Clase 2 MGarcia

BIOMASS THERMO-CHEMICAL CONVERSION
TECHNOLOGIES
LECTURER: MANUEL GARCIA-PEREZ , Ph.D.
Department of Biological Systems Engineering,

Washington State University
e-mail: mgarcia-perez@wsu.edu
Universidad Nacional de Colombia: Sede Medellin
December 3-14, 2018

A.- COURSE OUTLINE
COURSE GRADING: (OPTION 1)
Projects (60 %)
Project # 1 : Each team of three students will choose a biomass related with their research subject and will
study its thermal behavior at different heating rates using thermogravimetry under nitrogen. The students
will quantify the moisture content, the content of volatiles, fixed carbon and ash (5%) (LAB 1)
Project # 2 : Each team will measure the elemental composition (CHNS-O) of their biomass (5%) (LAB 2)
Project # 3 : Each team will measure the calorific value of their biomass (5%) (LAB 3)
Project # 4 : Each team will identify the nature of the compounds released during the thermal degradation of
the material selected using Pyrolysis – Gas Chromatography / Mass Spectroscopy (Py-GC/MS) (5 %) (LAB 4)
Project # 5: Use the Friedman and ASTM methods to obtain kinetic constants from data obtained by
Thermogravimetry (10 %)
Project # 6: To carry out mass and energy balances of a thermochemical reactor (gasification or pyrolysis) (10
%)
Project # 7: Use of kinetic constants obtained to estimate the total pyrolysis times of the biomass particle
processed (10 %)
Project # 8: Size the thermochemical Reactor (5 %)
Project # 9: Final Report and Defense (5 %)
Homeworks (10 %)
Homework # 1: (5 %)
Homework # 2 (5 %)
Exams (30 %)
First Exam: Questions related with Topics 1 and 2 (15 %)
Second Exam: Questions related with Topics 3 and 4 (15 %)
PREVIOUS LECTURE OUTLINE
A.- Torrefaction
B.- Slow Pyrolysis

A.- COURSE OUTILNE
Biomass Resources and Energy Situation

1.- Introduction
Introduction to Biomass Thermochemical Conversion Technologies
Biomass Composition (Cellulose, Hemicellulose, Lignin, Extractives and Ash)

2.- Biomass Chemistry
Experimental Methods to Quantify Biomass Components. Primary
Thermochemical Reactions of biomass components.
3.- Analytical Themogravimetric Analysis (TG) and Differential Scanning Calorimetry (DSC)
Pyrolysis and Study of
Thermochemical
Reactions Pyrolysis GC/MS, Elemental and Proximate analyses, Calorific Value,
Thermochemical reactors
4.- Design and evaluation of biomass themo-chemical conversion technologies
Kinetics of Primary Mass and Heat and Mass Hydrodynamics of Fluidized Characterization and
and Secondary Energy Transfer in Beds, Heat and Mass Transfer in uses of
Thermochemical Balances Biomass Particles Fluidized Beds Thermochemical
Reactions Products
LECTURE OUTLINE
A.- Fast Pyrolysis
B.- Gasification
A.- FAST PYROLYSIS (350-600 oC)
HISTORICAL DEVELOPMENTS OF PYROLYSIS TECHNOLOGY

1970s- OIL CRISIS
1980s- FUNDAMENTALS OF BIOMASS FAST PYROLYSIS AND
DEVELOPMENT OF NEW PYROLYSIS REACTORS
1980s- PROGRESS IN BIO-OIL CHARACTERIZATION
1990s- SEVERAL FAST PYROLYSIS TECHNOLOGIES REACH COMMERCIAL OR NEAR
COMMERCIAL STATUS
1990s- COMBUSTION OF CRUDE BIO-OILS AT ATMOSPHERIC PRESSURE IN FLAME
TUNNELS AND BOILERS.
1990s- COMBUSTION OF BIO-OILS IN GAS TURBINES AND DIESEL ENGINES AND

UNDERSTANDING BIO-OIL COMBUSTION PHENOMENA
1990s- PROPOSED SPECIFICATIONS FOR FUEL APPLICATIONS
1990s- BIO-OILS UPGRADING: (DEVELOPMENT OF BIO-OILS MICRO-EMULSIONS),

HOT VAPOR FILTRATION, USE OF ADITIVES.
HISTORICAL DEVELOPMENTS OF PYROLYSIS TECHNOLOGY
1990s- BIO-OIL PHYSICO CHEMICAL STRUCTURE

1990s- STUDY OF FUEL PROPERTIES OF BIO-OIL BLENDS
1990s- DEVELOPMENT OF NEW BIO-OIL SEPARATION METHODS
1990s- NEW PRODUCTS FROM CRUDE BIO-OILS (Bio-Lime, Slow Release
Fertilizers, Road de-icers, Wood Preservatives, Glues, Sealing materials, bio-
pitches, Hydrogen, Meat Browning Agents, Hydroxyacetaldehyde, Phenol-
formaldehyde resins)
2000s- FIRST STUDIES ON CHARCOAL USES AS SOIL AMENDMENT
2007- BETWEEN 36 AND 40 % OF CRUDE BIO-OIL CAN BE CONVERTED TO GREEN
GASOLINE AND GREEN DIESEL VIA HYDROTREATMENT. CURRENT TECHNOLOGIES
ARE ABLE TO CONVERT 24 - 30 mass % OF THE BIOMASS INTO GREEN GASOLINE
AND GREEN DIESEL (36 - 45 mass % of ETHANOL EQUIVALENTS) (ONLY VIABLE AT
PETROLEUM PRICES OVER 100 USD).
BUSINESS MODELS IN DEVELOPED NATIONS

