Final Year Report(2007) (1)

8/11/2019 Final Year Report(2007) (1)

http://slidepdf.com/reader/full/final-year-report2007-1 1/71

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 Chakraborty9('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 earths 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

dioide 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 etent 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 monoide" hydrogen and carbon dioide+ This is achie,ed by reacting the

material at high temperatures 9&'' FC:" without combustion" with a controlled amount

of oygen andGor steam+ The resulting gas miture 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 Carnots rule is higher

or not applicable+ -yngas may be burned directly in gas engines" or con,erted ,ia

the ischerITropsch process into synthetic fuel+

#naerobic digestion is a collection of processes by which microorganisms break

down biodegradable material in the absence of oygen+ 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 fromfossil 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

http://en.wikipedia.org/wiki/Biomass

http://en.wikipedia.org/wiki/Fossil_fuel


http://en.wikipedia.org/wiki/Carbon

http://en.wikipedia.org/wiki/Carbon_monoxide

http://en.wikipedia.org/wiki/Hydrogen

http://en.wikipedia.org/wiki/Carbon_dioxide


http://en.wikipedia.org/wiki/Oxygen

http://en.wikipedia.org/wiki/Syngas

http://en.wikipedia.org/wiki/Producer_gas



http://en.wikipedia.org/wiki/Renewable_energy


http://en.wikipedia.org/wiki/Fuel_cell

http://en.wikipedia.org/wiki/Carnot's_rule


http://en.wikipedia.org/wiki/Internal_combustion_engines


http://en.wikipedia.org/wiki/Fischer%E2%80%93Tropsch_process

http://en.wikipedia.org/wiki/Synthetic_fuel


http://en.wikipedia.org/wiki/Microorganisms

http://en.wikipedia.org/wiki/Biodegradable


http://en.wikipedia.org/wiki/Carbon_cycle

http://en.wikipedia.org/wiki/Biomass



http://en.wikipedia.org/wiki/Carbon_monoxide

http://en.wikipedia.org/wiki/Hydrogen



http://en.wikipedia.org/wiki/Syngas




http://en.wikipedia.org/wiki/Fuel_cell



http://en.wikipedia.org/wiki/Fischer%E2%80%93Tropsch_process


http://en.wikipedia.org/wiki/Microorganisms

http://en.wikipedia.org/wiki/Biodegradable


http://en.wikipedia.org/wiki/Carbon_cycle



for many millions of years" the combustion of which increases the o,erall le,els of

carbon dioide 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 temperaturesin the absence of oygen 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 eposed to high

temperatures+ t is one of the processes in,ol,ed in charring wood" starting at .''I1'' FC

913'I0&' F+ n general" pyrolysis of organic substances produces gas and liquid products

and lea,es a solid residue richer in carbon content" char + Etreme pyrolysis" which lea,es

mostly carbon as the residue" is called carboni8ation+ The process is used hea,ily in

the chemical industry" for eample" 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 oygen"

water" or any other reagents+ n practice" it is not possible to achie,e a completely

oygen%free atmosphere+ Because some oygen is present in any pyrolysis system" a

small amount of oidation occurs+

There are three types of pyrolysis) fast" flash and slow+ ast pyrolysis uses moderate to

high temperatures and rapid heating while slow pyrolysis is characteri8ed by gradualheating 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+ lash pyrolysis

is characteri8ed by moderate temperatures eist 95''%/''FC: and rapid heating rates

