This project report is submitted in the total fulfilment of the requirements

for the Degree of Bachelor in Technology

Project work carried out under the guidance of
Prof. Pinaki Bhattacharya
Department of Chemical Engineering
Heritage nstitute of Technology
Chowbagha !oad" #nandpur
$olkata% &''('&
Email) abmin*heritageit+edu
ACKNOWLEDGEMENT
Submitt! By"#
Nam $o%% No. $&i'tration No.
#,inash $umar -haw (./''/(''0/ ('(./'(('123
4agheshree Chakraborty (./''/(''(. ('(./'(('133
-aheli Biswas (./''/(''(' ('(./'(('5(.
-oumilli Chatterjee (./''/('''0 ('(./'(('5.5
T(E ST)D* O+ CATAL*T,C P*$OL*S,S
O+ L,GNOCELL)LOS,C MATE$,AL
P$O-ECT $EPO$T
6e our deepest gratitude to our department" Chemical Engineering" Heritage
nstitute of Technology" $olkata and Prof+ B+! -aha" Head of Department"
for wonderful 7pportunity of participating in the project conducted by the
Chemical Engineering Department+ #t the onset we would like to thank Prof+
Pinaki Bhattacharya" our mentor and project guide for his constant support"
ad,ice and encouragement throughout the process+ 6e would also like to
recogni8e the in,aluable support that we recei,e and show for each other+
#,inash $umar -haw 9('001.:
4agheshree Chakraborty 9('00.&:
-aheli Biswas 9('0055:
-oumilli Chatterjee 9('00(3:
Department of Chemical Engineering
Heritage nstitute of Technology%$olkata
6est Bengal ;ni,ersity of Technology
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E,er since the dawn of industrial re,olution" one of the major issues that has gradually
cropped up and today has manifested itself as a canker is global warming+ n simple
words it refers to the rise in temperature of the earthCs atmosphere+ There are a deluge of
causes for global warming" one of the major reasons being wide scale emission of green%
house gases+ This again has its root in the large amount of harmful gases like carbon
dioDide that are spewed by the ,ehicles+ -o" a major concern for the present day is the
formulation of alternati,e methods for the production of liquid fuels" which when used in
,ehicles will spread lesser air pollution" thereby reducing the eDtent of the social peril%
global warming+ The alternati,es are gasification" combustion" and pyrolysis" aerobic and
anaerobic digestion+
?asification is a process that con,erts organic or fossil based carbonaceous materials
into carbon monoDide" hydrogen and carbon dioDide+ This is achie,ed by reacting the
material at high temperatures 9E&'' FC:" without combustion" with a controlled amount
of oDygen andGor steam+ The resulting gas miDture is called syngas 9from synthesis
gas or synthetic gas: or producer gas and is itself a fuel+ The power deri,ed from
gasification and combustion of the resultant gas is considered to be a source of renewable
energy if the gasified compounds were obtained from biomass+ The ad,antage of
gasification is that using the syngas is potentially more efficient than direct combustion of
the original fuel because it can be combusted at higher temperatures or e,en in fuel cells"
so that the thermodynamic upper limit to the efficiency defined by CarnotHs rule is higher
or not applicable+ -yngas may be burned directly in gas engines" or con,erted ,ia
the BischerITropsch process into synthetic fuel+
#naerobic digestion is a collection of processes by which microorganisms break
down biodegradable material in the absence of oDygen+ The process is used for industrial
or domestic purposes to manage waste andGor to produce fuels+ 4ethane and power
produced in anaerobic digestion facilities can be used to replace energy deri,ed from
fossil fuels" and hence reduce emissions of greenhouse gases" because the carbon in
biodegradable material is part of a carbon cycle+ The carbon released into the atmosphere
from the combustion of biogas has been remo,ed by plants for them to grow in the recent
past" usually within the last decade" but more typically within the last growing season+ f
the plants are regrown" taking the carbon out of the atmosphere once more" the system
will be carbon neutral+ n contrast" carbon in fossil fuels has been sequestered in the earth
PAGE 1
for many millions of years" the combustion of which increases the o,erall le,els of
carbon dioDide in the atmosphere+ n aerobic digestion the process is carried out in
presence of air+
Pyrolysis is a thermochemical decomposition of organic material at ele,ated temperatures
in the absence of oDygen 9or any halogen:+ t in,ol,es the simultaneous change
of chemical composition and physical phase" and is irre,ersible+ The word is coined from
the ?reek%deri,ed elements pyro JfireJ and lysis JseparatingJ+ Pyrolysis is a type
of thermolysis" and is most commonly obser,ed in organic materials eDposed to high
temperatures+ t is one of the processes in,ol,ed in charring wood" starting at .''I1'' FC
913'I0&' FB+ n general" pyrolysis of organic substances produces gas and liquid products
and lea,es a solid residue richer in carbon content" char+ EDtreme pyrolysis" which lea,es
mostly carbon as the residue" is called carboni8ation+ The process is used hea,ily in
the chemical industry" for eDample" to produce charcoal" acti,ated carbon" methanol" and
other chemicals from wood and for transforming medium%
weight hydrocarbons from oil into lighter ones like gasoline+ These speciali8ed uses of
pyrolysis may be called ,arious names" such as dry distillation" destructi,e distillation" or
cracking+ Pyrolysis differs from other high%temperature processes
like combustion and hydrolysis in that it usually does not in,ol,e reactions with oDygen"
water" or any other reagents+ n practice" it is not possible to achie,e a completely
oDygen%free atmosphere+ Because some oDygen is present in any pyrolysis system" a
small amount of oDidation occurs+
There are three types of pyrolysis) fast" flash and slow+ Bast pyrolysis uses moderate to
high temperatures and rapid heating while slow pyrolysis is characteri8ed by gradual
heating at lower temperatures which produces a more pure and uniform product+ -low
pyrolysis yields a higher proportion of bio char than fast pyrolysis" from the amount of
raw material processed" gi,ing it the highest carbon sequestration potential+ Therefore"
slow pyrolysis is not only the most effecti,e means of producing bio char+ Blash pyrolysis
is characteri8ed by moderate temperatures eDist 95''%/''FC: and rapid heating rates
9E.FCGs:+ @apor residence times are usually less than two seconds+ Compared to slow
pyrolysis" considerably less tar and gas are produced+ Howe,er" the tar and oil products
are maDimi8ed+ The only difference between flash and fast pyrolysis 9more accurately
defined as thermolysis: is heating rates and hence residence times and products deri,ed+
Heating rates are between .'' and ('0FC per second and the pre,ailing temperatures are
usually higher than 00'FC+ Due to the short ,apor residence time" products are high
quality" ethylene%rich gases that could subsequently be used to produce alcohols or
gasoline+ =otably" the production of char and tar is considerably less during this process+
Different kinds of feedstock can be used for pyrolysis+ Due to its low cost and large
a,ailability" lignocellulosic biomass is being studied worldwide as a feedstock+
PAGE 2
C(APTE$ ." L,TE$AT)$E $E/,EW
AznarET. al. 9(331: studied the impro,edG two%stage steam gasification of biomass or
lignocellulosic residues in fluidi8ed bed with steam reforming catalysts placed in a
downstream secondary reactor has been studied+ Two commercial catalysts" !%/& and
!$-%( from Topme" were used at their incipient fluidi8ation conditions+ #t &.'%&/' JC
and space%times of only '+('%'+.' s" with catalyst si8es under (+' mm and with
steamGbiomass ratios of (+.%(+/" tarcon,ersions of 33+30K were achie,ed in the catalytic
reactor+ n this process tar" methane" flue gas can be easily lowered below 0 mgGm
1
9=TP:+
#nd '+0 ,olK" without using oDygen+
WangET. al. 9(33&: studied the hydrogen production ,ia pyrolysis of lignocellulosic
biomass followed by reforming of the pyro ligneous oils is a cost effecti,e alternati,e
hydrogen production process which poses competition to the con,entional methods+
6and et al+ proposed a regionali8ed system where bio%oil to be catalytically con,erted to
H. and C7.is pro,ided to a central reforming unit by small and medium%si8ed pyrolysis
units 9L0'' 4gGday:+ 6ith thermodynamic modelling" reforming was shown to be
possible within a wide range of temperatures and steam%to%carbon ratios+ #lmost
complete con,ersion to hydrogen" with =i%based catalysts" was shown+ t was concluded
that yielding ,aluable oDygenates by initial refining of bio%oil followed by hydrogen
production only from the residual fraction" would gi,e a possible opportunity+
Maldas ET. al. 9(33&: studied that eDtent of dissolution of lignocellulosic biomass