Pyrolysis Scheme to Produce Bio-char Pyrolysis Scheme to Produce Bio-char
and Heat and Bio-oil
FAST PYROLYSIS: IS A HIGH TEMPERATURE PROCESS IN WHICH BIOMASS IS RAPIDLY
HEATED (AROUND 300 oC PER MINUTES) IN THE ABSENCE OF OXYGEN. LIQUID
PRODUCTION REQUIERES VERY LOW VAPOR RESIDENCE TIME TO MINIMIZE
SECONDARY REACTIONS OF TYPICALLY 1 SECOND (BUT 5 SECONDS ARE ACCEPTABLE). IT
INVOLVES RAPID HEATING OF BIOMASS (HEATING RATES AROUND). GENERALLY FAST
PYROLYSIS IS USED TO OBTAIN HIGH-YIELD OF BIO-OIL. RESEARCHER HAS SHOWN THAT
MAXIMUM LIQUID YIELDS ARE OBTAINED WITH HIGH HEATING RATES AT
TEMPERATURES AROUND 500 oC
THE GROUP AT THE UNIVERSITY

OF WATERLOO, CANADA
DEVELOPED THE FLASH
PYROLYSIS PROCESS WHICH IS
BASED ON THE ADIABATIC
FLUIDIZED BED PYROLYSIS OF
LIGNOCELLULOSIC MATERIALS.
UNIVERSITY OF WATERLOO PILOT PLANT DIAGRAM

Fast
Slow pyrolysis
pyrolysis
20 wt %
Fast Slow
pyrolysis pyrolysis
327 427 527 627 727 327 427 527 627 727
Te [oC] Te [oC]
Fast
pyrolysis
20 wt %
Slow pyrolysis
327 427 527 627 727

Te [oC]
Di Blassi C: Combustion and Gasification of Lignocellulosic chars. Progresses in Energy and Combustion Sciences, 35 (2009) 121-140.
VALUES OF HEAT OF REACTION MEASURED BY MOK AND ANTAL1
SLOW PYROLYSIS
FAST PYROLYSIS
3Antal MJ, Gronli M: The Art, Science and Technology of Charcoal Production. Ind. Eng. Chem. Res. 2003, 42, 1619-1640.
FAST PYROLYSIS
Fast pyrolysis is a process in which very small biomass particles (less than 2
mm diameter) are heated at 450 – 600 °C in the absence of air/oxygen to
produce high bio-oil yield (60-75 mass%).
Syn Gas
Pyrolysis
Vapors
Fast Pyrolysis
Biomass Reactor
Bio-oil Aqueous
Phase
Bio-char
Conditions Liquid Char Gas
High heating rates, small particles, short

60-75 % 12-20 % 13-20 %
residence time of vapors
Model of Biomass Economy Based on Pyrolysis Potential Production (11.4 % of Current WA Oil
and Rural Refineries Consumption)
Biomass Biomass 5
4
Biomass 23
Mobile Pyrolysis Mobile Pyrolysis
Unit Unit
Stationary
Bio-char Pyrolysis Unit Bio-char
Crude Crude 6,140 t/day of 1
Forest Biomass
Bio-oil Bio-oil Biomass stabilized bio-oil
Bio-char
Mobile Pyrolysis Rural Bio-oil

Unit Mobile Pyrolysis
refinery Unit
Bio-char
Bio-char
Stabilized Bio-oil (Potentially:

Bio-plastics, lipids, 46,120 barrels/day) (11.4 % of current
Petroleum Refineries Rural Bio-oil Refineries
ethanol, consumption) 1 Tacoma (Oil US): 4,600 t crude oil/day
300 t crude bio-oil/day
chemicals…. 2 Anacortes (Tesoro): 14,400 t crude oil/day
1,200 t crude bio-oil/day
3 Anacortes (Shell): 19,000 t crude oil/day
2,400 t crude bio-oil/day
Petroleum or Oil 4 Ferndale (Conoco): 14,000 t crude oil/day
Cherry Point (BP): 30,000 t crude oil/day
Seed Refinery
5
Potential Production of Stabilized Bio-oil: 6,140 t/day (46,120 barrels/day)

Potential per-capita of Stabilized Bio-oil: 6.9 barrels per day/1000 people
Current WA per-capita consumption: 60.4 barrels per day/1000 people
Green Gasoline, Green World per capita consumption: 31.7 barrels per day/ 1000 people
Diesel and Jet Fuel
Assumptions: (1) Yield of crude bio-oil: 60 mass % of the biomass processed (2) Yield of
stabilized bio-oils: 50 mass % of the crude bio-oil obtained
A.- FASTPYROLYSIS (350-600 oC)
FAST PYROLYSIS
Ablative Fluid bed
The sand used to

Circulating Auger achieve high heating
Fluidized bed
rates contaminates
the bio-char and is
the source of several
technological
poblems
Vacuum Rotating cone
Vanderbosch RH, Prins W: Fast pyrolysis technology development . Biofuels, Bioproducts & Biorefining. 2010, p. 178-208
ABLATIVE PYROLYSIS: WOOD IS PRESSED AGAINST A HEATED SURFACE AND

RAPIDLY MOVED DURING WHICH THE WOOD MELTS AT THE HEATED
SURFACE AND LEAVES AN OIL FILM BEHIND WHICH EVAPORATES. THIS
PROCESS USES LARGER PARTICLES OF WOOD AND IS TYPICALLY LIMITED BY
THE RATE OF HEAT SUPPLY TO THE REACTOR. IT LEADS TO COMPACT AND
INTENSIVE REACTORS THAT DO NOT NEED CARRIER GAS BUT WITH THE
PENALTY OF A SURFACE AREA CONTROLLED SYSTEM AND MOVING PARTS AT
HIGH TEMPERATURE.
FLUID BED AND CIRCULATING FLUID BED PYROLYSIS: THE HEAT IS

