Page 1
PET
RO
LE
UM
R
EF
ININ
G
TE
CH
NO
LO
GY
Dr. R
AM P
RA
SAD
B
.E.(
HO
~S.)
, M.T
ech.
, Ph.
D.
ASS
ISTA
NT
PRO
FESS
OR
D
EPA
RTM
ENT OF C
HE
MIC
AL
ENGINEERING
HA
RC
OU
RT
BUTL
ER T
EC
HN
OL
OG
ICA
L IN
STIT
UTE
,
KH
AN
NA
PU
BL
ISH
ER
S O
pera
tion
al O
ffic
e: 4
5751
15, O
nkar
Hou
se, R
oom
No.
3-4
, Gro
und
Floo
r,
Dar
ya G
anj,
New
pel
hi-1
1000
2 Ph
one:
232
4304
2 F
ax:
2324
3043
D
esp
atch
Off
ice:
11
, Com
mun
ity
Cen
tre,
Ash
ok V
ihar
, Ph
ase
2 D
elhi
-110
052.
Pho
ne : 2
7224
179
Reg
d. O
ffic
e:
2-B
, Nat
h M
arke
t, N
ai S
arak
, Del
hi-1
1000
6.
Ph.
239
1238
0
Page 2
Published by :
R
omesh C
hander Khanna
for KH
AN
NA
PUBLISHERS
2-B, N
ath Market, N
ai Sarak D
elhi- 110 006 (India)
Q A
ll Riehfq,R
egerv,ed , , T
his book orpart thereof cannot be tmnslated or reprodued in
any form (except for review
or criticism
) without the w
ritten permission of the A
uthor and the Publishers.
First E
dition F
ifth Reprint : 2008
Price :
Rs. 185.00
Com
puter Typeset and Figures designed by :
S
teps Com
puters, D-2/77, D
ayd Pur, Delhi 110 094
Ph. 218-1367
Printed a
t.. Print India. Delhi-95
-,* It givesm
e a great pleasure in presenting the book on "Petroleum R
efining Technology'
.The relvant topics for working C
hemical/Petroleurn E
ngineers in Petroleum-R
efineries have .",, been covered.
The first chapter gives an account of theories of oil and gas form
ahon, methods fo
p,
exploration and drilling for oil and gas. It highlights the development of petroleum
refininB
industry in India. <
,.. T
he knowledge of chem
isty and compositionof crude oil isessentialin the selection of the
refining processes. The characteristics, constituents and classification of crude coils have been.
discussed. in chapter 2.
Indian crudes such as Bom
bay l-hgh, Assam
are waxy in nature. T
hese require sped; m
ethod for transportation. The problem
s related to the handling of waxy crude oils and their
feasible solutions have heen discussed in chapter 3. --
Quality control of petroleum
-products isa necessity if the products are to give satisfactory w
rformance to the custom
ers. Bureau of ,lndian~S
tandard; N
ew D
elhi sfandaLdizes ~
rocedure in
d issues specif cationsfor eachpetroleum
products. ~efktio
n,m
etho
d andsignifi-eof
the various laboratory tests have been given in chapter 4.
Chapter 5 discusses m
anufacture,properties and uses of petroleum products. This chapter
covers LPG, naphtha, gasoline, kerosine, ATF, diesel fuel, fuel oil, hydrocarbon solvenk "
'
lubricating oils, petroleum w
axes, bitumen and petroleum
coke.
Petroleum refining processes have been discussed in six chapter (611). C
rude ou distilla tion is the first unit in the refinery and carried out in tw
o stages-atmospheric and vacuum
, B
efore discucssing these processes the removal of im
purities by electrical desalting process ha, been discussed. The influence of the process variables on the opera tion of a fractionating colum
n ?.* and the scope for im
provement have been discussed in C
hapter 6.
Crude oil distilltion produces reside w
hich is to be upgraded. Thennal conversio~
~..
processes for this purpose include visbreaking and coking. These processes have been discussea
in chapter 7. lh
Catalytic conversion processes use catalyst and either change carbon num
ber or carbon/ hydrogen ratio. T
he most im
portant processes include fluid catalytic cracking, catalytic reform- -
ing, hydrocracking,catalyticalkyla tion, isomerizsl tion and polym
eriza tion Cataly tic isom
&
tion neither changes carbon num
ber nor carbon/hydrogen ratio. These processes have been dis-,.
cussed in chapter 8.
Finishing processes are necessary to make the petroleum
products suitable for use with .
respect to performance,corrosivity, suitability on storage, odour etc. Various finishing processes
such as hydrogen sulphide removal processes, sulphur recovery processes, sw
eetening process-,,. es, solvent extraction processes and hydrotreating processes have been discussed in chapter 9.
Page 3
(iv)
L@
~&&
@p@
b*ou
ld po
sses
s and
maintain p
rope
r vis
cosi
ty, f
low
as li
quid
at t
heha
ndlin
g an
d op
erat
ing t
empe
ratu
re an
d ha
ve g
ood
ther
mal
and
oxid
atio
n st
abili
ty. L
ubri
catin
g oils
of v
ario
us
grad
es a
re m
anuf
actu
red
by m
ixin
g of
the
sel
ecte
d lu
bric
atin
g oils
bas
e st
ock
and
addi
tives
. A
mod
em lu
be o
il co
mpl
ex c
onsi
sts o
f vac
uum
dis
tilla
tion u
nit,
solv
ent d
easp
halti
ng u
nit,
solv
ent
extr
actio
n un
it, s
olve
nt d
ewax
ing
unit
and
hydr
ofin
ishi
ng u
nit.
The
se p
roce
sses
hav
e be
en
disc
usse
d in
cha
pter
10.
The
det
ails
on
the
man
ufac
ture
of p
etro
leum
wax
es h
ave
also
bee
n pr
esen
ted
ir\ this c
hapt
er.
Cha
pter
11
disc
usse
s th
e m
anuf
attu
re o
f bi
tum
en fr
om c
rude
oil.
Gen
erat
ion o
f pro
cess
engi
neer
s hav
e acc
epte
d co
rros
ion a
s a fa
ct of
life
, an
incu
rabl
e vir
us
who
se p
rogr
ess m
ay b
e slo
wed
but n
ever
stop
ped.
Cor
rosi
oh ca
n re
duce
the l
ife o
f ref
iner
y units.
Chp
ater
12
disu
csse
s ty
pk a
nd f
orm
s of
cor
rosi
on a
nd th
eir
cont
rol i
n cr
ude
oil d
istil
latio
n,
ther
mal
cr?c
king
, flu
id ca
taly
tic cr
acki
ng, a
min
e gas
proc
essi
ng, a
nd st
eam
and
cond
ensa
te lin
es.
Air,
wat
er a
nd so
il ar
e vi
tal o
f lif
e on
this p
lane
t. T
hese
reso
urce
s are
to b
e pr
otec
ted
and
used
wis
ely.
Cha
pter
13
disc
usse
s ai
r po
llutio
ns, w
ater
pol
lutio
n an
d sl
udge
trea
tmen
t and
di
spos
al.
Cha
pter
14,
hig
hlig
hts,
des
igns
and
ope
ratio
n of
peb
bleu
rn p
roce
ssin
g eq
uipm
ents
.
It is h
oped
that
this
boo
k in
its
pres
ent f
orm
will
be useful f
or th
e st
uden
ts o
f ch
emic
al
engi
neer
ing.
I will
be
high
ly g
rate
ful,
if sh
ort comings o
f th
is e
ditio
n in
form
of
cont
ents
, err
ors
are
high
light
ed to
me.
-Ram
Pr
asad
K
~~
PW
k 1
PET
RO
LE
UM
EX
PLO
RA
TIO
N, P
RO
DU
CT
ION
AN
D R
EF
~NIN
G
1-14
1.
1 IN
TRO
DU
CTI
ON
1
1.2
FOR
MA
TIO
N O
F O
IL A
ND
GA
S 2
1.3
OIL
AN
D G
AS
EXPL
OR
ATI
ON
2
1.4
DR
ILLI
NG
FO
R O
IL A
ND
GA
S 3
1.5
PRO
DU
CTI
ON
OF
CR
UD
E O
IL A
ND
NA
TUR
AL
GA
S 5
1.6
PETR
OLE
UM
REF
ININ
G, O
PER
ATI
ON
AN
D O
PTIM
IZA
TIO
N
8 1.
6.1
Sele
ctio
n of
Proc
esse
s for
Opt
imiz
atio
n 9
1.6.
2 O
ptim
izat
ion
in a
Run
ning
Ref
iner
y 10
1.
6.3-
R
efin
ing
Cap
acity
in In
dia
11
2'
2 C
RU
DE
OIL
S - C
HE
MIS
TR
Y A
ND
CO
MPO
SIT
ION
15
-28
i 2.
1 IN
TRO
DU
CTI
ON
15
2.
2 C
HA
RA
CTE
RIS
TIC
S OF
CR
UD
E O
ILS
15
2.3
CO
NST
lTU
ENTS
OF
CR
UD
E O
ILS
16
2.3.
1 H
ydm
arbo
ns
17
2.3.
2 N
on-H
ydro
carb
ons
22
2.4
CLA
SSIF
ICA
TIO
N O
F C
RU
DE
OIL
S 25
2.
4.1
Cha
ract
eriz
atio
n Fac
tor
26
2.4.
2 C
orre
latio
n Ind
ex
28
2.4.
3 M
etho
d of
Str
uctu
ral G
roup
Ana
lysi
s 28
f 3
TR
AN
SPO
RT
AT
ION
OF
WA
XY
CR
UD
E O
ILS
29-4
4
3.1
INTR
OD
UC
TIO
N
3.2
PIPE
LIN
E TR
AN
SPO
RTA
TIO
N
3.3
WA
XY
CR
UD
E O
ILS
I 3.
3.1
Def
initi
ons o
f R
heol
ogic
al P
aram
eter
s 3.
3.2
Rhe
olog
ical
Cla
ssifi
catio
n of
Flu
ids
3.4
FLO
W P
RO
PER
TIES
OF
WA
XY
CR
UD
E O
ILS
3.5
PUM
PAB
ILIT
Y C
HA
RA
CT
ER
IS~C
S OF
WA
XY
CR
UD
E O
ILS
3.5.
1 T
empe
ratu
re
3.5.
2 Y
ield
Stre
ss-M
odel
Pip
elin
e Tes
t 3.
5.3
Flow
at R
esta
rt -
--
3.5.
4 Ef
fect
ive
Pip
elie
Vis
cosi
ty
3.6
MET
HO
DS
FOR
PIP
ELIN
E TR
AN
SPO
RTA
TIO
N O
F W
AX
Y C
RU
DE
OIL
S 3.
6.1
Use
of
Pow
-Poi
nt D
epre
ssan
ts/F
low
Im
prov
ers
3.6.
2 M
echa
nism
of F
low
Impr
ovem
ent
3.6.
3 Po
int o
f A
dditi
ve k
iject
ion
3.6.
4 Po
ur p
oint
Red
uctio
n by
Add
itive
s 3.
6.5
Effe
ct o
f Fl
ow I
mpr
over
s on
Yie
ld S
tres
s and
Vis
cosi
ty
3.6.
6 ln
corp
orat
ion
of L
ow P
our P
oint
Cru
des
in W
axy
Cru
des
3.6.
7 C
rude
Oil
Con
ditio
ning
Page 4
4 --Q~
~&
JT
Y~
ON
TR
OL
O
F PETRO
LEUM
PRO
DU
CT
S 45-64
4.1 IN
TRO
DU
CTIO
N
4.2 C
LASSIFIC
ATIO
N O
F LAB
OR
ATO
RY
TESTS 4.3
DISTILLA
TION
4.4
VA
POU
R PR
ESSUR
E 4.5
FLASH
POIN
T AN
D FIRE PO
INT
4.6
OC
TAN
E NU
MB
ER
4.7 PE
RFO
RM
AN
CE
NUM
BER
4.8
CETA
NE N
UM
BER
4.9
AN
ILINE PO
INT
4.10 DIESEL IN
DEX
4.11
CA
LCU
LATED
CETA
NE IN
DEX
4.12
CA
LOR
IFIC V
ALU
E 4.13
SMO
KE PO
INT
4.14 C
HA
R V
ALU
E 4.15
VISC
OSITY
4.16
VISC
OSITY
IND
EX
4.17 PENETR
ATIO
N TESTS
4.18 FR
EEZING
POIN
T 4.19
CLO
UD
POIN
T AN
D PQ
UR
POINT 4.20
DR
OP PO
INT
OF G
REASE 4.21
MELTIN
G A
ND
SEIT
ING
POINT OF W
AX
4.22 SO
FEN
ING
POIN
T OF BITUMEN
4.23 IN
DU
CTIO
N PER
IOD
OF G
ASO
LINE
4.24 THER
MA
L STAB
ILITY O
F JET FUELS
4.25 G
UM
CO
NTEN
T 4.26 TO
TAL SU
LPHU
R
4.27 AC
IDITY
AN
D A
LKA
LINITY
4.28
CO
PPER-STR
IP CO
RR
OSIO
N TEST
4.29 SILV
ER-STR
IP CO
RR
OSIO
N TEST FO
R AV
IATIO
N TU
RB
INE FU
ELS 4.30 A
SH
4.31 CA
RB
ON
RESID
UE
4.31.1 Conradson M
ethod 4.31.2 R
amsbottom
Method
4.32 C
OLO
UR
4.33
DEN
SITY A
ND
SPECIFIC
GR
AV
ITY
--.
4.34 G
AS C
HR
OM
ATO
GR
APH
Y O
F PETRO
LEUM
GA
SES AN
D LIQ
UID
S 4.35 R
EFRA
CTIV
E IND
EX O
F HY
DR
OC
AR
BO
N LIO
UID
S - -
--- 4.36 LEA
D IN
GA
SOLIN
E 4.37 W
ATER SEPA
RO
METER
IND
EX (M
OD
IFIED) (W
SIM)
4.38 D
UC
TILITY
S
PETRO
LEUM
PRO
DU
CT
S 65-176
5.1 LIQ
UEFIED
PEIRO
LUEM
GA
SES L
C
5.1.1 C
omposition of LPG
5.1.2
Properties of LPG
5.1.3 Production of L
K
5.1.4 Uses of LPG
N
APH
THA
S 5.2.1
Methods of M
anufacture of Naphthas
5.2.2 C
omposition of N
aphthas
(vii)
5.2.3 U
sesof Naphthas
5.3 M
OTO
R SPIR
IT 5.3.1
Spark-Ignition Engine
5.3.2 C
omposition of G
asolines 5.3.3
Properties of Gasolines
5.3.4 T
ypes of Additives U
sed in Gasolines
5.3.5 N
ew G
asoline Blending C
omponents
5.3.6 A
lternative Gasoline Fuels
5.4 K
ERO
SINE
/ 5.4.1
Manufacture of K
erosines 5.4.2
Com
position of Kerosines
5.4.3 Properties of K
erosines 5.4.4
Uses of K
erosines 5.5
AV
IATIO
N TU
RB
INE FU
ELS 5.5.1
Com
position of ATFs
5.5.2 Properties of A
TFs 5.5.3
ATF A
dditives 5.5.4
Storage and Handling Problem
s
Y'
5.6.1 C
ompression-Ignition
FUELS
(Diesel) Engine
5.6.2 C
omposition of D
iesel Fuels 5.6.3
Properties.of Diesel Fuels
5.6.4 A
dditives for Diesel Fuels
5.6.5 A
lternative Diesel Fuels
T,~
NE
LO
IL
S
@ 5.7.1
Nature and C
omposition of Fuel O
ils 5.7.2
Properties of Fuel Oils
5.7.3 C
ombustion of Fuel O
ils 5.7.4
Bum
ersCharacteristics and A
pplications 5.7.5
Storage, Handling and Preparationof Fuel O
ils 5.8
PETRO
LBU
M H
YD
RO
CA
RB
ON
SOLV
ENTS
5.8.1 C
~pposition of H
ydrocarbon Solvents 5.6.2
Classification of H
ydrocarbon Solvents 5.8.3
Manufacture of H
ydrocarbon Solvents 5.8.4
Properties of Hydrocarbon Solvents
5.8.5 U
ses of Hydrocarbon Solvents
d3w LUB
RIC
ATIN
G O
ILS , ,
5.9.1 M
ineral Oil-B
ased Lubricants
vt ! d'
5.9.2 Synthetic L
ubricants 5.9.3
Basic Functions of L
ubricants 5.9.4
Autom
otive Engine O
ils 5.9.5
Indushial Lubricating O
ils 5.9.6
Electrical Insulating O
ils 5.9.7
Jute Batching O
ils 5.9.8
White O
ils 5.9.9
Steam T
urbine Oils
5.9.10 M
etal Working O
ils 5.9.11
Miscellaneous O
ils 5.10
PETRO
LEUM
WA
XES
5.10.1 Types of Petroleum
Waxes
5.10.2 Properties of Petroleum W
axes 5.10.3
Manufacture of Petroleum
Waxes
5.10.4 U
ses of Petroleum W
axes 5.10.5 Q
uality Requ~rements-Industry-wise/End-use w
lsr
Page 5
A1
BIT
UM
ENS
5.11
.1
Asp
halts
5.
11.2
Pe
trol
eum
Bitu
men
s 5.
113
<
y
Spec
ifics
tiow
of
Bitu
men
s 5.
1 1.
4 Ph
ysic
al a
nd C
hem
ical
Cha
ract
eris
tics o
f B
itum
ens
5.11
.5
Use
s of
Bitu
men
s 5.
12
PETR
OLE
UM
CO
KE
5.12
.1
Typ
es o
f Pet
role
um C
okes
5.
12.2
Pr
oper
ties o
f Pet
role
um C
okes
5.