increased with the increase in temperature+ #t .0'oC" 50 min reaction time is optimum+
#queous alkali is moreeffecti,e than water+ Both residue and phenol K decreased with
increased concentration+ PH"temperature" type of biomass" type of sample" chelating
power" particularly for transition metals has profound influence+
Wang ET. al. 9(332: studied the two methods of thermo chemically con,erting biomass
into hydrogen" ,i8+ gasification followed by shift con,ersion and fast pyrolysis followed
by catalytic steam reforming then shift con,ersion" 6ang et al 9(332:+ EDplored and
analy8ed the fast pyrolysis route+ 6ith model compounds" aqueous fraction of poplar oil
and commercial nickel%based steam%reforming catalysts" the process was demonstrated at
bench scale+ High hydrogen yield of 20K and maintenance of initial catalyst acti,ity by
periodic steam regenerationG C7. gasification were reported+
Garcia ET. al.9(332: studiedthe influence of se,eral preparation parameters on the
performance of a coprecipitated nickel alumina catalyst for use in the pyrolysis of
lignocellulosic residues has been studied+ The ,ariables considered were calcination
PAGE 3
temperature 9&0' and 20' FC:" reduction time 9(" ." and 1 h:" and hydrogen flow in the
reduction step 9(&5' and 1'2' cm1 9-TP:Gmin:+ The catalyst performance was
e,aluated on a bench scale plant equipped with a continuous fluidi8ed bed reactor
using the 6aterloo fast pyrolysis process 96BPP: technology+ The biomass used was
pine sawdust and the reaction temperature was /0' FC+ The results show that when the
higher calcination temperature is applied" more se,ere operating conditions on
thereduction processmust also be applied" but catalyst sintering can appear when
,ery se,ere reduction conditions are used+
Garcia et al. (1999) performed catalytic steam gasification of pine sawdust in a low
temperature fluidi8ed bed with =i%#l catalyst prepared by co%precipitation and
calcination+ The ,arious influences of catalyst weightGbiomass flow rate 96Gmb: and
steamG biomass 9-GB: ratios on the product distribution and gaseous product quality were
studied+ t was obser,ed that an increase in 6Gmb ratio increased the total gas" H." C7"
and C7. yields" decreased CH5 and C. yields and influenced initial gas composition+ 7n
the other hand" an increase in the -GB ratio increased H. and C7. yields with decrease in
C7 and CH5and had positi,e influence on life of catalyst+
Olazar ET. al.9.''':has proposed many types of reactor for pyrolysis+ # capti,e sample
wire mesh reactor for fast pyrolysis produces H. rich gas+ -econd" a fiDed bed reactor for
catalytic or non%catalytic pyrolysis produces liquid product+ #lthough" Conical spouted
bed reactor in which flash pyrolysis is carried out assisted by a catalyst is considered as a
,ersatile alternati,e+
Demirbas 9.''(: studied that hydrogen has become an attracti,e fuel for the future
energy technology+ t is produced from solid waste by pyrolysis+ #n appreciable yield of
H. has been obtained from oli,e husk" cocoon shell and tea waste using MnCl. as catalyst+
?asification of the solid fuel produces H. and C7" followed by water gas shift reaction to
produce H. and C7. are also established processes for H. production+
Demirbas ET. al. 9.''(:studied that the pyrolysis process consists of a ,ery compleD set
of reactions in,ol,ing the formation of radicals+ The gasification of biomass is a thermal
treatment" which results in a high production of gaseous products and small quantities of
char and ash+ Hydrogen is produced from solid wastes by pyrolysis+ n this study" three
different biomass samples were subjected to direct and catalytic pyrolysis to obtain
hydrogen rich gaseous products at desired temperatures.
CzernikET. al+ 9.''.: studied an economic approach combining hydrogen production
with production of ,aluable coproduces was proposed by C8ernik et al+ The promising
process was based on the two stage process concept) bio%oil generation by fast pyrolysis
of biomass followed by hydrogen production by steam reforming of bio%oil+ The work
PAGE 4
focused on catalytic steam reforming of ,arious biomass%deri,ed liquids+ High hydrogen
yield" greater than 2'K" was accomplished by reforming of bio%mass deri,ed liquids in
fluidi8ed%bed reactor using commercial nickel%based naphtha reforming catalyst+
Yaman ET. al. 9.''5: re,iewed the wide range of bio%mass feed stocks used for pyrolysis"
different pyrolysis conditions and their influence on product composition and properties
for production of fuels and chemicals+ The liquid pyrolysis products were analy8ed and
,arious process modifications 9like catalytic upgrading or steam reforming: were
considered for producing economical and en,ironment friendly fuels G chemical feed
stocks from the liquid pyrolysis products+
Adam ET. al. 9.''/: compared these,en mesoporous catalysts in how they can con,ert
the pyrolysis ,apors of spruce wood in order to obtain impro,ed bio%oil properties+ Bour
#l%4C4%5( type catalysts were tested+ The catalytic properties of #l%4C4%5( catalyst
were modified by pore enlargement+ -pruce wood pyrolysis at 0'' NC was performed in a
lab%scale fiDed bed reactor" the solid" gaseous and liquid products were separated+ The gas
yield increased in each catalytic case" the coke yield remained the same or slightly
decreased compared to the non%catalytic eDperiments+ The aqueous part in the liquid
phase increased in the catalytic runs+ n the catalytic eDperiments the hydrocarbon and
acid yields increased" while the carbonyl and the acid yields decreased+ #ll catalysts
tested reduced the undesirable product yield" while the desirable product yield remained
the same or increased+ To study the feedstock effect on the catalytic upgrading of the
pyrolysis ,apors" some tests were performed with 4iscanthus biomass+ Concerning the
feed stocks" with 4iscanthus a better quality bio%oil has been obtained+
!berET+ al+ 9.''/: found that with decline in the petroleum resource clubbed with rising
demands of petroleum by the emerging economies" there is an urge to de,elop
economical and energy efficient processes for sustainable de,elopment+ Hence a shift to
the plant biomass and bio%fuels has been obser,ed which generates less greenhouse
emissions+ To start with" the cheapest and most abundant feedstock a,ailable worldwide
is lignocellulosic biomass+ >iquid fuel is obtained by remo,ing oDygen from it+
Trianta"#llidis et al+ 9.''&:tested the in situ up gradation of biomass pyrolysis ,apors
using two mesoporous aluminosilicate materials 9(MSU-SBEA): assembled from 8eoliteBeta
9BE#: seeds+ # comparison to con,entional #l%4C4%5( and to non%catalytic biomass
pyrolysis was also pro,ided+ The two samples eDhibited different mesoporous structures+
The use of the 4-;%- catalytic materials produced significantly lower organic and
higher coke and char compared to non%catalytic pyrolysisand to the use of #l%4C4%5(+
The 4-;%- catalytic materials also possessed stronger acid sites"showed selecti,ity
towards polycyclic aromatic hydrocarbons 9P#Hs:and hea,y fractions" thus producing
more aromatics" P#Hs" coke and propylenein the pyrolysis gases+
PAGE 5
$li%&%!l%sET.al.9.''&: studied the useof two mesoporous aluminosilicate #l%4C4%5(
materials 9-iG#l O 1' or 0': for the in sit! upgrading of biomass pyrolysis ,apors in
comparison to a siliceous 4C4%5( sample and to non%catalytic biomass pyrolysis+ The
change in the beha,ior of the bio%fuel was mainly attributed to the combination of the
large surface area and tubular mesoporous 9pore diameter .I1 nm: of 4C4%5(
materials" with their mild acidity that leads to the desired en,ironment for controlled
con,ersion of the high molecular weight lignocellulosic molecules+ The major
impro,ement in the quality of bio%oil was the increase of phenols concentration
9useful chemicals: and the reduction of corrosi,e acids 9undesirable in fuel bio%oils:+
Higher -iG#l ratios of the #l%4C4%5( samples enhanced the production of the organic
phase of the bio%oil" while lower -iG#l ratios fa,ored the con,ersion of the
hydrocarbons of the organic phase towards gases and coke+ 4oderate steaming of the
#l%4C4%5( samples 9at 00' and &0' PC" .'K steam partial pressure: decreased their
surface area and number of acid sites by 5'I/'K depending on the -iG#l ratio of the
samples and the steaming temperature+ Howe,er" the steamed samples were still acti,e in
the in sit! upgrading of biomass pyrolysis ,apors" resulting in different product yields
and bio%oil composition+
Ma'er ET. al.9.''&: studied 9(: direct thermal crackingand 9.: combination of thermal
and catalytic cracking+ Typically" four main catalyst types are used including transition
metal catalysts" molecular sie,e type catalysts" acti,ated alumina" and sodium carbonate+
