ENVIRONMENTAL ENGINEERING

Thermochemical conversion of
biomass

Dr. Tatiana Ivanova

 Thermochemical conversion
Controlled heating and/or oxidation of biomass to produce
intermediate energy carriers or heat.

 Amount of oxygen
 Temperature
 Time
 Material particle size

 Output products
Combustion
 Biomass combustion process
The fuel contains three chemical elements, which release heat during combustion: carbon
(C), hydrogen (H), and sulfur (S). (Air oxygen is used as oxidant). Their complete
combustion occurs by subsequent chemical reactions:
C + O2 -> CO2 + heat
2H2 + O2 -> 2H2O + heat
S + O2 -> SO2 + heat
carbon dioxide (CO2)
water vapor (H2O) + HEAT
sulfur dioxide (SO2)

Although combustion of sulfur produces heat, the presence of sulfur in fuels is considered as
extremely undesirable, because of its negative environmental impact and risk of corrosion of
heating surfaces.
Two methods of fuel combustion:
- Open method (without the use of any constructions and facilities);
- Closed method (using a special constructions (stoves and fireplaces) and equipment
(heating boilers..))

Produces thermal energy which can be used for space heating, water heating, cooking,
electricitygeneration.
 Stoves and fireplaces
• Stoves and fireplaces are the most
common types of heating facilities - first
type of facilities that man began to use
for more efficient combustion.
• Popularity is caused primarily by their
simplicity of construction, use of the
most affordable and common materials
(stone, clay, brick, metal), easy
exploitation.
• The main form of fuel used is a solid fuel
in the form of coal, firewood, briquettes.

• Their main disadvantage is low energy

conversion efficiency and inefficient
combustion of fuel in comparison with
other heating/combustion devices.
 Heating boilers
Classification according to:
⁻ Construction
⁻ Application area (households..)
⁻ Operation principle
⁻ Performance (power output)
⁻ Used fuel
⁻ Method of fuel feeding
⁻ Type of produced thermal agent
⁻ Energy conversion efficiency
⁻ Type of combustion chamber or burner
⁻ Ignition method
⁻ ……
 Solid fuel boiler with a classic principle of
combustion
• The most common type of boilers
• Operation principle:
- solid fuel load into combustion chamber
(furnace) and its ignition,
For support of combustion process the
combustion chamber is supplied with air
through the ash pit. By regulation the air
supply the intensity of combustion process
is controlled.
- resulting energy (heat) is transferred to
the coolant through the heat exchanger,
- combustion gases outlet through
chimney,
- ash is removed through ash pit.
• Adv.: simplicity of construction and
operation, reliability
• Disadv.: high fuel consumption
 Solid fuel boiler with long burning process
(pyrolysis boiler)
• Pyrolysis solid fuel boilers have a furnace,
which is divided into two parts. These parts
are divided by separation grate firing, where
fuel (briquettes or firewood) is placed.
-In the fuel chamber the fuel passes through
thermal decomposition in a lack of oxygen
(process of pyrolysis).
-In this stage the pyrolysis gases, which enter
the combustion chamber (the second part of
the furnace) are produced.
-The secondary air is added there too.
• Adv.: combustion is highly efficient
(economic) and less fuel is consumed (fuel
consumption is twice smaller than in the
boiler with classical combustion principles).
• Disadv.: if electricity for some reasons is cut
off, so the boiler can not work, because the
air is fed into the furnace, and the
combustion products are removed from it
by fans – gas pumps.
 Solid fuel boilers for pellets
• Today pellet boilers are becoming highly
popular due to high efficiency and
automatic process of fuel burning.
-Boiler has a hopper which is filled with
pellets.
- Pellets are transported by conveyer (or
scraper) to the boiler body, where fall into
the pellet burner/furnace. Usually burner
is constructed as metal "deep" bowl with
holes.
-Pellets are there distributed evenly and
electric ignition take place.
-During combustion pellets are periodically
replenished using automatic screw.
- Produced heat and gases heat the
exchanger. Water heated in the heat
exchanger circulate in the heating circuit.

Adv./disadv.: complex construction and

automatization - makes them expensive.
 Solid fuel boilers for straw
• Advantage of these boilers is the possibility
to load the furnace with several whole bales,
which simplifies maintenance. Due to the
thermoregulation system and pumping of air
f low to the furnace, the combustion is
efficient and stable.
• Among these boilers there are available
models, which are different in methods of
fuel loading, ignition and control of burning.
- In the models with continuous burning it is
possible to load new bales while previous are
still burning - constant maintain of required
combustion temperature.
- Modifications which allow periodic loading
of bale only after complete combustion of the
previous portion, have storage tanks, which
store thermal energy during combustion, and
give it to the furnace during the reloading of
fuel.
Combined heating system working on solid biofuels
and solar energy
 Methods of industrial combustion of biomass

 Fixed bed combustion (Horizontal/Inclined grate..)