TRANSFERRED BY A MIXTURE OF CONVECTION AND CONDUCTION. THE HEAT
TRANSFER LIMITATION IS WITHIN THE PARTICLE, THUS REQUIERING VERY
SMALL PARTICLES OF TYPICALLY NO MORE THAN 3 MM TO OBTAIN GOOD
YIELDS. SUBSTANTIAL CARRIER GAS IS NEEDED FOR FLUIDIZATION OR
TRANSPORT.
VACUUM PYROLYSIS: SLOW HEATING RATES BUT THE VAPOURS ARE

REMOVED FROM THE REACTOR IN THE PRESENCE OF VACUUM.
FAST PYROLYSIS
BTG Dynamotive Ensyn
Current technologies use high volumes of carrier gas and sand

as heat carriers. High yields of oil (60-75 wt. %)
Are the designs that have been scaled up reliable enough or will
they be replaced by new ones when bio-oil refineries are
deployed?
Small Particles: Less than 2 mm diameter

Low residence time of vapors: Less than 2 second
IT IS BELIEVED THAT AT TEMPERATURES OVER 400 oC SECONDARY CRACKING REATIONS

OCCUR AND THE AVERAGE MOLECULAR WEIGHT OF THE LIQUID PRODUCT DECREASES.
THE WINDOW FOR FUEL PRODUCTION REQUIERES MORE R & D TO BETTER UNDERSTAND
THE PROCESSES AND MATCH THE PRODUCT QUALITY REQUIREMENT TO PROCESS
PARAMETERS.
THE PRODUCT VAPORS ARE NOT TRUE VAPORS BUT RATHER A MIST OR FUME AND ARE
TYPICALLY PRESENT IN AN INERT GAS AT RELATIVELY LOW CONCENTRATIONS WHICH
INCREASES COOLING AND CONDENSATION PROBLEMS. THIS CONTRIBUTES TO THE
COLLECTION PROBLEMS AS THE AEROSOLS NEED TO BE IMPINGED ONTO SURFACE TO
PERMIT COLLECTION, EVEN AFTER COOLING TO BELLOW THE DREW POINT TEMPERATURE.
ELECTROSTATIC PRECIPITATORS ARE EFFECTIVE BUT CAN CREATE PROBLEMS FROM THE
POLAR NATURE OF THE PRODUCT AND ARCHING OF THE LIQUIDS AND THEY FLOW, CAUSING
ELECTROSTATIC PRECIPITATOR TO SHORT OUT. LARGE SCALE PROCESSING UNITS EMPLOYS
QUENCHING SYSTEMS (SCRUBBERS). CAREFULL DESIGN IS NEEDED TO AVOID BLOCKAGE
FROM DIFFERENTIAL CONDENSATION OF HEAVY ENDS. THE RATE OF COOLING SEEMS TO BE
IMPORTANT. TRANSFER LINES FROM THE REACTOR TO THROUGH THE CYCLONE(S) TO THE
LIQUID COLLECTION SYSTEM SHOULD BE MAINTAINED AT TEMPERATURES OVER 400 oC TO
MINIMIZE LIQUID DEPOSITION.
2s
FAST PYROLYSIS
EFFECT OF VAPORS RESIDENCE TIME
INSIDE THE PYROLYSIS REACTOR
(University of Twente)
Roel JM Westerhof: Refining Fast Pyrolysis of Biomass. PhD Thesis University of Twente 2011
FAST PYROLYSIS
EFFECT OF PARTICLE SIZE (C-Z Li, Monash University)
Shen J, Wang X-S, Garcia-Perez M, Mourant D, Rhodes MJ, Li C-Z: Effects of particle size on the fast pyrolysis of oil malee woody
biomass. Fuel 88 (2009) 1810-1817
FAST PYROLYSIS
EFFECT OF PARTICLE SIZE (University of Twente)
SEM Pictures of 1 mm beech wood particles
SEM Pictures of beech wood particles smaller than 80 micron

Roel JM Westerhof: Refining Fast Pyrolysis of Biomass. PhD Thesis University of Twente 2011
PYROLYSIS REGIMES
Zhou, S., Garcia-Perez, M., Pecha, B., McDonald, A. G., & Westerhof, R. J. (2014). Effect of particle size
on the composition of lignin derived oligomers obtained by fast pyrolysis of beech wood. Fuel, 125, 15-
19.
FAST PYROLYSIS
Novel Concepts for Pyrolysis Units studied at WSU
Additives (H2SO4)
(1) Use of Intermediate Pyrolysis reactors without sand

(2) Two Step Pyrolysis to reduce grinding energy
(3) Two Step Condensation Systems to Separate C1-C4 molecules and water
from bio-oil
Collaboration with Twente University (Netherlands) and Curtin University (Australia)
FAST PYROLYSIS
Performance of Auger Pyrolysis Reactor
Auger and
Feeder
Feeder Controllers
Oven
Condenser
Ice cooled Traps Temperature Motor