!eaction products are hea,ily dependent on the catalyst typeand reaction conditions and
can range from diesel like fractions to gasoline like fractions+
(in and !ber 9.''2: reported that heterogeneous catalysis offers immense potential in
helping to make lignocellulosic biofuels commercial reality+ n this article we discuss the
central role of heterogeneous catalysis in biomasscon,ersion+ 6e re,iew the science of
catalysis and the different routes to make biofuels+ During the lastse,eral decades
multiple new spectroscopic" theoretical" and synthesis tools are a,ailable that allow us to
study catalysis at a molecular le,el+ These new tools will allow us to rapidly de,elop new
catalytic processes for the production of cost%efficient lignocellulosic biofuels+
)!and (ad 9.''2:studied thedirect liquefaction of a woody biomass 9Aack pine sawdust:
in subGnear%critical water without and withcatalysts 9alkaline earth and iron ions: has been
in,estigated at temperatures of .2'I12' FC+ Hea,y oils with high caloric ,alue of 1'I10
4AGkg 9much greater than that of the crude wood sample used: were obtained"along with
water soluble oils with a caloric ,alue of (3I.0 4AGkg+ #ll the catalysts tested" i+e+"
Ca97H:." Ba97H:." and Be-75"were found effecti,e for enhancing the formation of
hea,y oil products at .2'I15' FC" while they significantlypromoted the formation of gas
and water at E15' FC+ The yield of hea,y oil in the operation at 1'' FC for 1'min was
impro,ed significantly from around 1'K without catalyst to greater than 50K by Ba
PAGE 6
97H: .+ ThemaDimum yield of total oil products reached 0(K in the operation without
catalyst" while it increased to about/0K with Ca 97H: . at 1'' FC+
*t%cker 9.''2: re,iewed and summari8ed numerous biomass resources which ha,e the
potential to gi,e alternati,e energy sources" fuels and chemicals+ n the paper" he mainly
focuses on the catalytic con,ersion of biomass deri,ed from wood+ He also addresses the
problems in processing lignocellulosic materials+ #pplication of porous materials as
catalysts in the process" de,elopment of the catalysts" understanding the compleD reaction
mechanism and process up%gradation ha,e been eDplored in the re,iew+
+inder ET. al. 9.''2: report that ,",%dimethylacetamide 9D4#: containing lithium
chloride 9>iCl: is a pri,ileged sol,ent that enables the synthesis of the renewable
platformchemical 0%hydroDymethylfurfural 9H4B: in a single step andunprecedented
yield from untreated lignocellulosic biomass" as well as from purified cellulose" glucose"
and fructose+ The con,ersion of cellulose into H4B is unabated by the presence of other
biomass D4#%>iCl are critical for the remarkable rapidity 9(%0 h: and yield 9up to 3.K:
of this low%temperature 9e(5' FC: process+ This chemical transformation of
lignocellulose is much simpler than the compleD+
T%rren ET. al. 9.''3: studied theconversion of biomss com!o"n#s $o
rom$ics b% $&erm' #ecom!osi$ion in $&e !resence of c$'%s$s (s
inves$i)$e# "sin) !%ro !robe n'%$ic' !r'%*er. +&e ,rs$ s$e! in
$&is !rocess is $&e $&erm' #ecom!osi$ion of $&e biomss $o sm''er
o-%)en$e $&$ $&en en$er $&e c$'%s$s !ores (&ere $&e% re
conver$e# $o ./0 ./20 ($er0 co1e n# vo'$i'e rom$ics. 2i)& &e$in)
r$es n# &i)& c$'%s$ $o fee# r$io fvor rom$ic !ro#"c$ion over
co1e form$ion. +&e rom$ic %ie'# for '' $&e !ro#"c$s (s simi'r
s"))es$in) $&$ '' of $&ese biomss-#erive# o-%)en$es )o $&ro")&
common in$erme#i$e. A$ 'o(er c$'%s$ $o fee# r$ios vo'$i'e
o-%)en$es re forme# inc'"#in) f"rn $%!e com!o"n#s0 ce$ic ci#
n# &%#ro-%ce$'#e&%#e. +&e !ro#"c$ se'ec$ivi$% is #e!en#en$ on
bo$& $&e si*e of $&e c$'%s$ !ores n# $&e n$"re of $&e c$ive si$es.
3ive c$'%s$s (ere $es$e# inc'"#in) 4SM-50 si'ic 'i$e0 be$0 n# 5-
*eo'i$e n# si'ic6 '"min. 4SM-5 &# $&e &i)&es$ rom$ic %ie'#s
(378 crbon %ie'#) n# $&e 'es$ mo"n$ of co1e.
-is&!te and !ber9.''3: showed that hydrogen" alkanes 9ranging from C( to C/:
andpolyols 9ethylene glycol" (" .%propanediol" (" 5%butanediol: can be produced from the
aqueousfraction of wood%deri,ed pyrolysis oils 9bio%oils:+ Theaqueous fraction was
subjected to a low temperature hydrogenation with !uGC catalyst at(.0I(&0 C and
/2+3bar+ Diols 9ranging from C.to C5: and sorbitol are obtained as major products in this
PAGE 9
step+ #fter the low temperaturehydrogenation step either hydrogen or alkanes can be
produced by aqueous%phase reforming 9#P!: or aqueous%phdehydrationGhydrogenation
9#PDGH: respecti,ely+ #P! was done witha ( wt+ KPt+ G#l.71 catalyst at ./0 C and
00+(bar+ Hydrogen selecti,ities of up to /'K were obser,ed+ The hydrogen selecti,ity
was a function of space ,elocity+ # 5 wt+ KPt+ G-i7.%#l.71catalyst at ./' C and 0(+&
bar was used for alkane production by #PDGH+
Ga#!b%ET. al+9.''3: studied that ,alorisation of the crude bio%oil 9two step process%
thermal and catalytic: is required due to the polymeri8ation of phenol deri,ed compounds
which results in deposition of carbonaceous material on the catalyst surface" thus
deacti,ating the catalyst and blocking the catalytic bed+
.renc'ET. al. 9.'(': reported that fast pyrolysis bio%oils ha,e potential to become an
acceptable fuel upon catalytic up gradation of the pyrolysis ,apour using 8eolite M-4%0"
alumina stabilised ceria 4%0&0 etc+ Catalyst is required to remo,e oDygen from the
organic compound to con,ert it to hydrocarbon and impro,e its heating ,alue+ Tests had
been performed on three feedstock% cellulose" lignin and wood where highest yield of
hydrocarbon was achie,ed with nickel" cobalt" iron and gallium substituted M-40+
/an ET. al. 9.'(': studied that=annochloropsis sp+ 9a kind of green microalga: residue
when pyroly8ed without catalyst or with different amount of HM-4%0 catalyst in a fiDed
bed reactor in nitrogen flow produced bio%oils that had lower oDygen content 9(3+0 wt+K:
and higherheating%,alue 91.+& 4A kgN(: than those obtained from direct pyrolysis
9B7DP:+ The B7DP mainly consisted of long carbon chain compounds with ,arious
terminal groups 9>CT?:" while the B7CP mainly consisted of aromatic hydrocarbons+
Al%ns%ET. al. 9.'(': studied the implications of utili8ing starchy and triglyceride feeds
tocks fromtraditional food crops+ The primary focus of this re,iew is an o,er,iew of
catalytic strategies to produce biofuels from aqueous solutions of carbohydrates" which
are isolated through biomass pretreatment and hydrolysis+ #lthough hydrolysis%based
platforms are associated with higher upstream costs arising from pretreatment and
hydrolysis" the aqueous solutions of biomass%deri,ed compounds can be processed
selecti,ely to yield hydrocarbons with targeted molecular weights and structuresfor each
of the platforms discussed" rele,ant strategies for the formation of C6C bonds" such as
aldol condensation of ketones and oligomeri8ation of alkenes+
PAGE :
C(APTE$ 0" A,MS AND OB-ECT,/ES
To determine the products obtained from pyrolysis of lignocellulosic paste like
lime peel waste and Aute along with sesame oil cake in a semibatch pyroly8er
To determine of pyrolysis kinetics of lignocellulosic paste by lumped parameter
model and ,alidation of kinetic model de,eloped theoretically+
7ptimi8ation of yield of ,olatiles using a statistical optimi8ation technique" ,i8"
!esponse -urface 4ethodology 9!-4:+ The response yield of ,olatiles has been
considered as a function of mutually interacti,e ,ariables namely weight"
temperature and time+ 1D figures showing the effects of the independent ,ariables
on the response will be drawn to draw the conclusion on the optimi8ed parameter+
PAGE ;
C(APTE$ 1" MATE$,ALS AND MET(ODS
Matria%'"
There are so many problems associated with the disposal of jute sacks+ This residual parts
i+e+ oil cakes contain high bulk density+ #s it increases the B7D le,el of water body" it is
harmful for our en,ironment+ 7n the other hand it can be used as a huge amount of
Carbon sink and energy sourceby Q6aste to Energy Con,ersion TechniquesR+
n ndia there are many oil cakes are a,ailableS among these jute sacks take the attention
in this study+ Due to its a,ailability in ndia and no commercial applications eDcept cattle
feed or fertili8er" its market price is ,ery low+ Bor these reasons jute sacks is used as the
raw material of Pyrolysis+ The oil cake is purchased from the local oil mill+ The samples
were broken into small pieces+ The si8e of the pieces was (' to .' mm+
Table 10 /r%1imate Anal#sis %" 2!te *acks
Pro2imat
Ana%y'i'
Moi'tur Contnt /o%ati%
Mattr
A'h Contnt +i2! Carbon
9 K 6G6 : ('+'.0 &&+(0 .+03 ('+.10
E23rimnta%"
Pyrolysis of -esame oil cake samples were carried out in a stainless steel Pyrolyser of 0'
mm diameter and /5' mm long+ The Pyrolyser" packed with -esame oil cake sample" was
hori8ontally placed in an electrically heated Tubular Burnace+ The inert atmosphere of the
PAGE 17
Pyrolyser was maintained by purging =. gas" at a rate of '+211 >Gminthroughout the