9.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 maimi8ed+ 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 areusually 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

http://en.wikipedia.org/wiki/Thermochemical

http://en.wikipedia.org/wiki/Decomposition


http://en.wikipedia.org/wiki/Organic_matter




http://en.wikipedia.org/wiki/Halogen

http://en.wikipedia.org/wiki/Chemical_composition

http://en.wikipedia.org/wiki/Greek_language

http://en.wikipedia.org/wiki/Morpheme

http://en.wikipedia.org/wiki/Lysis


http://en.wikipedia.org/wiki/Thermolysis

http://en.wikipedia.org/wiki/Organic_compound

http://en.wikipedia.org/wiki/Charring


http://en.wikipedia.org/wiki/Char



http://en.wikipedia.org/wiki/Carbonization

http://en.wikipedia.org/wiki/Chemical_industry

http://en.wikipedia.org/wiki/Charcoal

http://en.wikipedia.org/wiki/Activated_carbon



http://en.wikipedia.org/wiki/Methanol

http://en.wikipedia.org/wiki/Hydrocarbon

http://en.wikipedia.org/wiki/Petroleum

http://en.wikipedia.org/wiki/Lighter


http://en.wikipedia.org/wiki/Gasoline


http://en.wikipedia.org/wiki/Dry_distillation

http://en.wikipedia.org/wiki/Destructive_distillation


http://en.wikipedia.org/wiki/Cracking_(chemistry)


http://en.wikipedia.org/wiki/Combustion

http://en.wikipedia.org/wiki/Hydrolysis



http://en.wikipedia.org/wiki/Thermochemical




http://en.wikipedia.org/wiki/Halogen

http://en.wikipedia.org/wiki/Chemical_composition

http://en.wikipedia.org/wiki/Greek_language

http://en.wikipedia.org/wiki/Morpheme


http://en.wikipedia.org/wiki/Thermolysis

http://en.wikipedia.org/wiki/Organic_compound


http://en.wikipedia.org/wiki/Char


http://en.wikipedia.org/wiki/Carbonization

http://en.wikipedia.org/wiki/Chemical_industry

http://en.wikipedia.org/wiki/Charcoal


http://en.wikipedia.org/wiki/Methanol

http://en.wikipedia.org/wiki/Hydrocarbon

http://en.wikipedia.org/wiki/Petroleum



http://en.wikipedia.org/wiki/Dry_distillation



http://en.wikipedia.org/wiki/Combustion





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 mgGm1 9=TP:+

#nd '+0 ,olK" without using oygen+

Wang ET. 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 oygenates 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 etent 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:+ Eplored 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 96PP: technology+ The biomass used was

pine sawdust and the reaction temperature was /0' FC+ The results show that when thehigher 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+ 7nthe 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 fied 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 futureenergy 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 comple 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 obtainhydrogen rich gaseous products at desired temperatures.

Czernik ET. 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+ our

#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 alab%scale fied 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 eperiments+ The aqueous part in the liquid

phase increased in the catalytic runs+ n the catalytic eperiments 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+

!ber ET+ 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 oygen 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 ehibited 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' C" .'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 inthe 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 inhelping 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'I104AGkg 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 e-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 15' 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: .+ Themaimum 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 mainlyfocuses 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 comple reaction

mechanism and process up%gradation ha,e been eplored 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%hydroymethylfurfural 9H4: 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 H4 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 comple+

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 $er0 coe n# vo'$i'e rom$ics. i& &e$inr$es n# &i& c$'%s$ $o fee# r$io fvor rom$ic !ro#"c$ion over

coe 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$ 'oer 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.

ive c$'%s$s ere $es$e# inc'"#in SM-50 si'ic 'i$e0 be$0 n# -

*eo'i$e n# si'ic '"min. SM-5 &# $&e &i&es$ rom$ic %ie'#s

(378 crbon %ie'#) n# $&e 'es$ mo"n$ of coe.

-is&!te and !ber 9.''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 oygen from theorganic 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 fied

bed reactor in nitrogen flow produced bio%oils that had lower oygen 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 CC 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 ,ariableson 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 attentionin this study+ Due to its a,ailability in ndia and no commercial applications ecept cattle

feed or fertili8er" its market price is ,ery low+ or 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%imate 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 urnace+ The inert atmosphere of the