 Moving bed combustion (Forward moving grate; Reverse moving grate…)

 Fluidized bed combustion (Bubbling fluidized bed combustion; Circulation

fluidized bed combustion)

 Rotary hearth furnace combustion (Kiln furnace)

Boiler plant for straw
Boiler plant powered by one type of solid biofuels
Boiler plant powered by a mixture of different
types of solid fuels (co-firing)

https://www.youtube.com/watch?v=nL-J5tT1E1k
 Co-Firing
Co-firing is the combustion of two different types of materials at the same time.
One of the advantages of co-firing is that an existing plant can be used to burn a
new fuel, which may be cheaper or more environmentally friendly.
For example, biomass is sometimes co-fired in existing coal plants instead of new
biomass plants. Co-firing can also be used to improve the combustion of fuels
with low energy content.
 EMISSIONS FROM BIOMASS COMBUSTION
Carbon Dioxide (CO2)
- major combustion product from all biomass fuels, originated from the carbon
content in the fuel. In general, the emission of CO2 to the atmosphere is problematic,
since CO2 is considered a major cause of the greenhouse effect. However, during the
combustion of biomass, not more CO2 is developed than bound during its growth.
Biomass is thus considered CO2 -neutral.

Nitrous oxide (N2O)

N2O emissions are the result of complete oxidation of fuel nitrogen. The N2O
emissions of biomass combustion are very low but they contribute to some degree to
the greenhouse effect because of the high Global Warming Potential (GWP) factor of
N2O and to ozone depletion in the atmosphere. N2O emissions may be reduced by
primary emission reduction measures.

Mono-nitrogen oxides (NOx)

Nitric oxide NO and nitrogen dioxide NO2, summarised as NOx, from combustion
processes are formed from the nitrogen contained in the fuel.
Fuel NOx emissions increase with increasing nitrogen content in the biomass, excess
air ratio, and combustion temperature.
 EMISSIONS FROM BIOMASS COMBUSTION
Sulphur oxides (SOx)
Sulphur oxides are a result of complete oxidation of fuel sulphur. Mainly SO2 (>95%)
is formed. However, some SO3 (<5%) may be formed at lower temperatures. Sulphur
from the combustion of biomass comes from sulphur compounds that have been
absorbed by the plant during its growth.
Therefore, the combustion of biomass does not change the total amount of sulphur
present in the environment, but it entails that the emission of sulphur with the smoke
contributes to the pollution of the air. However, fresh wood from the forest contains
only a very limited amount of sulphur, and the sulphur content in fuel chips often show
values that are below the laboratory equipment limits of detection. Fuel sulphur will not
be completely converted to SOx; a significant fraction will remain in the ashes while a
minor fraction is emitted as salt (K2SO4) or as H2S at lower temperatures.

SO2 emissions may be reduced by primary measures such as lime or limestone

injection or by secondary measures.

Firing with biomass at heating plants causes much less SO2 emission than the fuel oil
or coal the biomass often replace.
 EMISSIONS FROM BIOMASS COMBUSTION
Hydrogen chloride (HCl)
Part of the chlorine content in the fuel will be released as HCl. The chlorine content of
wood is very low. However, significant amounts of HCl may be formed from biomass
fuels containing higher amounts of chlorine, such as miscanthus, grass and straw, or
when wood chips from near-shore forests containing salt from sea fog are used.
The fuel chlorine will not be completely converted to HCl; the main fraction is retained
in salts (KCl, NaCl) by reaction with K and Na, while traces are emitted as dioxins and
organic chlorine components. Like sulphur dioxide, hydrogen chloride (HCl)
contributes to the acidification, but condenses faster (to hydrochloric acid) and can
therefore locally contribute to damage of materials in particular, but also to plants.

HCl emissions may be reduced by washing of fuel, which is utilised to some extent
for straw due to its high chlorine content, and by secondary emission reduction
measures.
 POLLUTANTS FROM BIOMASS COMBUSTION
Heavy metals
All virgin biomass fuels contain heavy metals to some degree (most important: Cu, Pb,
Cd, and Hg). These will remain in the ash or evaporate, and also attach to the surface
of particles emitted to the atmosphere or be contained inside fly-ash particles.
Contaminated biomass fuels, such as impregnated or painted wood may contain
significantly higher values of heavy metals. One example is the presence of Cr and As
in impregnated wood. Heavy-metal emissions can be reduced by secondary emission
reduction measures.