eDperiment to sweep the ,olatiles produced during pyrolysis+
The isothermal paraly8ing conditions were maintained by using a PD temperature
controller" 9Honeywell DC%('5':+ Pyrolysis temperature was ,aried from 5''
'
C to 3''
'
C+
Heating rate was maintained at ('
o
CGmin+ 7nce the desired temperature is attained" the
paraly8er is placed into the furnace+ The ,olatile product" coming out from the reactor is
directed to a condensing system" consisting of a condenser and an ice%bath assembly+ The
eDit point of the paraly8er is connected with the condenser and the condenser is
connected with the ce%bath system+ (0
o
C temperature is maintained in the condenser and
'
o
C is maintained at the ce%bath system consists a series of ;%Tube containers+ The
condensable ,olatiles are collected from the condensing unit and non%condensable
gaseous products are dri,en out+ The Pyrolyser was hung by a -+- chain attached with a
weighing machine for continuous monitoring of the residual mass of solid in the
paraly8er+
The pH of the condensates i+e+ the pyrolysis oil was obtained for all eDperimental runs+
6hereas the organic part of tar which got dissol,ed in ben8ene was eDtracted in a rotary
e,aporator and the quantity of pyro%oil was established+
The calorific ,alues of eDtracted tar and char obtained at the temperature of 5''%3''
o
C
pyrolysis run were determined by using a Bomb calorimeter+
The 4orphological analysis of raw sample and char samples obtained at 0''
'
C and 2''
'
C
were also analy8ed using -canning Electron 4icroscope+
The eDtracted pyro%oil" thus obtained" was analy8ed with Bourier Transform nfrared
-pectroscopy 9BT!:+
The distillation characteristics of the ben8ene free hydrocarbon eDtract obtained from the
pyrolysis oil of 5''
o
C" /''
o
C and &''
o
C was also analy8ed+
The CH=- ,alues of the pyro%oil were determined by CH=- #naly8er+
The collected pyro%oils were then further cracked in a 4uffle Burnace to find out the
kinetics of secondary cracking reaction+
PAGE 11
.ig!re 10 E1&erimental set!& %" &#r%l#sis e1&eriment
,n'trumnta% Ana%y'i'"
The characteri8ation of raw sample and products are carried out into different
equipmentCs by following their own guidelines+
Table 30 Details %" t'e $nstr!ments !sed in t'e /r%4ect
#nalysis =ame of the
equipment
4odel =o+ =ame of the company
4oisture content Hot #ir o,en #-T4 D%555. Bhattacharya T Co+
#sh content 4uffle Burnace #-T4 E%(&00%'( Bhattacharya T Co+
@olatile matter 4uffle Burnace #-T4 D%5.'3 Bhattacharya T Co+
PAGE 12
$'3on' Surfac Mtho!o%o&y
Brief qualitative overview of RSM principle
!esponse -urface 4ethodology 9!-4: consists of statistical and mathematical tools
aimed at modelling" analysing and optimi8ing processes+ 4ostly" the problems that are
sol,ed using this method ha,e multi,ariable independent factors influencing the desired
r'3on'+ Here response refers to the performance character of the process+ Bor the
process under in,estigation i+e+ catalytic pyrolysis of lignocellulosic material" ,olatile
product yield is the desired response which is influenced by independent interacting
factors like temperature" time and feed weight+
The actual response function is unknown in most !-4 problems+ Taking data from
approDimate eDperiments" a function relating the response to the independent ,ariables is
approDimated in this method+ The optimum ,alue is then determined+
;sually low order polynomials ,i8+ (
st
order and .
nd
orderG Uuadratic are the commonly
used approDimations+ n the present process with three independent ,ariables" the
simulated equation is eDpected to be quadratic+
Second-Order Model
# general second%order model can be eDpressed as follows)
The first%order model fails when there is a cur,ature in the response surface+ n such a
case the second%order model impro,es the optimi8ation process appreciably+
Consideration of a number of functional forms and local approDimation of response
surface make the second order modelG quadratic model more significantly ,ersatile+ The
coefficients are estimated using least squares method+
PAGE 13
#mong the numerous methods of fitting second order models" the central composite
design 9CCD: is the most common one+ Here the Central Composite Design 9CCD:
program of the QDesign EDpert 2+'+&+(R software has been used to obtain the optimum
conditions+
The obser,ed result from a set of four pyrolysis reactions 9i+e+ $Cl V >ime peel waste"
=a#l-i V >ime peel waste" Aute V -esame oil cake V #l.71" Aute V -esame oil cake V
Mn7: each of which were carried out at three different temperatures ,i8+ &&1$" 3&1$ and
((&1$" were used+
PAGE 14
C(APTE$ 4" T(EO$ET,CAL MODELL,NG
# scheme has been proposed by Bandyapadhay et al 9(333: for the reaction pathway of
the pyrolysis of sesame oil cake+ This is as follows)
The following assumption has been made for kinetic modelling)
i+ The first step of the scheme" i+e+ the W#cti,e compleDC formation is
instantaneous+ Thus" the reaction is considered to be in equilibrium+
ii+ #ll the reactions occurring in the scheme are of first order with respect to the
solid reactant+
iii+ The solid residual obtained at infinite time" at any temperature in the pyrolysis
8one is entirely comprised of char+
i,+ -olid residue obtained at any time other than t O X is made up of unreacted solid
reactant and solid product char+
,+ #s the operation is a semi%batch one" the probability of occurrence of all the
secondary reactions has been assumed to be 8ero+
,i+ #bsolute inert atmosphere pre,ails during pyrolysis+
,ii+ Heat and mass transfer resistance in the samples may be negligible+ This may be
justified by a ,ery high specific surface area of the sample and ,ery small si8e
of the crucibles used+
PAGE 15
Biomass
#cti,e CompleD
$
$,
@olatile
Char
,iii+ #ny transport limitation within the eDperimental and the analytical part of the
system may be neglected+ This has been done by proper designing of the
system+
The weight loss profile of the solid reactant 6 with time may be gi,en by)
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.:
>et" k@V $cOk
=ow"
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 95:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 90:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9/:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9&:
=ow"
PAGE 16
7r" %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 92:
ntegrating both sides" we get)
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 93:
;nder isothermal conditions"
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(':
#t tO'" 6, O6,o
Thus" %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9((:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(.:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(1:
-imilarly"
PAGE 19
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(5
7r" %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(0:
ntegrating both sides" we get)
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(/:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(&:
#t tO'" 6C O6co
Thus" %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(2:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9(3:
Hence the profile of increase of weights of ,olatiles and char against time are gi,en
respecti,ely by the following eDpressions
PAGE 1:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.'
#nd
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.(:
6c I 6c' O $c 96'G$: Y(%e
%$t
Z %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9..:
6@ % 6,' O $, 96'G$: Y(%e
%$t
Z %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.1:
96C 9t: I 6c': G 96@ 9t: I 6,': O $cG$, O 96C 9t %EX: I 6c':G 96@ 9t%EX: I 6,':% 9.5:
96' 9t: I 6c':G 96@ 9t: I 6,': O 96C9t %E X: I 6c':G 96@ 9t%EX: I 6,':%%%%%%%%%%%% 9.0:
6C 9t: O 6c' V 96@ 9t: I 6,': %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9./:
6c' O 'S 6,'O 'S
6C 9t: O 96C 9t%EX:: G 96@ 9t%EX:: 96@ 9t:: %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.&:
6C 9t%EX: O 6! %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.2:
6C 9t: O 96! 9t:: G 96@ 9t%EX:: %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 91':
The weight of unreacted feed)
6 9t: O 6' I 96! G 6@ 9t %E ':: 96@ 9t:: I 6@ 9t:%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 91(:
6 9t: O 6' I 6@ Y96! G 6@ 9t %E X:: V (Z %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 91.:
PAGE 1;
C(APTE$ 5" $ES)LTS AND D,SC)SS,ON
O3timi6ation $'u%t'
KCl catalysed Pyrolysis of Lime Peel aste
The complete lists of coded and actual ,alues are pro,ided in Table 1" Table 5 and Table0+
Table 50 (ist %" C%ded and 6n7c%ded $nde&endent -ariables and T'eir 8anges
@ariables !anges
Coded ;ncoded ;nit %[ %( ' V( %[
\( >ime peel ?rams .5+/5 0/ ('. (52 (&3+1/
PAGE 27
waste
\. Temperature $el,in /'/+2. &0' 3/' ((&' (1(1+(2
\1 Time 4inutes (0 (0 .&+0'
5'
52+0.
