Energi Biomass

Semester 1/2011

Pyrolysis
Harmen Burhanuddin, S.T., M.T.

Fuel preparation, fuel upgrading and

other technologies

Bio-oil production from fast pyrolysis

Charcoal production
RDF
Briquetting technology

Pretreatment: mechanical

Conversion technologies

What is Pyrolysis?
Pirolisis proses
- konversi Thermal bahan padat dalam suasana inert dan tahap awal
dari proses pembakaran dan gasifikasi

- Pirolisis biomassa menghasilkan Char (padat), Bio-minyak (cair)

dan gas bahan bakar (gas)

Types of pyrolysis
Slow pyrolysis

Fast pyrolysis

Heating rate

Slow

Fast (rapid/flash)

Characteristic

Extensive tar
interaction with
solid and tar
cracking

Minimised interaction of
tar with solid and tar
cracking by immediate
quenching

Product

Solid

Liquid

Applications

Carbonisation for Rapid pyrolysis for bio-oil

charcoal
production
production
Synthesis gas production

Typical product yields (dry wood basis)

Mode

Conditions

Liquid

Char

Gas

Fast pyrolysis

moderate temperature,
high heating rate, short
residence time
particularly vapour

75%

12%

13%

Carbonisation

low temperature, very

long residence time

30%

35%

35%

Gasification

high temperature, long

residence times

5%

10%

85%

Applications of pyrolysis

Fast pyrolysis for bio-oil production

Fast heating rate process with

immediate quenching of liquid
product could result up to 70 %
bio-oil yield

Bio-oil is brownish, vicious liquid

(but still low compared to crude
oil) and immiscible with any form
of hydrocarbon liquid

Liquid products from fast pyrolysis

have significantly different
properties compared to those
from slow pyrolysis

Bio-oil production technologies

High yield of fast pyrolysis liquid can be obtained from

- Very high heating rates (i.e. >1000C/s)
- Moderate vapour temperatures (i.e. below around 600 C)
- Low vapour residence times
- Rapid quenching of the resultant vapour

High temperatures required from pyrolysis can be obtained

from
- Heating the gas-solid mix through the reactor wall
- Heating with a heat transfer medium (e.g. preheated
recycle gas)
- Heating through exothermic chemical reactions inside
the reactor (e.g. partial oxidation)
- Heating the particle directly through reactor wall

Since thermal conductivity of biomass is low, rapid heating to

achieve fast pyrolysis conditions imposes an upper particle
size of 3 to 5 mm, above which may cause slow rate of heat
of penetration and severe degradation of primary products

Reactors for bio-oil production

- Good temperature control
- Char removal is usually by
ejection and entrainment;
separation by cyclone
- Easy scaling
- Well understood technology
since first experiments at
University of Waterloo in
1980s
- Small particle sizes needed
Bubbling fluidised bed reactor
(BFB)

- Heat transfer to bed at large

scale has to be proven

- Good temperature control in reactor

- Larger particle sizes possible
- CFB suitable for very large
throughputs
- Well understood technology
- Hydrodynamics more complex,
larger gas flows in the system
- Char is finer due to more attrition at
higher velocities; separation is by
cyclone
- Closely integrated char combustion
requires careful control
Circulating fluidised bed reactor - Heat transfer to bed at large scale
(CFB)
has to be proven.

- Centrifugation drives hot

sand and biomass up rotating
heated cone
- Vapors are condensed
- Char is burned and hot sand
is recirculated

Rotating cone reactor

Overview of fast pyrolysis reactor

Property

Status
#

Bio-oil
wt%

Complex
ity

Feed
size

Inert
gas
need

Specific
size

Scale
up

Demo

75

Medium

Small

High

Medium

Easy

CFB

Pilot

75

High

Medium

High

Large

Easy

Entrained

None

65

High

Small

High

Large

Easy

Rotating cone

Pilot

65

High

V small

Low

Small

Hard

Ablative

Lab

75

High

Large

Low

Small

Hard

Vacuum

Demo

60

High

Large

Low

Large

Hard

Fluid bed

# Demo = demonstration (200 2000 kg h-1)

# Pilot = pilot plant (200 200 kg h-1)
# Lab = laboratory (1 20 kg h-1)

[* Countries that join PYNE network; Ref: www.pyne.co.uk]

