Lecture 8

Lecture 8
Biooil
• Biomass can be converted to bio-oil by two main routes:
• flash pyrolysis (for dry biomass) and
• hydrothermal liquefaction (HTL) (for wet biomass)
• Flash pyrolysis - rapid thermal decomposition of organic
compounds in the absence of oxygen to produce liquids,
gases, and char.
• HTL - reaction of biomass in water at elevated temperature
and pressure with or without the presence of a catalyst
Advantages of biooil
• has several environmental advantages over fossil fuels as a clean fuel
• Bio-oils are CO2/GHG neutral - can generate carbon dioxide credits
• No SOx emissions are generated, because plant biomass contains
insignificant amounts of sulfur
• Bio-oil fuels generate more than 50% lower NOx emissions than diesel oil
in a gas turbine.
• Renewable and locally produced with large volumes of organic wastes.
• bio-oils are cleaner and cause less pollution.
Demerits of biofuels
• Potential for direct substitution of bio-oil for petroleum fuels and
chemical feedstocks is limited due to
• their high viscosity
• high water and ash contents
• low heating value
• instability and
• high corrosiveness
• upgrading necessary to give a liquid product that can be used as a liquid
fuel or chemical feedstocks in various applications
Biooil production from biomass
• Flash pyrolysis
• HTL (direct liquefaction, hydrothermal
upgrading/pyrolysis, depolymerization, and solvolysis)
Flash pyrolysis
• involves the rapid thermal decomposition of organic
compounds by heat in the absence of oxygen, which results
in the production of charcoal, bio-oil, and gaseous products
• Flash pyrolysis is characterized by a short gas residence time
(~1 s), atmospheric pressure, and a relatively high
temperature (450–500oC).
• Furthermore, feedstock drying is necessary
• main product -bio-oil (yield - 80 wt% on dry feed)
Hydrothermal liquefaction
• conducted under elevated pressure and temperature to
keep water in either liquid or supercritical state.
• The use of water as a solvent obviates the need to dry
biomass and permits reactions to be carried out at lower
temperatures in comparison with flash pyrolysis.
• The primary product of HTL is bio-oil or bio-crude, and the
main byproducts are the solid residue, bio-char, and water
containing soluble organic compounds.
• Typical yields of liquid products for hydrothermal conversion
processes were in the range of 7–70%,
• Yield depends on
• substrate type,
• temperature,
• pressure,
• residence time,
• type of solvents, and
• catalysts employed
Properties of bio-oils
• dark brown, free-flowing liquids having a distinctive smoky odor.
• Bio-oil is a complex mixture of several hundreds of organic
compounds, mainly including acids, alcohols, aldehydes, esters,
ketones, phenols, and lignin-derived oligomers.
• Some of these compounds are directly related to the undesirable
properties of bio-oil.
Undesired properties of biooil for fuel
applications
• high water content