Table 90 (ist %" C%ded and 6n7C%ded -al!es %" $nde&endent -ariables
!un Beed TE4PE!#T;!E T4E
;ncoded Coded ;ncoded Coded ;ncoded Coded
(+ (52 V( &0' %( 5' V(
.+ (52 V( &0' %( (0 %(
1+ ('. ' 3/' ' 52+0. V[
5+ (52 V( ((&' V( 5' V(
0+ ('. ' /'/+2. %[ .&+0' '
/+ ('. ' 3/' ' .&+0' '
&+ 0/ %( &0' %( (0 %(
PAGE 21
2+ ('. ' 3/' ' .&+0' '
3+ (52 V( ((&' V( (0 %(
('+ 0/ %( &0' %( 5' V(
((+ ('. ' 3/' ' .&+0' '
(.+ ('. ' 3/' ' /+52 %[
(1+ .5+/5 %[ 3/' ' .&+0' '
(5+ 0/ %( ((&' V( 5' V(
(0+ ('. ' 3/' ' .&+0' '
(/+ ('. ' 3/' ' .&+0' '
(&+ (&3+1/ V[ 3/' ' .&+0' '
(2+ ('. ' (1(1+(2 V[ .&+0' '
(3+ 0/ %( ((&' V( (0 %(
.'+ ('. ' 3/' ' .&+0' '
PAGE 22
Table :0 Obser;ed< /redicted and 8esid!al -al!es %" 8es&%nses
!un Beed Temperature Time 7bser,ed Predicted !esidual
(+ (52 &0' 5' (+(52 (+(0 '+''.
.+ (52 &0' (0 '+51' '+51. '+''.
1+ ('. 3/' 52+0. (+551 (+50. '+''3
5+ (52 ((&' 5' (+&/3 (+&/1 '+''/
0+ ('. /'/+2. .&+0' '+2.1 '+2.1 '+2..
&+ 0/ &0' (0 '+(01 '+(// '+'(1
3+ (52 ((&' 5' (+''1 (+'. '+'(&
('+ 0/ &0' /+52 '+22 '+2& '+'(
(.+ ('. 3/' .&+0' '+(2& '+(/2 '+'(3
#nalysis showed that a quadratic model was the best fit 9Table /: with actual and
predicted regression coefficient !
.
as '+3330 and '+33&0 respecti,ely+
PAGE 23
Table =0 M%del .it *!mmar#
PAGE 24
The #=7@# analysis 9Table &: showed significance of model as well of the three
independent parameters 9QProb E BR L '+'''(:+
Table >0 A,O-A anal#sis
Bigure ." Bigure 1 and Bigure 5 show the contour graphs for $Cl catalysed lime peel
waste pyrolysis+
PAGE 25
.ig!re 50 C%nt%!r &l%t "%r AC
PAGE 26
.ig!re 30 C%nt%!r &l%t "%r A+
.ig!re 90 C%nt%!r &l%t %" +C
Bigure 0" Bigure / and Bigure & show the corresponding 1%D -urface mages+
.ig!re :0 57D *!r"ace "%r A+
PAGE 29
.ig!re =0 57*!r"ace "%r AC
.ig!re >0 57D *!r"ace "%r +C
PAGE 2:
Bigure 2 shows a chart of comparison between predicted ,s actual ,alues+
.ig!re ?0 /redicted ;s Act!al Gra&'
The optimi8ed operating conditions 9as marked in the contour plots and 1%D -urface
mages: for $Cl cataly8ed lime peel waste pyrolysis was found to be at 3/' $ with ('.
grams feed of lime peel waste for a time of .&+0 minutes+
PAGE 2;
!a"lSi catalysed Pyrolysis of Lime Peel aste
The complete lists of coded and actual ,alues are pro,ided in Table 2" Table 3 and
Table('+
Table ?0 (ist %" C%ded and 6n7c%ded $nde&endent -ariables and T'eir 8anges
@ariables !anges
Coded ;ncoded ;nits %[ %( ' V( V[
\(
>ime Peel
waste ?ram .5+/5 0/ ('. (52 (&3+1/
\. Temperature $el,in /'/+2. &0' 3/' ((&' (1(1+(2
\1 Time 4inutes /+52 (0 .&+0 5' 52+0.
Table 90 (ist %" C%ded and 6n7C%ded -al!es %" $nde&endent -ariables
!un Beed Temperature Time
;ncoded Coded ;ncoded Coded ;ncoded Coded
( //+/ ' 3&1 ' 1.+0 '
. /3 ( &&1 %( 0' (
1 //+/ ' 3&1 ' 1.+0 '
5 /5+. %( &&1 %( (0 %(
0 /.+0/ %[ 3&1 ' 1.+0 '
/ //+/ ' (1'3+1/ V[ 1.+0 '
& //+/ ' 3&1 ' 1.+0 '
2 &'+/5 V[ 3&1 ' 0/ '
3 /5+. %( ((&1 ( 1.+0 (
PAGE 37
(' //+/ ' 3&1 ' 0' '
(( /3 ( ((&1 ( 0' (
(. /5+. %( &&1 %( (0 (
(1 /3 ( ((&1 ' /(+31 %(
(5 //+/ ' 3&1 %( (0 V[
(0 /3 ( &&1 %[ 1.+0 %(
(/ //+/ ' /1/+15 ' 1.+0 '
(& //+/ ' 3&1 ' 1+'& '
(2 //+/ ' 3&1 ' 1.+0 %[
(3 //+/ ' 3&1 ( (0 '
.' /5+. %( ((&1 %( 1.+0 '
Table 1@0 Obser;ed< /redicted and 8esid!al -al!es %" 8es&%nses
!un Beed Temperature Time 7bser,ed Predicted !esidual
. /3 &&1 0' (+155 (+152 '+''5
5 /5+. &&1 (0 '+/31 '+/33 '+''/
0 /(+0/ 3&1 1.+0 (+'&. (+'2. '+'(
/ //+/ (1'3+1/ 1.+0 (+1. (+15/ '+'./
2 &'+/5 3&1 1.+0 (+./( (+.&1 '+'(.
3 /5+. ((&1 0/ (+5'2 (+5 '+''2
(( /3 ((&1 0' (+/.. (+/ '+''.
(. /5+. &&1 0' (+(35 (+(2& '+''&
(1 /3 ((&1 (0 '+&1 '+&.. '+''2
PAGE 31
(5 //+/ 3&1 /(+31 (+13 (+5'. '+'(.
(/ //+/ /1/+/5 1.+0 (+((& (+((1 '+''5
(2 //+1 3&1 1+'& '+.(2 '+..2 '+'(
(3 //+/ 3&1 1.+0 (+1&2 (+1&& '+''(
.' /5+. ((&1 (0 '+/0/ '+/1& '+'(3
#nalysis showed that a quadratic model was the best fit 9Table ((: with actual and
predicted regression coefficient !
.
as '+3311 and '+3&.& respecti,ely+
Table 110 M%del .it *!mmar#
The #=7@# analysis 9Table (.: showed significance of model as well of the three
independent parameters 9QProb E BR L '+'''(:+
PAGE 32
Table 130 A,O-A anal#sis
Bigure 3" Bigure (' and Bigure (( show the contour graphs for =a#l-i catalysed lime
peel waste pyrolysis+
PAGE 33
.ig!re 90 C%nt%!r &l%t "%r A+
.ig!re 1@0 C%nt%!r &l%t "%r AC
PAGE 34
.ig!re 110 C%nt%!r &l%t "%r +C
Bigure (." Bigure (1 and Bigure (5 show the corresponding 1%D -urface mages+
.ig!re 130 57D *!r"ace "%r A+
PAGE 35
.ig!re 150 57D *!r"ace "%r AC
.ig!re 190 57D *!r"ace "%r +C
Bigure (5 shows a chart of comparison between predicted ,s actual ,alues+
PAGE 36
.ig!re 1:0 /redicted ;s Act!al Gra&'
The optimi8ed operating conditions 9as marked in the contour plots and 1%D -urface
mages: for $Cl catalysed lime peel waste pyrolysis was found to be at 3&1 $ with //+/
grams feed of lime peel waste for a reaction time of 1.+0 minutes+
#nO catalysed Co-Pyrolysis of $ute and Sesame oil ca%e
The complete lists of coded and actual ,alues are pro,ided in Table (1" Table (5 and
Table (0+
Table 150 (ist %" C%ded and 6n7c%ded $nde&endent -ariables and T'eir 8anges
@ariables !anges
Coded ;ncoded ;nits %[ %( ' V( V[
\(
AuteV-esame
oil cake ?ram 3.+00 ((1 (51 (&1 (31+50
\. Temperature $el,in /1/+/5 &&1 3&1 ((&1 (1'3+1/
\1 Time 4inutes /+52 (0 .&+0 5' 52+0.