Char Pot Controller
Vacuum Pump
Effect of Pyrolysis Temperature

B.- GASIFICATION (700 -1400 oC)
THERMOCHEMICAL GASIFICATION IS THE CONVERSION BY PARTIAL OXIDATION AT ELEVATED

TEMPERATURES OF A CARBONACEOUS FEEDSTOCK INTO A GASEOUS ENERGY CARRIER
CONSISTING OF PERMANENT GASES AND TARS. DEVELOPMENT OF GASIFICATION
TECHNOLOGIES DATES BACK TO THE END OF THE 18TH CENTURY WHEN HOT GASES FROM
COAL AND COKE FURNACES WERE USED IN BOILER AND LIGHTING APPLICATIONS.
GASIFICATION OF COAL IS NOW WELL ESTABLISHED, AND BIOMASS GASIFICATION HAS
BENEFITED FROM ACTIVITY IN THIS SECTOR. HOWEVER, THE TWO TECHNOLOGIES ARE NOT
DIRECTLY COMPARABLE DUE TO DIFFERENCES BETWEEN THE FEEDSTOCKS (E.G. CHAR
REACTIVITY, PROXIMATE COMPOSITION, ASH COMPOSITION, MOISTURE CONTENT, DENSITY).
ALTHOUGH MANY BIOMASS GASIFICATION

PROCESSES HAVE BEEN DEVELOPED
COMMERCIALLY, ONLY THE FLUID BED
CONFIGURATION ARE BEING CONSIDERED IN
APPLICATIONS THAT GENERATE OVER 1 MWe.
FLUID BED GASIFIERS ARE AVAILABLE FROM A
NUMBER OF MANUFACTURERS IN THERMAL
CAPACITIES RANGING FROM 2.5 TO 150 MW
FOR OPERATIONS AT ATMOSPHERIC AND
ELEVATED PRESSURE.
GASIFICATION MEDIUM: AIR, STEAM, CARBON DIOXIDE AND A STEAM-OXYGEN MIXTURE

Comparison of Gasification and Combustion
With heat or power production, the obvious question is why a solid should be
gasified and then the gas burned for heat, losing some of its energy content in the
process. Does it not make more sense to directly burn the fuel to produce heat?
Answers:
1.- For a given throughput of fuel processed, the volume of gas obtained from
gasification is much less compared to that obtained form a direct combustion
system. The lower volume of gas requires small equipment and hence results in lower
overall costs.
2.- A gasified fuel can be used in a wide range of applications than can its precursor
solid fuel. For example, sensitive industrial processes such as glass blowing and drying
cannot use dirty flue gas from combustion of coal or biomass, but they can use heat
from the cleaner and more controllable combustion of gas produced through
gasification.
3.- Gasification produces much less NOx than a combustion system
4.- The gas produced in a central gasification plant can be distributed to individual
houses or units in a medium-size to large community
5.- If heat is the only product that is desired, combustion seems preferable, especially
in small scale plants, central heating, and power, combustion may be more economical
Basu P: Biomass Gasification and Pyrolysis. Practical Design and Theory. Elsevier. 2010
2500
Constant Volume Adiabatic Flame

2000
Pyrolysis Combustion
Temperature [ oC]
1500
FAST PROCESSES NEAR
EQUILIBRIUM
1000
800 oC
Gasification
500
REACTIONS CONTROLLED BY
KINETICS
0
Torrefaction
0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8 2
1/ f
Combustion > 1500 oC, Gasification 600 – 1400 oC, Fast Pyrolysis 350 – 600 oC,
Torrefaction: 220 – 300 oC
ADIABATIC FLAME TEMPERATURE VS. EQUIVALENT RATIO (f)

Common Gas-Solid Reactors used in Thermochemical Conversion
Screw conveyers
Moving beds Fluidized beds Rotary drums
(Auger Reactors)
Biomass
Steam ,
nitrogen,
oxygen or air
Gas
Biomass
Gas
Biomass
Heat
Solid Steam , nitrogen,
oxygen or air
Gas
Gas Heat Biomass
Steam , nitrogen,
oxygen or air Solid
Heat
Solid
Steam , nitrogen,
Heat
oxygen or air Solid
Milestones in Gasification development
1788 1920 1931 1997

Robert Gardner: First Carl von Linde: Cryogenic Lurgi: Pressurized Fist commercial
Gasification Patent separation of air, fully moving bed process gasification plant in US
continuous gasification process
1659
Thomas Shirley: 1801 1926 1974
Discovered gas Fourcroy: Water Winkler fluidized Arab oil embargo renewed
from coal mine gas shift reaction gasifier gasification interest
1739 1792 1861 1945 - 1974 2001

Dean Clayton: Murdoc: First use Siemens gasifier: Post-war “oil glut” Advanced gasification
Distilled coal in a of coal gas for First successful unit biomass renewable
closed vessel interior lighting energy projects
1798 : William Murdoch used coal-gas to light the main building at a foundry (Technology).
1802: Gas lighting public display (Technology).
1812: Fondation of the London Gas, light and coke company for the production of Town Gas (Market)
1900: Electric bulbs replaced gas as a source of light (Market).
1920: Only gas of low heating value (3.5-6 MJ/m3) could be produced
1926: Franz Fischer and Hans Tropsch developed the Fischer-Tropsch Process in Germany (Science).
1920: Carl Von Linde commercialized the cryogenic separation of air allowing to develop oxygen blast
for the production of synthesis gas and hydrogen (Science and Technology)
1920-1940: Development of new gasification concepts: 1926- the Winkler (Fluid bed process), 1931- the
Lurgi (Moving-bed pressurized gasification process), 1940- the Koppers-Totzek (Entrained-flow process).
1920-1960: Little further technical progress in the gasification of solid fuels but these technologies
played a critical role in Germany’s wartime synthesis fuel program and on the worldwide development
of the Ammonia industry.
1950: Texaco and shell developed the oil gasification process, decline in importance of gasification
because of the large production of of natural gas and naphtha.
1970: Sasol uses coal gasification and Fischer Tropsch synthesis as the basis for its Synfuels Complex.
1970: First oil crisis investment in coal hydrogenation (hydrogasification) to produce methane and liquid
fuels. Lack of commercial success due to the need for high pressure.
1972- Prototype gasification plants to produce electricity from coal gasification via IGCC
have been built and tested (COOL WATER, 1984; LUNEN, 1972, BUGGENUM, 1994; WABASH
RIVER, 1995; POLK, 1996; PUERTOLLANO 1998).
1978: Koppers and Shell joined forces to produce a pressurized version of the Koppers-
Totzek gasifier.
1981: Reinbraum developed the high temperature Winkler fluidized-bed reactor
1984: Lurgi developed a slagging version of its existing technology in partnership with
British gas.
1984: Texaco extended its oil gasification process to accept a slurried coal.
1984- Coal to chemicals is receiving increased attention (EASTMAN METHANOL PLANT IN
KINSPORT STARTED UP IN 1984; Ube IN JAPAN BEGAN WITH COAL TO AMMONIA).
1990- Gasification of heavy oil residues in refineries. Four plants have been built in Italy.
2000s- The increase in energy prices is fueling a renaissance of gasification technologies.
Many plants have been built in China.
Gasification Technologies
Entrained Flow Moving bed Fluidized bed