12.3
Sto
rage
and
Tra
nspo
rtat
ion
of Pe
trol
eum
Cok
es
5.12
.4 U
ses o
f Pe
trol
eum
Cok
es
6 C
RU
DE
OIL
DIS
TIL
LA
TIO
N
177-
191
I
6.1
INT
RO
DU
CT
ION
17
7 6.
2 IM
PUR
ITIE
S IN
CR
UD
E O
ILS
177
6 3
NEE
D F
OR
DES
ALT
ING
OF
CR
UD
E O
ILS
1 78
6.4
ELEC
TRIC
AL
DES
ALT
ING
OF
CR
UD
E O
ILS
178
6.4.
1 Pr
oces
s Des
crip
tion
178
6.4.
2 P
ro
m V
aria
bles
18
0 6.
4.3
Typ
ical
Ope
ratin
g C
ondi
tions
18
1 6
5 C
RU
DE
OIL
Drs
TnL
AT
ION
18
1 I
6 6
ATM
OSP
HER
IC D
ISTI
LLA
TIO
N O
F C
RU
DE
OIL
18
2 6.
6.1
Proc
ess D
escr
iptio
n 18
2 6.
6.2
Pref
ract
iona
tion
184
6.63
T
ypic
al Y
ield
Pat
tern
6.
7 V
AC
UU
M D
ISTI
LLA
TIO
N O
F R
EDU
CED
CR
UD
E O
IL
6.7.
1 Pr
oces
s Des
crip
tion
6.8
OPE
RA
TIO
N O
F FR
AC
TIO
NA
TIN
G C
OL
UM
NS
6.8.
1 T
empe
ratu
re
6.8.
2 C
olum
n Pr
essu
re
6.8.
3 Fl
ow R
ates
6.
8.4
Ref
lux
6.8.
5 R
eboi
ler/
Stri
ppin
g St
e?
. 6.
8.6
Stab
ility
of C
olum
n O
pe;
hon
6.9
IMPR
OV
EMEN
TS IN
FlZ
AC
TIO
NA
TIN
G C
OL
UM
NS
'4.
TH
ER
MA
L C
ON
VE
RSI
ON
PR
OC
ESSE
S 19
2-22
1 7.
1 IN
TR
OD
UC
TIO
N
192
7.2
THER
MA
L C
RA
CK
ING
REA
CTI
ON
S 19
3 7.
3 TH
ERM
AL
CR
AC
KIN
G
194
7.3.
1 Pr
oces
s D
escr
iptio
n 19
5 7.
3.2
Typ
ical
Ope
ratin
g C
ondi
tions
19
5 7.
3.3
Typi
cak
Yie
ld P
atte
rn
1%
7.4
VIS
BR
EAK
ING
19
6 7.
5 C
ON
VE
NT
ION
AL
VIS
BR
EAK
ING
19
6 7.
5.1
Proc
ess D
escr
iptio
n 19
7 7.
5.2
Proc
ess V
aria
bles
13
8 7.
5.3
Typ
ical
Ope
ratin
g C
ondi
tions
19
9 7.
5.4
Typ
ical
Yie
ld P
atte
rn
200
7.5.
5 D
ecok
ing
of F
urna
ce T
ubes
20
0
7.5.
6 M
axim
izat
ion
of D
iese
l Oil
Prod
uctio
n 7.
6 SO
AK
ER V
ISB
REA
KIN
G
7.6.1
Con
vent
iona
l Soa
ker V
isbr
eaki
ng
7.6.
2 H
igh
Con
vers
ion
Soak
er V
isbr
eaki
ng
7.7
CO
KIN
C -
7.8
DEL
AY
ED C
OK
ING
7.
8.1
Proc
ess
Des
crip
tion
7 8.
2 Pr
oces
s Var
iabl
es
7.8.
3 T
ypic
al O
pera
ting
Con
di tio
ns
7.8.
4 T
ypic
al Y
ield
Pat
tern
7.
8.5
Nee
dle
Cok
e Pr
oces
sing
7.
9 FL
UID
CO
KIN
C
7.9.
1 R
oces
s D
escr
iptio
n 7.
9.2
Typ
ical
Ope
ratin
g C
ondi
tions
7.
9.3
Typ
ical
Yie
ld P
atte
rn
7.10
R
EX
ICO
KIN
G
7.10
.1
Proc
ess
Des
crip
tion
7.10
.2
Dua
l Gas
ific
atio
n Fle
xico
king
Pro
cess
7.
10.3
Com
pari
son
of C
onve
ntio
nal a
nd D
ual G
asif
icat
ion
Pror
esse
s 7.
11 OTHER
CO
KIN
G P
RO
CES
SES
7.12
C
AL
CIN
AT
ION
OF
GR
EEN
CO
KE
7.12
.1
Proc
ess
Des
crip
tion
7.12
.2 T
ypic
al C
alci
natio
n D
ata
8 C
ATA
LYTI
C C
ON
VE
RSI
ON
PR
OC
ESSE
S 22
2-26
6 8.
1 IN
TR
OD
UC
rlnN
8.2.
1 8.
2.2
8.2.
3 8.
2.4
8.2.
5 8.
2.6
8.2.
7 8.
2.8
8.2.
9 8.
3 C
AT
AI
-
Dev
elop
men
t of F
luid
Cat
alyt
ic ~
ra
ch
g
Tec
hnol
ogic
al A
spec
ts of
Flu
id C
atal
ytic
Cra
ckin
g Pr
inci
ples
of O
perh
tion
Proc
ess
Des
crip
tion
Proc
ess
Var
iabl
es-R
eact
or S
ectio
n Pr
oces
s V
aria
bles
-Reg
ener
atio
n Se
ctio
n Fe
edst
ock
Cha
ract
eris
tics
Typ
ical
Ope
ratin
g C
ondi
tiow
T
ypic
al Y
ield
Pat
tern
.Y
TIC
REF
OR
MIN
G
8.3.
1 Re
form
ing
Rea
ctio
ns
8.3.
2 R
efor
min
g Cat
alys
ts
8.3.
3 Pr
oces
s Des
crip
tion
8.3.
4 Pr
oces
s V
aria
bles
8.
3.5
Typ
ical
Ope
ratin
g C
ondi
tions
5.
3.6
Typ
ical
Yie
lds a
nd P
rodu
ct Q
ualit
y 8.
3.7
Pret
reat
men
t of
Cat
alyt
ic R
efom
er F
eeds
tock
8.
3.8
Cat
alyt
ic R
efor
min
g Fo
r Aro
mti
cs P
rodu
ctio
n 8.
4 H
YD
RO
CR
AC
KN
G
8.4.
1 A
pplic
atio
ns o
f Hyd
rocr
acki
ng
8.4.
2 T
ypes
of
I-ly
droc
rack
ing
8.4.
3 H
ydro
crac
king
Rea
ctio
ns
8.4.
4 H
ydro
crac
king
Cat
alys
ts
8.4.
5 Pr
oces
s D
escr
iptio
n 8.
4.6
Typ
ical
Ope
ratin
g C
ondi
tions
Page 6
(4
8.4.7 T
ypical Yield Pattern
8.5 CA
TALY
TIC A
LKY
LATIO
N
8.5.1 A
lkylation Reactions
8.5.2 H
,SO, A
lkylation Processes 8.5.3
HF A
lkylation Processes 8.5.4
Process Variables
8.5.5 T
ypical Operating C
onditions 8.5.6
Com
parison of %SO
, and HF A
lklation Processes 18.6
CA
TALY
TIC ISO
ME
RIZ
AT
ION
8.6.1
Chem
istry and Catalysts of the Process
8.6.2 U
OP B
utamer Isom
erization Process 8.6.3
UO
P Penex Process 8.7
CA
TALY
TIC PO
LY
ME
RIZ
AT
ION
8.7.1
Chem
istry and Catalysts of the Process
8.7.2 U
OP C
atalytic Polymerization Process
8.7.3 IFP D
imersol Process
9.1 IN
TR
OD
UC
TIO
N
9.2 H
YD
RO
GEN
SUL
PHID
E R
EMO
VA
L PRO
CESSES
9.2.1 A
bsorption by Regenerative Solvents
9.2 2 A
dsorption on Solid Beds
9.3 SU
LPH
UR
CO
NV
ER
SION
PRO
CESSES
9.3.1 C
laus Process 9.3.2
Selective Oxidation Processes
9.3.3 W
et Oxidation B
ased on Aqueous Solutions
9.3.4 T
hermal C
racking of YS
19.4
SWEETEN
ING
PRO
CESSES
9.4.1 C
austic Treatm
ent 9.4.2
Solutizer Process 9.4.3
Doctor T
reating Process 9.4.4
Copper C
hloride Sweetening
9.4.5 H
ypochlorite Sweetening
9.4.6 A
ir and Inhibitor Treating Process
9.4.7 M
erok Processes 9.4.8
Sulphuric Acid T
reatment
9.4.9 C
lay Treatm
ent 9.5
SOLV
ENT EX
TRA
CTIO
N PR
OC
ESSES 4.5.1
Edeleanu Process
9.5.2 U
dex Process 9.5 3
Sulfolane Process 9.6
HY
DR
OTR
EATIN
G PR
OC
ESSES 9.6.1
Applications of H
ydrotreating 9.6.2
Hydrotreating R
eactions 9.6 3
Hydrotreating Process for D
istillate Desulphurization
9.6.4 H
ydrotreating Process for Smoke Point Im
provement
10 LUBE O
IL MA
NU
FAC
TU
RIN
G PR
OC
ESSE
S 296-319
10 1 IN
TR
OD
UC
TIO
N
296 10.2
EVA
LUA
TION
OF C
RU
DE
OIL
S FOR
LUBE O
IL BA
SE STOCKS MA
NU
FAC
TU
RE
296
(xi)
10.3 VA
CU
UM
DISTILLA
TION
10.3.1 Process D
escription 10.3.2 T
ypical Operating C
onditions 10.3.3 T
ypical Yield Pattern and Product Q
uality 10.4
SOLV
ENT D
EA
SPHA
LT
ING
PRO
CESS
10.4.1 Process D
escription 10.4.2
Process Variables
10.4.3 Typical O
perating Conditions
10.4.4 Typical Y
ield Pattern and Feed/Product Quality
10.5 SO
LVEN
T EXTR
AC
TION
OF LU
BE O
IL FR
AC
TIO
NS
10.5.1 Com
parison of Furfural, NM
P and Phenol 10.5.2
Process Description
10.5.3 T
ypical Operating C
onditions 10.5.4
Typical Y
ield Pattern and Feed/Product Quality
10.6 SO
LVEN
T DEW
AX
WG
PRO
CESS
10.6.1 Process Description
10.6.2 Typical O
perating Conditions
10.6.5 Typical Y
ield Pattern and Feed/Product Quality
10.7 H
YD
RO
FINISH
ING
PRO
CESS
10.7.1 Process D
escrition 10.7.2 T
ypical Operating C
onditions 10.7.3
Feed and Prod:lct Q
uality 10.8
MA
NU
FAC
TU
RE
OF PETR
OLEU
M W
AX
ES 10.9
WA
X SW
EA
TIN
G-PR
INC
IPLE
S AN
D A
PPLIC
AT
ION
S 10.10 SO
LVEN
T DE
OIL
ING
10.10.1 Fundam
entals of Solvent Deoilig
10.10.2 Process Description
10.10.3 Process Variables
10.10.4 Typical O
perating Conditions
10.10.5 Fish
ing
of Waxes
11 MA
NU
FAC
TU
RE
OF B
ITU
ME
NS
320-327
11.1 IN
TR
OD
UC
TIO
N
11.2 SELEC
TION
OF C
RU
DE O
IL
11.3 M
ET
HO
DS O
F MA
NU
FAC
TU
RE
OF B
ITU
ME
NS
11.3.1 D
istillation 11.3.2 Solvent Precipitation 11.3.3
Air B
lowing
11.4 A
IR B
LOW
ING
PRO
CESS
11.4.1 Process Description
11.4.2 Process V
ariables 11.4.3 T
ypical Operating C
onditions 11.5
TYP!CA
L R
EFINER
Y PR
OD
UC
TIO
N
11.5.1 C
utback Bihunens
11.5.2 Bihunen E
mulsions
11.6 H
AN
DL
ING
AN
D D
ISTRIB
UTIO
N
12 CO
RR
OSIO
N C
ON
TR
OL
IN RE
FININ
G PR
OC
ESSE
S 328-338
12.1 TY
PES OF C
OR
RO
SION
12.2
FOR
MS O
F CO
RR
OSIO
N
Page 7
2 PE
TRO
LEUM
RERN
lMp T
ECH
Np4
OQ
Y
1.2
FOR
MA
TIO
N O
F O
IL A
ND
GA
S T
here
are
two
theo
ries
of
the
gene
sis
of p
etro
leum
: th
e or
gani
c the
ory
and
non-
orgM
c th
eory
. T
he
form
er
hold
s th
at p
etro
leum
is
of a
n o
rgan
ic o
rigi
n an
d is
th
e cu
rren
tly
favo
ured
pro
posa
l. It
pre
dict
s lim
ited
rese
rves
wor
ldw
ide;
mor
eove
r In
dian
res
erve
s ar
e pr
edic
ted
as m
inim
al. T
he la
tter
mai
ntai
ns t
hat
it i
s of
non
-org
anic
gen
esis
, sup
pose
dly
of
prim
ordi
al o
rigi
n. O
n th
e ba
sis
of th
is th
eory
, oil
rese
rves
wou
ld b
e m
uch
larg
er th
an th
ose
pred
icte
d by
the o
rgan
ic th
eory
. Ind
ia, o
il-po
or i
n th
e or
gani
c the
ory,
is pr
edic
ted
to b
e oi
l-ri
ch
in th
e no
n-or
gani
c on
e.
The
non
-org
anic
the
ory
that
was
muc
h pr
eval
ent
earl
ier
sugg
ests
tha
t oil
is fo
rmed
by
the
act
ion
'of
wai
kr o
n m
etal
lic c
aibi
des
or b
y at
mos
pher
ic ra
dioa
ctiv
ity o
r by
co
smic
ra
diat
ion.
?he
rm
e oc
curr
ence
of
oil i
n,m
eteo
rite
~, ig
neou
s dy
kes
and
in p
etro
zoic
rock
s w
eigh
s in
favo
ur o
f the
non
-org
anic
theo
ry.
The
org
anic
the
ory
whi
ch i
s th
e m
ost
prev
alen
t to
day,
sug
gest
s th
at th
e pe
trol
eum
w
as fo
rmed
from r
emai
ns o
f pla
nts
and
anim
als t
hat d
ied
mill
ions
of y
ears
ago
and
acc
umu-
la
ted
on
ocea
n fl
oors
. Tin
y, m
inut
e m
arin
e an
imal
s an
d pl
ants
co
mpr
isin
g m
ainl
y al
gae,
fu
ngi,
diat
oms
and
fora
min
ifer
a us
ed t
o fl
oat
on t
he su
rfac
e of
the
sea
and
wer
e ab
unda
nt
duri
ng t
he M
esoz
oic
(abo
ut 2
25 m
illio
n ye
ars b
ack)
and
Cai
nozo
ic (
abou
t 65
mill
ion
year
s ba
ck) p
erio
d. O
n th
e ot
her
hand
, ro
ck s
urfa
ce a
nd l
and
are
cont
inuo
usly
get
ting
ero
ded.
B
roke
n pi
eces
of
mat
eria
l lik
e sa
nd, c
lay,
lim
e ar
e ca
rrie
d aw
ay b
y ra
in a
nd s
ubse
quen
tJy
depa
mte
d on
bed
s of o
cean
s. I
n m
illio
ns o
f yea
rs t
he s
edim
ents
pile
up
to a
gre
at h
eigh
t (s
ever
al t
hous
ands
of
met
res)
and
sub
sequ
ently
, pre
ssur
e an
d te
mpe
ratu
re co
ntin
ue tq
ris
e in
*os
e ro
cks.
She
lls a
nd sk
elet
ons
of d
ead
plan
kton
g, sp
onge
s and
jelly
fish
sub
lime.
on se
a be
d an
d su
bseq
uent
ly g
et b
urie
d un
der
the
pilin
g se
dim
ents
. Aer
obic
bac
teri
a pr
esen
t in
fie
ocea
n fl
gor a
nd s
edim
ents
act
as
scav
enge
rs a
nd a
ttac
k th
e or
gani
c pa
tter
. So
me
com
plex
ch
emic
al b
ansf
orm
atio
n ta
kes
plac
e th
at is
fac
ilita
ted
by t
he e
norm
ous o
verb
urde
q,:p
res-
su
re,
risi
ng
tem
pera
ture
an
d th
e ab
senc
e of
oxi
dizi
ng a
gent
. The
pro
cess
con
tinue
s th
roug
h va
riou
s co
mpl
icat
ed st
ages
and
che
mic
al re
actio
nsfo
rmin
g fa
ts,
amin
o ac
ids,
lip
ids
and
fina
lly
into
oi
l an
d ga
s.
Oil
is
prod
uced
w
ithi
n th
e te
mpe
ratu
re r
ange
of
100-
200D
C. S
ourc
e ro
ck w
hen
subj
ecte
d to
gre
ater
ove
rbur
den
pres
sure
and
tem
pera
ture
be
yond
160
°C f
or a
long
per
iod
does
not
gen
erat
e liq
uid
oil b
ut g
as.
Am
ongs
t the
dif
fere
nt s
edim
enta
ry r
ocks
lik
e sa
ndst
ones
, sha
les,
cla
ys a
nd li
mes
tone
s,
the
clay
s ar
e m
ore
suit
able
for
form
atio
n of
oil
and
serv
e as
'sou
rce
rock
s'. W
ith th
e pi
ling
up o
f se
dim
ents
, low
er s
edim
ents
get
pro
gres
sive
ly c
ompr
esse
d an
d th
e fl
uids
in
them
are
sq
ueez
ed o
ut.
Oil
form
ed i
n th
e cl
ay r
ises
up
or
side
way
s an
d if
the
roc
k ab
ove
is,l
ike
a sa
ndat
me
wit
h po
re s
pace
o, fi
ssur
es a
nd fr
actu
res,
the
oil t
ends
to g
et a
ccum
ulat
ed in
suc
h a
rese
rvoi
r, p
rovi
ded
this
upw
ard
and
side
way
s m
igra
tion
is p
reve
nted
by
the
inte
rven
tion
of
an
impe
rvio
us l
ayer
of
rock
kno
wn
as ca
p ro
ck fr
om m
ovin
g fu
rthe
r. T
his
laye
r tra
ps
the
oil.
In a
nor
mal
oil
pool
gas
rem
ains
at t
he t
op,
oil
belo
w i
t an
d w
ater
fur
ther
bel
ow. T
hese
po
ols
rem
ain
inta
d ti
ll d
istu
rbed
by
eart
h.
1.3
OIL
AN
D G
AS
EX
PLO
RA
TIO
N
Oil
expl
orat
ion
is a
com
plex
pro
cess
. It
beg
ins
wit
h pr
ogno
stic
atio
n an
d in
volv
es au
enti
re g
amut
of
activ
ities
. m
e hu
nt f
or t
he h
ydro
carb
ons
is f
ocus
ed a
t th
e fa
vour
able
or
pro
mis
ing
area
s ba
sed
on g
eolo
gica
l co
nsid
erat
ions
. G
eolo
gica
l sur
vey
aim
s at
sele
ctio
n 'an
d m
appi
ng o
f suc
h ar
eas
whi
ch s
atis
fy th
e cr
iter
ia o
f be
ing
sedi
men
tary
rock
s pr
efer
ably
of
m
arin
e or
igin
wit
h th
e pr
esen
ce o
f an
ticlin
e st
ruct
ures
of
Mes
ozoi
c (5
0 pe
rcen
t of
oil
prod
uced
bel
ongs
to
this
era
), C
aino
zic
(40
perc
ent
of o
il pr
oduc
ed b
elon
gs t
o th
is e
ra) a
nd
Pale
ozic
(10
perc
ent
of o
il pr
oduc
ed b
elon
gs to
this
era
) per
iods
.
kfik
wkr
; ~x
~t
~~
A~
~o
h;
~R
b~
ar
cn
o~
AN
D R
EFIN
ING
Owing to
the
pres
ence
of f
ault
pla
nes
and
fiss
ures
, a s
eepa
ge of
oil
to ih
e su
rfac
e m
ay ta
ke
plac
e. T
he a
naly
sis
of
surf
ace
sam
ples
of s
oil,
wat
er a
nd o
il or
gG
y'in
suc
h ca
ke$';
fo
r de
tect
ion
of o
il an
d ga
s is k
now
n as
geo
chem
ical
pro
spec
ting.
M
agne
tic s
urve
ys a
re t
hen
done
. M
agne
tom
eter
sur
vey
is c
arri
ed o
ut e
ithe
r on
the
gr
ound
or
from
the
air
by
air-
born
e m
agne
tom
eter
. It i
s ba
sed
on t
he p
rinc
iple
th
at t
he
mag
netic
att
ract
ion
on th
e su
rfac
e de
pend
s on
the
mag
netic
int
ensi
ties
of t
he ro
cks
and
thei
r di
stan
ce f
rom
the
sur
face
. It
hel
ps t
o de
linea
te th
e na
ture
and
pos
sibl
e di
p an
gle
of
the
subs
urfa
ce ro
cks.
Dip
is th
e an
gle
that
a g
eolo
gica
l st
ratu
m m
akes
wit
h a
hori
zont
al p
lane
(t
he h
oriz
on):
the
incl
inat
ion
dow
nwar
d or
upw
ard
of a
str
atum
or
bed.
The
sam
e pr
inci
ple
can
be
appl
ied
to
the
mea
sure
men
t of
the
gra
vita
tion
al a
ttra
ctio
n at
the
surf
ace
by
a gr
avim
eter
. T
hese
two
met
hods
toge
ther
hel
p in
dem
arca
ting
are
as h
avin
g th
icke
r pi
le o
f se
dim
ents
wit
h be
tter
cha
nces
of o
il.
The
seis
mic
met
hod
of o
il an
d ga
s ex
plor
atio
n in
volv
es g
ener
atio
n of
a s
erie
s of
sho
ck
wav
es i
n t
he s
ubsu
rfac
e an
d pi
ckin
g up
the
refl
ecte
d w
aves
by
sens
itive
geo
phon
es w
hich
ar
e la
id a
long
a l
ine
on t
he s
urfa
ce. T
he ti
me
take
n fo
r th
e re
turn
sig
nifi
es th
e ve
loci
ties
thro
ugh
the
subs
urfa
ce r
ocks
and
the
se c
an b
e in
terp
rete
d to
ass
ess t
he n
atur
e of
rock
s an
d th
eir
angl
e of
dip
. T
he fi
eld
stud
ies
are
supp
orte
d by
an
eq
ud
y e
labo
rate
test
ing
of
sam
ples
in
the
labo
rato
ry.
Sop
hist
icat
ed
mod
ern
equi
pmen
t li
ke
Ele
ctro
n M
icro
scop
e,
Mas
s Sp
ectr
ogra
ph,
X-r
ays C
hrom
atog
raph
, Nuc
lear
Mag
netic
Res
onan
ce (NMR), S
pect
rosc
opy,
In
fia-
red,
Ultr
a-vi
olet
and
Dif
fere
ntia
l T
herm
al Analysis
(DT
A) a
re in
disp
ensa
ble
aids
. On
the
basi
s of
a
ll t
hese
stu
dies
, th
e m
ost s
uita
ble
plac
es w
here
oil
is l
ikel
y ta b
e fo
und
is
sele
cted
for d
rilli
ng.
11
~Q
L~
NG
FO
R O
IL A
ND
GA
S
The
dri
llin
g eq
uipm
ent
(sho
wn
in F
ig. 1.1
) con
sist
s of
a t
all h
uge
tow
er c
alle
d 'd
erri
ck'
anch
ored
to th
e gr
ound
, en
gine
s, Q
d pu
mps
, w
ater
tan
ks,
draw
-wor
ks a
nd m
any
othe
r m
odul
es.
The
trav
ellin
g bl
ock
is s
uspe
nded
from
the
crow
n bl
ock
(a la
rge
pulle
y at
the
top
of th
e de
rric
k). T
he sw
ivel
, att
ache
d by
a l
arge
hoo
k to
the
trav
elli
ng b
lock
, can
rot
ate
free
ly,
and
the
kelly
is f
itte
d on
to th
is. R
otar
y ta
ble
at th
e ce
ntre
of th
e de
rric
k flo
or h
olds
the
kelly
(w
hich
has
a s
quar
e or
hex
agon
al c
ross
-sec
tion)
and
can
be
rota
ted
at a
des
ired
spe
ed b
y th
e en
gine
. T
o be
gin
drill
ing,
the
kelly
is h
aule
d u
p th
e de
rric
k, it
s bo
ttom
is f
itted
wit
h a
dril
l bit
and
low
ered
thro
ugh
the
rota
ry ta
ble
unti
l th
at b
it is
rest
ing
on th
e ea
rth.
With
the
star
ting
of
the
engi
ne,
the
rota
ry ta
ble
rota
tes
the
kelly
and
the
dri
ll b
it w
hich
is p
ress
ed
hard
aga
inst
the
ear
th b
y th
e w
eigh
t of t
he d
rill
stri
ng a
bove
, cut
s an
d pe
netr
ates
the
rock
at
the
botto
m.
Muc
h of
the
succ
ess o
f dri
lling
dep
ends
on
the
qual
ity
of m
ud w
hich
is a
spe
cial
ly pr
epar
ed
slur
ry o
f wat
er,
vari
ous
chem
ical
s and
adh
esiv
es li
ke b
aryt
es, b
ento
nite
s, x
anth
anit
e. I
t is
pu
mpe
d th
roug
h th
e dr
ill c
olum
n to
car
ry o
ut s
ever
al im
port
ant
func
tions
suc
h as
rem
ovin
g cu
ttin
gs to
the
surf
ace,
coo
ling
the
bit
(hea
t gen
erat
ed is
due
to
fric
tion)
, lu
bric
atin
g th
e bi
t, pr
ovid
ing
buoy
ancy
to th
e dr
ill s
trin
g to
redu
ce th
e ho
ok l
oad,
ret
aini
ng th
e si
de w
all o
f th
e w
ell f
rom
cav
ing
in, a
llow
ing t
o ex
amin
e th
e ho
le b
y lo
wer
ing'
a v
arie
ty o
f in
stru
men
ts
and
bala
ncin
g th
e fo
rmat
ion
pres
sure
tha
t pr
even
ts t
he fo
rmat
ion
flui
ds fr
om r
unni
ng in
to
the
wel
l. W
ith th
e in
crea
se in
dep
th of
the
open
hol
e, t
he si
de w
alls
of t
he w
ell t
end
to c
olla
pse.
To
avo
id th
is,
a ca
sing
pip
e is
intr
oduc
ed in
to th
e ho
le. T
he a
nnul
ar p
ortio
n be
twee
n th
e ho
le
and
the
casi
ng p
ipe
is c
emen
ted.
Mh
er
drill
ing
is c
arri
ed o
ut w
ith s
mal
ler d
iam
eter
bit,
and
at
a ce
rtai
n de
pth
a sm
alle
r dia
met
er ca
sing
is in
trod
uced
and
cem
ente
d in
the
sam
e man
ner.
Page 8
v
3 J LC.
z
20"s " W X = Z m = * 1 Fa; 8 c l m e m 5." c ? r- $. g
1 8 - g P ::&g 5: - i g s e . c a c 8 - 0 Z " Z ~ E " % 2 r -a$ 1 ". 8' 2. 0 9 C w m @'" 3 u:gg ! $ a m Fr m q s
0 % C a w D a m ! $ u, ;ilc
E k " " g a g $ ? ;1
a p e " 8. B i.3 1 €i g g f 8 g B "9 a g g: s:P 3 e n g s't ID
k z " 9 - g 1 g.c * e, * $ z9E ZB m m u CLg w,. g 3 q g"c$ g $ g * C P g
- 0 m g s p 3 q * , . g g 3 s l$go"*g m o -
C g g g 5 1 E . m
R $ 3 g 3 kg,pg o m < q U w E ' m g g $ $ 2 B $ 6 . ; gap ~ 3 , ~ e =
+ a s r n $ B r , e l t r 1 8 E&e:&g E e ~ s g 8 8 .1 .&
g 9 m m 0 E m m g a g a 3 * g r E v -
m e , e ?Ear , 6.9. = &g.gQ
4 . d g i k, p 2 o m a e , - m
kg: gJ g s g g B 0% . OP 3 xgEi
g: P z u -,
Page 9
pore
s. S
econ
d li
mit
atio
n is, $
hat,
the
adva
pcin
g. w
ater
fq
nt
:byp
aqse
s sjg
pif~
qt.~
rt$n
?~~
of
the
rese
rvoi
r du
e to
di
ffic
ult :
wel
l pla
cem
ents
and
wex
pe+g
:.,ge
olog
i+
cd
gu
rati
~n
s.
Thi
s la
ck o
f a p
erfe
ct! s
wee
p ef
fici
ency
is re
spon
sibl
e fo
r lea
ving
behi
nd c
rude
oil'
$ -!a
s no
t re
ache
d by
wat
er. fl
ood.
, .
A
num
ber o
f met
hods
ltech
niqu
es a
re em
ploy
ed to
rec
qver
the
rem
&in
g oi
l. T
he d
iffk
rent
te
chni
ques
may
be
,bro
adly
cla
ssif
ied
into
thre
e ca
tego
ries
:
(a) M
isci
ble/
imm
isci
ble d
ispl
acem
ent p
roce
ss
Mis
cibl
e hy
droc
arbo
n di
spla
cem
ent (
LPG
enr
iche
d ga
s &
lean
gas
) o
Car
bon
diox
ide
inje
ctio
n In
ert g
as in
ject
ion
(Nitr
ogen
, air
, etc
.)
(b) T
herm
al re
cove
ry p
roce
sses
S
team
sti
mul
atib
n S
team
floo
ding
(inc
ludi
ng h
ot w
ater
) In
-sit
u co
mbu
stio
n
(c)
Che
mic
al fl
oodi
ng p
roce
sses
Su
ifac
tant
$oly
rnei
in
ject
ion
Poly
mer
inje
ctio
n A
lkal
ine
floo
ding
Sele
ctio
n of
a
suit
able
EO
R
met
hod
requ
ires
a
care
ful
anal
ysis
of
re
serv
oir
conf
igur
atio
n an
d th
e oi
l pr
oper
ties.
Tra
ppin
g an
d re
leas
e of
flu
ids
from
por
ous
med
ia i
s a
com
plex
phe
nom
ena.
For
a sp
e.ci
fic s
yste
m, t
rapp
ing
beha
viou
r is c
ontr
olle
d by
Ci),
the
pore
ge
omet
ry o
f ro
ck m
atri
x, (
ii)
flui
d-ro
ck p
rope
rtie
s,
in p
arti
cula
r, w
etta
bili
ty a
nd (
iii)
fl
uid-
flui
d in
tera
~o
ns in
clud
ing
visc
osity
, ro
ck
dens
ity
diff
eren
ce, i
nter
faci
al
tens
ion
and,
par
titi
on
coef
fici
ent.
The
ge
nera
l pr
oper
ties
of p
ore
syst
em,
its
shap
e, s
ize
and
dist
ribu
tion
in
the
rock
pla
ys a
n im
port
ant r
ole
in tr
appi
ng o
f oi
l. It
is e
stab
lish
ed t
hat
(1)
Tra
ppin
g of
flu
ids
occu
rs
in
uniq
ue
and
repr
oduc
ible
pat
tern
s w
hich
are
con
trol
led
by
capi
llary
for
ces,
(2)
Nea
rly
com
plet
e ne
twor
ks o
f in
terc
onne
cted
equ
al s
ize
pore
s ex
ist
thro
ugho
ut t
he p
ore
size
dis
trib
utio
n, (
3). in
divi
dual
po
res
have
goo
d ac
cess
ibili
ty w
ith
adja
cent
por
es, t
here
by a
llow
ing
alte
rnat
e pa
ths
of fl
ow a
roun
d ig
olat
ed im
mob
ile p
hase
s, (
4)
Flui
ds
can
be t
rapp
ed
at p
ore
cons
tric
tions
for
all
degr
ees
of
wet
ting.
Non
-wet
ting
pqas
es a
re t
rapp
ed in
dis
cont
inuo
us m
asse
s w
hose
leng
ths
are
larg
ely
dete
rmin
ed b
y in
terf
acia
l te
nsio
n an
d po
tent
ial
grad
ient
. Fo
r se
lect
ion
of
suit
able
E
OR
m
etho
ds
labo
rato
ry in
vest
igat
ion
unde
r si
mul
ated
con
ditio
ns o
f re
serv
oir
are
nece
ssar
y. M
athe
mat
i-
cal
mod
els
(3 p
hase
, 3
dim
ensi
on)
are
used
to
anal
yze
the
rese
rvoi
r ge
omet
ry.
The
pa
st
perf
orm
ance
of
th
e re
serv
oir
is m
atch
ed t
o pr
edic
t th
e pe
rfor
man
ce o
f re
serv
oir
unde
r di
ffer
ent
oper
atin
g co
nditi
ons.
Bas
ed
on t
hese
mod
ellin
g st
udie
s, t
he m
ost
suit
able
EO
R
met
hoai
s se
lect
ed fo
r max
imum
~pro
duct
ion of
the
oil
in p
lace
. In
Ind
ia,
the
incr
ease
in
crud
e oi
l pr
oduc
tion
is n
ot s
igni
fica
nt d
urin
g th
e la
st 4
5
year
s. N
o ne
w
oil
fiel
ds
wit
h su
bsta
ntia
l re
serv
e is
di
scov
ered
. T
he
perc
enta
ge
of
prim
ary
reco
very
in th
e to
tal o
ilgro
duct
ion
is g
radu
ally
dec
reas
ing.
Rat
e of
pro
duct
ion
from
B
omba
y H
igh
is r
epor
ted
to h
ave
alre
ady
show
n th
e de
clin
ing
tren
d. S
ome
of t
he o
ld
oil
fiel
ds o
f A
ssam
and
Guj
arat
und
er p
reva
iling
pri
ce s
truc
ture
hav
e al
read
y re
ache
d th
eir
econ
omic
lim
it. O
n ec
onom
ic te
rms,
bot
h O
NG
C a
nd O
IL m
ay p
refe
r to
plu
g th
e w
ell,
pull
ptliw
Uk,
&:'
A
.:: .;,
'' ;
~to
~A
no
~;~
~b
~u
cn
o~
A
ND
RER
NIN
G
7
the
pipe
and
aba
ndon
th
e lf
ield
. It
is b
eWr t
s us
e E
OR
met
h6da
aft
er p
rim
ary
reco
very
. It
is i
mpe
rati
ve th
at p
rope
r ass
essm
ent o
f EO
R p
oten
tial i
n th
e co
untr
y is
requ
ired
for m
akin
g re
cove
ry p
lans
. T
he s
ucce
ssfu
l ap
plic
atio
n of
any
EO
R p
roce
ss d
epen
ds o
n it
s vi
abili
ty. T
he
pric
e of
oi
l is
the
mos
t im
port
ant
fact
or f
or h
ow m
uch
will
be
prod
uced
and
w
hen.
Gas
in
ject
ion
may
not
find
wid
eapp
lica
tion
in In
dia.
It
is t
rue
that
nat
ural
gas
or
asso
ciat
ed g
as,
prop
ane,
enr
iche
d ga
s an
d le
an g
as a
re av
aila
ble i
n In
dia.
But
the
pres
sure
requ
ired
to
lique
fy
the
gas
is h
igh
and
it m
ay n
ot s
uit t
he s
hallo
w In
dian
rese
rvoi
rs. S
o is
the
cas
e w
ith
air
and
nitr
ogen
gas
inj
ectio
n.
But
in
so
me
rese
rvoi
rs c
arbo
n di
oxid
e co
uld
be i
njec
ted.
Aga
in i
t de
pend
s on
the
avai
labi
lity
of lo
w c
ost
carb
on d
ioxi
de i
n pl
enty
. It
is
esti
mat
ed th
at a
bout
4-
6 m
illio
n cu
bic f
eet o
f CO
2 is
requ
ired
to
reco
ver
a ba
rrel
of
crud
e oi
l, A
lthou
gh t
herm
al
met
hods
pre
dom
inat
e as
mos
t suc
cess
ful E
OR
pro
cess
es,
they
may
not
be
appl
icab
le on
a
larg
e sc
ale
in I
ndia
. D
epq
of
the
Indi
an re
serv
oir
and
API
val
ues
of 2
8 - 4
5 re
stri
ct t
he
inje
ctio
n of
ste
am o
r ho
t w
ater
for
add
ition
al r
ecov
ery
beca
use
of a
ppar
entl
y un
attr
acti
ve
cost
ben
efit
rati
o. O
f cou
rse i
n W
este
rn s
ecto
r it
may
be
succ
essf
ul in
som
e res
ervo
irs.
In-s
itu
com
bust
ion
is t
he m
ost
diff
icul
t m
etho
d to
pre
dict
pro
perl
y. M
oreo
ver,
it i
s ec
onom
ical
an
d su
cces
sful
in h
eavy
oil
reco
very
onl
y.
It a
ppea
rs t
hat
the
chem
ical
fl
oodi
ng v
iz.
poly
mer
fl
oodi
ng
or s
urfa
ctan
t-po
lym
er f
lood
ing
may
pro
ve
succ
essf
ul i
n In
dia.
Fo
r al
kali
ne fl
oodi
ng, a
cid
num
ber
of t
he c
rude
mus
t be
high
whi
ch i
s no
t so
with
Ind
ian
crud
es.
Poly
mer
floo
ding
met
hod
may
bec
ome
mor
e pop
ular
in In
dia
not o
nly
for i
ts ea
sy h
andl
ing
but
also
fo
r th
e ec
onom
ic r
etur
ns.
Surf
acta
nt/p
olym
er f
lood
ing
is
requ
ired
to
be
ass
esse
d pr
oper
ly,
part
icul
arly
the
non
-com
patib
le n
atur
e of
sur
fada
nt to
var
ious
mon
oval
ent a
nd
biva
lent
met
al i
ons
and
in In
dian
rese
rvoi
mkh
ese
met
als
are
plen
ty.
The
pro
duct
ion
of c
rude
oil
in I
ndia
is g
iven
in
Tab
le 1
.1. F
rom
a m
eagr
e 0.
5 m
illio
n to
nnes
of
oil p
rodu
ced
from
one
of
the
old
est o
ilfie
lds
in t
he w
orld
-Dig
boi i
n A
ssam
, th
e in
dige
nous
cru
de p
rodu
ctio
n is
exp
ecte
d to
go
up t
o 44
.45
MM
TPA
(m
illio
n m
etri
c to
nnes
*r
d
urn
) by
the
turn
of t
he c
entu
ry.
Till
194
7, In
dia
used
to
prod
uce
arou
nd 0
.5 to
1.0
M
MTP
A of
cr
ude
oil
from
Dig
boi
and
Nah
arka
tia
fiel
ds o
f Ass
am. A
fter
ind
epen
denc
e in
19
47, t
wo
publ
ic s
ecto
r co
mpa
nie~
wet
e fo
rmed
by
Gov
ernm
ent
of
Indi
a, n
amel
y O
il &
N
atur
al G
as C
omm
issi
on (O
NG
C) a
nd O
il In
dia
Lim
ited
(OIL
) to
expl
ore a
nd p
rodu
co o
il an
d li
atur
al g
as i
n In
dia
from
bot
h on
shor
e an
d of
fsho
re f
ield
s. Up
to 1
960,
In
dia
was
pr
actic
ally
dep
endi
ng o
n im
port
ed c
rude
oil.
O
NG
C fi
rst s
truc
k oi
l in
Cam
bay
in 1
958-
59 an
d in
Ank
alea
hwar
fiel
ds (G
ujar
at) i
n 19
60,
follo
wed
by
oil f
inds
in
oth
er p
mta
of
Guj
arat
suc
h as N
awag
am, A
hmed
abad
, Meh
sana
, G
andh
ar, K
alol
, Tap
ti b
asin
, 'et
c. B
igge
st o
il fi
eld
stru
ck b
y O
NG
C
was
B
omba
y H
igh
offi
hore
fiel
da in
Ara
bian
sea
in 1
974.
In
1976
, O
NG
C f
ound
a la
rge
sour
gas
re
se~
oir
at
S
outh
Bas
sein
, so
uth
of
Bom
bay
Hig
h of
fsho
re f
ield
s. A
lso,
gad
oil w
as f
ound
in
smal
ler
quan
titi
es a
t Hee
ra, P
anna
, Rat
na a
nd N
eela
m o
ffsh
ore f
ield
a in
Ara
bian
sea
.
Cru
de p
rodu
ctio
n in
the
cou
ntry
has
bee
n go
ing
thro
ugh
fluc
tuat
ing
fort
unes
. Fro
m a
hi
gh o
f 34
.09
mill
ion
tom
eu i
n 19
89-9
0, it
dip
ped
to 2
6.95
mill
ion
tom
es in
199
2-93
and
stay
ed a
t th
at le
vel i
n th
e fo
llow
ing
year
als
o. B
ut in
the
past
cou
ple
of y
ears
ther
e ha
s be
en
a re
cove
ry a
nd t
he
crud
e pr
oduc
tion
was
33.
865
mill
ion
tom
es i
n 19
97-9
8. T
he o
ffsh
ore
rese
rves
acc
ount
for
abo
ut 6
3 p
erce
nt o
f tot
al o
il pr
oduc
ed i
n th
e co
untr
y. T
his
reve
als
how
po
or t
he
coun
try
is in
on
shor
e oi
l res
erve
s an
d ho
w m
uch
it is
dep
ende
nt o
n B
omba
y H
igh.
T
he p
rodu
ctio
n of
nat
ural
gas
in
the
coun
try
is c
urre
ntly
abo
ut 7
4 m
illio
n st
anda
rd c
ubic
m
etre
s pe
r day
and
the
tota
l gas
ava
ilabi
lity
for s
ale
is a
bout
61
mill
ion
stan
dard
cubi
c met
res
per
day.
Page 10
Table 1.1 P
rod
uctio
n of C
rud
e Oil4n &
dia *
1.6 PETRO
LEUM
REFIN
ING
, OPER
ATIO
N AND O
PTIMIZA
TION
C
rude oil in its raw form
has got very limited use. B
y adopting various refining processes in the refineries, crude oils are separated into a num
ber of fractions which are suitable for
various uses. Crude oils received from
oil fields are stored in refinery storage tanks. .From
these takes crude oil is fed to the atmospheric distillation unit. A
ll the crude oils are basically m
ixture of hydrocarbons which can be physically separated in groups of different boiling range
by the conventional process of distillation. The fractionation of crude oil yields the follow
ing stream
s in the order of rising boiling ranges : M
ethane, Ethane and Propane m
ixture L
iquefied Petroleum G
as (LPG
) N
aphthasfGasoline fractions
KerosindA
viation Turbine F
uel (AT
F) H
igh Speed Diesel O
il (HSD
) and Light D
iesel Oil (L
DO
) R
educed crude oil (RC
O)
Depending upon the crude oils properties and im
purities present in them, the above
products are further treated to meet the required specification. R
educed Crude O
il is further distilled under vacuum
to recover some m
ore lighter fractions. This process produces light
vacuum gas oil (L
VG
O), heavy vacuum
gas oil (HV
GO
) and vacuum residue (VR). In order to
meet the viscosity specification of fuel oil, heavy residues such as H
VG
O, R
CO
and VR are processed in visbreaking unit to reduce their viscosity. To produce bitum
en, the vaccum
residue is air-blown in B
itumen B
lowing U
nit. To m
aximize the production of m
iddle distil- lates, heavy residues such as H
VG
O are processed in fluid catalytic cracking (FC
C) unit,
hydrocracking unit and coking unit. Straight-run naphtha of low
Octane N
umber is processed
in catalytic reforming unit to enhance its O
ctane Num
ber. Reform
ate rich in ben
zenh
luen
e
~F
TR
[31;EL
lM,~
ER
PT
OR
AT
ION
~~
OD
UC
TIO
N
AN
D R
EFIN
ING
a r9
is used as feedstock-fon Udex unitito prPduce benzene an& toluene. K
erosine fkacti~ns from
certain crudes such as A
ssam crude do'not m
eet specification on amoke point due to higb - -
aromatic content. To im
prove smoke point of these fractions, E
deleanu process is usually em
ployed.
1.6.1 Selection of P
rocesses for O
ptimization
Optim
ization is the process of determining the best poseible w
ay of selecting the proces. schem
e and fixing the unit capacities etc. The selection of procesdprocessing schem
e is to be optim
ized considering all the objective functions. The follow
ing factors would influence + .
decision making in the selection of processes and process schem
e for a given refinery : T
ype of crude Product slate P
roduct specification ~nve*tm
e;t and operating costs M
erits/demerits of alternative processes.
L T
yp
e of crude. The tyR
e of cvd
e to be processed in a refinery y
ill have a bearipg on t;
process scheme? For exam
ple, crudes containing high sulphur require the iqstallation of desulphq+ation
processps/sweetening processes for stream
s. Kerosine from
Aghajari c
n
has a peculiar problem of colour dekrioragon on ptorage w
hich cannot be corrected by treating I
in an Merox upit apd hence desulphurieatiop w
it would be req%
ed. Som
e crudes are I suitable for m
&ing lu
bricab
g oils, a
nd
,qp
~e
are not suitable for m
aking bitumen. In som
e cases the prodpcts do not require any tieatm
ent like some of the in9genous crudes e+
- T
herefore, each and every stream from
the crude distillap?,n unit has to be evaluated tol m
aking a suitable scheme of treatm
entd
secon
dq
processing facilities. e
od
uc
t slate. The capacity of the refiney, the type (lube or non-lube) and size oft.,
secondary groceseiffg wjb
is largely governed by the product slate which jn turn is decided
by the dem
,pd
of petroleum, ~ro
du
cts, The process scheme is selected so as to m
atch with t-
product slate. b Indiq, generally the yaxim
ization of middle distillates is,the m
ain criteria. J
In U.S.A
., the production ,of light djetillateq particularly, m
otor spirit is maxim
ized in Fr
' unit by keeping high severity operations, If the objective is to m
aximize H
SD in a refinery
processing high sulphur crudes, it would be advantageous to provide an FC
C unit w
ith 9
desulphurisation unit either for straight-run gap oil or cycle oils so as to,upgrade the heavl-. ends to the m
aximum
poaeible extent as limited by sulphur specifications. For extrem
e m
aximization of m
iddle distillates, a hydrociacker can also be considered which upgrades t
heavy ends to the middle distillates (A
TFkerosineiH
SD) better than any other know
nprocess. Y
ield of kerosin$HSD
from a hydracracker is of the order of 80 to 85 percent as com
pared about 50 percent from
FCC
unit. P
rod
uct specifications. G
eaerally the treatment processes are governed by tF
specifications of the products. Depending on the type of crude processed and the quality or
streams, a judicious selection of treating processes has to be m
ade from a sim
ple chustic wash
Merox sw
eetening units to a hydro=deeulphurisation unit. The flash point of the m
idc.- distillates are often relaxed, w
ith a view to m
-ize these products. T
herefore, to take advantage of such relaxed specifications, it w
ould be desirable to provide a naphtha splitt colum
n in the process schem
e, sa that heavy naphtha can be injected into kerosinddiesel cuts. In
vestm
ent and operating aosts, T
his is a very important point to be kept in view
whil-
fixing the refrnery capacity, selecting the processes and sizing the unit capacities. How
ever, the selection of process technology at tim
es may entirely be'governed by the products dem
and rather than by investm
ent cost limitations. Investm
ent costs are function of refinery size ar.-
Page 11
it
&a
sn
p~
~~
~y
t~
f~
hl
et
:f
ox
~
tihe
m'1
~1w
mp
1~xi
tyi~
ze6u
lts
as! t
he ca
pa@
f in
crea
ses.
~
nv
88
kr
n~
n~
pe
m~
rw
ess
ing
,ca
pa
cit
y
prog
ress
ivel
y go,
dow
n. h so
me c
as$s
,,ap
arti
dar
planh~siree~~~eomeieW~miud~md
kso
me
oth
ea w
ee it
may
pot
be.e
coao
mie
;JI.
For
exam
ple;
som
e oi
l com
pani
es d
o no
t co
nsid
er i
t eco
nom
ical
to p
rovi
de F
CC
Uni
t of l
ess
than
0.
6 M
MTP
A c
apac
ity. S
imila
rly,
the
late
st tr
ends
are
to p
rovi
de s
ingl
e cr
ude
dist
illa
tion
uni
t of
8 to
10
MM
TPA
cap
acity
. ,
i
i -
,I-
.. .-$Q
xp~f
$he,
plan
ts*t
ve co
nsum
ing h
igh
amou
nt o
f fue
1,ah
d util
ities
. T
his
aspe
ct has to
be
kept
iP~
Xie
w~
~w
~~
se3
ecti
ng
. a
proc
ess-
For e
xam
ple,
inxa
se o
fhyQ
rgcr
acke
r, th
etot
al e
nerg
y c
~n
s~
pt'
iop
b
sr~
b~
ut
$.6
tim
es t
han
that
of
Flui
d ca
taly
tic c
rack
er. F
ufih
er,
a su
bsta
ntia
l q
uan
tity
,q&
p~
pS
lth
ai~
co
psum
ed t
o m
eet t
he h
ydro
gen,
requ
irel
pent
of
hy
&g
c~~
&n
g. The
to
tal e
nerg
y co
nsum
ptio
n in
a fu
el re
fine
ry w
ould
.be
of t
he o
rder
of 1
0 to
11
perc
ent.
One
has
to
be c
auti
ous
in t
he s
elec
tion
of n
ew p
roce
ss t
echn
olog
y ke
epin
g in
vie
y th
e si
tuat
ion,
loca
tion
and
avai
labi
lity
of lo
cal e
xper
tise.
Som
e of t
he te
chno
l~gi
es for u
pgra
dati
on
of t
he h
eavy
resi
dues
may
not
be
stra
ight
way
mad
e ap
plic
able
@ In
dian
con
ditio
ns. D
evel
op
men
ts l
ike
cont
inuo
us c
atal
yst
rege
nera
tion
may
not
be
verJ
;atr
acti
ve to
refi
neri
es w
hich
up
qaSI
& qa
phth
a f?r
#e
prod
uctio
n of
mot
or s
piri
t ?f b
qder
*te
oc
hk
qu
m~
t.'~
esu
lPh
~sa
- ti
o~
i of G
el oi
l whi
ch is
$ow
bein
g pr
actic
ed e
lsew
here
with
7 the
oki
jedi
ve df
rM
ucin
g$ol
lutio
n in
con
cd+q
a$ed
@au
$+al
flr
ei-i?
rim
y-no
t &
e ap
pli,c
able
+@ s?
in_e
oth
er s
itua
tion
s, y
he
p
p:ol
$t$m
-
h@
s a
$$ow
. H
ydro
qack
inP
dd
ug
b a
"e$j
yitd
pmck
$s fo
; h&
hiki
ng'n
iidd
le
dist
illa
tes
hp
a so
Eh@
dcat
kd m
i!llurgy
an
d ik
gu+e
a sz
ecid
ope
rati
bnd
&d
rnew
nq
nce
c
aie
:~o
ce
s,o
,w a
@te
d,f
orJ
Fct
hyd
iocr
ack@
g"of
reei
du'e
s abu
ld c
all yo
; sf
i&q
t high
i'?v
estm
~ts
and
Gg'
hop,
perq
kirig
cost
s bec
aube
df t
he h
jrdr
dgen
rkqu
irem
enth
,,pa&
~ula
rly ko
r hi
gh &
[email protected]
&de
s'.'R
.eddc
ed
dvd
e oi
l; fi
od
indi
gent
&
crucY
$d b
ecau
se o
fthe
ir lo
w ?
ulpR
ur
and
met
al c
onbl
;t$ &
ohla
dre b
ette
r su
ited
to th
ikty
pe of
te&
olog
y.
Me$
ta/d
emqe
ts
OF alt
erq
div
q p
yoce
s&ir
: T
here
may
be
mor
e th
an q
ne p
rves
s to
do
the '
&m
e m
e OF
oper
atid
in. F
br e
xhlj
k, th
'e'r~
are
vari
ous'
type
s of
sw
ebte
nihg
l$hc
e~s f
or
naph
tha@
and
ulti
hat&
ly c
hohh
has
to b
e &
be
on th
e m
eritk
&&
dem
erits
of a
eihd
iyid
ual
proc
esse
s, o
pkra
ting
cpqp
t+d
qual
ity
of t&
e pf
oduc
t et
c. F
o* e
xtra
ctip
n of
aro
mat
ics:
fiom
ke
rosi
ne,
apar
t fr
om c
onve
ntio
nal
Ed
elea
d~
prdc
ess
one
coqd
pos
sibl
y ch
oose
shl
fola
ne
proc
ess
or &
d,hy
dr"d
gena
tion
in o
rddr
to
irp
~ro
ve th
ec'a
mok
e'po
iht.
For
the
extr
actio
n of
ar
qmat
ics
fr~
mth
e
lube
oil
dist
illa
tes
eith
er fu
rfur
al o
r phe
nol e
xtra
ctio
n co
uld
be a
dopt
ed.
1.6.
2 ~
~t
&i
?h
ti
~n
in
a R
~n
nin
g
Ref
iner
y dP
tim
izat
ion
ofth
e op
erit
ion
bf a
runx
i&;!
refi
neiy
is su
tij&
d to
the
infl
uenc
e of v
ario
us
fact
ors.
The
re ar
e, so
me f
acto
rs w
hich
are
bey
ond
refi
nery
's c
ontr
ol. T
hese
incl
ude :
(a)
ch
he
mix
ture
I
(b)
Typ
e of
pro
cess
ing
units
(c
) D
emaq
d pa
tter
n (d
) M
ovem
ent c
onst
rain
ts
(el
Prod
uct s
peci
fica
tions
E
arn
al s
trea
ms
(g)
Indu
stri
al re
latio
ns.
Tho
se fa
ctor
s w
hich
are
with
in r
efin
ery'
s co
ntro
l are
giv
en b
elow
. (a
) To
inve
stig
ate
the
poss
ibili
ties o
f im
prov
ing
over
pro
cess
ing
capa
citie
s not
onl
y fo
r cr
ude
oil b
ut a
lso
for s
econ
dary
pro
cess
ing
unit
s.
(b)
To
adop
t var
ious
eff
ectiv
e mea
sure
s of c
ontr
ollin
g the
eros
ion/
corr
osio
n in
proc
essi
ng
unit
s to
impr
ove
thei
r se
rvic
e fac
tors
.
PE
7R
r%g
EU
MfE
XW
a~
~~
EIM
:TlO
N
AN
D R
EFIN
ING
rw
(c)
To.
plan
(shu
t dow
ns of
var
i6us
uni
tsra
topt
imum
tim
e tu a
void
the&
@?&
ed h
tiiiti
eb
cons
qmpt
ions
. 1
,,I,
,
(d)
Var
ious
str
eam
s ob
tain
ed f
~m
di
ffvr
ent
pftc
essl
irg
unit
s a
i 6<
ikgn
tili
zed to
prod
uce
the
fini
shed
prod
ncts
. Se
vera
l str
eam
s ca
n be
util
ized
in th
e pr
oduc
tion
of
mor
e th
an o
ne p
rodu
ct. T
he b
lend
itig
phtt
ern
of s
ome
prod
ucts
like
mbt
or s
piri
t and
H
SD &
o si
gnif
ican
tly in
flue
nce t
he c
onsu
mpt
ion
of h
igh
pric
ed in
tpbt
ted
chem
ical
s lik
e an
tikno
ck c
ompo
unds
, cet
ane
impr
over
s et
c. T
his
aspe
ct s
houl
d al
so b
e ke
pt in
vi
ew w
hile
rout
ing
the
diff
eren
t str
eam
s fo
r pro
duct
ion
of t
hese
pro
duct
s.
(e)
The
pro
fita
bilit
y of
a r
efin
ery
can,
be in
crea
sed
cons
ider
ably
by s
light
red
uctio
n in
th
e bp
erat
ing
cost
s of i
ts u
nits
. In
ord
er to
ach
ieve
this
, the
ope
ratjn
g co
nditi
ons
of
the
unit
sho
uld
be o
ptim
ized
by
optim
izin
g th
e re
flw
ratio
s of
col
umns
, exc
ess
air
in t
he h
eate
rs a
nd m
aint
aini
ng a
pro
per c
ontr
ol o
n ut
ilitie
s an
d ch
emic
al co
mpo
si-
tions
in th
ese
unit
s.
1.6.3
Ref
Jnin
g C
apac
ity
in I
nd
ia
l'hd
tota
l xef
m$g
.i{pa
yjty
in
I?$+
as
' on,
\.Qi1
997
stan
ds a
t 61.
55 M
MT
PA of
whi
ch 5
8.55
M
Sd'I'P
A i
s ac
cbu
n~
d for by t
he p
uljli
c se
ctor
refi
neri
es @
able
1.2
). ~
'~R
PL
ac
cduh
ts fo
r the
b
tlb
ce. ~
jt$
'th
e ~
ng
oi~
~g
com
h$
,~io
nin
g
of IO
C'a
Pqn
ipat
re@
ery,
,+e,
~@re
~in
$cap
acit
y wh
ri?a
ch k~ 67
.55
~lk
'&~
.'~
e"el
'al ex
pans
ion
proj
ectk
ahd
gra
ssfo
ot ik
fine
ries
hiv
e be
en
plan
ned
to e
nhan
ce th
e,re
hip
g ca
paqi
ty in
the
co
mS
. Abo
ut 3
1 m
yion
tonn
es o
f adq
tion
al
&.dIA
i%k '
capa
city
is li
~e1
P tb bk
i cr'
@~
d'ib
Be
?om
try
1b9
Fti
i'th:
co
mm
i&i6
:n$k
of
a li&
ge ~
riv@
f$ sect
or r
efin
e'rj
. a$d
com
plet
ion'
of th
e eX
li+di
on,
p~dq
-es &
p
Publ
ic
s&&
r/jd
int
sect
or r
'efi
neri
es. T
hi'm
ajor
con
9bii
tion
is
e,xp
ecte
d to
c6r
ne4f
i6h +
! rii
iner
y be
ing
set u
p at
Jam
naga
r' by
Rel
ianc
e: T
he c
ompi
i(y
has
heel
ed u
p th
d ca
paci
ty #
%re
fine*
to
27
MIL
ITPA
from
the-
earl
ier p
lan
of 1
5,M
MT
PA re
Fner
y. A
mon
g th
e pu
blic
secp
~!ef
iner
ies,
Id
C's
Guj
arat
refi
nery
has
und
erta
ken
a h. 74
9 cr
ore
prog
ram
me
to e
xban
d it
s ~
apac
ity
by
3 M
MT
PA. H
PCL
's V
isak
hapa
tnam
ref
iner
y ha
s un
dert
aken
a R
s. 9
98 c
rore
pro
gram
me
to
expa
nd i
ts c
apac
ity b
y 3
MM
TPA
. MR
PL, t
he jo
int
vent
ure
betw
een
HPC
L a
nd t
he A
dity
a B
irla
gro
up is
exp
andi
ng it
scca
padi
tY bjr 8
MM
TPA
at'&
e'st
irha
tedl
cost
of Rs. 34
90 c
rore
. IO
C
Bar
auni
ref
iner
y ha
s an
inst
alle
d ca
paci
wof
3.3
MM
TPA
. The
cap
acity
is p
rim
arily
lim
ited
due
to c
rude
supp
ly c
onst
rain
ts fr
om A
ssam
oilf
ield
s. N
ow, t
he H
aldi
a-B
arau
ni c
rude
pip
elin
e Ii
ns b
een
laid
and
is u
nder
com
mis
sion
ing
to s
uppl
y im
port
ed c
rude
to B
arau
ni. A
part
from
th
ese
capa
city
add
ition
s in
1999
, Ess
ar's
ref
iner
y at
rJam
naga
r is l
ikel
y to
be
com
mis
sion
ed in
X
inrc
h 2G
02. T
he re
fine
ry w
as p
lann
ed w
ith
a 9
MM
TPA
cap
acity
, but
Ess
ar h
as s
ince
scal
ed
up
the
capa
city
to 1
2,M
MT
PA.
Tab
le 1
.2 R
efin
ing
Cap
acit
y in
Ind
ia Cap
acity
MMTPA
(as
on 1
.4. 1
997)
,
1.0
3.3
9.5
3.75
7.5
0.65
Com
pany
IOC
Ref
inev
Guw
ahat
i B
arau
ni
Guj
arat
H
aldi
a M
athu
ra
Dig
boi*
Page 12
*AO
C, D
igboi was taken over by the governm
ent in October 1981 and m
erged with IO
C
The refinery production and consum
ption of petdeqm+
products is giyen $
Tables 1.3-1.4.
In In$a the consum
ption of light. and heavy distillateshave beensfagnatkdgver t$epe.eod of last S
iie years. How
+, the dem
and foi m
idd1,e ,&atjljates' ia'~'&
ei$big 's@
ong'50h$
.ip
rec
kt tim
es. In order to m
eet :the' increasing d.em?d
for, middle disF
la%s:!60-65%
),'the second&
and tertiary processink f@
$ilities' . &
e . becoming$&
bf1;1.bd.y~ yelink$
. .
cpmplqxts.
' .
.
.. .. .::....,
'
H4
to
pmqesscrud? bib,?=
gpttihgg+temati&
awti6n:L
d$&
l?*%~+&
<~j$?s ki+ couM
'increase ihe
refin
e~
efficienqies.'@
e n,eed to co'nv* bottom
cif:?+e b,arrelil:iii$o cleiitofuel as~~mes,si~ific.mtim~;twce,
ip In,$a p@icul,+lyj@
09 pool 4aficit,c?nt$e tddb$lw
h a&d
Ind
ia costiflues to dep,pnd feafly
on impoited crude 'oil. '&
e.,e$sting refineries skbuld
therefore upgrade,t&eir technologies, o
p~
ize
sn
erg
y:c
@s
~p
ti~
*d fm
pro+e&
fficiency of furnaces and process equipm
erits to kclude the f1exib;iQt.y t;d p+c&
g the broad spect,mm
.
..
c
~d
e
oil.
Tablg 1.3 R
efinery Production in India
(In Thousand T
onnee)
ATF I
1001
HSD
[
7371
Pp
,QL
EU
WE
vb
PR
wQ
M; PblQ
pUG
TION
AN
D R
EFIN
IN0
3.
.- ,
Table 1.4 C
onsumption of P
etroleum P
rodu
cts in India
(In Thousand T
onn
es)
1519 . ...
14624 LD
O
Heavy ends
Furnace oil LSH
SHSH
WR
FO
1801 1636
1108
7907
4041 2079
. $j85
' , 1,
18289
1177 10016 3791 4164
1609
18196
4879 4550
1453 13389
6358 4044
Page 13
PETR
QLC
UM1R
EFIN
ING
TEC
HNO
LOG
Y
. . 1. S
. Abb
as, p
e no
xi-o
rgap
ic th
eory
of t
he g
enes
is of
pet
role
um, C
urre
nt S
cien
ce, V
ol. 7
1,
NO
, 9, p
pF87
7-68
4 (1
996X
, "
2. P
. Dut
ia, T
he o
il re
fini
ng in
dust
ry in
Indi
a, C
hem
ical
Indu
stry
Dig
est,
pp.
103-
110
(hhrc
h 1
997)
. 3. A
. Bor
thak
ur, K
.V.
Rao
and
B. S
ubra
hman
yam
, Rec
ent t
rend
s in
enh
ance
d oi
l rec
over
y by
che
mic
al m
etho
ds, C
hem
ical
Eng
inee
ring
Wor
ld, V
ol. XXXII, N
o. 4,
pp.
83-
86 (1
997)
. 4.
A.X
'~r0
r.a:
Sta
tus.
&pr
ojec
tions
in th
e oi
l ref
inin
g se
ctor
, Che
m. E
ngg.
Pro
gres
s, V
ol.
XX
XE.
N,o
. 4,
pp.
87-
88 (1
997)
. 5.
Aqo
nym
ous.
Ind
ia s
till l
aggi
ng p
oten
tial a
s m
ajor
pla
yer o
n w
orid
ene
rgy
mar
kets
, Oil
&
Gas
J.,
pp.
19-2
2 (Fe
b. 1
2,19
96).
CR
UD
E O
lLS
- CH
EM
ISTR
Y A
ND
CO
MP
OS
ITIO
N
2.1
INTR
OD
UC
TIO
N
Pet
role
um,
etym
olog
ical
ly, m
eans
roc
k oi
l. It
is
natu
ral
orga
nic
mat
eria
l co
mpo
sed
prin
cipa
lly o
f hyd
roca
rbon
s whi
ch o
ccur
in th
e ga
seou
s or
liqu
id s
tate
in g
eolo
gica
l tra
ps. T
he
liqu
id ,p
art o
btai
ned
afte
r th
e re
mov
al o
f di
ssol
ved
gas
is c
omm
only
ref
erre
d fto
as c
rude
pe
trol
eum
or
crud
e oi
l or
sim
ply
crud
e.
Cru
de o
il o
cm
in m
any
diff
eren
t pa
rts
of t
he w
orld
, and
its
stru
ctur
e an
d co
mpo
sitio
n va
ries
tacc
ordi
ng t
o it
s so
urce
to
such
an
exte
nt t
hat
each
pro
duci
ng a
rea,
and
fie
ld,
and
rese
ryoi
r bears
its
own
prof
ile ju
st a
s in
divi
dual
ly a
s fin
ger p
rint
s id
entif
y m
an.
2.2
CH
AR
AC
TER
ISTI
CS
OF
CR
UD
E O
lLS
C
rude
oil
has
been
def
ined
as
a na
tura
lly
occu
rrin
g m
ixtu
re, c
onsi
stin
g pr
edom
inan
tly
of
hydr
acar
bons
an
do
r of s
ulph
ur, n
itro
gen
and
or o
xyge
n de
riva
tive
s of h
ydro
carb
ons,
whi
ch is
re
mov
ed &
om th
e ea
rth
in a
liqu
id s
tate
or i
s cap
able
of b
eing
rem
oved
. Cru
de o
il is
com
mon
ly
acco
mpa
nied
by
vary
ing
quan
titi
es o
f ext
rane
ous s
ubst
ance
s suc
h as
wat
er, i
norg
anic
mat
ter
and
gas.
The
rem
oval
of s
uch
extr
aneo
us s
ubst
ance
s al
one
does
not
cha
nge
the
stat
us o
f the
m
ixtu
re a
s cr
ude
oil.
If s
uch
rem
oval
app
reci
ably
aff
eds
the
com
posi
tion
of t
he o
il m
ixtu
re,
then
the
resu
ltin
g pr
oduc
t is
no lo
nger
cru
de o
il.
Cru
de o
ils r
ange
wid
ely
in th
eir p
hysi
cal a
nd c
hem
ical
pro
pert
ies.
Typ
ical
pro
pert
ies
of
seve
ral c
rude
s are
giv
en in
Tab
le 2
.1. C
rude
oils
are
brow
nish
(lig
ht o
ils h
avin
g la
rge
amou
nts
of d
isti
llat
es) t
o br
owni
sh b
lack
(he
avy
oils
) in
colo
ur. H
eavy
oils
hav
e an
unp
leas
ant o
dour
(g
arlic
like
) due
to th
e su
lphu
r com
poun
ds, w
hile
the
ligh
t cru
des h
ave
plea
sant
aro
mat
ic li
ke
smel
l. T
houg
h ge
nera
l, th
is is
-not
$w
ays
true
. Dat
a fo
r a
cons
ider
able
num
ber
of c
rude
oils
in
dica
te t
he s
peci
fic
grav
itie
s be
twee
n 0.
73 id' 1.02
; mos
t cr
udes
gav
ing
spec
ific
gra
viti
es
lyin
g -&
twee
n 0.
80 a
nd 0
.95.
The
se v
alue
s ar
e fo
r su
rfac
e co
nditi
ons
of t
empe
ratu
re a
nd
pres
sure
. The
kin
emat
ic v
isco
sitie
s va
ry fr
om 0
.7 to
130
0 cS
t at 3
7.8"
C; t
he b
ulk
of t
he v
alue
s
! be
ing
in th
e ra
nge
of 2
.3-2
3 cS
t. In
term
s of
ele
men
ts, c
rude
oils
are
com
pose
d pr
inci
pally
of c
arbo
n an
d hy
drog
en. O
f the
ot
her e
lem
ents
pre
sent
, sul
phur
, nit
roge
n an
d ox
ygen
app
ear a
s het
eroa
tom
s in
hyd
roca
rbon
I
deri
vativ
es, s
ome
of w
hich
occ
ur a
s pet
ropo
rphy
rins
, i.e
. com
plex
es in
volv
ing
trac
es o
f met
als
I I (m
ainl
y va
nadi
um a
nd n
icke
l). C
arbo
nthy
drog
en ra
tio
is u
sual
ly b
etw
een
6 an
d 8.
A w
ide r
ange
of
met
alli
c el
emen
ts h
ave
been
foun
d, g
ener
elly
as t
race
s, in
the
smal
l am
ount
of a
sh o
btai
ned
by b
urni
ng m
any
crud
e oi
ls. T
he e
lem
enta
l com
posi
tion
of c
rude
oils
is g
iven
in T
able
2.2
. ! I G
Page 14
16 PETR
OLEU
M R
EFININ
G TEC
HN
OLQ
GY
2.3 CO
NSTITU
ENTS O
F CR
UD
E O
ILS
T
he main constituents of crude oils are hydrocarbons. T
he proportions of the different types of hydrocarbona vary from
one crude oil to another. Many m
embers of each type are
presegt. Naphthenic acids, com
plex nitrogen compounds, and m
ercaptans account for some of
the-yxygen, nitrogen and sulphur present in crude oils. In additioq, the resinous and asphaltic substances
present in some crudes contain oxygen and sulphur. Inorganic sulphur can be
present as hydrogen sulphide (HzS) dissolved in th
e oil. Crude oil also contains trace elem
ents suth as m
etals, mostly in -sm
all quantities-some contained in w
ater impuritieg and som
e existing as com
plexes in the hydrocarbon phase.
Tab
le 2.1 Typical P
rop
erties of Cru
de O
ils
Tab
le 2.2 Elem
ental com
position of crud
e oils
15. (
~e
h
conten
t, wt. %
(
- (
0.0047 (
0.006 (
0.004 1
-
~h
lbr
bi,~
~~
. pi,iphyrin&
,a+e tj.eeII'1y$,d8 &
.sinam,;af d
@+
~.~
#&
~
~~
&l&
l~
P%
$$
e
.. -. ... A
,%.
C. com
poun$s indicate a contributio? from,plant 6O
u,Kei3, a
~o
~~
~~
~~
~~
~,
_l
~~
~p
pr ku!$
Hi$tp~ji,dnd hob$ljly B ~
'ed$cin&eriiri~
iiibnf: @
&l$
pi
iio@hynns hm
%%
dn i.a
*&&:
bd+it.i$b0$ b
ow
n h
bt c61p"hli
$~
vh
~s':in
kP
+$
~<
&{
~&
~#
&,
&egikihblebom
ilaht tjbdrees: 1
so
jxid
hy&r:,brbo$s 8'iG
been r.e~<&~ed:th'e'~:bFdd$&
%ai
have structurkri tjrpital of substaixes'formea biologically: O
ther hydrocarboiii'st~u~tu~es~~ith
16. (K
UO
P
( 12.0
1 11.8
1 11.7
( -
-
Elem
ent
C H
S
N
---- 0
--- M
etals
biol'dg;icali*ni&,
li'a"sbeen.detecb'd. .' , :
. , - ::;< :,
;. :
. , ;:
. <.;; .;.:<
. -
: ;: <.Th& w&&
p, &#b&
ted .w
ith ?oil :ma. gas &
cc
um
yl~
t~o
n~
$8: :usually - jn&
&$aljri s~
lifiB)i and
appears Mm
any fnstmces to' be m
odified$eaWater, tkepnncipa1:diKere'nc~s~bei~
a'deficiency in sulphates, relatively less m
agnesium and com
monly.,greater concentration than norm
al sea w
ater. Traces of hydrocarbons andorgrtllic acids are p
ksen
t.
Am
ount, wf 8
83.9-86.8
11.0-14.0
0.06-8.00
0.02-1.70
0.08-1.82
0.0-0.14
2.3.1 Hy
dro
carbo
ns
Hydrocarbons are com
pounds composed solely of hydrogen (H
) and carbon (C). T
he main
types of hydrocarbons present in crude oils are alkanes, cycloalkanes, arenes and hybrids involving com
bination of these types. They range w
idely in boiling point, and many cannot be
distilled under atmospheric pressure w
ithout breakdown.
Alkanes.T
hese are open-chain saturated hydrocarbons. They are also know
n asparaffins. T
hey can be divided into two types:
Straight chain alkanes - x~orm
al B
ranched chain alkanes - iso or neo W
hen carbon atoms are connected in a straight chain, they are know
n as straight chain alkanes. W
hen carbon atoms are connected in a branched fashion, they are know
n as branched chain alkanes.
' '
Alkanes have a general form
ula Cn H2n + 2, w
here n is the number of carbon atom
s. The
names ofthe alkanes end in -m
e. The first four alkanes have special nam
es (methane, ethane,
propane, butane) related to their histories H
H
H
H
H
H
H
H
H
H
I
I I
I
1 I
II
II
H
-C-H
H
-C-C
-H
H-C
-C-C
-H
H-C
-C-C
-C-H
I,
I I
I I
ll
I
II
I
H
H
H
H
H
H
HH
HH
m
ethane ethane
propane butane
,t
if
From pentane (C
5 Hlz) onw
ards, Latin or G
reek numerals are used to reveal the num
ber of carbon atom
s per molecule. A
few exam
ples are given below:
CH
3 - CH
z - CH
Z - C
HZ
- CH
3 C
H3 - C
Hz - C
Hz - C
Hz - C
H2 - C
Hz - C
Hz - C
H3
n-pentane n-octane
,
From butane (C
4Hio) onw
ards, alkanes may exist in tw
o or more form
s (isomers) differing
in structure. For example, butane m
ay exist in two form
s as follows:
n-butane I
cH3
isobutane
Page 16
Blphenyl
Naphthalene
Anthracene
Phenanthrene
The m
oat comm
on mononuclear am
matics found in crude oils, are toluene and m
-xylene. T
he possible constituents of crude oils. include polynuclear species containing up to at least eight condensed rings. M
any polycyclic aromatic hydrocarbons present in petroleum
are carcinogens.
Alkenes. ,T
hese are openchain unsaturated hydrocarbons, co
nw
g a carbon-cirbon
d&&
rh:!b. ona;
7 ' T
~~
~,
~
tgn&
the : chbbn-h,+ddi6h
pr!op,c~~
hk.xrPi.it:~
'd 'driabsgj,cli,c
m4; *t{a%
ahe;. C
iH,,
, G
oS :A,
:efi
ylei
e.;(
Si
eak.e)i :, ,an.d,,:& ?-1
;'d;a:v
i8r
.. I .......f...... 'th *e., w
e .' '..
*em
rs o
C~
W
l~
l
pF&,
.Ad
$&.&
64
?',le;&:,6f
.$&.&
;::hd&
,$p& *ivL
fd s&dtutai,is&
h&&
:& po8diti1;,d'e ped&
g,,od ,&ei'&
Pti:bh' s;i
hl,&Ij: 6$d
within the basic
hain
, mu.&
for =h
pr8',
.~6
:iti~g
hc
~w
&'b
~&
nn
~~
6.a
~
ljre expected, as follow
s:
HH
HH
I
ll
1
C=
C-C
-C-H
HH
HH
I
II
I
H-C
-C=
C-C
-H
I I
H
H
but-2-ene
The num
ber indicates the number of the first of the doubly bonded carbon atom
s, num
bered from the end nearer the double bond. In addition, the typical side-chain isoniei is
. .
..
..
..
.
,:
, ,
. .
. .
expected, that.is >
I!;,;, ,,.
H3C
H
,
, I
' ,.: : ;
j,
VC
,,
.
' I
..
, .-8
, : .;;
,.
C=
C
' I
H
3C
H
I.
I
isobutene (2methylpropene)
The tw
o possible geometrical isom
ers of but-2-me are the foliow
ing: H
-C-C
H3
CH
R-C
-H
These isom
ers are classified by the Latin preiixes cis (on this side) and trans (across)
indicating the relative locations of the two end m
ethyl groups. Coneequeptly, there are four
isomeric butenesin all.
,; ,,~m&~,.pe!mn~~in~bt';s~~~~;dii~b~~b~~~3j~~Iw~j.~wf~~8~.I!Q~,'s'~~
.... - ...
5
,: F
. am
Y1um
for in
e fBh~ii~~~O~~'b~fiv~~ti'6~.~di.;~!&t~~~IB~~~$t~~, nsm
r
pentylenes may supersede this. F
or the higher mem
bers of the series the IUPA
C system
is used. F
or example,
'H
I H
%
I H
-C-H
H
p,@adlene .
..
..
!
.:; :
. l;'3-butadl@ne:
:I ,:&penW
eriw
-..:. .I; 3, b'he~ttiine , .
.. .
..
;
;, ,!.
.'; ;;.<
!.:. v
. '
.'
t ':.
;, ,<,
;,! 2
! , : .: :'
' .
Al~
ee~~
ee.areo
pen
-cha
in~
hy
dro
earb
on
s co
~tah
ing
onecarbon-ctybon triple bond.
The fin&
.mem
ber:o$th
i~~s~eesi~acetylene,
Cfia,:wbich,appe~~8;injexten44 fo
h'la
as:the linear m
olecule: H-C
GH
. Additional m
embers of the alkyne seriea:.com
phe,-open-chain m
olecules somew
hat similar to the higher alkenes but w
ith each double bond replaced by a tri~
le bond. T
he.IW
AC
system of nom
enclature.ri~plies throughout th
e series as with the
alcenes, but the des&
tem
treats tho
!~~
htah
&ab
ers. as d&
vativee,:of acetylene. Thus, .I:
for example,. H
.arnW
fijj. cbuld be desd
&d
!& .&
ither but-l--ge' bi s&
ylacetylene. The
,
boiling and relative densities of the alkynes are slightly higher than those of the
corresponding alkanes. , .,
Cycloalkanoarenes. T
hese, also called naphthenoaromatics, are m
ixed polycyclic hydrocarbons and possess structures involving fusion of arom
atic with alicyclic rings, and m
ay .....
carry aliphatic side chains. These h
y$
~~
&~
~;~
Qu
$
appearing in the kerosine fraction,
increasing in concentration in the higher-boiling dbtillaticn fractions and residues. Bicyclic
~?!p~
t$enp~~
m~
$c.. $nee. tu.prn~ti-~
rhg
. &dfpop alicxy&
c) .ingee.? :p.$+in
and ..theic ,alkyl 4$vativ$ - 3
;" r'la!jiy$~. +&dadt' .9, keroeifte..apd:h&
.
. 7 ......<
... gas L
.
,oi4, ..... ,E
wpl+
: ,.-
of ,C
Q~
PO
~W
&
present .
are. .. giyen. belpw
: :
... .
. I .
..
.
. .
..
>
..
.
..
.
...
..
..
i.,.
! :
., .
.
...,.. .
..
.
..
..
.
In~
an
O'(~
~",o
~
':: "
..
.
I .k(~
ln.~
Cio
,H,2)
, -
(1,2, 3, Ctetrahydm
naphaalene)
Page 17
d'
2.
3.2
Non
-Hyd
roca
rbon
s C
rude
oils
con
tain
app
reci
able
am
ount
s of o
rgan
ic co
mpo
unds
wit
h st
ruct
ures
inco
rpor
at-
ing
one
or m
ore
(the
sam
e or
dif
fere
nt) a
tom
s of
sul
phur
, nitr
ogen
, or
oxyg
en in
add
ition
to
carb
on a
nd h
ydro
gen
and
som
e of
the
se a
re a
ssoc
iate
d w
ith m
etal
s su
ch a
n va
nadi
um a
nd
nick
el, i
.e. t
hey
are
orga
nom
etal
lic in
nat
ure.
S
ulp
hu
r co
mpo
unds
. Sul
phik
r'is
th8
mas
t. ab
unda
nt a
tom
ic c
onst
itue
nt o
f &de
oi
ls,
othe
rtha
n ca
rbon
and
hyd
roge
n. O
ne o
f the
ori
gins
of s
ulph
ur c
ompo
.yds
in th
e cv
de
oils
is
~~&~
~tci
rd:k
ulph
iw~h
-*~i
;it
.d tigs;s
iie$ .
bf&
e .fi
lari
t an
d'mirr
iLl
$&&
;ns'd;p
o&ted
,&
.;<,
:<,..
, .
,<
.,,
!
geol
ogic
al b
eds.
The
oth
er o
rigi
n is
the
bio
geni
c re
duct
ion
~f'"
dil$
h'&
.~'&
de
oil*
"&
-y
cons
ider
ably
in
thei
r su
lphu
r co
nten
t ra
ngin
g fr
om a
few
hun
dred
ths
by w
eigh
t to
as ;p
uch
#rce
ht
OT s
db
hd
i. ~
ulb
hu
y
coke
df o
f 13
.95%
fodd
d $ d
ad
po
int (
inet
ah S
tate
in
Ui$
.;Aj?
. is #
e,&
ghks
t . I
:.. re
cord
&
. su
lphu
r cdp
tent
of a
ny c
qde:
oil.
. . .,
'. ..
I'.
..
,*
.
The
*u
lph
~
com
~~
un
ds~
'~re
'se'
nt
in c
kd
e o
ils c
an' b
e di
vide
dlin
to t
hiol
q, &
on&
and
W
lph
ides
and
thio
phen
es. (
': i -
" .
,.,,.>.v-
@-
. .
.Thi
olsi
.als
o cal
led
mer
capt
ans,
-are
&he
sulp
hur a
na1o
gues
:of th
e al
coho
ls (i
.d.th
iodc
ohol
s)
and
char
acte
rize
d by
the
pre
senc
e of
the
sul
p-hy
dryl
gro
up, -
SHd
whi
ch ta
kes
the
plac
e of
a
hydr
ogen
. ato
m in
,an
alka
ne-p
~:cy
cloa
lk.a
ne
mol
scul
e.;T
hiol
s: are.t&amain;sul$hur.compo~ds
of lower~boiling.(.petroleum~~fraotioh~
(blo
w 20
0°C
). E
tam
ples
uf.t
his'd
ltrss
oh
aul~
hu
r CO
W-
poun
ds a
re g
ivep
bel
aw:
CH
3 SH
Q
HG
HzS
H
'(CH
sh Ck
SH
m
etha
peth
ld
, e@
anet
hiio
l ~s
opro
pane
thlo
l (m
ethy
l mer
capt
an)
(eth
yl,m
erw
~tan
) (~
sopm
p$im
erca
ptan
)
'. 'T
he #
rese
nce
of th
iols
:'in
the.
~~et
r~~c
!u~i
l"h
atti
ons
ca;i+
ies
-cof
p5si
oR ,I!
rcib
kem
s, c
'ta
lyit
p&
sdin
&
an.d
~p
le'&
*t'
i~6
0ra
ta~
,&d
pf&
oa
ouis
. mb
jg:a't
e n&
bM
c:h&
lj;
poi*
oi;d
&
.?C,..
.. I ..
~.
in lo
w c
once
ntra
tion,
how
ever
, and
they
are
oft
en u
sed
as o
dour
ants
iii L
PQ
The
ibw
er th
ibls
ar
e th
e in
ost m
alod
ouro
us..O
ne p
art i
n 50
mill
ion
of e
than
ethi
ol c
an b
e de
tect
ed in
air
by
the
hum
an n
ose.
The
odo
ur is
str
ong
at 0
.6 p
pm a
rid d
istin
ct a
t 0.0
3-0.
07 p
pm. I
n h
igh
conc
entr
a-
tions
, the
odo
ur o
hang
es to
som
ethi
ng li
ke th
at of
chl
orof
orm
. T
hiol
s are
stro
nger
aci
ds th
an a
lcoh
ols,
and
use
is m
ade
of t
his
to re
mov
e lo
w m
olec
ular
w
eigh
t thi
ols f
rom
ligh
t gas
olin
es w
ith
caus
tic so
da so
lutio
n. H
ydro
proc
essi
ng te
chni
ques
are
em
ploy
ed to
desu
lphu
rise
oth
er o
il fr
actio
ns a
nd h
ere
com
bine
d su
lphu
r is
elim
inat
ed a
s hy
drog
en s
ulph
ide f
rom
all
type
of-
com
poun
d con
tain
ing
this
het
eroa
tom
.
CH
3 C
HSC
HC
H3
I I
(CH
I C
Hdz
S
CH
3 C
H3
3-th
iap'
enta
ne
2,4-
dlm
ethy
l-3th
iipen
tane
(d
leth
yl su
lphl
de)
A
(dh
wrw
yl su
lphi
de)
- m
~h
ex
an
am
wp
hl
de
)
As
in th
e ca
se o
f thi
ols,
the
sulp
hide
s are
gen
eral
ly v
ery
mal
odou
roue
. A
few
low
mol
ecul
ar w
eigh
t dis
ulph
ides
(d
ith
iaab
nw
) hav
e al
so b
eens
how
nto
be p
rese
nt
in c
rude
&. The a
ccur
renc
e of
dis
ulph
ides
in;p
rude
oile
may
be
owin
g to
the
seco
ndar
y re
actio
n of
thi
ols
wit
h tln
olri
aant
suc
h as
air
or free su
lphu
r. O
rgan
ic d
isul
phid
es a
re is
olog
s of
the
or
gani
c pe
roxi
des,
RO
OR
, but
are
muc
h m
ores
tabl
e. E
xam
plea
are
giv
en b
elow
:
23-d
lthla
buta
ne
CH
s (m
ethy
l dls
ulph
lde)
2-
mem
yC3!
<h
iehu
xane
~
a~
~.
dl
su
lp
hI
de
)
Som
e ex
ampl
es o
f thi
ophe
nes
foun
d in
cru
des
are
give
n be
low
:
thlo
phen
e 2-
emyt
thlo
phen
e be
nzo(
b)th
loph
ene
Thi
ophe
ne a
nd
its
alk$
dN
vati
vee
are n
o~
y,r
~la
tiv
~I
y.s
c~
ce
co
nsti
tuen
ts o
f cr
ude
oils
, but
con
dens
ed sy
stem
-ben
zoth
ioph
enes
, dib
enzo
thio
phen
es, a
nd h
ighe
r po
lycy
clic
s (e
.g.
ben
ibn
aph
th~
thio
~h
enes
) ar
e im
part
ant
com
pone
nt8 o
fall
hig
h au
lphu
r cr
udes
. T
hiop
hene
de
riva
tives
are
pd
cula
rly
abu
ndan
t in
erud
e oi
ls c
onta
inin
g hi
gh p
ropo
rtio
ns o
fmm
atic
s,
resi
ns a
nd a
spha
lten
es.
Page 19
910
aplu
3 JO
uo!
pa&
ssa1
3 j
o-
po
ql
a~
d~
go
np
amg Sn p
.g e
lq
~~
:shi
o~~
oj
SB a
m s
u0q~
eoo"
pbqj
o sass
el:,
pa
ra
m 10
3 dbn
x jo
f~~
rip
A
.s!s
ap.jq
+am
E u
o an
gp
pe
SF
lgae
j uog
e5pa
jSs.
req3
sm
spuq
q L
O s
aq
qx
rod
.pa,
ws!
p s3
tim1o
n gua
arad
(jd p
w (~i
'09
"0s
'01
qF! s
amqe
&&
&q'
~*'I
@B
X$A
B
Kq
ahm
a u
orp
ms
i~~
N
J,
~
u1
0~
~~
paq
e$4
ds~
~1
og
a~rg
rt
rna~
oiqa
d a9
30
qqo
d ~
Utf
i0~
'&83
3~%
? aq
L .3
;g9
a9~
/30
~b
'g
3~ ~
~~
~~
?q
&s
:~
p
i j
p~ 7 i 'P
:yo
'F&
xZ;!~
:dq
as
e~
a~
e
aw
r! u a:?
qm
(TIZ
)-- -
3
1 - = a
onx
I ,
(9J)
:u
qskd
i&
Bp
on
dJ a
p7 q
'8r@
p~
om
' 'k
+ef
i~g
aad
s qq
y $$
dd
Zq
oq
&qq
a.uoa
IW
BJ
'(*0
3~s?
sn~
q'E
@ti
,61a
rim
n)
sod i
dq p&
~aA
ap%
! 'd
onx
'i$$b
& u
o~
e~
~b
qj
a
u '
I i
o~
~~
~~
o~
~&
~p
~~
~~
1
.v~
,
,I
,
, t
.
~P
aq
d~
g~
qE
. ?F
I!O
;aP!v
30
uoR
e~J!
$m ?!.I%
W
+:(
PU
O!T
W.
Xaq
, sy
~~
?~
,?~
,;~
~),
jo~
~&
ye
@
?K
J!?
~~
S
RY
~W
pa
s~w
y
.sau
!m~
nea
mp
sn<
eyq s
3 9*n
p303
3a ~I
!Q, a
pr
u~
jo,~
wp
~m
~~
~1
r3
~a
~
syao
~sp
aaj jo d
0n)F
se n
am s
e .-a
'le
aq a
g!aa
ds
'que
qsuo
a bl
pad-
bq!s
oasr
~ 'q
uquo
3 ua
Sorp
6q
s-e q
ans
sava
dord
ia
qo
pue
d0n
x u
aa
wq
pad
o~
a~ap
su
o!+8
1auo
a L
xequ
aura
~dur
oa aq
q u!
saq
lo33
ej a
wjo
etl
aqnJ
asn
uy
ur
aq
, 'uo!
qaeq
a
w u!
suoq
ieao
lplC
qjo a
dLq
~ep
!+%
d re
jo
aaue
u!ur
opa~
d aw
qe
3!p
~ 03 p
asn
aq tr
ea s
uoga
eq w
na~
oqad
jo d
on
xjo
sanI
ea a
q? '
mu
0'11 - 0'6
0'zT - 0
.11
O'ET - 9'ZT
sa!la
mox
v sa
uayq
qd8~
su
gsis
d
Page 20
2.4.2 C
orrela$inqJn~@
xi ..
: .,;:,
..
-~
~e
c
o~
Fp
index ((311, developed by U
S Bureav of ~
ine
s, is B
iven by the following
empiiiical eqfiation:;
: .., : ,:I.,: ; ,.
. 1
1
., .., . ..
where fi ie'the average boiling point, O
R ,'determ
ined by the standard-BureaU
8'df Mbes
distillation method and G
is the specific gravity at 15.56°C/15.560C
. C
I values of a petroleum fraction betw
een 0 and 15 indicate that the components of the
fraction are'predominantly paraffinic in nature. C
I values between 15 and 50 indicate a
predominance either of naphthencs or of m
ixtures of paraffins, naphthenes ad qom
atics in the p&
roleum
fraction. CI values above 50 indicate a predom
inance of aromatics in the
fraction. ,
I,
..
,
2.4.3 Method of stru
ctural G
roup Analysis
The m
ethodi?f.siyctyd group analysk.,deseribq? the .ch$ajier; qf. the fraction in terms
of elements constituting a h
, theticalaverage molecule2Paving the chem
ical and pbxeiqal p..,
.. !...I ...'
properties of the eum
of
'e. indiiridual comporien&
..,p;f ;@2:B
acti,on,. awp
rdb
..to .thek
concentration. This m
ethodclarjsifies the crude.oils into:.sev& C
lasses (Table 2.7).
Table 2.15D
enomination an
d C
lassification of Cru
de O
il Classes
1. G
.D. H
obson (ed.), Modem
Petroleum T
echnology, Part 1
(Chapter 91, 5th edition,
John Wiley &
Sons, New
York, (1984).
2. L.F. H
atch and S. Matar, From
Hydrocarbons to Petrochem
icals, ~u
lf
Pubyishing
Com
pany, (1981). 3.
L.F. H
atch, A chem
ical view of refining, H
ydrocarbon Processing, Vol. 48, N
o. 2, 77-78 (1967).
4. B
.B. A
grawal and I.B
.Gulati, T
race metals in petrolem
and petroleum products;
Part I - O
ccurrence, nature & significance, Petroleum
and Hydrocarbons, V
ol. 6, N
O. 4, 193-197 (1972).
5. B
.B. A
grawal and I.B
. Gulati, T
race metals in petroleum
and petroleum produds ;
Part 11 - Individual constituents and their significance. Petroleum and H
ydrocar- bons, V
ol. 6, No. 4,
198-202 (1972). 6.
P. Jones, The presence of trace elem
ents in crude oils and allied substances, The
Institute of Petroleum, 73-76 (A
pril Jun
e 1988).
Class I I1
,u
, i',.
TRA
NS
PO
RTA
TION
OF W
AX
Y C
RU
DE
OILS
3.1 INTR
OD
UC
TION
C
rude oils contain a mixture of light and heavy hydrocarbons. T
ypically, a stabilized oil m
ay contaitl paraffinic, naphthenic and aromatic com
ponents as heavy as Cso. In addition,
poli& ahd asphaltenes M
&
also be'present. The lighter com
ponents in the crude oil kdep the
he&d&
toxhpohents in solution. This solubility depends very strongly on the tem
perature. If the tem
perature of the oil is decreased, the soldbility of the heaw
hjkirocarbons atiy be
sufficiently reduced to cause precipitation of these components in the form
of solid wax crystals.
The polars and asphaltenes m
ay also co-precipitate with w
ax crystals. The phenom
enon of w
ax separation from petroleum
fluids at low tem
peratures has been a problem to users of
petroleum products for a long period. It can occur in
lubricating oils, residual fuels and crude oils. '
The presence of w
ax crystals changes the flow behaviour of the crude oil from
New
tonian to non-N
ewtonian. T
he wax crystals usually lead to higher viscosity w
ith increased energy consum
ption for'pumping and a decreased capacity. In addition, if the oil is cooled during
transportation, the w
ax crystals tend to deposit on the colder pipe wall. W
ax deposits can lead to increased pipeline roughness, reduced effective diam
eter, more frequent pigging require-
ment and potential blockage. If these deposits get too thick, they can reduce the capacity of
the pipeline and cause problems during pigging. W
ax deposition in process equipment m
ay lead to m
ore frequent shutdowns and operational problem
s. In extreme cases, w
ax crystals m
ay also cause oil to gel and lead to problems of restarting the pipeline.
Great potential savings can be derived from
accurate prediction of wax form
ation. The
knowledge of the m
agnitude of wax deposition can lead to reduction of insulation requirem
ents for production and transportation system
s. Conversely, problem
s with w
ax can be addressed in an early stage of a project so that sufficient therm
al insulation is planned for instead of
1 expensive chem
ical injection and loss in capacjty or loss of availability. Process heat loads can
I be reduced by increasing efficiency of heat transfer. C
apacity reduction in heat exchangers can be overcom
e. This reduction results from
blockage or vibration problems. T
he size of export
i pum
p8 and flow lines c+
be reduced by an accurate knowledge of the effect of,w
ax formation
on crude viscosity. The m
inimum
pigging frequency can be estimated. In addition, problem
s
I related to start up and shutdow
n can be solved cost effectively. T
he crystallization of wax in crude oils causes severe difficulties in pipelining and storage.
I T
he crystallization of waxes at low
temperature causes reduced liquidity of w
axy crude oils I
which considerably w
pe
rs
the transportation of crude oils through long distance pipelines. 1 I
Several m
ethods exist for handling waxy crudes for ease of transportation. For exam
ple,
1 pigging the pipeline is useful for rem
oving thin layers of wax only. A
highly waxy crude m
ay
Denom
ination of crude oils P
ar
ec
Parfinic-naphthenic
-
--
Class delim
itation by structuml in&
values
%C, 2 72 %CP 2
50; %CP + %CN 2 90
Page 21
PETR
OLE
UM'R
EFIN
ING
TECH
NOLO
GY
requ
ire
fieq
uent
.pig
ging
to ke
ep th
e w
ax a
ccum
ulat
ion
man
agea
ble.
Api
ggin
g op
erat
ion
ofte
n ra
ttir
es si
gnif
ican
t am
ount
s of
cos
tly o
ffsh
ore
man
-hou
rs. T
akin
g in
to c
onsi
dera
tion
all
the
&o-
econ
omic
as
pect
s ad
diti
ve tr
eatm
ent i
s rep
orte
d to
be
the
mos
t sui
tabl
e m
etho
d fo
r th
e tk
wo
rta
tio
n o
f w
axy
crud
e oi
l, w
hich
can
dep
ress
the
pou
r po
int
and
impr
ove
the
flow
ch
arac
teri
stic
s at
low
tem
pera
ture
s.
,\,
~.$
+~
P~
~~
U~
~'~
R~
NS
PO
RT
AT
ION
F
or t
he
tran
spor
tati
on o
f lar
ge q
uant
itie
s of
cru
de o
ils, p
ipel
ines
are
the
mos
t ec
onom
ic
mea
ns. U
nder
saf
ety
aspe
cts,
tran
spor
tati
on b
y pi
peli
ne g
uara
ntee
s the
bes
t pro
tect
ion
for t
he
envi
ronm
ent.
Fur
ther
, the
re is
no
hand
ling
of o
ther
traf
fic
and
no d
istu
rban
ce b
y no
ise
or a
ir
poll
utio
n. A
cont
inuo
us su
pply
to th
e re
fine
ries
is n
orm
ally
ass
ured
and
this
is n
ot e
ndan
gere
d by
wea
ther
con
diti
ons s
uch
as fo
g, ic
y ro
ads,
or t
raff
ic c
ondi
tion
s alo
ng in
land
wat
erw
ays,
suc
h as
hig
h or
low
wat
er le
vel,
ice,
etc
. H
owev
er, e
ach
pipe
line
sys
tem
requ
ires
ver
y hi
gh in
vest
men
t whi
ch s
houl
d be
use
d m
ost
econ
omic
ally
. The
mos
t ec
onom
ical
and
eff
icie
nt o
pera
tion
of
a pi
peli
ne c
ould
be
reac
hed
by
mai
ntai
ning
a c
onti
nuou
s co
nsta
nt f
low
rat
e w
itho
ut a
ny in
terr
upti
on.
Als
o, i
p r
espe
ct o
f a
reli
able
and
cont
inuo
us su
pply
to th
e re
fine
ries
, a st
eady
-sta
te th
roug
hput
, wit
h so
me s
easo
nal
fluc
tuat
ions
due
to m
arke
t req
uire
men
ts, s
houl
d be
env
isag
ed. O
ther
wis
e, a
ddit
iona
l sto
rage
vo
lum
e h
as to
be
prov
ided
for
larg
e qu
anti
ties
of c
rude
oil
and
this
wou
ld b
e ve
ry e
xpen
sive
. In
terr
upti
ons
by s
hutd
own
of a
pip
elin
e ar
e by
no
mea
ns d
esir
able
. How
ever
, a s
hutd
own
may
occ
ur d
ue to
the
follo
win
g op
erat
iona
l re
ason
s:
(a) T
here
ia a
n in
adeq
uate
sto
ck of
oil
in th
e te
rrni
nd. T
his c
ould
be
caus
ed b
y di
stri
buti
on
in ta
nker
sch
edul
es, f
or in
stan
ce, d
ue to
wea
ther
con
ditio
ns.
(b) T
here
are
no
deli
very
req
uire
men
ts b
y th
e re
fine
ries
fed
by
pipe
line
. Thi
s co
uld
be
caus
ed b
y di
srup
tion
in
oper
atio
ns s
f one
or m
ore
of t
he p
roce
ssin
g un
its
of t
he
refi
neri
es, f
or
inst
ance
, due
to e
quip
men
t bre
akdo
wn.
(c
) A p
ress
ure
test
for l
eaka
ge c
ontr
ol of
the
pip
elin
e ha
s to
be
perf
orm
ed.
(d) R
epai
r, m
aint
enan
ce w
ork
on t
he p
ipel
ine
syst
em in
clud
ing
pum
ps i
s re
quir
ed.
(e) T
he p
ipel
ine
mig
ht b
e sh
utdo
wn
auto
mat
ical
ly b
y ex
ceed
ing
the
oper
atio
nal
safe
ty
lim
its.
T
hese
shu
tdow
ns a
re n
ot e
xpec
ted
to la
st lo
nger
than
3-4
day
. Und
er e
xtre
me
cond
itio
ns
one
coul
d th
ink
of e
xtra
ordi
nary
long
shu
tdow
ns. T
he re
ason
s m
ight
be
gove
rnm
ent
acti
on,
eart
hqua
ke, s
trik
e, w
ar, e
tc. H
owev
er, u
nder
nor
mal
con
diti
ons,
they
are
'not
exp
ecte
d.
Ine
n tr
ansp
orti
ng w
axy
crud
e oi
ls, t
hese
ope
rati
onal
poi
nts
of v
iew
'are
of
cons
ider
able
im
port
ance
.
3.3
WA
XY C
RU
DE
OlL
S
The
cru
de o
ils p
umpe
d in
pip
elin
es u
p to
the
ear
ly s
ixti
es g
ener
ally
sho
wed
nor
mal
ch
arac
teri
stic
s in
resp
ect o
f pum
ping
con
diti
ons s
uch
as vi
scos
ity'a
nd lo
w p
our p
oint
. now
ever
, th
e op
enin
g up
of
rem
ote
oil f
ield
s in
Nor
th A
fric
a an
d In
dia
in th
e 19
60's
to e
xplo
it th
e lo
w
sulp
hur
(but
wax
y) c
rude
s in
thes
e lo
cati
ons,
and
th
e ne
ed t
o pu
mp
tKes
e oi
ls th
roug
h th
e m
uch
cold
er p
ipel
ines
has
led
'oil
pro
duce
rs t
o st
udy
the
pum
pabi
lity
of
wax
y cr
udes
at
tem
pera
ture
s be
low
th
e po
ur p
oint
lim
it. T
he a
dvan
tage
s of
thes
e cr
ude'
oils
in
resp
ect o
f hig
h re
serv
es, l
ow s
ulph
ur c
onte
nt, g
ood
dist
illa
te p
rodu
ct y
ield
and
its
low
dsc
ous
flow
und
er fa
ir
tem
pera
ture
con
diti
ons
are,
how
ever
, par
tly
com
pens
ated
by
the
disa
dvan
tage
of
high
wax
co
nten
t, w
hich
res
ults
in a
hig
h po
ur p
oint
and
und
er c
erta
in c
ondi
tion
s of l
ow te
mpe
ratu
res
coul
d cr
eate
ope
rati
onal
dif
ficu
ltie
s af
ter
a lo
ng-t
erm
shu
tdow
n of
the
pip
elin
e. W
orld
wid
e,
one
can
dist
ingu
ish
abou
t 15
00 va
riet
ies
of c
rude
oil
of w
hich
10
to 2
0 pe
rcen
t are
con
side
red
TRAS
PORT
ATIQ
N QR
WAX
Y,CR
UDE
OIL
S 31
to b
e th
e:w
axy.
Suc
h a,
clas
sifi
cati
oo~
was
base
d-on
the
wax
con
tent
.oE
the,
cmde
aad
itsp
ou
r po
int;
The
,cha
ract
eris
tics
of
som
e of
thes
e cr
udes
are
giv
en in
-Tab
le3:
l. In
-con
tras
t, mos
$of
the
Mid
dleE
ast c
rude
oil
s hav
e a
pour
poi
ntbe
low
0 OC
and
wax
con
tent
less
than
7w
t.k
and
th
eref
ore
pose
no
prob
lem
s in
pip
elin
e tr
ansp
orta
tion
eve
n at
low
tem
pera
ture
s.
Wax
y cr
ude
oils
exh
ibit
non
-New
toni
an b
ehav
iour
at
tem
pera
ture
s be
low
abo
ut 1
0°C
ab
ove
the
pour
poi
nt. T
he w
ax c
an c
ryst
alli
ze a
s th
e cr
ude
is co
oled
to fo
rm g
el o
r a p
arti
al g
el.
Und
er s
tati
c co
ndit
ions
a r
igid
gel
is
form
ed, b
ut i
f th
e cr
ude
is c
oole
d w
hile
in
mot
ion,
th
e ap
pare
nt v
isco
sity
will
inc
reas
e bu
t th
e m
ater
ial
rem
ains
flu
id:
The
refo
re, t
he
rheo
logi
cal
prop
erti
es a
re fu
ncti
ons
of t
empe
ratu
re, s
hear
rat
e, s
hear
str
ess
and
past
his
tory
. Pro
blem
s in
pum
ping
the
se c
rude
s w
ill o
ccur
if t
he te
mpe
ratu
re d
rops
and
the
flui
d be
com
es n
on-N
ew-
toni
an a
nd if
gel
form
atio
n oc
curs
aft
er a
shu
tdow
n. T
he p
ipel
ine
faci
lity
mus
t be
desi
gned
to
reco
ver f
rom
thes
e pr
oble
ms
or p
reve
nt th
em. A
real
isti
c ap
proa
ch s
houl
d be
dev
elop
ed b
ased
up
on a
n ex
tens
ive
eval
uati
on of
the
rheo
logi
cal b
ehav
iour
of th
e cr
ude
oil u
nder
repr
esen
tati
ve
tem
pera
ture
and
she
ar c
ondi
tion
s. T
he tw
o rh
eolo
gica
l par
amet
ers
of w
hich
kno
wle
dge
is
indi
spen
sabl
e fo
r tra
nspo
rtin
g w
axy
crud
e oi
l thr
ough
pip
elin
e ar
e vi
scos
ity a
nd y
ield
str
ess.