PAGE 39
Table 190 (ist %" C%ded and 6n7C%ded -al!es %" $nde&endent -ariables
!un Beed Temp Time
;ncoded Coded ;ncoded Coded ;ncoded Coded
( (&1 ( &&1 %( (0 %(
. (51 ' 3&1 ' .&+0 '
1 (51 ' /1/+/5 %[ .&+0 '
5 (51 ' 3&1 ' .&+0 '
0 (31+50 V[ 3&1 ' .&+0 '
/ ((1 %( &&1 %( 5' (
& (51 ' 3&1 ' /+52 %[
2 (51 ' 3&1 ' .&+0 '
3 (51 ' 3&1 ' .&+0 '
(' ((1 %( ((&1 ( 5' (
(( (51 ' 3&1 ' .&+0 '
(. (51 ' 3&1 ' 52+0. V[
(1 (51 ' 3&1 ' .&+0 '
(5 (&1 ( ((&1 ( (0 %(
(0 (&1 ( ((&1 ( 5' (
(/ ((1 %( &&1 %( (0 %(
(& 3.+00 %[ 3&1 ' .&+0 '
(2 (&1 ( &&1 %( 5' (
(3 (51 ' (1'3+1/ V[ .&+0 '
.' ((1 %( ((&1 ( (0 %(
PAGE 3:
Table 1:0 Obser;ed< /redicted and 8esid!al -al!es %" 8es&%nses
!un Beed Temp Time 7bser,ed Predicted !esidual
( (&1 &&1 (0 '+(30 '+.'2 '+'(1
1 (51 /1/+/5 .&+0 '+5.. '+5.0 '+''1
0 (31+50 3&1 .&+0 '+&. '+&.2 '+''2
/ ((1 &&1 5' '+255 '+2/ '+'(/
& (51 3&1 /+52 '+(/( '+(53 '+'(.
(' ((1 ((&1 5' '+&& '+&/1 '+''&
(( (51 3&1 .&+0 '+&03 '+&03 '
(. (51 3&1 52+0. (+(51 (+(5& '+''5
(5 (&1 ((&1 (0 '+001 '+051 '+'(
(0 (&1 ((&1 5' (+'50 (+'0& '+'(.
(/ ((1 &&1 (0 '+(/& '+(/( '+''/
(& 3.+00 3&1 .&+0 '+5/0 '+553 '+'(/
(2 (&1 &&1 5' '+20. '+2.3 '+'.1
(3 (51 (1'3+1/ .&+0 '+//( '+/0 '+'((
.' ((1 ((&1 (0 '+.0& '+.2/ '+'.3
#nalysis showed that a quadratic model was the best fit 9Table (/: with actual and
predicted regression coefficient !
.
as '+33// and '+3252 respecti,ely+
PAGE 3;
Table 1=0 M%del .it *!mmar#
The #=7@# analysis 9Table (& : showed significance of model as well of the three
independent parameters 9QProb E BR L '+'''(:+
Table 1>0 A,O-A Anal#sis
PAGE 47
Bigure (/" Bigure (& and Bigure (2 show the contour graphs for Mn7 catalysed jute and
sesame oil cake co%pyrolysis+
.ig!re 1=0 C%nt%!r /l%t "%r A+
PAGE 41
.ig!re 1>0 C%nt%!r /l%t "%r AC
.ig!re 1?0 C%nt%!r /l%t "%r +C
PAGE 42
Bigure (3" Bigure .' and Bigure .( show the corresponding 1%D -urface mages+
PAGE 43
.ig!re 190 57D *!r"ace "%r A+
.ig!re 3@0 57D *!r"ace "%r AC
.ig!re 310 57D *!r"ace "%r +C
Bigure .. shows a chart of comparison between predicted ,s actual ,alues+
PAGE 44
.ig!re 330 /redicted ;s Act!al Gra&'
The optimi8ed operating conditions 9as marked in the contour plots and 1%D -urface
mages: for Mn7 catalysed jute and sesame oil cake co%pyrolysis was found to be at 3&1
$ with (51 grams feed of jute and sesame oil cake for a reaction time of .&+0 minutes+
"l&O' catalysed Co-Pyrolysis of $ute and Sesame Oil Ca%e
The complete lists of coded and actual ,alues are pro,ided in Table " Table and Table +
Table 1?0 (ist %" C%ded and 6n7c%ded $nde&endent -ariables and T'eir 8anges
@ariables !anges
Coded ;ncoded ;nits %[ %( ' V( V[
\(
AuteV-esame
oil cake ?ram 2.+2. 3( ('1 ((0 (.1+(2
\. Temperature $el,in /1/+/5 &&1 3&1 ((&1 (1'3+1/
\1 Time 4inutes 1+'& (0 1.+0 0' /(+31
PAGE 45
Table 190 (ist %" C%ded and 6n7C%ded -al!es %" $nde&endent -ariables
!un Beed Temp Time
;ncoded Coded ;ncoded Coded ;ncoded Coded
( ('1 ' 3&1 ' 1.+0 '
. ((0 ( ((&1 ( 0' (
1 ('1 ' 3&1 ' 1+'& %[
5 ('1 ' /1/+/5 %[ 1.+0 '
0 ((0 ( &&1 %( (0 %(
/ 3( %( &&1 %( (0 %(
& ('1 ' 3&1 ' 1.+0 '
2 ('1 ' 3&1 ' 1.+0 '
3 ('1 ' 3&1 ' 1.+0 '
(' ('1 ' 3&1 ' /(+31 V[
(( ((0 ( ((&1 ( (0 %(
(. ('1 ' (1'0+1/ V[ 1.+0 '
(1 ('1 ' 3&1 ' 1.+0 '
(5 (.1+(2 V[ 3&1 ' 1.+0 '
(0 3( %( ((&1 ( (0 %(
(/ ('1 ' 3&1 ' 1.+0 '
(& 3( %( &&1 %( 0' (
(2 ((0 ( &&1 %( 0' (
(3 3( %( ((&1 ( 0' (
.' 2.+2. %[ 3&1 ' 1.+0 '
PAGE 46
Table 3@0 Obser;ed< /redicted and 8esid!al -al!es %" 8es&%nses
!un Beed Temp Time 7bser,ed Predicted !esidual
. ((0 ((&1 0' (+100 (+1/ '+''0
1 ('1 3&1 1+'& '+''& '+'02 '+0(
5 ('1 /1/+/5 1.+0 (+(( (+((3 '+''2
0 ((0 &&1 (0 '+00& '+05 '+'(&
/ 3( &&1 (0 '+5/1 '+510 '+'.2
(' ('1 3&1 /(+31 (+''2 '+33 '+'(2
(( ((0 ((&1 (0 '+&'& '+//3 '+'12
(. ('1 (1'0+1/ 1.+0 (+.// (+.3 '+'.5
(5 (.1+(2 3&1 1.+0 (+.. (+.5 '+'.
(0 3( &&1 0' '+0'5 '+521 '+'.(
(/ ('1 3&1 1.+0 (+23( (+23 '+''(
(& 3( &&1 0' (+''0 (+'. '+'(0
(2 ((0 &&1 0' (+.(( (+.'2 '+''1
(3 3( ((&1 0' (+'5 (+'10 '+''0
.' 2.+2. 3&1 1.+0 '+2&/ '+223 '+'(1
#nalysis showed that a quadratic model was the best fit 9Table : with actual and predicted
regression coefficient !
.
as '+33&& and '+33'3 respecti,ely+
PAGE 49
Table 310 M%del .it *!mmar#
PAGE 4:
The #=7@# analysis 9Table : showed significance of model as well of the three
independent parameters 9QProb E BR L '+'''(:+
Table 330 A,O-A Anal#sis
PAGE 4;
Bigure 2" Bigure 3 and Bigure (' show the contour graphs for #l.71 catalysed jute and
sesame oil cake co%pyrolysis+
.ig!re 390 C%nt%!r /l%t "%r AC
PAGE 57
.ig!re 350 C%nt%!r /l%t "%r A+
.ig!re 3:0 C%nt%!r /l%t "%r +C
Bigure" Bigure and Bigure show the corresponding 1%D -urface mages+
PAGE 51
.ig!re 3=0 57D *!r"ace "%r A+
.ig!re 3?0 57D *!r"ace "%r +C
PAGE 52
.ig!re 3>0 57D *!r"ace "%r AC
Bigure (5 shows a chart of comparison between predicted ,s actual ,alues+
.ig!re 390 /redicted ;s Act!al Gra&'
The optimi8ed operating conditions 9as marked in the contour plots and 1%D -urface
mages: for #l.71 catalysed jute and sesame oil cake co%pyrolysis was found to be at 3&1
$ with ('1 grams feed of jute and sesame oil cake for a reaction time of 1.+0 minutes+
()perimental Result*
Wi&ht %o''"

Table 350 A Bt. l%ss
+ime
(mins)
8<$.