PAGE 17







$'3on' Surfac Mtho!o%o&y

Brief qualitative overview of RSM principle

!esponse -urface 4ethodology 9!-4: consists of statistical and mathematical toolsaimed at modelling" analysing and optimi8ing processes+ 4ostly" the problems that aresol,ed using this method ha,e multi,ariable independent factors influencing the desiredr'3on'+ Here response refers to the performance character of the process+ or 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 fromapproimate eperiments" a function relating the response to the independent ,ariables isapproimated in this method+ The optimum ,alue is then determined+

;sually low order polynomials ,i8+ (st order and .nd orderG Uuadratic are the commonlyused approimations+ n the present process with three independent ,ariables" the

simulated equation is epected to be quadratic+

Second-Order Model

# general second%order model can be epressed as follows)

The first%order model fails when there is a cur,ature in the response surface+ n such acase the second%order model impro,es the optimi8ation process appreciably+Consideration of a number of functional forms and local approimation of responsesurface make the second order modelG quadratic model more significantly ,ersatile+ Thecoefficients are estimated using least squares method+

PAGE 13



#mong the numerous methods of fitting second order models" the central compositedesign 9CCD: is the most common one+ Here the Central Composite Design 9CCD: program of the QDesign Epert 2+'+&+(R software has been used to obtain the optimumconditions+

The obser,ed result from a set of four pyrolysis reactions 9i+e+ $Cl V >ime peel waste" =a#l-i V >ime peel waste" Aute V -esame oil cake V #l.71" Aute V -esame oil cake VMn7: each of which were carried out at three different temperatures ,i8+ &&1$" 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 comple 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 Comple

$ $,

@olatile

Char



,iii+ #ny transport limitation within the eperimental 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 epressions

PAGE 1:



%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.'

#nd

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.(:

6c I 6c' O $ c 96'G$: Y(%e%$tZ %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 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 %X: I 6c':G 96@ 9t%X: I 6,':% 9.5:

96' 9t: I 6c':G 96@ 9t: I 6,': O 96C9t % X: I 6c':G 96@ 9t%X: 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%X:: G 96@ 9t%X:: 96@ 9t:: %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.&:

6C 9t%X: O 6! %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 9.2:

6C 9t: O 96! 9t:: G 96@ 9t%X:: %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 91':

The weight of unreacted feed)

6 9t: O 6' I 96! G 6@ 9t % ':: 96@ 9t:: I 6@ 9t:%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 91(:

6 9t: O 6' I 6@ Y96! G 6@ 9t % 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 0 ist %" C%ded and 6n7C%ded -al!es %" $nde&endent -ariables

!un eed 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 eed 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 threeindependent parameters 9QProb R L '+'''(:+

Table >0 A,O-A anal#sis

igure ." igure 1 and igure 5 show the contour graphs for $Cl catalysed lime peelwaste 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 0 C%nt%!r &l%t %" +C

igure 0" igure / and igure & 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:



igure 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 andTable('+

Table ?0 ist %" C%ded and 6n7c%ded $nde&endent -ariables and T'eir 8anges

@ariables !anges

Coded ;ncoded ;nits %[ %( ' V( V[

\(>ime Peelwaste ?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.


!un eed Temperature Time


( //+/ ' 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 eed 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 threeindependent parameters 9QProb R L '+'''(:+

PAGE 32



Table 130 A,O-A anal#sis

igure 3" igure (' and igure (( 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

igure (." igure (1 and igure (5 show the corresponding 1%D -urface mages+

ig!re 130 57D *!r"ace "%r A+

PAGE 35





ig!re 1:0 /redicted ;s Act!al Gra&'


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 andTable (0+

Table 150 ist %" C%ded and 6n7c%ded $nde&endent -ariables and T'eir 8anges

@ariables !anges


\(

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




!un eed Temp Time


( (&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 eed 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;





igure (/" igure (& and igure (2 show the contour graphs for Mn7 catalysed jute andsesame 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



igure (3" igure .' and igure .( show the corresponding 1%D -urface mages+

PAGE 43

ig!re 190 57D *!r"ace "%r A+





ig!re 330 /redicted ;s Act!al Gra&'