Bio-oil characteristics

Typical properties of wood pyrolysis bio-oil

Physical property
Moisture content
pH
Specific gravity
Elemental analysis

Typical value

20-30%
2.5
1.20
C
55-58%
H
5.5-7.0%
O
35-40%
N
0-0.2%
Ash
0-0.2%
HHV as produced
16-19 MJ/kg
Viscosity (40 C and 25% water)
40-100 cp
Solids (char)
0.1 0.5%
Vacuum distillation residue up to 50%

Characteristics

Liquid fuel
Ready substitution for
conventional fuels in many
stationary applications such as
boilers, engines, turbines
Heating value of 17 MJ/kg at
25%wt. water, is about 40%
that of fuel oil/diesel
Does not mix with hydrocarbon
fuels
Not as stable as fossil fuels
Quality needs definition for
each application

Advantages of fast pyrolysis

for bio-oil production
Bio-oil is cheaper to transport than biomass
Bio-oil has a volumetric energy density of 20 GJ/m 3, but only 4
GJ/m3 for woodchips
Bio-oil is cleaner and has low ash content than biomass
Minerals like K, Cr, and Cu remain in the char (solid product),
not in liquid product
The cost of bio-oil production is relatively low due to the mild
conditions

Technical barriers for bio-oil utilisation

Poor fuel quality (relative to conventional fuel oils)

Chemical instability
Variable moisture content and heating value
Inconsistent physical properties
Corrosion in equipment
Contamination by particulates
No quality standard for bio-oil
High cost of production (compared to other alternative fuels,
10-100% more than fossil fuel)
Immiscible with crude oil, therefore a need of
i) conversion or upgrading
ii) discrete pyrolysis liquid storage, distribution and
utilisation systems

The most important issues that need to be addressed are:

- Scale-up
- Cost reduction
- Improving product quality including setting norms and
standards for producers and users
- Environment health and safety issues in handling,
transport and usage
- Encouragement for developers to implement processes
and users to implement applications
- Information dissemination

Upgrading of bio-oil
Since properties of bio-oil change with time: viscosity
increases, volatility decreases, phase separation, deposits,
gums, upgrading is necessary to increase stability
The most reactive compounds in bio-oils have unsaturated
double bonds which could be used as a measure for instability
Physical upgrading
- Filtration for char removal
- Emulsification with hydrocarbons
- Addition of low-viscosity solvent
Chemical upgrading
- Reaction with alcohols or phenolic derivatives
- Catalytic deoxygenation: mild hydrotreating
- Catalytic (zeolite) vapor cracking

Applications of pyrolysis liquid

Combustion application
- Bio-oil can be used as a retrofit to the existing oil-fired
burners with minor modifications, when raw biomass cannot be
used without major reconstruction
- Problems reported are suspended char causing
problems in atomisation and incomplete combustion

Power generation
- Peak power provision is possible with a small pyrolysis
plant or transportation of liquid to the plant
- Bio-oil has been successfully fired in a diesel test engine
and behave similar to diesel in term of engine parameters and
emissions

- Power generation using bio-oil has potential for short-term

opportunity, esp. for small-scale

- Due to its high efficiency, the cost for power generation is

reduced

- Growth in size of fast pyrolysis plants

Bio-oil production & utilisation

references

Forestera, Finland
- Liquefied woodchip pilot plant
- Liquid fuel is produced by fast pyrolysis up to 500 C
followed by condensation of vapours
- Yield of liquid is 60-70 %
- Installed solid separation process (solid content reduced to
0.1 % wt) is found to improve stability, reduce particulate
emissions during combustion and eliminate sludge formation
during storage