'oss
7 7
PAGE 53
5 6.1
17 2;.2
15 34.2
27 47.2
25 41.9
37 4;.9
35 53.4
47 56.9
45 5;
57 61.3
55 69.:
67 94.:
The results show that the weight loss gradually increases with time+ 6e ha,e also
prepared a plot of weight loss ,ersus time and drawn the mean cur,e" which is a straight
line+ The line has a slope of (+( min]
(
and the intercept is ((+'1+ # graph showing the
yield of products has also been made in the form of a bar chart+ ^ield of tar is around
(.+20K and that of char and gas are approDimately (0+&(K and &(+51K respecti,ely+ Tar
can be blended with fuel" used in automobiles" to reduce fuel consumption and thereby
decrease the release of harmful gases that cause pollution leading to greenhouse effect+
PAGE 54
.ig!re 5@0 A Bt. l%ss ;s. time
Brom the figure 1'" it can be concluded that weight loss of the feed is a linear function of
time+ Brom the bar graph" it can be concluded that among the three products yield is much
higher for gas followed by char and tar+
Pro!uct *i%!"
.ig!re 510 /r%d!ct #ield %" c'ar< tar and gas at >>5C
PAGE 55
The main aim of pyrolysis is to obtain liquid and gaseous product from biomass+ #fter
performing the eDperiment we obtained three products% tar" char and gas+ Tar is the
,olatile part of the product which is condensed to obtain it in liquid form+ t has been
obser,ed that tar comprises of two phases" lighter aqueous phase and hea,ier dark
colored organic phase which settles down at the bottom+ Tar can be blended with fuel oil
and can be used in automobiles+ The solid product obtained inside the paraly8er is the
char" which can be utili8ed for the generation of electricity+ 6e ha,e not e,aluated the
composition of the gas but as pyrolysis reaction takes place in the absence of oDygen so
we can infer that mainly oDides of nitrogen are released+ The use of catalyst" aluminum
oDide" has enhanced the product yield+
Brom the abo,e figure" it can be concluded that weight loss of the feed is a linear function
of time+ Brom the bar graph" it can be concluded that among the three products yield is
much higher for gas followed by char and tar+
$action En&inrin&"
7ne of the main objecti,es of the study is the find the kinetic parameters like rate
constant" acti,ation energy and frequency factor+ @arious feeds were taken with different
catalysts at different temperatures in the eDperiments+ Then the data of weight of the
reaction miDture with time were taken and studied to calculate the rate constants for the
different reactions+
Then we plotted rate ,s+ concentration graph and calculated the ,alue of rate constants
from the slope of the graph directly as the reactions are first order+ Then we plotted (GT
,s+ ln 9k: to get the ,alues of acti,ation energy and frequency factor+
Bor obtaining the rate ,s+ concentration cur,e" differential method was used+ !ate of
change of weight was calculated using the weight ,s+ time data numerically+ Then this
rate change which is nothing but rate was plotted against a,erage weight for e,ery gi,en
range of time+ # straight line was obtained+ The slope of this line is the ,alue of rate
constant+ This procedure was repeated with e,ery sample of which one has been shown+
PAGE 56
The following sample is for lime peel waste V $Cl system at &&1 $+
Table 390 Calc!lati%n table "%r &l%tting rate ;s. c%ncentrati%n c!r;e
$ime s. ($ -VH
8 ($
'oss <v($) <=><.
8 <+
=ES?@UE
7 113.1 2791.1 7 7 7 177
5 2753.4
15.64;
:9
7.1564;
;
7.:4357
1
:4.35713
263
17 2757.1
1:.569
64
7.1:569
6
7.:1432
4
:1.43236
794
15 2749.2
21.131
94
7.21131
9
7.9::6:
3
9:.:6:25
:1:
27 2741.4
26.25;
;5
7.2625;
;
7.93947
1
93.94775
375
25 272;.6
36.6;3
1;
7.366;3
2
7.63376
:
63.376:7
:13
37 2712.9
51.635
92
7.51635
9
7.4:364
3
4:.36429
;4
35 2779.;
55.:9;
95
7.55:9;
:
7.44127
2
44.12724
959
47 1;;4.2
69.;;2
;3
7.69;;2
;
7.32779
1
32.77979
33;
45 1;:1.3
9;.3;:
96
7.9;3;:
:
7.27671
2
27.67123
9:4
57 1;9:.4
:1.;62
:6
7.:1;62
;
7.1:739
1
1:.73913
52:
55 1;6;.5
:;.:32
71 7.:;:32
7.1:739
1
1:.73913
52:
67 1;53.:
173.91
35
1.73913
5 7.1716:
17.169;;
2;3
<7 <.($) +v) <$v)
_<v($)A
B$
_<c($)AB
$
1 7 2.5
7.;12:
;4 7.7231 7.77256
1
7.7199
14 9.5
7.:7;5
49 7.7271
7.77231
2
1
7.7217
19 12.5
7.99;7
35 7.71;:9
7.7721:
1
1
7.723;
1; 19.5
7.9362
2 7.71922 7.77274
PAGE 59
1
7.72;9
23 22.5
7.64;6
76 7.71611 7.771;1
1
7.7415
33 29.5
7.57:3
66 7.712; 7.77145
1
7.75:4
46 32.5
7.4715
95 7.71771
7.77115
1
1
7.7632
5 39.5
7.3175
31 7.77;2
7.777:;
4
1
7.796;
6 42.5
7.19;6
26 7.7745;
7.77757
3
1
7.7:;:
91 49.5
7.171:
9 7.77254
7.77724
9
1
7.7;29
93 52.5
7.7439
;;
7.771;7
2
7.77712
;
1
7.1716
: 59.5
7.7171
2
7.72996
3
7.77314
25
1
7.1193
;2 37 7.77;1
7.7192:
6
7.771;5
65
PAGE 5:
.ig!re 530 8ate ;s. C%ncentrati%n &l%ts
Table 3:0 Obtained ;al!es %" C< C;< Cc "r%m t'e "ig!re 53
C
7.7722
min
-1
Cv
7.725 min-
1
Cc
7.772:
min-1
The different samples and there results are as follows)
7. Lim 3% 8a't f! an! KC% cata%y't
PAGE 5;
Table 3=0 Calc!lati%n table "%r &l%tting ln (k) ;s. 1DT "%r lime &eel Baste E CCl s#stem
+ (C) 1/T C ln K Cv ln Kv Ktrue ln K Kv True ln Kv
993
7.7712
;4
7.772
2
-
6.11;
3 7.725
-
3.6:::
9
7.7721;7
429
-
6.12365:
67
7.725794
4:9
-
3.6:5
;
;93
7.7717
2: 7.774
-
5.521
4
7.72:
;
-
3.543;
1
7.774744
:6:
-
5.517376
39
7.7459;7
945
-
3.7:3
6
1193
7.777:
53
7.776
1
-
5.7;;
4
7.731
2
-
3.4693
3
7.731341
355
-
3.462:16
9;
7.74:233
591
-
3.731
9

.ig!re 550 ln (k) ;s. 1DT "%r lime &eel Baste E CCl s#stem
Table 3>0 Obtained ;al!es %" acti;ati%n energ# and "reF!enc# "act%r "%r lime &eel Baste
ECCl s#stem

3reD"enc%
3c$or(min
-1
)
Ac$iv$ion
Ener)%(CEAm
o')
C 7.7432;6 1;.19979
Cv 7.74:234 4.2743;
PAGE 67
.. -ut 9 ''am f! an! :nO cata%y't
Table 3?0 Calc!lati%n table "%r &l%tting ln (k) ;s. 1DT "%r 4!te Esesame %il cake E GnO
s#stem
+ C 1/T C ln K Cv ln Kv Ktrue ln K
993
7.7712
;4 7.729
-
3.611
;
7.73:
;
-
3.246
9
7.71;4
35
-
3.;47
6
;93
7.7717
2: 7.72;
-
3.547
4
7.742
3
-
3.162
;
7.7224
11
-
3.9;:
1
1193
7.777:
53
7.737
6
-
3.4:6
9
7.74;
9
-
3.771
9
7.7246
1:
-
3.974
2
Kv
True ln Kv Kc ln Kc KcTrue
ln
KcTrue
check
K
7.7537
;
-
2.;35
9 7.72
-
3.;12
7
7.7177
72 -4.675
7.75:
;
7.7592
32
-
2.:67
6 7.71;
-
3.;63
3
7.7179
46
-
4.533
1
7.761
3
7.7671
39
-
2.:11
1
7.719
9
-
4.734
1
7.7112
69
-
4.4:5
:
7.769
4
PAGE 61
.ig!re 590 ln (k) ;s. 1DT "%r 4!te E sesame %il cake E GnO s#stem
Table 390 Obtained ;al!es %" acti;ati%n energ# and "reF!enc# "act%r "%r 4!te E sesame %il
cakeEGnO s#stem

3reD"enc%
3c$or(min
-1
)
Ac$iv$ion
Ener)%(CEAm
o')
C 7.73::91 4.454:79
Cv 7.796513 2.34:975
Cc 7.7141:5 2.24552:
0. -ut 9 S'am f! an! A%.O0 cata%y't
Table 5@0 Calc!lati%n table "%r &l%tting ln (k) ;s. 1DT "%r 4!te E sesame %il cake E Al3O5
s#stem
+ C 1/T C ln K Cv ln Kv Ktrue
993
7.7712
;4
7.72:
9
-
3.557
:
7.751
6
-
2.;64
2
7.7119
39
;93
7.7717
2:
7.726
4
-
3.634
3
7.731
2
-
3.469
3
7.712:
9
PAGE 62
1193
7.777:
53
7.724
6
-
3.975
7
7.725
2
-
3.6:7
;
7.7136
96
ln K
Kv
True ln Kv Kc ln Kc
KcTru
e
ln
KcTru
e
check
K
-
4.445
7
7.7779
16
-
2.;64
2
7.721
2
-
3.:53
9
7.77;:
2;
-
4.622
3
7.792
:
-
4.352
:
7.7711
7;
-
3.469
3
7.727
1
-
3.;79
7
7.7176
46
-
4.542
6
7.751
3
-
4.2;2
1
7.771:
;
-
3.6:7
;
7.71:
5
-
3.;:;
;
7.7112
2
-
4.4;7
7
7.743
9
.ig!re 5:0 ln (k) ;s. 1DT "%r 4!te E sesame %il cake E Al3O5 s#stem
PAGE 63
Table 510 Obtained ;al!es %" acti;ati%n energ# and "reF!enc# "act%r "%r 4!te E sesame
%il cake EAl3O5 s#stem

3reD"enc%
3c$or(min
-1
)
Ac$iv$ion
Ener)%(CEAm
o')
C 7.71:396 2.::13
Cv 7.77672 13.6::19
Cc 7.7144; 2.4;4734
Thus" from Table .0" Table .& and Table .3 we can find the rate constant at any
temperature+ 6e will use this table to calculate the rate constant for the formation of
,olatile matter and char at the temperature obtained by the optimi8ation study of the
system+
#fter the optimi8ation study" optimum ,alues of weight" temperature and time were
obtained for different systems+ 7f the obtained results" the ,alues of optimum
temperature for different systems were used to calculate the rate constants with the help
of parameters in Table .0" Table .& and Table .3+ The final results has been gi,en in the
following Table 1')
Table 530 .inal ;al!es %" rate c%nstants at %&tim!m tem&erat!re "%r di""erent s#stems
S%s$em
/!$im"m
+em!er$"re(
C)
=$e
.ons$n$s(min
-1
)
Fime !ee' (s$e > C.'