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


\(

AuteV-esameoil 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




!un eed Temp Time


( ('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 eed 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 predictedregression 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 threeindependent parameters 9QProb R L '+'''(:+

Table 330 A,O-A Anal#sis

PAGE 4;



igure 2" igure 3 and igure (' show the contour graphs for #l .71 catalysed jute andsesame oil cake co%pyrolysis+

ig!re 30 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

igure" igure and igure 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



igure (5 shows a chart of comparison between predicted ,s actual ,alues+

ig!re 390 /redicted ;s Act!al Gra&'


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 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+ îeld of tar is around

(.+20K and that of char and gas are approimately (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 Bt. l%ss ;s. time

rom the figure 1'" it can be concluded that weight loss of the feed is a linear function of

time+ rom 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 >>5

PAGE 55



The main aim of pyrolysis is to obtain liquid and gaseous product from biomass+ #fter

performing the eperiment 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 oiland 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 oygen so

we can infer that mainly oides of nitrogen are released+ The use of catalyst" aluminum

oide" has enhanced the product yield+

rom the abo,e figure" it can be concluded that weight loss of the feed is a linear function

of time+ rom 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 eperiments+ Then the data of weight of the

reaction miture 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+

or 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 30 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 2753.415.64;

:97.1564;

;7.:4357

1:4.35713

263

17 2757.11:.569

647.1:569

67.:1432

4:1.43236

794

15 2749.221.131

947.21131

97.9::6:

39:.:6:25

:1:

27 2741.426.25;

;57.2625;

;7.93947

193.94775

375

25 272;.6

36.6;3

1;

7.366;3

2

7.63376

:

63.376:7

:13

37 2712.951.635

927.51635

97.4:364

34:.36429

;4

35 2779.;55.:9;

957.55:9;

:7.44127

244.12724

959

47 1;;4.269.;;2

;37.69;;2

;7.32779

132.77979

33;

45 1;:1.39;.3;:

967.9;3;:

:7.27671

227.67123

9:4

57 1;9:.4:1.;62

:67.:1;62

;7.1:739

11:.73913

52:

55 1;6;.5:;.:32

71 7.:;:327.1:739

11:.73913

52:

67 1;53.:173.91

351.73913

5 7.1716:17.169;;

2;3

<7 <($) +v <$v_<v($)

$_<c($)

$

1 7 2.57.;12:

;4 7.7231 7.77256

17.7199

14 9.57.:7;5

49 7.72717.77231

2

17.7217

19 12.57.99;7

35 7.71;:97.7721:

1

17.723;

1; 19.57.9362

2 7.71922 7.77274

PAGE 59





ig!re 530 8ate ;s. C%ncentrati%n &l%ts

Table 3:0 Obtained ;al!es %" < ;< c "r%m t'e "ig!re 53

C 7.7722min-1

Cv7.725 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. 1T "%r lime &eel Baste Cl s#stem

+ (C) 1/T C ln K Cv ln Kv K true ln K Kv True ln

9937.7712

;47.772

2

-6.11;

3 7.725

-3.6:::

97.7721;7

429

-6.12365:

677.725794

4:93

;937.7717

2: 7.774

-5.521

47.72:

;

-3.543;

17.774744

:6:

-5.517376

397.7459;7

9453

11937.777:

537.776

1

-5.7;;

47.731

2

-3.4693

37.731341

355

-3.462:16

9;7.74:233

5913

ig!re 550 ln (k) ;s. 1T "%r lime &eel Baste Cl s#stem

Table 3>0 Obtained ;al!es %" acti;ati%n energ# and "reF!enc# "act%r "%r lime &eel Baste

Cl s#stem

reD"enc%c$or(min-1)

Ac$iv$ionEner%(Cmo')

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. 1T "%r 4!te sesame %il cake nO

s#stem

+ C 1/T C ln K Cv ln Kv K true ln K

9937.7712

;4 7.729

-3.611

;7.73:

;

-3.246

97.71;4

35

-3.;47

6

;937.7717

2: 7.72;