1.- Koppers-Totzek gasifier 1.- Lurgi dry-bottom 1.- Winkler process
2.- Seimens SFG gasifier 2.- BGL slagging gasifier 2.- KBR transport gasifier
3.- E-gas gasifier 3.- Twin-recator gasifier
4.- MHI gasifier 4.- EBARA Gasifier
5.- EAGLE gasifier 5.- GTI membrane gasifier
6.- Rotating fluidized bed
7.- Internal circulating
8.- Foster wheeler CFB
Unsuitable for Biomass
Coaxial Opposed jet Downdraft Updraft Crossdraft Bubbling Circulating Twin bed
downflow
Common Gasification Reactors
PRODUCT GAS CHARACTERISTICS

Gas Quality
Gas composition % v/v dry HHV
H2 CO CO2 CH4 N2 MJ/Nm3 Tars Dust
Fluid bed air-blown 9 14 20 7 50 5.4 Fair Poor
Updraft, air-blown 11 24 9 3 53 5.5 Poor Good
Downdraft, air-blown 17 21 13 1 48 5.7 Good Fair
Good Good
Downdraft, oxygen-blown 32 48 15 2 3 10.4
Fair Poor
Multi-solid fluid bed 15 47 15 23 0 16.1
17.4 Fair Poor
Twin fluidized bed gasification 31 48 0 21 0
Moving bed gasifiers (sometimes called fixed-bed gasifiers) are characterized by a bed in
which the carbonaceous material moves slowly downward under gravity as it is gasified by
a blast that is generally but not always, in counter-current blast to the carbonaceous
material. In such a counter-current arrangement, the hot synthesis gas from the
gasification zone is used to preheat and pyrolyse the downward flowing solid. With this
process the oxygen consumption is very low, but pyrolysis products are present in the
product synthesis gas.
Up-draft Gasifier: Biomass is fed from the top and a gasification medium (air, steam) is fed
from the bottom. The product gas leaves from the top while solids leave from the bottom.
Downdraft Gasifier: Both gas and feed travel downward. The temperature is higher in the
downstream combustion zone.
Fluid-bed gasifiers offer extremely good mixing between feed and oxidant, which promotes
both heat and mass transfer. Certain amount of only partially reacted fuel is inevitably
removed with the ash. This places a limitation on the carbon conversion of fluid bed processes.
The operation of fluid bed gasifiers is generally restricted to temperatures below the softening
point of the ash, since ash slagging will disturb fluidization. Sizing of the particle is very
important . The lower temperature operation of fluid bed processes means that they are more
suited for gasifying reactive feedsctocks, such as biomass and low-rank coal.
Source: Higman C, van der Burgt: Gasification, Gulf Professional Publishing, Second Edition, 2008.
Entrained-flow gasifiers operate with fed and blast in co-current flow. The residence time of
these processes is short (a few seconds). The feed is ground to a size of 100 mm or less to
promote mass transfer and allow transport in the gas. Given the short residence time, high
temperatures are required to ensure a good conversion and therefore all entrained flow
gasifiers operate in the slagging range.
One important point to keep in mind is the significance of the slagging behavior of the ash. At
temperatures above the ash softening point, the ash becomes sticky and will agglomerate,
causing blockage of beds or fouling the heat exchange equipment.
Traditional Processes:
Gas producer: humidified air is blown upward through a deep bed of coal or coke. The air
reacts with the coal, thereby producing a gas with a lower heating value of about 6.5 MJ/m3.
When using low rank feedstocks the calorific value can be as low as 3.5 MJ/m3.
Water gas: Steam reacts in a batch process with red-hot coke to form hydrogen and carbon
monoxide. First the coal or coke is heated by blowing air upward through the bed at 1300 oC.
Then the air is stoped and the steam is passed to produce synthesis gas. When the temperature
drop to about 900 oC the cycle is repeated.
Reference: Higman C, van der Burgt M: Gasification. Gulf Professional Publishing, Second Edition, 2008
Characteristics of different categories of gasification processes
A survey of gasifiers in Europe, the United States and Canada shows that downdraft
gasifiers are the most common.
1.- DOWNDRAFT: 75 %
2.- UPDRAFT: 2.5 %
3.-FLUID-BED : 20 %
4.-OTHER DESIGNS: 2.5 %
Range of applicability for biomass gasifier types
Fluid bed
Updraft Entrained flow

