal is © The Royal Society of Chemistry 2010
View Online
Biomass feedstocks: conversion technologies
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ubli from their intrinsic recalcitrance, these feedstocks are charac- pretreatment–hydrolysis steps to yield aqueous solutions of C5
P terized bya highdegree of chemicaland structuralcomplexity, andC6sugarsderivedfromlignocellulose.WhilegasificaCtioonnafniddential 7
and, consequently, technologies for the conversion of these pyrolysis are pure thermal routes in which lignocellulose is
resources into liquid hydrocarbon fuels typically involve decomposed with temperature under controlled atmosphere,
a combination of different processes. The methodology most aqueous-phaseprocessing,incontrast,involvesaseriesofcata-
commonlyusedto overcomelignocellulose complexity involves lytic reactions to selectively convert sugars and important plat-
the transformation of non-edible feedstocks into simpler frac- form chemicals derived from them into targeted liquid
tionsthataresubsequentlymoreeasilyconvertedintoavariety hydrocarbon fuels with molecular weights and structures
of useful products. This approach, similar to that used in appropriateforgasoline,dieselandjetfuelapplications.
conventionalpetroleumrefineries,wouldallowthesimultaneous
productionoffuels,power,andchemicalsfromlignocellulosein
4. Production of liquid hydrocarbon transportation
anintegratedfacilitydenotedasabiorefinery.50,51Currenttech-
nologies for converting lignocellulose to liquid hydrocarbon fuels from lignocellulose
transportation fuels involve three major routes: gasification,
4.1 Biomasstoliquids(BTL)
pyrolysis and pretreatment–hydrolysis (Fig. 4). By means of
theseprimaryroutes,lignocelluloseisconvertedintogaseousand Biomass to liquids can be described as a renewable version of
liquid fractions that are subsequently upgraded to liquid fossilfuel-basedtechnologieslikecoaltoliquids(CTL)andgas
hydrocarbonfuels.Thus,gasificationconvertssolid biomassto to liquids (GTL), involving the integration of two different
synthesisgas(syngas),avaluablemixtureofCOandH which processes: biomass gasification to syngas (H /CO) and F–T
2 2
serves as a precursor of liquid hydrocarbon fuels by Fischer– synthesis. Even though both technologies are well known and
Tropsch(F–T) reactions. This pathwayis commonly known as relatively mature, integration remains a challenge in BTL,
biomass to liquids (BTL). Pyrolysis allows transformation of becausetheutilizationoflignocellulosicbiomassasafeedstock
lignocellulosic biomass into a liquid fraction known as bio-oil (in substitution for classical carbon sources such as coal and
that can be subsequently upgraded to hydrocarbon fuels by natural gas) introduces new difficulties in the overall process.
a variety of catalytic processes. The third route involves Biomass gasification is achieved by treatment at high
Energy Environ. Sci. Thisjournal isªTheRoyalSociety ofChemistry2010
Biomass feedstock: lignocellulose
●  One of the best sources for alternative biofuels is
lignocellulose.
●  This material is the most abundant form of biomass in the
planet.
●  It is widely available in the form of:
- Conventional wood
- Waste biomass
- Fast rotation crops
●  It is a low cost raw material.
●  However, its processing and transformation is complex and
expensive.
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the formation of C–C bonds to control the molecular weight ars formed by treatment of lignocellulosic biomass undergo cat-
of the final hydrocarbons, and requiring the least amount of alyticdehydrationtoproducefurancompounds,suchasfurfural
hydrogen from an external source (such as the steam reforming andhydroxymethylfurfural(HMF).Thesefuranicaldehydescan
of petroleum). The strategy for achieving this goal is typically thenbeusedasfeedstocksforaldol-condensationreactionsover
comprised of two broad types of steps: (i) conversion of the basic catalysts to produce hydrocarbons suitable for Diesel fuel
solid lignocellulosic biomass feedstock to a gaseous or liquid- applications by achieving controlled C–C coupling reactions
phase chemical platform, involving partial removal of oxygen; while minimizing undesirable branching processes. Finally, we
and (ii) catalytic upgrading of this chemical platform to the consider the levulinic acid platform, in which lignocellulosic
finalhydrocarbonfuelbycontrolledC–Ccouplingreactionsand biomass first undergoes treatment in acid solutions to produce
removal of the remaining oxygen functionality. In the following levulinic acid. The aqueous solution of levulinic acid (in the
sectionswewillillustratethisgeneralstrategyforvariousspecific presence of formic acid) then undergoes catalytic reduction to
approaches. g-valerolactone (GVL), which serves as an intermediate for
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1 First, we will briefly explore gasification combined with the production of nonane for Diesel fuel or the production
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4 Fischer–Tropsch synthesis, in which the first step in lignocellu- of branched alkanes with molecular weights appropriate for
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m 4 losic biomass conversion is gasification to produce synthesis gas jet fuel. In particular, GVL can undergo ring-opening and
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pt C (i.e., CO:H gas mixtures), and the second step is the catalytic reduction to pentanoic acid, followed by ketonization to form
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8 03 conversion of synthesis gas platform to linear hydrocarbons in 5-nonanone, and completed by hydrodeoxygenation to nonane.
2 1
n 0. the Diesel fuel range. Second, we will consider pyrolysis and Alternatively, GVL can undergo catalytic conversion to butene
o 1
i: liquefaction, where the first step involves anaerobic thermal and CO , combined with butene oligomerization to form C –
I - do 2 8
OS g | treatment of lignocellulosic biomass to form liquid bio-oil, C20 alkenes.
L r
R o leading to the removal of ~80% of the oxygen in the feed, and
.
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C .rs the second step involves the catalytic upgrading of this bio-oil 5. General approaches for conversion of cellulosic
N bs
u in the presence of H to achieve C–C coupling and to remove
A p 2 biomass: thermochemical and hydrolysis pathways
U // the remainder of the oxygen moieties. Third, we will address
J p:

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E ht aqueous-phase reforming, in which the lignocellulosic biomass Fig. 7 presents two of the most frequently considered strate-

R n
o must first undergo treatment to produce an aqueous solution of gies for biomass processing. The first approach involves ther-
Y
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T 1 sugarsorpolyols.Thisplatformofaqueouscompoundshavinga mochemical routes that process whole lignocellulose at high
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R t C:Ostoichiometryof1:1isthenconvertedbyacombinationof temperatures and/or pressures (e.g., pyrolysis, gasification,
E s
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g C–CandC–Ocleavage reactionstoproduceamixtureofmono- liquefaction). The thermal deconstruction of biomass yields
I u
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U functional organic compounds (alcohols, ketones, carboxylic upgradeable intermediates such as bio-oils by pyrolysis and
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b n acids, heterocyclics). These mono-functional intermediates then synthesis gas by gasification (CO:H gas mixtures, denoted as
d o 2
e d undergo catalytic upgrading to hydrocarbon fuels by various syngas). Thermal processing is typically coupled with subse-
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o s routes to control C–C coupling and oxygen removal, such as quentchemical/catalyticupgrading(Fischer–Tropschsynthesis,
nl li
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u dehydration, aromatization and alkylation over acid zeolite hydrodeoxygenation) to produce fuel range hydrocarbons. The
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catalysts, aldol-condensation of alcohols and ketones over second processing option for lignocellulosic biomass is frac-
bifunctional catalysts containing metal and basic sites, and tionation/hydrolysis, an option by which sugars and lignin are
ketonization of carboxylic acids over basic oxides. Fourth, we isolated from lignocellulosic biomass and processed selectively
briefly consider an approach in which aqueous solutions of sug- through either biological or chemical pathways. In general,
Lignocellulose conversion technologies
Fig. 7 Strategies for conversion of lignocellulosic biomass to liquid biofuels by thermochemical and hydrolysis routes.
1498 | GreenChem., 2010, 12, 1493–1513 This journal is © The Royal Society of Chemistry 2010
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The thermochemical route for the conversion of
lignocellulose into biofuels
●  It Involves thermochemical processing of lignocelluloses at high
temperature and/or pressures.
●  The thermal deconstruction of biomass yields intermediates such
as bio-oils by pyrolysis and synthesis gas by gasification.
●  Thermal processing is coupled with the subsequent chemical
catalytic upgrading to produce fuel range hydrocarbons.
●  It employs strong conditions, which usually leads to a wide variety
of products.

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