Rotating cone reactor, University of Twente

- 75 wt% bio-oil and only 15 wt% char and gas are produced as
primary products
- 250 kg/h pilot plant
- Rotational speed of the cone:
300 rpm
- Require:
Particle size < 6 mm
Moisture content < 10 wt%

Bio-oil production using sugarcane biomass residues at Fast

Pyrolysis Pilot Plant in Brazil
- Bioware Technology, Fluidised bed design

Co-firing of bio-oil with coal at Manitowoc, Wisconsin

- 25 tonnes of dry feed per day
- Hardwood derived bio-oil is co-fired with coal for the
commercial production of electricity
- The effect of bio-oil combustion on emissions and boiler
operation was observed during operation when the bio-oil co-firing
was about 5% of the total fuel input to the boiler

ENERSLUDGE Technology, Australia

- Bio-oil from sewage sludge
- When produced oil is combusted in an engine to produce
electricity, the process generates 925 kWh/ t of sludge
processed
- Average conversion product data
_________________________________________________
Product
Yield
GCV
% of Biosolids
(%)
(MJ / kg)
Energy
_________________________________________________
Oil
29
30
45
Char
43
18
40
NCG
14
15
11
RW
14
6
4
___________________________________________________

Charcoal production

Production of char, material of high carbon content, low ash,

high heating value
Slow pyrolysis process: carbonisation
Carbonisation for charcoal production, mainly from wood, but
other sources may be coconut shells and crop residues

History of charcoal production

Charcoal is produced by burning wood under conditions that

severely limit the amount of oxygen available for combustion
The object is to reduce the wood to a form of carbon by
removing the other constituents
Produced gases and other volatiles in the smoke are
allowed to escape
may be recaptured, condensed, and converted to useful
byproducts. Example is wood vinegar.
Because of their removal in large part, charcoal burns more
"cleanly"--that is, with little or no smoke or flame

Production cycle

Typical properties:
Properties
Moisture (%)
Volatile matter (%)
Ash (%)
Fixed carbon (%)
Calorific value (kcal/kg)

Charcoal

Rice husk

5.0-9.5
6.3-9.0
1.1-2.5
82-92
7200-8500

8.2
58.9
13.2
19.7
3380

Applications:
Charcoal for the barbecue and cooking market
Charcoal for heating, energy production, mineral refining,
and industrial use
Charcoal as a precursor to the production of carbon for
industrial use and activated carbon

Charcoal kilns

Charcoal manufacturing kilns generally can be classified as

either batch or continuous multiple hearth kilns; continuous
multiple hearth kilns

Batch units

A small, manually-loaded
and -unloaded kilns
producing typically 17.6
tons of charcoal during a
3-week cycle

Continuous units

Herreshoff patent

Refused Derived Fuel - RDF

RDF covers a wide range of waste materials which have

been processed to fulfil guideline, regulatory or industry
specifications mainly to achieve a high calorific value
Waste derived fuels include residues from MSW recycling,
industrial/trade waste, sewage sludge, industrial hazardous
waste, biomass waste, etc
RDF is uniformed, stable, high heating value, low in
pollutants, easy for storage and transportation and
combustible stability

Terms for MSW derived fuels

1
Refuse derived fuel (RDF)

Recovered Fuel (REF), Packaging

Derived Fuels (PDF), Paper and
Plastic Fraction (PPF) and Process
Engineered Fuel (PEF).
Mixed waste
Source-separated waste
The segregated high calorific Processed, dry combustible MSW
fraction of municipal solid
fraction (e.g. plastics and/or paper)
waste (MSW), commercial or
which are too contaminated to be
industrial process wastes
recycled.
It has a poorer quality than 2. It has a higher calorific value, lower
moisture content and lower ash
content (on combustion) than RDF
derived from mixed waste fractions.