Downdraft
10 kW 100 kW 1 MW 10 MW 100 MW 1000 MW
Higman C, van der Burgt: Gasification, Gulf Professional Publishing, Second Edition, 2008.
Comparison of Some Commercial Gasifiers
Parameters Fixed/Moving Bed Fluidized Bed Entrained bed
Feed size < 51 mm < 6 mm < 0.15 mm
Tolerance for fines Limited Good Excellent
Tolerance for coarse Very good Poor Poor
Exit gas temperature 450-650 oC 800-1000 oC > 1260 oC
Feedstock tolerance Low-rank coal Low-rank coal and Any coal including caking
excellent for biomass but unsuitable for biomass
Oxidant requirements Low Moderate High

Reaction Zone 1090 oC 800 - 1000 oC 1990 oC
Temperature
Steam requirement High Moderate Low
Nature of ash produced Dry Dry Slagging
Cold-gas efficiency 80 % 89 % 80 %
Application Small capabilities Medium size units Large capabilities
Problem area Tar production and Carbon Conversion Raw-gas cooling
utilization of fines
Moving Bed Processes
Moving-bed processes are the oldest processes.
The patent for the Lurgi dry bottom process of “coal pressure gasification” as it is
known was granted in 1927. In 1931 Lurgi started to develop a pressurized version
of existing atmospheric producer gas technology. The development was made in
close colaboration with the Technical University in Berlin under the direction of
professor Rudolf Drawe. The first commercial application was built in 1936. Further
technical development has been placed in a joint venture between Lurgi and the
largest operator of this technology “Sasol”. Today the technology is referred as the
Sasol-Lurgi Dry bottom gasifier.
The hearth of the Lurgi process is the reactor in which the blast and syngas flow
upward in counter-current to the solid. The reactor vessel itself is a double-walled
pressure vessel in which the annual space between the two walls is filled with boiling
water. The steam is generated at a pressure similar to the gasification pressure,
thus allowing a thin inner wall , which enhances the cooling effect. The ash is
recovered via a rotating grade is precooled by incoming blast (oxygen or steam) to
about 300-400 oC.
Reaction Zones in a Standard Updraft Gasifier

BIOMASS
DRYING ZONE
PYROLYSIS ZONE
Gasification
zone
OXYGEN, CO2
or STEAM
Downdraft Gasifiers
A downdraft gasifier is a co-current reactor where air enters the gasifier at a certain
height below top. The product gas flows downward (giving the name downward) and
leaves through a bed of hot ash. Since it passes through the high temperature zone of
hot ash, the tar in the product gas find favorable conditions for cracking. For this
reason, a downdraft gasifier, of all types, has the lowest tar production rate.
Biomass
I Biomass Drying
Drying
II. Flaming pyrolysis
Pyrolysis Air
Air III.- Charcoal
Air Air Combustion
Combustion
IV.- Char
Gas Gasification
Gasification
Product
Gas 500 1000 1500
Temperature (K)
Ash
Characteristics of Moving Bed Gasifiers
Fuel (wood) Updraft Downdraft Crossdraft
Moisture wet basis (mass %) 60 max 25 max 10 - 20
Dry-ash basis (mass %) 25 max 6 max 0.5 – 1.0
Ash melting temperature (oC) > 1000 > 1250
Size (mm) 5 - 100 20 - 100 5 - 20
Application range (MW) 2 - 30 1-2
Gas exit temperature (oC) 200 - 400 700 1250
Tar (g/Nm3) 30 - 150 0.015 – 3.0 0.01-0.1
Gas LHV (MJ/Nm3) 5- 6 4.5 - 5.0 4.0 - 4.5
Hot-gas efficiency (%) 90 - 95 85 - 90 75 - 90
Sasol-Lurgi Dry Bottom Gasifier (MOVING BED)
PROCESS FLOWSHEET OF SASOL-LURGI DRY BOTTOM GASIFICATION

BGL Gasifier (MOVING BED)

Comparative Performance of Lurgi Dry Bottom and Bgl
Gasifiers
The lower portion of the reactor incorporates a molten slag bath. The molten slag is drained through a slag
tap into the slag quench chamber, where it is quenched with water and solidified. The solid slag is discharged
through a slag lock.
Fluid-bed Processes (Winkler Process)
The history of development of coal gasification and fluid-bed technology have

been intimately linked since development of the Winkler process in the early
1920s.
In fluid-bed gasification processes the blast has two functions: (1) as a
reactant and (2) as a fluidizing medium for the bed.
Operating temperature: if the ash content of the fuel start to soften then the
individual particles begin to agglomerate. The larger particles formed will fall
to the bottom of the bed and their removal poses a considerable problem.
Fluid bed gasifiers all operate at temperatures below the softening point of
the ash which is typically in the range 950-1100 oC for coal and 800-950 oC for
biomass.
Feed quality: fluid-bed gasifiers typically operate on low rank coal such as
lignite, peat or biomass (these materials have higher reactivities and can be
gasified at lower temperatures). These reactors operate with ground coal.
Carbon Conversion: There is wide range of residence times of the individual particles,
thus removal of fully reacted particles, which consist only of ash, will inevitably be
associated with removal of unreacted carbon. Maximum conversion efficiencies (97
%).
The Winkler Process (Fluidized bed)
The Winkler atmospheric fluid-bed process Winkler Atmospheric Fluid Bed Gasification
was the first continuous gasification process
using oxygen rather than air as blast. The
process was patented in 1922 and the first
plant built in 1925. Since then some 70
reactors have been nuilt and brought into
commercial service but has now been shut
down for economic reasons. In most
systems operation temperature is
maintained below the ash melting point
(950-1050 oC).
The High-Temperature Winkler (HTW) Process (Fluidized Bed)
The name “high-temperature Winkler” for the process developed by Rheinbraun is to

some extent a misnomer. The most important development vis-à-vis the original
Winkler process is the increase of pressure which has now been demonstrated at 30
bar.
WINKLER (HTW) PROCESS
The feed system comprises a lock-
hopper for pressurized and a screw
feeder for the transport of coal from
the high-pressure charge bin into the
gasifier. The htw process includes heat
recovery in a syngas cooler in which
the raw synthesis gas is cooled from
900 to about 300 oC. A ceramic candle
filter is used downstream of the
syngas cooler for particle removal.
Circulating Fluidized Bed (CFD) Processes (Lurgi circulating bed gasifier)
The characteristics of a circulating fluidized LURGI CIRCULATING FLUID-BED GASIFIER

bed combined many advantages of the
stationary fluidized bed and the transport
reactor. The high slip velocities ensure good
mixing of gas and solids, and thus promote
excellent heat and mass transfer. Small
particles are converted in one pass, or are
entrained, separated from the gas and
returned via an external recycle. One
advantage of this system is that the size and
shape of the particles is less important. This
type of gasifier is eminently suitable for the
gasification of biomass and wastes, of which
the size, shape, and hence the fluidization
characteristics are more difficult to control.
Production and Composition

In principle syngas (primarily consisting of CO and H2) can be produced from any
hydrocarbon feedstock including: natural gas, naphtha, residual oil, petroleum coke,
coal and biomass. The conversion of syngas into liquid fuels amount for more than
half the capital cost of these plants. The choice of technology for syngas production
also depends on the scale of the synthesis gas operation. Syngas production from
solid fuels is more expensive than from natural gas because it requires higher capital
investments with the addition of feedstock handling and more complex syngas
purifiation operations.
In its simplest form, syngas is composed of two diatiomic molecules CO and H2 that
building blocks upon which an entire field of fuel
provide the
science and technology is based. This mixture had many names depending
on how it was formed and used: producer gas, town gas, blue water gas, synthesis gas
and syngas. The beginning of the 20th century saw the dawn of fuels and chemicals
synthesis from syngas.
Spath PL, Dayton DC: Preliminary Screening-Technical and Economic Assessment of Synthesis Gas to Fuels and Chemicals with
Emphasis on the Potential for Biomass-Derived Syngas. NREL/tp-510-34929
Production and Composition
The syngas composition, most importantly the H2/CO ratio, varies as a function of
production and feedstock. Steam methane reforming yields H2/CO ratios of 3/1 while
coal gasification yields ratios closer to unity or lower. Syngas conversion processes are
thermodynamically favored at high H2 and CO partial pressures. The optimum
pressures depend on the specific synthesis process.
With the exception of methane steam reforming, catalytic syngas conversion

processes are exothermic reactions generating large excesses of heat. This highlight
the specific need for removing this heat of reaction to carefully control reaction
temperatures and maintain optimized process conditions.
Spath PL, Dayton DC: Preliminary Screening-Technical and Economic Assessment of Synthesis Gas to Fuels and Chemicals with Emphasis
on the Potential for Biomass-Derived Syngas. NREL/tp-510-34929
Many of the syngas conversion processes were developed in Germany during

the first and second world wars at a time when natural resources were
becoming scarce and alternative routes for hydrogen production, ammonia
synthesis and transportation fuels were of little consequence. With the
development of the petroleum industry in the 1940s and beyond, the
unattractive economics of many of these syngas routes became an issue and
were replaced by petroleum based processed. Methanol and ammonia
continue to be produced from syngas using similar processes. Apart from
hydrogen production these processes constitute the major uses of syngas.
The latest environmental driver to likely increase demand for syngas is the goal
of establishing a hydrogen economy.
METHANOL
SYNTHESIS OR
CONVERSION ETHERS
MHV DIESEL
STEAM OR
OXYGEN GAS FUEL CELLS GASOLINE
HYDROGEN
BIOMASS GASIFICATION AMMONIA
TURBINES
AIR LHV
GAS ENGINE
ELECTRICITY
HEAT
BOILER
Development of Processes to Produce Fuel and Chemicals from Syngas
1902 Synthesis of hydrocarbons from H2 and CO was discovered by Sabatier and

Sanderens who produced methane passing CO and H2 over Ni, Fe and co
catalysts.
1900s The first commercial hydrogen plant from the steam reforming of methane was
commercialized
1910s Haber and Bosch discovered the synthesis of ammonia from H2 and N2
1913 The first industrial ammonia synthesis plant was commissioned
1923 The production of liquid hydrocarbons and oxygenates from syngas conversion
over iron catalysts was discovered by Fischer and Tropsch. Variations on this
synthesis pathway were soon to follow for the selective production of
methanol, mixed alcohols, and isoynthesis products.
1938 The hydroformylation of olefins (another outgrowth of Fischer-Tropsch

synthesis (FTS) was discovered in 1938.
Synthesis Gas Conversion Processes
Products from Synthesis Gas (Advantages And Disadvantages)
Products from Synthesis Gas (Advantages and Disadvantages)
Summary of Syngas Conversion Processes and Conditions
Summary of Poisons
Gasification offers several options for processing biomass into

power, chemicals and fuels
Air
CO2 + H2O Thermal

Combustion
Power
Biomass Steam
Gasification Water-gas H2 + CO2 Hydrogen

CO + H2
shift reaction Fuel
Organic acids
Catalyst / Alcohols Fuels &
Biocatalysis Esters Chemicals
Hydrocarbons
Brown R: Thermochemical Processing of Biomass. Conversion into Fuels, Chemicals and Power. Wiley 2011
Vehicle gasifier in the 1970’s after the fuel crisis