;67 C G 7.73;194
Cv G 7.72:4:
Cc G 7.71;29
Fime !ee' (s$e >
HA'Si
;93 C G 7.73175
Cv G 7.72351
Cc G 7.72715
E"$e > Sesme /i' .1e
> 4n/
;93 C G 7.72;796
Cv G 7.744114
PAGE 64
Cc G 7.71:923
E"$e > Sesme /i' .1e
> A'2/3 ;93 C G 7.72623;
Cv G 7.73297
Cc G 7.71;992
CONCL)S,ON
n the present in,estigation" an attempt has been made to pyroly8e the lignocellulosic
material in presence of four selecti,e catalysts namely $Cl" =#l-i" #l.'1 and Mn7 with
an eDpectation to achie,e enhance ,olatile yield+
7ptimi8ation of yield of ,olatile matter is related to the three independent ,ariables
namely temperature" time and weight of feed in a form of second order polynomial+ 6e
ha,e carried out the optimi8ation process using !-4 technique in Design EDpert
software 2+'+&+(
Detailed reaction engineering study indicates the rates of formation of ,olatile matter and
char can be represented by simple (
st
order reaction+ !eaction rate constant of the
indi,idual reaction ha,e been e,aluated using the eDperimental data+
PAGE 65
$E+E$ENCES
(+ D+ 6ang" -+ C8ernik" E+ Chornet" QProduction of Hydrogen from Biomass by Catalytic
-team !eforming of Bast Pyrolysis 7ilsR" Energy T Buels" (332" (." (3%.5+
.+ D+ 6ang" -+ C8ernik" D+ 4ontane`" 4+ 4ann" E+ Chornet" QBiomass to Hydrogen ,ia Bast
Pyrolysis and Catalytic -team !eforming of the Pyrolysis 7il or ts BractionsR" nd+ Eng+
Chem+ !es+" (33&" 1/" (0'&%(0(2+
1+ -+ C8ernik" !+ Brench" C+ Beik" E+ Chornet" QHydrogen by Catalytic -team !eforming of
>iquid Byproducts from Biomass Thermocon,ersion ProcessesR" nd+ Eng+ Chem+ !es+"
.''." 5(" 5.'3%5.(0+
5+ $+-+ Triantafyllidis" E+B+ liopoulou" E+@+ #ntonakou" #+#+ >appas" H+ 6ang" T+A+
Pinna,aia" QHydrothermally stable mesoporous aluminosilicates 94-;%-: assembled
from 8eolite seeds as catalysts for biomass pyrolysisR" 4icroporous and 4esoporous
4aterials" .''&" 33" (1.I(13+
0+ >+ ?arca`a" 4+ >+ -al,ador" A+ #rau8o" and !+ Bilbao" QCatalytic -team ?asification of
Pine -awdust+ Effect of Catalyst 6eightGBiomass Blow !ate and -teamGBiomass !atios
on ?as Production and CompositionR" Energy T Buels" (333" (1" 20(%203+
/+ -+ ^aman" QPyrolysis of biomass to produce fuels and chemical feedstocksR" Energy
Con,ersion and 4anagement" .''5" 50" /0(I/&(+
&+ 4+ -tocker" QBiofuels and Biomass%To%>iquid Buels in the Biorefinery) Catalytic
Con,ersion of >ignocellulosic Biomass using Porous 4aterialsR" #ngew+ Chem+ nt+ Ed+
.''2" 5&" 3.'' I 3.((+
PAGE 66
2+ E+B+ liopoulou a"b" E+@+ #ntonakou b" -+#+ $arakoulia c" +#+ @asalos b" #+#+ >appas b"
$+-+ Triantafyllidis
3+ Department of Chemical Education" Baith Educational Baculty" $aradeni8 Technical
;ni,ersity" P+$+ .(/" T!%/('10 Trab8on" Turkey !ecei,ed & December .'''Saccepted
3 #pril .''(+
('+ Aoseph B+ Binderb and !onald T+ !ainesc" b" dDepartments of Chemistry and
Biochemistry" ;ni@ersity of 6isconsins4adison" 4adison" 6isconsin 01&'/ !ecei,ed
7ctober 1'" .''2+
((+ Pan Pan a" Changwei Hu a"c" 6enyan ^ang a" ^uesong >i a" >inlin Dong a" >iangfang
Mhu a" Dongmei Tong a" !enwei Uing b" ^ong Ban b+
(.+ Torren !+ Carlson e ?eoffrey #+ Tompsett e 6illiam C+ Conner e ?eorge 6+ Huber+
(1+ Da,id 4artin #lonso" Aesse U+ Bond and Aames #+ Dumesicc !ecei,ed .0th 4arch .'('"
#ccepted (5th Auly .'(' D7) ('+('13Gc''5/05j+
(5+ >+ ?arcia" 4+ >+ -al,ador" !+ Bilbao"c and A+ #rau8o Department of Chemical and
En,ironmental Engineering" ;ni,ersity of Marago8a" 0'''3 Marago8a" -pain+
(0+ Audit #dam a"c" Eleni #ntonakou b" #ngelos >appas b" 4ichael -tofcker c" 4erete
H+ =ilsen c" #ud Bou8ga c" Aohan E+ Hustad a" ?isle gye da Department of Energy and
Process Engineering" =orwegian ;ni,ersity of -cience+
(/+ Department of 6ood -cience and Technology" $yoto ;ni,ersity $itashirakawa" 7iwake%
cho
(&+ Biomass and Bioenergy ,ol (." =o+5S pp.&1%.&3" (33&+
(2+ Department of #griculture" Bood and =utritional -ciences" ;ni,ersity of #lberta" 5('
#gGBor Building" Edmonton" #B" Canada T/? .P0 Bioresource Technology 32 9.''&:
.10(I.1/2+
(3+ 4aria P+ #8nar" Aos/ Corella"ch AVe stis Delgado" t and Aoaquin >aho8 Department of Bio
Technology" ;ni,ersity of Marago8a nd+Eng+Chem+!es+(331" 1." (%('+
.'+ ^u%Chuan >in and ?eorge 6+ Huber !ecei,ed .&th #ugust .''2" #ccepted (&th 7ctober
.''2 first published as an #d,ance #rticle on the web .'th =o,ember .''2+
.(+ Tushar P+ @ispute and ?eorge 6+ Huberc !ecei,ed 2th #pril .''3" #ccepted 5th Aune
.''3 Birst published as an #d,ance #rticle on the web 3th Auly .''3+
..+ Chunbao \uc and =imisha >ad Department of Chemical Engineering" >akehead
;ni@ersity" Thunder Bay" 7=" Canada P&B 0E( Energy T Buels .''2".." /10I/5.
PAGE 69
PAGE 6: