Pe

tr
ol
euma
ndp
etr
och
emi
cal
ind
ust
ry
Composi t
ionofcrudepetroleum,Refi
ninganddif
fer
entt
ypesofpetrol
eum pr oduct
sandt hei
r
applicati
ons.
FractionalDist
il
l
ati
on(Pri
ncipleandprocess)
,Cracki
ng(Thermalandcatalyt
iccracking)
,Reformi
ng
Petroleum andnonpet r
oleum fuel
s(LPG,CNG,LNG,biogas,fuel
sderivedfrom biomass),f
uels
fr
om wast e,syntheti
cfuels(gaseousandli
qui
ds),cl
eanf
uels.

Pet
rol
eum
Pet
rol
eum orcrudeoi
li
sanatur
all
yoccurr
ingbrowntobl
ackcol
ouredviscousoi
lformedundert
he
cr
ustofeart
h,onshoreorof
fshore.Chemical
l
yitisamixt
ureofvar
ioushydrocarbonswi
thsmall
amountsofN,O,Scompounds.

Theappr
oxi
mat
ecomposi
ti
onofpet
rol
eum isC=80-84%
H=10-1 4%
S=0.1-0.5%
N+O=Negl i
gibl
e

Cl
assi
fi
cat
ion
Pet
rol
eum i
scl
assi
fi
edont
hebasi
sofvar
ioust
ypesofhydr
ocar
bons
.

1
.Par
aff
inbasedoi
l-Cont
ainsmai
nlyn–al
kanes

(
Ex:Pennsyl
vani
anandgul
fcoastoi
l
)

2.
Asphal
tbaseoi
l-Cont
ainsar
omat
icandal
i
cycl
i
chydr
ocar
bons
.

(
Ex:Cal
i
for
nianoi
l
)

3.Mixedbaseoil-Cont
ainshi
gherpr
opor
ti
onofar
omat
icsandnapht
henes
(cycl
oal
kanes)
.

(
Ex:Mexi
canoi
l
)

Ref
ini
ngofPet
rol
eum (
or)Cr
udeOi
l

Def
ini
ti
on

Thepr
ocessofremovingimpuri
ti
esandsepar
ati
ngoutt
heoi
lint
ovar
iousf
ract
ionshavi
ngdi
ff
erent
boi
l
ingpoi
ntsi
sknownasrefi
ningofpet
rol
eum.
Removal
ofI
mpur
it
ies

Thei
mpurit
iespresenti
ntheoilarethefi
newat erdroplet
s,NaCl,MgCl 2,Sul
phuretc.The
crudeoili
sanextremelystabl
eemulsionofoilandsaltwater.Waterisseparatedfrom t
heoilby
Cottr
ell
’spr
ocessusingri
ngelectr
odes .I
nthismethod,thecrudeoilisal
lowedt oflowbetweentwo
highl
ychargedelectr
odes.Thecoll
oidalwaterdropl
etscombi netoformlargedr ops,whi
char et
hen
separatedfr
om oil
.

Moder
ntechni
quesl
i
keel
ect
ri
cal
desal
ti
ngar
eusedt
oremoveNaCl
andMgCl
2fr
om oi
l
.

Sul
phuri
sremovedbyt
reat
ingt
heoi
lwi
thcopperoxi
deandsepar
atedbyf
il
tr
ati
on.

i
)Fr
act
ional
Dist
il
l
ati
on

Thepuri
fi
edcrudeoi
lisheat
edinafurnacecal
ledoil
heaterwherethetemperat
urewill
be
o
around400 C.Heret
heoil
getsvapouri
sed.Thehotvapoursar
et hensentt
othefract
ionat
ing
column(Fi
g.1.
3).

Iti
satal
lcyl
indr
icalt
owerconsi
sti
ngofanumberofhori
zontalst
ainl
esssteel
trayatshort
di
stances.Eachtr
ayisprovi
dedwithasmallchi
mney,whi
chiscoveredwi t
haloosecap.Thet ower
wi
llbehotatthelowerendandcompar at
ivel
ycool
eratt
heupperend.

Whentheoil
vapour sgoupinthet
ower,theybecomecool andcondense.Theheavier
compoundshavinghigherboil
i
ngpoint
sgetcool
edf i
rstandcondensedi
nthetrayswhereasthe
fr
act
ionshavi
nglowerboili
ngpoint
scondensenearthetopofthetower.

Lowerfr
acti
onsareusedaf
terpur
if
icat
ionwhilet
hehi
ghboi
l
ingpoi
ntf
ract
ionsar
esubj
ect
ed
t
ocr
ackingoperat
iont
ogetmoreuseful
lowerfract
ions
.

Thegasoli
neobt
ainedbythisf
ract
ional
dist
il
l
ati
oniscal
l
edst
rai
ght
-rungasol
i
ne.Var
ious
f
ract
ionsobt
ainedatdi
ff
erentt
raysaregi
veninTable1.2.
 Table 4.
2 Var
ious f
ract
ions,
Composi
ti
onsandthei
ruses
Sl
.No Name of t
he Boi
li
ng Rangeof Uses
fr
acti
on RangeoC C-Atoms
1. Uncondensed Bel
ow30 C1-C4 As a
gases fuel under
t
he
name of
LPG
2. Petrol
eum 30-70 C5-C7 Asa
ether solvent
3. Gasoline or 40-120 C5-C9 Fuel for I
C
petrol engi nes
4. Napht ha 120-180 C9-C10 Asa
or solventi n
solventspi
ri
t pai nts
andi ndr y
cleani ng
5. Ker
oseneoi
l 1
80-
250 C10-C16 Fuel f or
stoves
and
j
et engi nes
6. Di
esel
oil 250-
320 C15-C18 Diesel
engi nef uel
7. Heavyoi
l 320-
400 C17-
C30 Fuel f or
ships
andf or
product i
o
n
ofgasol ine
by
cracki ng.

Heavyoi
l
sonr
efr
act
iongi
ves

S.N Nameoft he Use

o Fraction s
1. Lubricati
ngoil aslubri
cants
2. Petroleum j
ell
y or Used i n medi cines and
Vasel i
ne cosmet i
cs
3. Grease Usedasl ubri
cant
4. Paraf f
inwax Usedincandl es,boot
poli
shes
etc.
,
5. Pit
chatabove Usedf ormakingr oads,
0
400C water
proofroofi
nget c.
Somei
mpor
tantf
ract
ionsofpet
rol
eum

i
)Pet
rol
(or
)Gasol
i
ne(
C5-
C9)
o I
tisalowboi l
ingfr
acti
onofpet rol
eum obtai
nedbetween40-1 20oC.
o I
tisami xtureofhydrocarbonspent anetononane(i
ntermsofcarbonatomsC5-
C9)
.
o I
tscalorif
icvalueisabout11,
250kcal s/
kg.
o I
tisusedasf ueli
nICEofaut omobilesandaeropl
anes.
o I
tsantiknockvaluecanbei mpr ovedbyt headdi
ti
onofTetr
aEt
hylLead(TEL)
.

Uses:I
tisusedasaf
uel
inI
Cengi
neandal
sousedi
ndr
ycl
eani
ngandasasol
vent
.

1
.Napht ha( C9-C10)
I
tisacol ourl
ess,li
ghtfracti
onobtai
nedbet ween1200Ct o1800Cduri
ngfracti
onal
disti
ll
ati
onofpet rol
eum.I tisamixtur
eofhydrocarbonssuchasnonaneanddecane.
Uses
Naphthai salsocalledaswhi t
espir
it
,whichisgeneral
lyusedindrycl
eaningandas
thinnerforvarnish,floorandf ur
nit
urepoli
shesetc.Theli
ghtestport
ionoft
hedisti
l
lat
eisused
assol ventforfatsandr ubbers,wher east
heheaviestport
ionofthesameisusedasaf uel
.

2.
Ker osene( C10-C16)
I
tisrelati
velyahi
ghboil
i
ngfract
ionobt
ainedbet
ween1 80-250oCdur
ingfr
acti
onal
disti
l
lati
onofpet rol
eum.Iti
samist
ureofhydr
ocarbonssuchasdecanetohexadecane.s
appr oxi
mat ecomposi ti
onisC=84%,H=1 6%,>0.1% S.I
tscal
orif
icval
uei
sabout11,1
00
kcal/kg.
Uses:
I
tismainl
yusedasadomesti
cfuel
inst
ovesandlamps.I
t
i
salsousedasjetengi
nef
uel
andformaki
ngoilgas.

3.
Diesel(C15-
C18)
Iti
salsoahighboi
l
ingf r
acti
onobt ai ween250-320oCdur
nedbet ingfr
actional
disti
l
lat
ionofpetr
oleum.I
tisami xtureofhydr
ocar
bonssuchasC15H32t
oC18H38.It
scalor
if
ic
valueisabout11,
000kcal
/kg.
Uses
I
tisusedasaver ygooddi eselenginefuel
.

4.Heavyoi l
orResi dual f
ueloil
(C17–C30)
Theleftoverpor ti
onofpet r
oleum aft
erdist
il
l
ingoffal
ltheli
ght
erfr
acti
onsar
ecal
l
edFuel
Oil.Theappr oximatecomposi ti
onoff ueloi
li
sC=86%,H=1 2%,S=1 %,H2O=0.6%;
sediment s=0. 4%.I t
scalori
fi
cvalueisabout9200kcal/kg.
Thef ol
lowingf racti
onsareobtainedonf urt
hervacuum dist
il
l
ati
onofthefuel
oil
.
i
)Lightfueloil=350- 420oC
ii
)Heavyneut r
aloi l
=420- 500oC

Uses:
I
tisusedasfuelf
orshi
psandalsousedinmetal
l
urgi
cal
f
urnaces.Gasol
i
neisal
soobtai
nedfrom oi
lbycr
acki
ngprocess
.

i
i
)Asphal
t
 Asphal
tsar
eobt
ainedby
● Theoxi
dati
onofresi
dualheavyoili
npresenceofairathi
ghert
emperat
ure.
● Thedeepvacuum di
sti
l
lat
ionofresi
dualheavyoi
l.
Asphal
tsar
eavai
labl
einthemar keti
nli
quid,semi-sol
i
dandsoli
dfor
ms.
Uses:
I
tisusedforr
oadmakingandmaki
ngwater
-pr
oofi
ng
roof
s.Iti
sal
sousedf
orthemanuf
actur
eofwaterpr
oof
ingconcr
eteandwat
erpr
oof
ingpai
nts.

CRACKI
NG:

Cracki
ngisdef
inedas“thedecomposi
ti
onofhigh boi
l
inghydr
ocar
bonsofhi
ghmol
ecul
arwei
ghti
nto
small
er,l
owboi
l
inghydr
ocarbonsofl
owmolecul
arwei
ght
”

Thecrudeoilonfr
act
ionaldi
sti
l
lat
ionyi
eldsonl
yabout15-20 % gasol
i
ne.Thi
sisknownas
Strai
ghtRunGasol
i
ne.

Thequali
tyofstr
aightr
ungasoli
neisnotsogood.Itcont
ainsmainl
yst
rai
ghtchainparaf
fi
n’s,
which i
gni
tereadil
yand mor erapi
dlythan anyot
herhydrocarbonsand hence i
tproduces
knocki
ng(unwantedsound)i
nICengines
.

Inordert
oover comethesedif
fi
cul
ti
esandalsotoimprovet
hequali
tyofgasol
ine,hi
ghboil
i
ng
fr
acti
onsarecrackedint
omor eval
uabl
elowboili
ngfr
acti
onssui
tabl
ef nes.Thegasol
orSIengi i
ne
obtai
nedbycrackingiscal
l
edCrackedGasol
ine.

Dur
ingcr
acki
ng

1.
Str
aightchainalkanesareconvert
edintobranchedchai
nhydr ocar
bons.
2.
Saturat
edhydr ocarbonsareconvert
edintomixtur
eofSaturat
edandUnsat urat
edhydr
ocar
bons
.
3.
Ali
phatical
kanesar econvert
edintocycli
cal
kanes.
4.
All
hydrocar
bonsobt ai
nedbycr
acki
nghavelowerboil
i
ngpoi
ntthanthepar
ent
hydrocar
bons.

Typesofcr
acki
ng

Ther
ear
etwoki
ndsofcr
acki
ng

1.Thermalcr
acking
2.Catal
yti
ccracking
1.
Ther
mal
Cracki
ng

Whencracki
ngiscar
ri
edoutahi
ghert
emperat
ureandpressur
ewi
thoutanycat
alyst
,it
i
scal
l
edTher
mal cr
acki
ng.Ther
earet
wotypesoft
hermalcr
acki
ng:

i
)Li
qui
dphaseTher
mal
cracki
ng

I
nthi
smet hod,theheavyoili
scrackedatatemper at
ureof475-5300Cunderhigh
2
pressur
eof1 00kg/ cm t okeepthereacti
onproductinl
iqui
dstate.Thecr
ackedproductsar
e
t
hensepar at
edi ntovariousfr
act
ionsinafract
ionat
ingcolumn.Theyiel
dofgasol
ineisabout
50-60% andt heoct anenumberis65- 70.

i
i
)Vapourphaset
her
mal
cracki
ng

I
nthismethod,t
heheavyoilisf
ir
stvapour
isedandt hencrackedatatemperat
ureof
0 2
600-650Cunderal owerpressur
eof1 0-20kg/
cm .Theyi el
dofgasoli
neisabout70%.Thi
s
processissui
tabl
eonlyfort
hoseoilswhicharer
eadilyvapouri
sed.

2.
Cat
alyt
icCr
acki
ng

Whencr acki
ngiscarri
edoutatlowertemperatur
eandpressur
einthepresenceofsui
tabl
e
catal
yst
,iti
scal
ledCatal
yti
cCr acki
ng.TheCat
alystusedar
ealumini
um si
l
icateoral
umina.Ther
e
aretwotypesofcat
alyti
ccracking.

i
)Fi
xedbedcat
alyt
iccr
acki
ng

Theheavyoilvapourisheatedto420-450oCinapreheatedchamber.Thehotvapoursar e
thenpassedt hr
oughacat al
yti
cchamber,maint
ainedat425-450oCand1 .
5kg/cm2pressure,
wher ecat
alyst(art
if
ici
alclaymixedwit
hzirconi
um oxi
de),ar
ekeptinfi
xedbeds.Duri
ngt his
passagethroughthecat alyt
icchamberabout40% oft
heheavyoi l
isconvert
edint
ogasolineand
about2-4% carboni sf
or med.

Thecar bongetsadsorbedont hecatal

ystbed.Thecrackedvapour sar
ethenpassedt hr
ough
thefracti
onat
ingcolumn,whereheavyoi l
getscondensedatt hebottom.Thevapoursofgasoli
ne
arethensentthroughthecoolerwheregasoli
negetscondensedal ongwithsomegas es.The
gasolinecont
aini
ngsomedi ssol
vedgasesi st
hensenttoast abi
li
zer,wherethedi
ssolvedgases
areremovedandpur egasol
ineisrecover
ed.

Aft
er8-1
0hours,t
hecatalystl
osesi
tsact
ivi
tyduet
othedeposi
ti
onofcar
bon.I
tisr
eact
ivat
ed
byburni
ngofft
hedeposi
tedcarbon.
 FI
XEDBEDCATALYTI
CCRACKI
NG

i
i
).Movi
ngbedorFl
uidbedcat
alyt
iccr
acki
ng

Int
hispr
ocess,t
hesol
idcatal
ysti
sfi
nel
ypowder
ed,sot
hati
tbehavesasaf
lui
d,whi
chcanbe
ci
rcul
atedi
noil
vapour(
Fig1.5).

Theheavyoilvapourisheatedto420- 450oCi napreheaterandi tismixedwiththecatal

yst
powder.Thenthi
smi xt
ureisforcedintothereactor
,whichismai nt
ai nedatat emperat
ureof
500oCandapr essur
eof5kg/ cm2,wher ecracki
ngtakesplace.Neart hetopofthereact
or,ther
e
i
sacent r
if
ugalsepar
ator(calledcyclone),whichal
lowsonlythecr ackedoi l
vapourstopasson
t
othefracti
onati
ngcolumnl eavi
ngbehi ndthecatal
ystpowderi nther eactor
it
self
.

Thecat
alystpowdergradual
l
ybecomesheavi er
,duetocoat i
ngofcar
bonandi tsettl
esdown
o
att
hebott
om ofthereactor
.Theniti
sforcedi
ntotheregenerat
ormaint
ainedat600C,wher e
car
bonisburntandtheregener
atedcatal
ysti
sagainreci
rcul
atedal
ongtheheavyoi lvapour
.
 Fi
g4.
5Movi
ngbedcat
alyt
iccr
acki
ng

Fr
om thereactor,t
hecrackedoilvapour
sarepassedint
othefr
acti
onati
ngcolumn,
whereheavyoi
lsett
lesdownandt hevapoursar
ethenpassedthr
oughthecoolerwhere
gasol
i
necondensesal ongwithsomegases.Thedissol
vedgasesareseparat
edfrom gasol
i
ne
bypassi
ngitt
hroughast abi
l
izer.

Manuf
act
ureofSynt
het
icPet
rol

Pet
rol
canbesynt
hesi
zedbyanyoneoft
hef
oll
owi
ngmet
hods
.

I.Polymeri
zat
ion
a.ThermalPol
ymeri
zati
on
b.Catal
yti
cPolymer
izat
ion

l
l
.Hydr
ogenat
ionof
Coal

c.
BergiusProcess(
or)Di
rect
Process.
d.
FisherTr
opschProcess(or
)Indi
rect
Process.

I
l
l.Al
kyl
ati
on

Pol
ymer
isat
ion

Thegasesproducedincrackingcont
ainC3andC4ol efi
ns(i
sopr
opyl
ene,i
sobutyl
eneetc)and
al
kanes(met hane,et
hane,propane,but
ane).Thesegasesundergopolymer
isat
ioni
npresence
ofcatal
yst,(
H3PO4)atsui
tabletemperat
ureandpr essuretogi
vegasol
i
ne(Polymerpet
rol
),r
ichi
n
branchedchainhydrocar
bons.

Hence,pol
ymer
isat
ioni
smai
nlyf
ort
hepr
oduct
ionofsuper
iorgasol
i
neandi
scompl
ement
ary
t
ocat
alyt
iccr
acki
ng.

Pol
ymer
isat
ioni
soft
wot
ypes

i
)Ther
mal
Pol
ymer
isat
ion

Polymeri
sat
ionofcrackedgasesi
scar
redoutat500-600oCand70-350kg/
i cm2
pressure.Theproducti
sthegasoli
neandgasoi
lmi
xture,f
rom whi
chgasol
i
nei
ssepar
atedby
fr
actionati
on.

i
i
)Cat
alyt
icPol
ymer
isat
ion

Thisprocessi
scarri
edouti
npresenceofcatalystl
i
keH3PO4.Bythi
smethod
i
sobutylenecanbepol ymeri
sedt
ogivehigherol
efi
n’swhichi
shydrogenat
edt
ogasoli
ne
hydr
ocar bons.

I
. Hydr
ogenat
ionof
Coal

Coalcontai
ns4.5% ofHydrogen,whereaspet
rol
ium contains18% ofhydr
ogen.Socoalis
ahydrogendefici
entcompound,i
fcoali
sheatedwit
hhydrogenathi ghtemperat
ureandhigh
pr
essure,i
tisconvert
edint
ogasoli
ne.Theprepar
ati
onofliquidfuel
sfr
om soli
dcoali
scal
led
Hydrogenat
ionofcoal.

Petr
olcanbesynt
hesi
sedbydest
ruct
ivehydr
ogenat
ionofcoal
(Ber
giuspr
ocess
)and
l
i
qui
fi
cat
ionofcoal
(Fi
scher-Tr
opschpr
ocess).

i
)Ber
giusPr
ocess(
or)Di
rectPr
ocess

Ther
awmat
eri
alsusedi
nthi
spr
ocessar
ecoal
dust
,heavyoi
landni
ckel
oleat
eort
inol
eat
e.

Acoalpast
eisprepar
edbymi xi
ngcoaldus
twi
thheavyoi
landcat
alyst
.Iti
sthenpumpedi nt
o
theconver
terwher
et hepast
eisheat o450-500oCunder200-250at
edt minpr esenceof
hydrogen.
Ther
eact
ionpr
oduct
smai
nlycont
ainmi
xtur
eofhydr
ocar
bons
.

Coaldust 450°
C
suspendedi
nheavy+ H2 mi
xtur
eofhydr
ocar
bons
oil 200-
250at
m
condensat
ion
cr
udeoi
l

Sincethereacti
onisexot
hermi
ct hevapour
sleavi
ngt
heconver
terar
econdensedi
nthe
condensertogivesynthet
icpet
rol
eum orcrudeoi
l
.

Theoi
li
sthenf
ract
ional
l
ydi
sti
l
ledt
ogi
ve

i
)Petr
ol
j
i
)Middleoi
i
i
i)Heavyoi
l
.

Middl
eoil
isagai
nhydrogenat
edinpr
esenceofsol
idcat
alyst
stoproducemoreamountof
gasol
i
ne.Heavyoil
isus
edf ormaki
ngpast
ewithf
reshcoaldust
.Yiel
disabout60%.

I
IFi
scher-Tr
opschPr
ocess

Therawmateri
alsusedi
nthi
sprocessarehar
dcoke,st
eam t
opr
oducewat
ergasi
.e.
,
wat
ergasi
sobt
ained,bypassi
ngsteam overr
edhotcoke.
 1
200°
c
C+ H2O CO+H2
Wat
ergas

Thef i
rstst
epint
hispr
ocessi
spuri
fi
cati
onofgas.Tor
emoveH2S,thegasi
spassedthroughFe2O3
andtoremoveor gani
csul
phurcompounds,t
hegasisagai
npassedt
hroughamixt
ureofFe2O3and
Na2CO3.(Fi
g.4.7)

Thepurif
iedgasi
scompressedto5-25atm.andpassedoveracat
alystbedcontai
ning
desofTh,CoandMgat200-300oC.Whi
oxi l
epassi
ngthepur
if
iedgasthrought
hiscatalyst
bed,i
tisconver
tedt
ostr
aightchai
npar
aff
inandol
e

nCO+(
2n+1
)H2 CnH2n+2 +nH2O

n–par
aff
ins

nCO+2nH2 CnH2n +nH2O

ol
efi
ns

Sincethereact
ionsareexot
hermic,t
hevapoursl
eavi
ngthevessel
arecondensedi
nthe
condensertogivepet
roleum.I
tisf
ract
ional
lydi
sti
l
ledt
oyiel
dpetr
olandheavyoi
l
.

I
I. Al
kyl
ati
on

Repl
acementofhydr
ogenat
om f
rom ahydr
ocar
bonbyanal
kyl
groupi
sknown
asAl
kyl
ati
on.

Thereact
ionofisobutaneandisobut
eneinthepresenceofanhydr
ousHFatroom
t
emper
aturegivesi
sooctane.Thi
sprocessi
shighlyuseful
fort
heproduct
ionofhi
ghqual
i
typet
rol
.

Pur
if
icat
ionofPet
rol
(or
)Gasol
i
ne

Gasol
i
neorpet
rol
obt
ainedei
therf
rom cr
udeoi
lorsynt
het
icpr
ocessmaycont
ainsome
 undesi
rabl
eimpuri
ti
es.Theyar
emai
nlyunsat
urat
edol
efi
ns,col
our
ingmat
ter
s,sul
phur
compoundsetc.

Theunsat
urat
edolef
insgetoxi
disedandpol
ymer
isedt
her
ebycausi
nggum andsl
udge
f
ormati
ononstori
ng

Ontheotherhand,sul
phurcompoundsl eadtocorr
osionofI
CEandal soaff
ecttet
raethyl
lead
(TEL)whichisaddedtogasoli
net oobtai
ngoodpetrol
.Sotheseundesi
rablecont
entsmustbe
removedf r
om gasoli
ne.Unsaturat
edolefi
nsandcol
ouringmatt
erareremovedbyusi ng
adsorbentl
ikeKiesel
guhr
,ful
ler’
seart
h.

Sul
phurcont
aini
ngpet
rol
isknownassourspi
ri
t.

Thepr
ocessofdesul
phur
isat
ionofpet
rol
iscal
l
edsweet
eni
ngofpet
rol
.

Desul
phur
isat
ion

I
tcanbedonebyDoctor
’st
reat
ment.i
.e.
;pet
roli
str
eat
edwi
thanal
kal
i
ne sol
uti
onof
sodi
um pl
umbi
te(Doct
or’
ssol
uti
on)andl
it
tl
eofsul
phur.

2RHS+Na2PbO2 (
R-S-
S-R)
Pb+2NaOH

Sodi
umPl
umbi
te Leadmer
capt
ide

Theresul
ti
ngdisul
phide(l
eadmer capti
de)i
ngasol
ineareextr
act
edbyusi ngsuit
ablesol
vent
.
Aft
erref
ini
ngofgasoli
ne,someinhi
bitor
soranti
oxi
dantsareaddedinordert
or et
ardthe
oxi
dat
ionofolef
ins(ol
efi
nperoxi
de)whichcausetheformati
onofgum onstorage.

REFORMI
NG:

Reformingi sapr ocessofbr i

ngi
ngaboutst r
uctural
modifi
cat
ionsinthecomponentsof
st
raight-
r ungas oline( preparedbythefract
ionaldi
sti
ll
ati
onofthecrudeoil
),wit
hthepri
mary
objectofimpr ovingi tsanti-knockchar
acteri
sti
cs.Iti
scarri
edouteit
herthermal
lyori
nthe
presenceofacat alyst.

1
)THERMALREFORMI
NG:

Thermal reformingiscarr
iedouti
nareactor(orheater)at500°candapressur
eof85at m.
Thefeed- stockisstrai
ght-rungasol
i
ne.Toavoidtheformationofgas(att
heexpenseof
gasoli
ne),thecondi ti
onsarecontrol
l
edcaref
ull
ybyquenchi ng( r
apidcool
i
ng)theproductsby
sprayofcol doil.Thereformedproduct
sarethenfract
ionatedtoremoveresi
dualgas(stabi
l
izi
ng)
.
 Dur i
ngt her
malreformingsomecr acki
ngalsooccurst
oyiel
dalkanesandalekenes;andthese
mightunder godehydrogenati
on,fol
lowedbycycli
zati
on(Dehydr
ocycli
zat
ion)t
oyield
naphthalenes(ar
omat i
zati
on).Conversi
onofn-al
kanestobeached-chai
nalkanesalsotakes
pl
acedur i
ngther
mal ref
orming.

2)
CATALYTI
CREFORMI
NG:

Togetbet
tergradeandyiel
dofgasoli
nes,catal
yti
cr efor
mi ng[
Pt(0.
75)suppor
tedonal
umi
na]
i
scar
ri
edoutbyusi ngbyusi
ngeit
herafixed-
bedorf uidized-bedat460-530°
Cand35-50
at
mospher
icpressure.Themai
nreact
ionsduringcatal
yt i
creformi
ngprocessare:
 Thehydr
ogent
husevol
veddur
ingcat
alyt
icr
efor
mingi
susedt
o:

a)hydr
ogenat
eal
kenes,

b)pr
omot
ecr
acki
ngofl
argeal
kanemol
ecul
es(hydr
ocr
aki
ng)
,and

c)r
emovesul
phuri
nthef
eed-
stockasH2Sgas.

NONPETROLEUM FUEL

Li
quef
iedpet
rol
eum gas:
I
tisami
xtur
eofpr
opaneandbut
ane.
I
tisobtai
nedasoneoft hetopfract
ionsinthefr
acti
onaldi
sti
l
lati
onofpet
rol
eum.I
tiseasi
l
y
l
i
quif
iedandsocanbeeconomical
l
ystoredandtr
anspor
tedincyl
inders.

Composi
ti
on

I
tsappr
oxi
mat
ecomposi
ti
oni
s
nBut
ane =70%
I
sobut
ane =1
7%
n-
Propane =1
1%

But
yleneandEt
hane=r
est
.

Cal
ori
fi
cVal
ue
I
tsCal
ori
fi
cVal
uei
s27,
000kcal
s/m3.
Uses
i
.Iti
susedasaf
uel
fordomest
iccooki
ng.
i
i
. Us
edf
orheat
ingi
ndust
ri
alf
urnaces
.
i
i
i.Us
edasanal
ter
nat
eforGasol
i
nei
naut
omobi
l
es.
 Li
quef
iednat
ural
gas:
Naturalgasisal
waysfoundabovetheoi
lintheoi
lwell
s.Iti
sal
socal
ledMarshgas.I
tconssi
sts
ofmet haneandot hersat
urat
edhydrocar
bons.Theaver agecomposit
ionofnat
uralgasisas
fol
l
ows:
I
tscalor
if
icval
uevari
esfrom 1
2,000t
o14,000kcalm3.
/

Consti
tuent
s Per
centage(
%)
Methane 88.5
Et
hane 5.5
Propane 4
Butane 1
.5
Pentane 0.5

I
fnatur
algascont
ainsl
owerhydrocarbonsli
kemet
haneandet haneitiscal
l
edleanordry
gas.I
nthenatur
algascontai
nshi
gherhydrocarbonsl
i
kepropane,butanealongwithmethanei
t
i
scall
edri
chorwetgas.

Uses
1
.Iti
susedasadomest
icandi
ndust
ri
al
fuel
.
2.I
tisusedasar
awmat
eri
alf
ort
hemanuf
act
ureofcar
bonbl
ackandhydr
ogen.
3.I
tisal
sous
edf
ort
hegener
ati
onofel
ect
ri
cit
ybyusi
ngi
ti
nfuel
cel
l
s.

BI
OGAS:
Thesegasesgener
all
ypr
oducedbyt
hef
erment
ati
onofbi
owast
es,sewagewast
eset
c.,
byanaer
obi
cbact
eri
a.

Forexampl e,natur
algasi saBi ogas,whichr
esult
saf
teralongperi
odi
cdecayofanimaland
vegetablematter
sbur r
iedinsi
detheearth.
The cheapestand easi l
yobt ai
nable bi
ogasisGobargas,which i
sproduced byanaerobi
c
fermentati
onofcat tl
edung.Thebi ogasisburntt
orai
sesteam,whichcandr i
vetur
binesto
produceelectr
ici
ty.

Steelgas
holder
Gas
I
nlet outl
et
t
ank toki
tche
n
Outl
ett
ank
formanur
e
Ground
evelDung+
l
water
sl
urry
1
0cm pi
pe
1
0cmpi
pe

Di
gesti
o
nwell

Masonr
ywork
 Gobar
Gas

i
) I
tisessent
ial
l
ymet
hane.
i
i
) ItsCalori
fi
cVal
ueis5400kcal
s/m3.
i
i
i) I
tsaveragecomposi
ti
oni
s
CH4 =60%
CO2 =30%
H2 =1 0%

I
tisobt
ainedbyfer
mentat
ionofGobar(dung)i
nabsenceofai
r.I
nat
ypical
Gobargasplant,t
hedungintheform ofsl
urr
yisint
roducedi
ntoabri
ck-li
ned
wel
lcal
ledfer
mentati
onwell
.
Ani
nver
teddr
um i
spl
acedai
rti
ghtl
yont
hewell
.Itact
sasgashol
derandi
t
canbemovedupanddownwit
hthehel
pofpul
l
eys(
Fig.
1 .
10)
.

Formati
onofgasst ar
tsinaweek.Theopt i
mum temperaturefort
hisfer
mentat
ionis34-
48oC.Asthegasstartscol
lecti
nginthedr
um,thedrum beginstoriseandf
loat
.Thegas
i
stakenoutfrom t
heexitprovidedatthet
opofthedrum.I ti
susedasadomest icf
ueli
n
vi
ll
ages.I
tisusedfordomest i
cheati
ngandsmallpumpr unning.

FUELFROM WASTE:

WHATI SFUEL?
•Fuelsar eanymat eri
alst
hatst or
epot entialenergyinformst hatcanbe
practi
cablyreleasedandusedf orwor korasheatener gy.Theconceptor igi
nall
y
appli
edsol elytothosemat er
ialsstor
ingener gyint heform ofchemi cal
ener gythat
couldber eleasedthroughcombust i
on,buttheconcepthassi ncebeenal soappl i
ed
toothersour cesofheatenergysuchasnucl earener gy.
Whati sWast eToFuel?
Wast e-t
o- energyorenergy-from- wasteisthepr ocessofgener at
ingener gyinthe
form ofelectri
cit
yand/orheatf rom t
heinciner at
ionofwast e.Wt Eisaform of
energyrecover y.MostWt Epr ocessesproduceel ectr
ici
tyand/orheatdirectly
thr
oughcombust i
on,orproduceacombust i
blef uelcommodi ty,suchasmet hane,
methanol,et hanolorsynt
heti
cf uels.

ANewVi
si
on-I
nci
ner
ati
on

•Incinerat
ion,t
hecombust ionoforgani
cmateri
al suchaswastewi thener gy
r
ecover y,i
sthemostcommonWt Eimpl
ementat
ion.Themet hodofusi ng
i
ncinerati
ontoconver tmuni ci
palsol
idwast
e(MSW)t oenergyisar elativel
yold
methodofWt Epr oducti
on.Inci
nerati
ongener
all
yent ai
lsbur
ningwast e( r
esi
dual
MSW,commer cial,i
ndustr
ialandRDF)toboil
wat erwhichpower ssteam gener ator
s
t
hatmakeel ect
ri
cener gyandheatt obeusedinhomes,busi nesses,i nsti
tut
ionsand
i
ndustr
ies.Oneproblem associ
atedwit
hinci
ner
ati
ngMSW tomakeelect
ri
calener
gy,
i
sthepot ent
ial
forpoll
utant
stoentert
heatmospherewi
tht
hefl
uegasesfrom t
he
boi
ler
.

ThePr
obl
em

I
NCI
NERATI
ON:

Bur
ningor 700-
1100°
c t
oxi
cgasesl
i
keco,
co2andash(oxi
des)
i
nci
nerat
ion

1)Ai
rpollut
ion(dust,et
c)
2)l
ossofsol i
dwaste
3)gl
obal warming
4)monsoonf ail
ure
5)costismore
6)i
mpr opertechnology
7)di
oxin?

Al
ter
nat
ivest
oInci
ner
ati
on:

•Ther eareanumberofot hernewandemer gi

ngtechnol ogi
esthatar eablet o
produceener gyf r
om wast eandotherfuelswit
houtdirectcombust i
on.Manyof
thesetechnologieshavet hepot enti
alt
opr oducemor eelectr
icpowerf rom thesame
amountoff uelthanwoul dbepossi bl
ebydi r
ectcombust i
on.Thisismai nl
yduet o
theseparati
onofcor rosivecomponent s(ash)fr
om theconver t
edfuel ,ther
eby
all
owinghighercombust iont emperat
uresine.g.boi
lers,gasturbi
nes ,inter
nal
combust i
onengi nes,fuel cell
s.Somear eabletoeff
ici
entlyconverttheener gyinto
l
iquidorgaseousf uels:

•Theyar
ebr
oadl
ycl
assi
fi
edast
her
mal
andnont
her
mal
.

Thermal t
echnol ogi es Non-t
her
mal t
echnologi
es
 Gasi f
icati
on(pr oduces  Anaer
obicdi
gest
ion(biogasri
ch
combust i
blegas,hydr ogen, i
nmethane)
syntheticfuels)
 Ther mal depolymer izati
on  Fermentat
ionpr oducti
on
(producessynt heti
ccr udeoil
, (examplesareet hanol,lact
icaci
d,
whichcanbef urtherr efi
ned) hydrogen)
 Pyrolysis9pr oducescombust ibl
e  Mechanicalbiologi
caltreatment
tar/biooi l
andchar s0 (MBT)
MBT+aner obicdigesti
on
MBTt oRefuseder ivedfuel
 Plasmaar egasi
fi
cati
onorplasma
gasif
icat
ionprocess(PGP)
(Producesri
chsyngasincl
uding
 hydrogenandcarbonmonoxi
de
usableforf
uel
cell
sorgener
ati
ng
el
ectri
cit
ytodr
ivethepl
asma
arch,
)

Pyr
olysi
sofpl
ast
ic:

Af l
uidized- bedr eact orhasbeendevel opedforconver ti
ngwast epl ast
icsinto
fueloiltoreduce.Pl asticproduct saremadef r
om petroleum.Themai nconst i
tutes
arecar bonandhydr ogen.I not herwor ds,wasteplasti
cscoul dber eversely
pyrolysedi ntofueloi l
.Af lui
dized- bedreactorhasbeendevel opedf orconverting
wastepl asticsIntofuel oi
l.Pl
asticsar echoppedandf edi ntoreactor.Wi t
hbubbl i
ng
fl
uidi
zedbedr eactor ,hotsandssur roundthechoppedpl ast
icsandheatqui ckly
pyrolyzest hepl ast
icsi ntofueloil.Waxi sproducedfrom someoft hewast eplasti
cs
andwi llcl
ogt hepipel i
nes.Thepyr olysi
ssystem operatescont i
nuouslywi t
hade-
waxappar at usdevisedt osepar atethewaxf rom t
hef ueloil
.

Appl
i
edObj
ect
s:

Fuel oil
der i
vedf r
om wast eplasti
cscanbeusedi nboi l
erforheatingordiesel
enginef orelectri
cit
y.Heat i
ngvalueofwaste-plast
icderivedf ueli
shigherthanthat
ofdiesel oi
l.Manywast eplasti
cshavebeentestedforpr oducingfuel oi
l
,suchas
pl
asticsofpol ypropylene(PP) ,polyet
hyl
ene(PE),polyst
yrene( PS),acryl
onit
ri
le
butadienest yr
ene( ABS) ,orthemixoftheabove-ment i
onedpl ast
ics.Fuel
gener at
edbypl asti
c

Benef
it
sofPyr
olysi
sofpl
ast
ic:

Theprobl em ofi
ncr easi
ngwasteplast
icsisnowagl obalone,andonet hatmus
t
beaddr essedinor dertosol
vetheworld’
slimitedr
esourceandener gyprobl
em.
Fueloilderi
vedf r
om wast epl
asti
cs,apromisingapproachwithpotenti
al
appli
cations,notonl yr
esol
vewasteproblem butalsoprovi
defueloilf
orthe
subst
ituteforpetroleum pr
oducts
.

CLEANFUEL

I
NTRODUCTI
ON

Convent
ional
Fuel
s:
-

Fossi
lfuel
s(pet
rol
eum )
,coal
andnucl
earmat
eri
alssuchasur
ani
um.

CLEANFUELS:
 Alsoknownasnon-
convent
ional
fuel
s.
  Highl
yoxidized,sulphurfree,envi
ronment
alfr
iendly.
 Anymat eri
alsorsubst ancesthatcanbeusedasf uel
s,othert
han
conventi
onal f
uels.
 Example:alcoholfuel,vegetabl
eoilbi
odi
esel
,naturalgas.

SELECTI
ONALOFCLEANFUEL
 3E’s(Eco-
fri
endl
y,ef
fi
cient
,economi
cal
)

WHYWECHOOSECLEANFUEL

 Conventionalfuelsar
egoingtorunout
 Toreducepol l
ut i
on
 Toprotectagai nstgl
obalwar
ming
 Tosavemoney
 Bi
odegr adableandnont oxi
c
 Easytohandl eandst or
e
 Rural
devel opment

DI
FFERENTTYPESOFCLEANFUELS:

 Alcohol f
uels(et
hanolandmet
hanol
)
 Wat ergasoli
nemixtur
e
 Veget abl
eoil
 Biodiesel
 Hydr ogen
 LPG&CNG
 El
ect ri
cit
y
 Benzol etc.
.

ETHANOL:

Et
hanol i
sarenewable,domesticall
ypr oducedal coholfuelmadeFr om pl
ant
materi
al,suchascorn,sugarcane,orgr asses.Usinget hanolcanreduceoil
dependenceandgr eenhousegas( GHG)emi ssi
ons .Ethanolfuelusei
nt heU.S.has
i
ncreaseddr amat
ical
lyfr
om about1 .
7billi
ongallonsin2001t oabout1 6.4bil
l
ioni
n
2016.

Ethanol
isal
soknownaset
hyl
alcohol
.It
’st
heal
cohol
inbeer
,wi
ne,r
um,vodka,
et
c.
Ethanolwasusedtofuelsomeofthefi
rstaut
omobil
es…
Thefir
stproduct
ioncarr
unningenti
rel
yonethanol
wasthef
iat1
47,i
ntr
oducedi
n
1978inbrazil
byFiat
.

 Alchol basedcl
eanfuel
producedbyf ermenti
nganddist
il
l
ingstar
chcropsor
cell
ulose.
 Mostcommonl yusedtii
ncreaseoctaneandimprovetheemissi
onsquali
tyof
gasoline.
 Canbebl endedwit
hgasoli
net ocreat
eE85,ablendof85% ethanol
and1 5%
gasoline,
(FLEXFUEL)
 ANEXCELLENT,CLEANBURNI NGFUEL,HASAHI GHEROCTANERATI NG
(OVER1 00)andburnscoolerthangasol
ine.

Hi
ghethanol
blendspr
esentapr
obl
em t
oachi
eveenoughvapourpr
essur
efor
t
hefuelt
oevaporat
eandsparkt
hei
gni
ti
ondur
ingcol
dweather.

METHANOL:

Methanolofal
lt
hefuelbei
ngconsi
deredasanalt
ernatet
ogasol
ine,met
hanoli
s
oneofthemostpromisi
ngandexperi
encedmajorresear
chanddevel
opment
.

 Methanol,alsoknownaswoodal cohol
,canbeusedasanal ternati
vefuel i
n
fl
exi
blefuelvehicl
esthatrunonM85.
 Thebenef i
tsincl
ude loweremissi
ons,higherperf
ormance,andl owerr i
skof
fl
exi
bil
it
ythangas oli
ne.
 Methanolcaneasi l
ybemadei nt
ohydrogenf orhydr
ogenfuel cell
vehiclesin
thefut
ure.
 Methanolisextremelycorrosi
ve,r
equir
ingspecialmater
ial
sfordeliver
yand
stor
age.

VEGETABLEOI
L
  RUDOLFDI ESELDesi gnedadi esel engi nei n1984t or unonpeanutoi l.
 Theuseofveget ableoi l
sf orengi nefuel mayseem i nsignifi
cantt oday.But
suchoi l
smaybecomei nthecour seoft i
measi mpor tantaspet r
oleum ancoal
tarproduct soft hepr esenttime.
 Mostdi esel carengi nesar esuitablef ort heuseofst raightveget ableoil(SVO),
alsocommonl ycal ledpur epl antoi l
(PPO) ,withcer t
ainmodi ficati
ons.
Princi
pally,thevi scosi t
yandsur facet ensi onoft heSVO/ PPOmustbe
reducedbypr eheat ingit,typical
lybyusi ngwast eheatf r
om t heengi neor
electr
ici
ty,ot herwisepoorat omizat i
on,i ncompl etecombust i
onand
carbonizationmayr esul
t.Onecommonsol uti
oni stoaddaheatexchanger
andanaddi t
ional fuel t
ankf orthepet rodi eselorbi odiesel bl
endandt oswitch
betweent hi
saddi t
ional tankandt hemai nt ankofSVO/ PPO.Theengi neis
start
edondi esel,swi t
chedovert oveget abl eoilassoonasi tiswar medup
ands witchedbackt odiesel shortlybef orebei ngswi tchedof ftoensur ethat
noveget abl eoilremai nsintheengi neorf uell
ineswheni tisst ar
tedfrom cold
again.

BI
ODI
ESEL

 Biodi
esel
isadomest i
call
ypr oduced,renewablefuelthatcanbe
manufact
uredfrom vegetableoil
s,ani
mal fat
s,orrecycledrest
aurantgreases.
 Biodi
esel
issaf
e,biodegradableandr educeairpoll
utantssuchaspar t
iculat
es,
carbonmonoxi
de,hydr ocarbons,andairtoxi
cs.
 Biodi
esel
canalsobeusedi nit
spuref or
m butitmayr equir
ecertai
nengi ne
modifi
cat
ionst
oavoi dmaintenanceandper f
ormancepr oblemsandmaynot
 besui
tabl
eforwint
ert
imeuse.
 Needtoheatst
oraget
anksi
ncoldercl
i
mat
est
o pr
event
sthef
uel
from gel
l
ing.

I
MPORTANCEOFBI
ODI
ESEL

•Environmentalf
ri
endly
•Cleanbur ni
ng
•Renewabl efuel
•Noengi nemodi f
icat
ion
•I
ncr easeinengi
nel i
fe
•Bi
odegr adableandnon- t
oxi
c
•Easyt ohandleandstore
•Compl eteCO2cycl e
•Sulphurfree
Fat
tyaci
dal
kyl
est
erpr
epar
edf
rom anyoi
lorf
at….

TRANSESTERI
FICATI
ON

Fat
tyaci
dmet
hyest
eri
swel
lknownmol
ecul
esf
orvegi
tabl
eoi
l

BI
ODI
ESELCO2CYCLE

NOFOSSI
LECO2RELEASED:NOGLOBAALWARMI
NG
HYDROGEN:

Advant
ages

 Emitsonlywat
ervapour,assumi
ngther
eisnoleakageofhydrogengas
 Itcanstoreupto3xasmuchener gyasconvent
ional
natur
algas.
 Produceddomest i
call
y
 Envir
onmental
lyfr
iendl
y.

.Di
sadvant
ages:

 Itst
il
lcost
saconsi
derabl
eamountofmoneyt
orunahydr
ogenvehi
cl
e
Envi
ronmental
l
yfr
iendl
y.
 Dangerous.

APot
ent
ial
l
yemi ssi
ons-
freeal
ternat
ivef
uelpr
oducedf
rom domedt
icr
esour
ces.Not
wi
del
yusedtodayasatransport
ati
onfuel
.

COMPRESSEDNATURALGAS

Iti
smuchsaf
erthanotherfuel
sint
heeventofaspi
l
l,becausenat
ural
gasi
sli
ght
er
t
hanai
randdisper
sesquickl
ywhenr el
eased
 ADVANTAGES DISADVANTAGES
 i
tcanbeef fi
cient
lyandsafel
y  stil
ldoescr eategr eenhousegas
stor
ed. emi ssions
 moreenvironmentall
yfri
endl
ydue  highlyvol ati
leandcanbe
toit
slowemi ssi
onsafterbur
ning. danger ousi shandl edor
transpor tedcar elessly
 mostofthenat ur
al r
eser
vesof  theyar en' tasroomyasgasol i
ne
natur
algasfiel
dar eunderut
il
i
zed. cars
 I
mpr ovelubri
cati
onbecauset he  higherover all
cost sofanat ur
al-
cyl
inder
sar enotwashedbypet rol gasvehi clecompar edtoa
excess gasol i
ne-power edcar .