Typical vehicle gasifier demonstrating the Spark ignition system producer gas engine
gas cooler and cyclone.
Gasification for Heat Production
Kwant KE, Knoef H: Status of Biomass Gasification in countries participating in the IEA Bioenergy Task 33 Biomass Gasification and EU
Gasnet Oct. 2004. Technical Report
Gasification for Power Production
Kwant KE, Knoef H: Status of Biomass Gasification in countries participating in the IEA Bioenergy Task 33 Biomass Gasification and EU
Gasnet Oct. 2004. Technical Report
Integrated Gasification Combined Cycle (more than 35 % electrical efficiency)
Low Pressure Integrated Gasification Combined Cycle
Craig KR, Mann MK: Cost and Performance Analysis of Biomass Based Integrated Gasification Combined Cycle (BIGCC)
Power Systems. October 1996 NREL/TP-430-21657
Integrated Gasification Combined Cycle
High Pressure, Air Blown Integrated Gasification Combined Cycle
Craig KR, Mann MK: Cost and Performance Analysis of Biomass Based Integrated Gasification Combined Cycle (BIGCC)
Power Systems. October 1996 NREL/TP-430-21657
C.- CONCLUSIONS
Main Thermochemical Technologies to be Studied in this Course

TORREFACTION: Pre-treatment method carried out at 225-300 °C in absence of
oxygen. The biomass become completely dried and loose its tenacious and fibrous
structure. The grindability and the calorific value of biomass is improved
significantly.
PYROLYSIS: Process in the absence of air/oxygen carried out at temperatures

between 350 and 600 oC. This process can be controlled to maximize either the
production of charcoal or liquid products.
GASIFICATION: Process that converts carbonaceous materials, such as biomass, into

gases rich in carbon monoxide and hydrogen by reacting the raw material at high
temperatures with a controlled amount of oxigen and/or steam. The resulting gas
mixture is called synthesis gas or syngas (700 – 1400 oC).
COMBUSTION : Complex sequence of exothermic chemical reactions between a the

biomass and an oxidant (usually air) to produce heat (Temperatures over 1400 oC) .

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BIOMASS THERMO-CHEMICAL CONVERSION

LECTURER: MANUEL GARCIA-PEREZ , Ph.D.

Department of Biological Systems Engineering,

Universidad Nacional de Colombia: Sede Medellin

December 3-14, 2018

B.- Slow Pyrolysis

Biomass Resources and Energy Situation

Biomass Composition (Cellulose, Hemicellulose, Lignin, Extractives and Ash)

4.- Design and evaluation of biomass themo-chemical conversion technologies

A.- Fast Pyrolysis

HISTORICAL DEVELOPMENTS OF PYROLYSIS TECHNOLOGY

1990s- COMBUSTION OF BIO-OILS IN GAS TURBINES AND DIESEL ENGINES AND

1990s- PROPOSED SPECIFICATIONS FOR FUEL APPLICATIONS

1990s- BIO-OILS UPGRADING: (DEVELOPMENT OF BIO-OILS MICRO-EMULSIONS),

HISTORICAL DEVELOPMENTS OF PYROLYSIS TECHNOLOGY

1990s- BIO-OIL PHYSICO CHEMICAL STRUCTURE

BUSINESS MODELS IN DEVELOPED NATIONS

THE GROUP AT THE UNIVERSITY

UNIVERSITY OF WATERLOO PILOT PLANT DIAGRAM

327 427 527 627 727

VALUES OF HEAT OF REACTION MEASURED BY MOK AND ANTAL1

Conditions Liquid Char Gas

High heating rates, small particles, short

Mobile Pyrolysis Rural Bio-oil

Stabilized Bio-oil (Potentially:

Potential Production of Stabilized Bio-oil: 6,140 t/day (46,120 barrels/day)

The sand used to

Vacuum Rotating cone

ABLATIVE PYROLYSIS: WOOD IS PRESSED AGAINST A HEATED SURFACE AND

FLUID BED AND CIRCULATING FLUID BED PYROLYSIS: THE HEAT IS

VACUUM PYROLYSIS: SLOW HEATING RATES BUT THE VAPOURS ARE

Current technologies use high volumes of carrier gas and sand

Small Particles: Less than 2 mm diameter

IT IS BELIEVED THAT AT TEMPERATURES OVER 400 oC SECONDARY CRACKING REATIONS

SEM Pictures of 1 mm beech wood particles

SEM Pictures of beech wood particles smaller than 80 micron

(1) Use of Intermediate Pyrolysis reactors without sand

Ice cooled Traps Temperature Motor

Effect of Pyrolysis Temperature

THERMOCHEMICAL GASIFICATION IS THE CONVERSION BY PARTIAL OXIDATION AT ELEVATED

ALTHOUGH MANY BIOMASS GASIFICATION

GASIFICATION MEDIUM: AIR, STEAM, CARBON DIOXIDE AND A STEAM-OXYGEN MIXTURE

Constant Volume Adiabatic Flame

ADIABATIC FLAME TEMPERATURE VS. EQUIVALENT RATIO (f)

Common Gas-Solid Reactors used in Thermochemical Conversion

Milestones in Gasification development

1788 1920 1931 1997

1739 1792 1861 1945 - 1974 2001

Entrained Flow Moving bed Fluidized bed

Common Gasification Reactors

PRODUCT GAS CHARACTERISTICS

Characteristics of different categories of gasification processes

Range of applicability for biomass gasifier types

Updraft Entrained flow

10 kW 100 kW 1 MW 10 MW 100 MW 1000 MW

Oxidant requirements Low Moderate High

Reaction Zones in a Standard Updraft Gasifier

Characteristics of Moving Bed Gasifiers

Fuel (wood) Updraft Downdraft Crossdraft

Moisture wet basis (mass %) 60 max 25 max 10 - 20

Dry-ash basis (mass %) 25 max 6 max 0.5 – 1.0

Ash melting temperature (oC) > 1000 > 1250

Size (mm) 5 - 100 20 - 100 5 - 20