• high viscosity
• high ash content
• high oxygen content (low heating value)
• high corrosiveness (acidity)
Uses of biooils
can serve as a substitute for fuel oil or diesel in many static
applications including
•boilers,
•furnaces,
•engines, and
•turbines for electricity generation
Industrial uses of biooil
• Combustion fuel in boiler/burner/furnace systems for heat generation
• Combustion in diesel engines/turbines for power generation
• Can be used as a transportation fuel after upgrading
• Production of anhydro sugars like levoglucosan, for the manufacturing of
pharmaceuticals, surfactants, biodegradable polymers
• Can be used as liquid smoke and wood flavors
• Production of chemicals and resins (e.g., agri-chemicals, fertilizers, acids
and emission control agents)
• Can be used in making adhesives, e.g., asphalt bio-binder
Upgrading of bio-oil
Hydrotreating
• higher the hydrogen content of a petroleum product, especially
the fuel products, the better the quality
• Hydrogen adding process in the refinery – hydrogenation
• most widely used hydrogenation processes for the conversion
of petroleum and petroleum products is hydrotreating
• Hydrotreating is a non-destructive, hydrogenation process that
is used for the purpose of improving product quality without
appreciable alteration of the boiling range.
• Hydrogenation without simultaneous cracking is used for saturating
olefins or for converting aromatics to naphthenes.
• Under atmospheric pressure, olefins can be hydrogenated up to about
500oC, but beyond this temperature hydrogenation commences.
• the most common process in modern petroleum refineries.
• Bio-crude may also be processed by a conventional refinery and
potentially augmented with petroleum crude.
• oxygen in bio-oils can be removed via hydrotreating.
• catalysts commonly used are sulphide CoMo/Al2O3, NiMo/Al2O3 systems
• Hydrotreating requires mild conditions, while the yield of biooil
is relatively low.
• The process also produces a large amount of char, coke, and tar,
which will result in catalyst deactivation and reactor clogging
Hydro-cracking
• less popular than the hydrotreating in the petroleum industry
• thermal process (>350oC) in which hydrogenation accompanies
cracking.
• Relatively high pressure (100 to 2000 psi) is employed, and the
overall result is usually a change in the character or quality of
the end products
• wide range of products possible from hydro-cracking is the
results of combining catalytic cracking reactions with
hydrogenation and the multiplicity of reactions that can occur
• performed by dual-function catalysts, in which silica–alumina (or
zeolite) catalysts provide the cracking function, and platinum and
tungsten oxide catalyze the reactions, or nickel provides the
hydrogenation function.
• Alumina is by far the most widely used support.
• Hydro-cracking is an effective way to make a large amount of
light product,
• but it requires more severe conditions such as higher
temperature and hydrogen pressure to deal with acids, which is
not economical and energy efficient.
Supercritical fluids
• A fluid is considered supercritical when its temperature and
pressure go above its critical point.
• SCFs possess unique transport properties.
• They can effuse through solids like a gas and dissolve
materials like a liquid.
• In particular, SCFs have the ability to dissolve materials not
normally soluble in either liquid or gaseous phase of the
solvent, and hence to promote the gasification/ liquefaction
reactions
• SCFs have been recently used to improve oil yield and quality and
have demonstrated a great potential for producing bio-oil or bio-
crude with much higher caloric values and lower viscosity.
• Water is the cheapest and most commonly used supercritical fluid
in hydrothermal processing
• utilizing water as the solvent for liquefaction of biomass has the
following drawbacks:
• lower yields of the water-insoluble oil product
• yields a bio-oil that is very viscous, with high oxygen content.
To enhance the oil yields and qualities, the utilization of following organic
solvents has been adopted.
•ethanol
•butanol
•acetone
•2-propanol
•n-hexanol
•1,4-dioxane and
•Methanol
SCFs can be produced at relatively lower temperature and the process is
environmentally friendly, these organic solvents are too expensive to make it
economically feasible on a large scale
Solvent addition/esterification
• Polar solvents such as methanol, ethanol, and furfural have
been used for many years to homogenize and to reduce
viscosity of biomass oils
• The immediate effects of adding these polar solvents are
decreased viscosity and increased heating value.
• The increase in heating value for bio-oils mixed with solvents
occurs because the solvent has a higher heating value than
that of most bio-oils
The solvent addition reduces the oil viscosity due to the
following three mechanisms:
•(1) physical dilution without affecting the chemical
reaction rates;
•(2) reducing the reaction rate by molecular dilution or by
changing the oil microstructure;
•(3) chemical reactions between the solvent and the oil
components that prevent further chain growth
Emulsification (emulsions)
• Pyrolysis oils are not miscible with hydrocarbon fuels,
but with the aid of surfactants they can be emulsified
wit diesel oil
• A process for producing stable microemulsions, with
5-30% of bio-oil in diesel has been developed at Canmet
Energy Technology Centre
• Those emulsions are less corrosive and show promising
ignition characteristics.
Steam reforming
• Fast pyrolysis of biomass followed by catalytic steam reforming
and shift conversion of specific fractions to obtain H2 from bio-oil
was presented as an effective way to upgrade biomass pyrolysis
oils.
• Production of hydrogen from reforming bio-oil was investigated
by NREL extensively, including the reactions in a fixed bed and a
fluidized bed
• Commercial nickel catalysts showed good activity in processing
biomass derived liquids
Chemicals extracted from the bio-oils
• phenols used in the resins industry,
• volatile organic acids,
• nitrogen herocycles and
• n-alkanes
• Triacetonamine
• Hydrothermal bio-oil contains up to 50 wt% asphalt, which makes it a
good candidate for the asphalt industry

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• high water content

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