 The quantity of RDF produced per tonne of MSW varies

depending on
the type of collection
treatment process
quality requirement for recovered solid fuels
The rate of RDF production from MSW can vary between 23
and 85% by weight of waste processed depending on the
treatment process used and country

Schematic Representation of MBT Process (Mechanical biological

treatment)

RDF Process (Taiwan): involves putting solid waste into fuel

pellets through
1. Crashing
2. Selection - Taking out materials large and not good for
combustion, e.g. metals, ceramics, glass
3. Drying
4. Mixing - Adding limes
and using catalyser
de-odorizing system
5. Pelletising

Quality of RDF from household and industrial sources

(EU references)

Utilisation of RDF from MSW

The following options for the utilisation and conversion of

RDF from MSW to energy have been used or could be used
in the future:
on-site in an integrated thermal conversion device, which
could include grate or fluidised bed combustion,
gasification or pyrolysis
off-site at a remote facility employing grate or fluidised
bed combustion, gasification or pyrolysis
co-combustion in coal fired boilers
co-incineration in cement kilns
co-gasification with coal or biomass

Number of industrial plants co-incinerating RDF from

industrial wastes in Europe

Briquetting

Briquetting or densification is used to improve characteristics

of materials for transport and use as energy source
Raw materials include sawdust, loose crop residues, and
charcoal fines
Use mechanical means, but additional binders may be
needed to bind the material
Main briquetting technologies are:
Piston press - using a high pressure to punch the
material into a die
Screw press - using a screw to continuously compact
the material, also producing briquettes of higher quality

Block chart of a briquetting system

Powdery Material

Briquetting
machine

return

Over size
Under size

Screen

Briquette

Products

Rough Structure of High Pressure Roll Press

Raw Material
Auto feeder

Screw Hydraulic compressive

force controller

Roll

Roll bearing

Bio-briquette
Features of bio-briquette
A wide variety of coal grades can be used as a raw
material
Biomass materials of low utility value can be used
It is excellent both in ignitability and burning property, and
generates little smoke
It produces little clinker, and ashes become sandy first
from the surface
70 to 80% of sulfur content in coal can be fixed in the ash

Outline of Process
Coal Pre-Treatment Section
Raw coal

Drying

Grinding

Mixing and Briquetting

Section

Biomass Pre-Treatment Section

Biomass

Drying

Grinding

Mixing

Desulfurisation Agent Supply Section

Desulfurisation Agent

Slaked lime react to Sulfur

Ca(OH)2 CaO H2O
CaO SO2 O2 CaSO4

Briquetting

Bio-Briquette

Properties of Bio-Briquette

Mixing ratio: Coal 80%, Bagasse 20%, Slaked Lime 5%

Shape:
Almond type
Size:
approx. 38mm26mm16mm
Compressive strength
40kgf or more

Relation between Time Lapsed and Smoke No.

Coal
Smoke No.
0
1
23
45
69

Bio-Briquette
Valuation Basis
Smoke doesnt occur.
Smoke occurs a little, and it cant be confirmed with the eyes.
Smoke occurs a little, and it can be confirmed with the eyes.
Smoke occurs, and feels an unpleasantness.
Smoke occurs in quantity, and it cant be used.

Bagasse blending ratio vs. Ignition time

180

Mark Coal Fuel Ratio

Ignition time [sec]

150

120

A 4.4
B 4.4
C 2.4
D 1.1

E 0.9

90

60

30

10

15

20

Bagasse blending ratio [%]

25

30

Unburnt Matters in Ash

Mix Ratio
Coal: Biomass

Unburnt matters
In ash [%]

100 : 0

17.68

90 : 10

3.45

80 : 20

2.63

70 : 30

3.66

Coal properties:
Ash content 11.3%
Volatile matters 40.8%
Fixed carbon
46.3%

Percentage of Fixed Sulfur [ % ]

Ca/S Ratio vs. Percentage of Fixed Sulfur

100
80
60
40
20
0

A n a ly s is o f e x h a u s t g a s

A n a ly s is o f a s h

1
2
3
Ca/S Ratio [ - ]

Other briquette
shapes, raw
materials

Banknotes