Particles
Particles originate from several sources. Among these are fly ash, which is a result of
entrainment of ash particles in the flue gas, and salts (KCl, NaCl, K2SO4) which are
result of reactions between K or Na and Cl or S. Secondary particle emission
reduction measures are utilised to reduce the particle emission level in large-scale
biomass combustion applications. By optimal design of combustion chambers, fly ash
particles entrained in the flue gas may to some degree be prevented from leaving the
combustion chamber, instead falling down to the bottom of the combustion chamber to
be removed as bottom ash.
 Emission reduction measures
Emission reduction measures aim at preventing or reducing formation of
emissions and/or reduction of emissions within the combustion chamber.

Several possible measures exist:

- modification of the moisture content of the fuel,

- modification of the particle size of the fuel,
- selection of the type of combustion equipment,
- combustion process control optimization,
- lime/limestone injections…

- staged-air combustion,
- staged fuel combustion and re-burning,
- filters
Consequences of using low-quality solid biofuel in the
boilers
Thermochemical conversion
 Gasification
Gasification is the exothermic partial oxidation of biomass with process
conditions optimized for high yields of gaseous products (syngas or
producer gas) rich in carbon monoxide (CO), hydrogen (H2), methane (CH4),
nitrogen (N2), carbon dioxide (CO2), and smaller quantities of higher
hydrocarbons.

The gas can be cleaned and used directly as an engine

fuel, for electricity production or upgraded to liquid fuel biomethanol
Gasification - something new?
Example of biomass Gasification
Types of Gasifiers
Pyrolysis
Is always the first step in combustion and
gasification processes.
Known as a technology for producing
charcoal and chemicals for thousands years.
 Fast Pyrolysis of biomass
 Rapid heat of biomass to a carefully controlled
temperature (~500°C), then very quick cool of
Drying the volatile products (<2 sec) formed in the
reactor.
 Offers the unique advantage of producing a
Crushing
liquid that can be stored and transported

Fast
pyrolysis

Char
separation

Liquid
recovery
Pyrolysis Technology with
Fluid Bed Reactor
 Pyrolysis Technology with
Circulating Fluid Beds Reactor
 Fast Pyrolysis Bio-oil

Bio-oil is water miscible and is comprised of many oxygenated organic chemicals.

 Dark brown liquid
 Combustible
 Not miscible with hydrocarbons
 Heating value ~ 17 MJ/kg
 Density ~ 1.2 kg/l
 Acid, pH ~ 2.5
 Pungent odour
 “Ages” - viscosity increases with time
 Charcoal production
Charcoal is a light, black residue, consisting of carbon and any
remaining ash, obtained by removing water and other volatile
constituents from animal and vegetation substances.
Impure form of carbon as it contains ash.
• Produced by slow pyrolysis (low temperatures), the heating of
wood or other biomass in the absence of oxygen (bio-char).

http://www.youtube.com/watch?v=77w5uPLvKVg
http://www.youtube.com/watch?v=O-R-8OPRJz4
 Solid biofuels - torrefaction
Torrefaction - thermochemical treatment of biomass at 200 to 300°C
(mild form of pyrolysis, low temperatures, relatively short residence
time).
Under atmospheric pressure & absence of oxygen.
During the torrefaction process, the water contained in the biomass
as well as superfluous volatiles are released, and the biopolymers
(cellulose, hemicellulose and lignin) partly decompose, giving off
various types of volatiles.
• The final product is the remaining solid, dry, blackened material
with no biological activity like rotting which is referred to as
“torrefied biomass” or “bio-coal”.
http://www.youtube.com/watch?v=biWNh1iPnzQ
Torrefaction process diagram
 Torrefaction
• After the biomass is torrefied it can be densified (compressed),
usually into briquettes or pellets, to increase its mass and energy
density and to improve its hydrophobic properties. The final product
may repel water and thus can be stored in moist air or rain without
appreciable change in moisture content or calorific value.
• Torrefaction combined with compaction leads to a very energy-
dense fuel with NCV of 20 - 23 Mg.kg-1.
• Better fuel quality for combustion.

http://vimeo.com/92747073
http://www.youtube.com/watch?v=zee7BvswFfg
Torrefaction process
 Torrefied biomass/solid biofuels
- Mass loss 10 - 15 m-% (or up to 50 %);
- Heating value increases from 17 - 19 to 20 - 23 MJ/kg (dry);
- Density increases - density after treatment 180 - 300 kg/m3
Density after pelletizing 750 - 850 kg/m3
- Decomposition of hemicellulose;
- Dehydrogenation (chemical elimination of water);
- Elimination of CO2 and CO;
- Elimination of volatiles;
- Cracking of organic structures.