-3.547

47.742

3

-3.162

;7.7224

11

-3.9;:

1

11937.777:

537.737

6

-3.4:6

97.74;

9

-3.771

97.7246

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

77.7177

72 -4.6757.75:

;

7.759232

-2.:67

6 7.71;

-3.;63

37.7179

46

-4.533

17.761

3

7.767139

-2.:11

17.719

9

-4.734

17.7112

69

-4.4:5

:7.769

4

PAGE 61



ig!re 50 ln (k) ;s. 1T "%r 4!te sesame %il cake nO s#stem

Table 390 Obtained ;al!es %" acti;ati%n energ# and "reF!enc# "act%r "%r 4!te sesame %il

cakenO s#stem

reD"enc%c$or(min-1)


C 7.73::91 4.454:79

Cv 7.796513 2.34:975Cc 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. 1T "%r 4!te sesame %il cake Al 3O5

s#stem

+ C 1/T C ln K Cv ln Kv Ktrue

9937.7712

;47.72:

9

-3.557

:7.751

6

-2.;64

27.7119

39

;937.7717

2:7.726

4

-3.634

37.731

2

-3.469

37.712:

9

PAGE 62



11937.777:

537.724

6

-3.975

77.725

2

-3.6:7

;7.7136

96

ln K KvTrue ln Kv Kc ln Kc KcTrue

ln

KcTrue check K

-4.445

77.7779

16

-2.;64

27.721

2

-3.:53

97.77;:

2;

-4.622

37.792

:-

4.352:

7.77117;

-3.469

37.727

1

-3.;79

77.7176

46

-4.542

67.751

3-

4.2;21

7.771:;

-3.6:7

;7.71:

5

-3.;:;

;7.7112

2

-4.4;7

77.743

9

ig!re 5:0 ln (k) ;s. 1T "%r 4!te sesame %il cake Al 3O5 s#stem

PAGE 63



Table 510 Obtained ;al!es %" acti;ati%n energ# and "reF!enc# "act%r "%r 4!te sesame

%il cake Al 3O5 s#stem

reD"enc%c$or(min-1)


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)

=$eons$n$s(min-1)

Fime !ee' s$e > C';67 C 7.73;194

Cv 7.72:4:

Cc 7.71;29Fime !ee' s$e >HA'Si

;93 C 7.73175

Cv 7.72351

Cc 7.72715 "$e > Sesme /i' e> n/

;93 C 7.72;796

Cv 7.744114

PAGE 64



Cc 7.71:923 "$e > Sesme /i' e> A'2/3 ;93 C 7.72623;

Cv 7.73297

Cc 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 withan epectation 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 Epert

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 eperimental data+

PAGE 65



$E+E$ENCES

(+ D+ 6ang" -+ C8ernik" E+ Chornet" QProduction of Hydrogen from Biomass by Catalytic

-team !eforming of ast Pyrolysis 7ilsR" Energy uels" (332" (." (3%.5+.+ D+ 6ang" -+ C8ernik" D+ 4ontane`" 4+ 4ann" E+ Chornet" QBiomass to Hydrogen ,ia ast

Pyrolysis and Catalytic -team !eforming of the Pyrolysis 7il or ts ractionsR" nd+ Eng+

Chem+ !es+" (33&" 1/" (0'&%(0(2+1+ -+ C8ernik" !+ rench" C+ eik" 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++ 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+ >+ ?arcà" 4+ >+ -al,ador" A+ #rau8o" and !+ Bilbao" QCatalytic -team ?asification of

Pine -awdust+ Effect of Catalyst 6eightGBiomass low !ate and -teamGBiomass !atios

on ?as Production and CompositionR" Energy uels" (333" (1" 20(%203+/+ -+ âman" 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 uels in the Biorefinery) Catalytic

Con,ersion of >ignocellulosic Biomass using Porous 4aterialsR" #ngew+ Chem+ nt+ Ed+

.''2" 5&" 3.'' I 3.((+

PAGE 66





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