B
efor
e we
go fu
rthe
r int
o rh
ealo
gica
l beh
avio
ur o
f the
cru
de o
ils,
a fe
w re
leva
nt te
rms
that
will
be
freq
uent
ly u
sed
are
defi
ned
belo
w.
abl
e 3.1
Ch
arac
teri
stic
s of
Wax
y C
rud
e O
ils
I I 3.3.1
Def
init
ion
s of
Rh
eolo
gic
al P
aram
eter
s S
Hea
r str
ess.
Con
side
r th
e st
eady
flow
of a
flui
d in
a h
oriz
onta
l pip
e of
cir
cula
r cr
oss-
sec-
ti
on. T
he fl
uid
flow
s wit
h an
ave
rage
vel
ocity
of U
in a
pip
e of
insi
de d
iam
eter
D. T
he p
ress
ure
diff
eren
ce b
etw
een
two
poin
ts 1 a
nd 2
, sep
arat
ed b
y a
dist
ance
of L
is (
Pi -
P2).
qe
decr
ease
in
pres
sure
in
the
flui
d re
flec
ts t
he
appl
ied
forc
e ca
usin
g th
e fl
uid
to fl
ow
and
if th
e fl
ow is
ste
ady
(i.e
. no
chan
ge i
n th
e flo
w a
nd h
ence
vel
ocity
), th
is f
orce
mus
t be
co
unte
r-ba
lanc
ed b
y a
shea
r for
ce of
equ
al m
agni
tude
at t
he
wal
l of t
he
pipe
. If r
, is
the
shea
r st
ress
at
the
pipe
wal
l, th
en f
orce
act
ing
on t
he f
luid
at
the
wal
l m
ust
be -
71 D
L r
w. T
he
nega
tive
sig
n in
dica
tes t
hat
this
forc
e ac
ts in
a d
irec
tion
opp
osit
e to
the
dire
ctio
n of
flo
w. T
he
1 fo
rce
acti
ng u
pon
the
flui
d du
e to
pre
ssur
e di
ffer
ence
is
(Pi -
P2).
In s
tead
y st
ate
(no
1 ac
cele
rati
on),
the
sum
of t
hese
two
forc
es is
zer
o. T
here
fo;e
, w
6 ca
n w
rite
Page 22
The above eQ
Uatibh rneteliy shew
s thaCthe,sheaps&
ss at-the pipe w
l i@
jUsti&
pther ~
ea
ns
of e*@
&ioh bP
"dti%n~
losd.-~rbin
E1$,3j1, itfdlfow
ru that.avddab1e~hear'strgSs~or a
particular pipeline depends,on the leligtbd
the line between tw
a,pump stations! and the
pressure difference. The availdble sheatj $tress can< be1 increased by increasing the initial
pressure, PI, and/or, reducing the section length of pipe, L. An exam
ple of calcu\ati~n of
available shear 'stress is given,below.
STA
TIO
N : V
IRA
MG
AN
TO AB
U R
OA
D
SVatic head at V
iramgan
Static head dt";sb'u Road
Pump puction
Differential heaq of each of the pum
pa at rated flow
Tw
o pumps w
illtbe operated in series. R
essure drop ah A
bu Road
Resdure dtop in the liile
Density of crude at pum
ping temperature
:. P
ressure drop
Inside diameter of line
Line length
Shear strees
= 0.000339 psi
= 23.4 dynes/m
2 If the available shear stress is equal to or m
ore than the. forcp peeded to
overcome the shear streas at the.innersqfape of the pjpe, $hen tbe,flow
3 l$e initiated.
Sh
ear rate. consider two p&
allq;l planes of area A, separated by &
:d~erqntiai&
jtance dr. T
he space between the tw
o planes is filled with a fluid. T
he lower plane is fixed. A
small
force F applied to the upper plane wiv give it a velocity dU in the direction of the force. If there
is no slip between the w
all and the flGd, the fluid adjacent to the upper plane or w
all &q also
have a velocity dU in the direction of the applied force and the fluid next to the low
er plane or w
hll will have a zero velocity. T
hus, a un
ifoy
velocity gradient of magnitude dU
/&r is set up
in the fluid since the shear force F is uniform across the distance dr;T
he velbcity gradient, dU
/cir, is comm
only referred to as the rate of shear. The shear force per unit area, F/A
, is called the shear stress.
Viscosity. It m
easures the ability of fluid to flow during steady state condition. It is the
property of a fluid that resisp a shear force. It can be thought of as the friction resulting when
one layer of fluid moves relative to another. V
iscosity, p, can be defined as the ratio of the shear stress to the rate of shear.
I /
TRA&&RYAT~ON O
F WA
XY CR
UbE
OILS
,For lam
inar flow in pipes, friction loss ie given by
. /
2
&.
(PI -P
2) 32 p
U
-= /
L
o2 w
hich can be rearranged in the form
[(PI - P2) D
I4LI
TW
-- '=
(8UD
) -(8U
D)
Therefore, for lam
inar flow,
. .
Rate of shear =
8U/D
J3.3)
and for turbulent flow,
Rate of shear =
(SU/D
) Cr
*..(3.4)
where C
ri3 correction factor which depends upon R
eynolds number.
Yield stress. It m
easures the ability of fluid to restart its flow aR
er shutdown of the
transportation system. T
he yield stress of an oil, at a given temperature is defined as the shear
stress required to initiate flow. It can thus be directly com
pared with theshear stress available or allow
able in a pipeline. T
he yield stress of waxy crudes ie influenced by-ite temperature
history, shear history, aging and composition.
3.3.2 R
heological Classification of Fluids
There exists a rate of shear and shear stress at each point in a flow
ing fluid. In determining
the rheology of fluids, any one of the following b
aic behaviour patterns (fluid types) may be
found upon agitation of the fluid at constant temperature.
New
ton
ian fluids. A
New
tonian fluid is one whose visco~
ity at a given temperature ie
independent of the rate of shear. There is a linear rdationship betw
een the shear streas and the rate of shear for a N
ewtonian fluid. T
he viscosity of a New
tonian fluid at a given
temperature is constant regardless of the velocity, previous agitation or shearing of the fluid.
Fluids
P
Purely viscour flddr
Tim
e dependent
P
I Flg. 3.1 R
heologlcal classlficaUon of lulds.
I
Page 23
Non
-New
toni
an fl
uids
. A no
n-N
ewto
nian
flui
d is
one
who
se vi
scos
ity a
t a g
iven
tem
pera
- tu
re is d
epen
dent
on
the
rate
of s
hear
. A fl
uid
havi
ng a
vis
cosi
ty g
reat
er th
an 20
Pa.
s is l
ikel
y to
be n
on-N
ewto
nian
. The
vis
cosi
ty of
non
-New
toni
an fl
uids
may
incr
ease
or d
ecre
ase
wit
h th
e ra
te o
f sh
ear,
dep
endi
ng o
n th
e ty
pe o
f fl
uid.
The
cla
ssif
icat
ion
of n
on-N
ewto
nian
flui
ds is
de
pict
ed in
Fig
. 3.1.
Tim
e-in
depe
nden
t non
-New
toni
an fl
uids
. A
non
-New
toni
an fl
uid
is s
aid
to b
e tim
e-
inde
pend
ent i
f the
she
ar s
tres
s at
any
rate
of
shea
r is
cons
tant
wit
h tim
e. T
he p
rope
rtie
s of
su
ch fl
uids
dep
endo
nly
on th
e m
agni
tude
of t
heim
pose
d sh
ear s
tres
ses a
nd n
ot o
n th
edur
atio
n of
the
stre
sses
. If
the
visc
osity
dec
reas
es w
ith
incr
ease
in
the
rate
of
shea
r, t
he f
luid
is
know
n as
a
pseu
dopl
astic
flui
d. T
his b
ehav
iour
,is g
ener
ally
rest
rict
ed to
a c
erta
in ra
nge
of s
hear
rate
s. A
t a
very
low
or h
igh
shea
r rat
e, fl
uid,
may
be N
ewto
nian
. If
the
visc
osity
inke
ases
wit
h in
crea
se in
rate
of s
hear
,the
flui
d is
know
n as
dil
atpn
t flu
id.
Bin
gham
-pla
stic
flui
ds e
xhib
it a
defi
nite
yie
ld s
tres
s be
low
whi
th n
o flo
w o
ccui
s (t
he
beha
viou
r is
that
of a
sol
id).
A fi
nite
forc
e mus
t be
appl
ied
to p
rodu
ce m
oven
lent
. The
line
* re
latio
nshi
p be
twee
n th
e ra
te o
f sh
ear
and
shea
r str
ess
for
Bin
gham
-pla
stic
flui
ds d
oes
not
pass
thm
ugh
the
orig
in.
Tim
e-de
pend
ent n
on-N
ewto
nian
-flu
ids,
A n
on-N
ewto
nian
flui
d is
sai
d to
be
time-
de-
pend
ent i
f th
e sh
ear
stre
ss c
hang
es w
ith th
e du
rati
on o
f sh
ear.
In
othe
r wor
ds, t
he v
isco
sity
of
suc
h flu
ids
at an
y ti
me
depe
nds
on th
e am
ount
of p
revi
ous
agita
tidn
or s
hear
ihg
of th
e fl
uid.
A
flui
d w
hose
vis
cosi
ty d
ecre
ases
wit
h ti
me
at a
giv
en s
hear
rate
is c
alle
d th
ixot
ropi
c.'If
the
visc
osity
of a
flui
d in
crea
ses
with
tim
e at
a g
iven
she
ar ra
te, W
e fl
uid
is c
alle
d rh
eope
ctic
. 1
) Vis
coel
asti
c fl
uid
s. T
hese
exh
ibit
man
y ch
arac
teri
stic
s of
sol
ids.
The
ir r
esis
tanc
e to
de
form
atio
n is
pro
port
iona
l to
the
usua
l vis
cous
eff
ect, p
lus an e
lhti
ceff
ect t
hat
is a
ac
tio
n
of ti
me.
Whe
n th
e ra
te of
str
ain
of s
uch
a fl
uid
is su
dden
Iy in
crea
sed,
ther
e is
a re
laxa
tion
tim
e du
ring
whi
ch t
he s
tres
s ch
ange
s fr
om i
ts o
rigi
dal t
o a
new
ste
ady-
stat
e va
lue.
Equ
atio
ns
deve
lope
d for
pse
udop
last
ic fl
uids
can
be
appl
ied
to th
e st
eady
-sta
te fl
ow of
vis
coel
astic
flui
ds.
Figu
re 3.2 s
how
8 the
vari
atio
n of
vis
cosi
ty w
ith s
hear
rate
for d
iffe
rent
type
s of f
luid
. Cur
ve
num
ber 1
is ty
pica
l of t
he re
spon
se o
f a
New
toni
an fl
uid.
A B
ingh
am-p
last
ic fl
uid
is c
hara
c-
teri
zed
by a
flow
cur
ve 2 w
hich
is
a st
raig
ht li
ne h
avin
g an
inte
rcep
t b o
n th
e sh
ear
stre
ss
axis
. The
stre
ss
is c
alle
d th
e yi
eld
stre
ss w
hich
mus
t be
exce
eded
for f
low
to co
mm
ence
. The
flo
w b
ehav
iour
is d
escr
ibed
by an e
quat
ion
.,-.-,
With
pse
udop
last
ic b
ehav
iour
, th
e fl
uid
disp
lays
inc
reas
ing
visc
osity
wit
h de
crea
sing
sh
ear r
ate.
Thi
s mea
ns th
at th
ere
is a
no
n-h
ear
rela
tion
ship
bet
wee
n sh
ear s
tres
s an
d sh
ear
rate
. Cur
ve n
umbe
r 3 re
pres
ents
pse
udop
last
ic b
ehav
iour
. Dila
tent
beh
evio
ur is
dep
icte
d by
cu
rve
num
ber
4.
Mos
t wax
y cr
ude
oil g
els e
xhib
it th
ixot
ropi
c or
occ
asio
nally
rheo
pect
ic b
ehav
iour
. Whe
n a
waxy c
rude
oil
is a
llow
ed to
coo
l bel
ow it
s po
ur p
oint
und
er s
tati
c co
nditi
on in
a p
ipel
ine,
the
para
ffin
s will
cry
stal
lize
caus
ing
the
enti
re m
ass o
f cru
de to
gel
. To
init
iate
flow
aga
in, a
fini
te
pres
sure
is re
quir
ed. F
or w
axy
crud
es, y
ield
str
ess
is a
n in
vers
e fu
nctio
n of
tem
pera
ture
and
in
crea
ses w
ith
decr
easi
ng te
mpe
ratu
re. W
ith th
e cr
ude o
il th
at is
belo
w it
s pou
r poi
nt, t
he w
ax
crys
tal s
truc
ture
s in
the
oil s
tart
to b
reak
dow
n as
flow
beg
ins.
Thi
s br
eakd
own
depe
nds
both
on
the
tim
e an
d ra
te of
she
ar.
Sta
rt u
p pr
essu
re d
epen
ds to
a l
arge
ext
ent o
n w
heth
er t
he o
il is
coo
led
unde
r st
atic
or
dyna
mic
con
ditio
n. F
or in
stan
ce, t
he a
dditi
onal
res
tart
pre
ssur
e w
ill b
e su
bsta
ntia
lly
high
er
I - W
RASP
ORT
ATIO
N OF W
AXY
CR
UM
,OIL
S
35
/2
Shea
r rat
e -
fig
. 3.2
Typ
ical
non
-~ew
tioni
onflu
ids.
for
a st
atic
ally
coo
led
pipe
line
(the
flui
d w
as a
bove
the
pour
poi
nt w
hile
flow
ing
and
allo
wed
to
coo
l dur
ing
shut
dow
n of
the
pip
elin
e) th
an fo
r on
e th
at h
as b
een
dyna
mic
ally
cool
ed (
the
flui
d was
alre
ady
belo
w p
our p
oint
whe
n pi
pelin
e w
as s
l~ut
dow
n), i.e
. the
cool
ing
occu
rred
due
-- to th
e flo
w o
f the
cru
de in
the
pipe
line.
3.4.
FLO
W P
RO
PE
RTI
ES
OF
WA
XY C
RU
DE
OIL
S
The
vis
cosi
ty of
cru
de o
il is p
erha
ps it
. mos
t im
port
ant p
hysi
cal p
rope
rty.
For
mos
t cru
des,
at
suff
icie
ntly
high
tem
pera
ture
, the
visc
osity
at a
give
n te
mpe
rahu
e is
cons
tant
and
the
crud
e,
alth
ough
chem
ical
ly ve
rym
mpl
?~, is
a si
mpl
e Ne
v
is re
duce
d,
how
ever
, the
flow
pro
pert
ies
of a
cru
de o
il ca
n re
adil
y ch
ange
ve
ry c
ompl
ex fl
ow b
eh
aw
due to th
e cr
ysta
lliza
tion
of
of a
spha
lten
es. T
he w
axes
bas
ical
ly c
onsi
st o
f fo
rm an
inte
rloc
king
str
uctu
re o
f pl
ates
, ne
edle
or
mal
form
ed ~
sta
ls. The
se c
ryst
als
Can
entr
ap th
e oi
l int
o a
gel-
like
stru
ehue
that
is c
apab
le o
f for
min
g th
ick
depo
sits
in p
ipes
and
Page 25
Cor
rela
tion
of t
he m
odel
pip
elin
e te
st re
sult
s fo
r act
ual p
ipel
ine
de
sip
ie tl
orm
ally
bas
ed
on th
e pr
evio
us e
xper
ienc
e. S
ome o
f the
se c
orre
latio
ns a
re d
evel
oped
by th
e de
sign
ers
by p
ilot
plan
t tes
ts si
mul
atin
g th
e fi
eld
cond
ition
s in
a te
st lo
op.
A g
ener
al e
quat
ion
for c
alcu
latin
g re
star
t re
q~
rem
eh
fo
r a c
oole
d li
ne is
YLC
p=
- A
... (
3.6)
w
here
P i
s th
e pr
essu
re r
equi
red,
Y i
s th
e yi
eld
stre
ss o
f ge
lled
crud
e (th
itr v
alue
mus
t be
de
term
ined
in
labo
rato
ry te
sts
and
is d
iffe
rent
for
sta
tic
and
dyna
mic
coo
ling)
, L is
the
line
le
ngth
, C is
the
circ
umfe
renc
e of i
nsid
e pi
pe w
all a
nd A
is th
e cr
oss
sect
iona
l are
a of
pip
e.
3.5.
3 F
low
at R
esta
rt
kc A
t the
tim
e of
res
tart
of t
he p
ipel
ine
beca
use
of v
ery
high
vis
cosi
ty, t
he fl
ow ra
te is
ejrp
ecte
d to
be
low
. Thi
s, h
owev
er, d
epen
ds o
n av
aila
ble
shea
r str
ess a
s com
pare
d to
thej
riel
d st
ress
. In
any
case
, the
min
imum
flo
w c
ondi
tiori
s of
the
pum
ps h
ave
to b
e in
vest
igat
ed.
If a
pum
p is
op
erat
ed a
t a v
ery
low
flow
rate
, add
itio
nal w
ear d
ue to
unb
alan
ced
flow
is ex
pect
ed. F
urth
er,
due t
o th
e po
or e
ffic
ienc
y, th
e oi
l will
be h
eate
d an
d, a
fter
a sh
ort w
hile
, the
allo
wab
le m
axim
um
tem
pera
ture
will
be
exce
eded
. Thi
s li
mit
s th
e al
low
able
tim
e fo
r the
ope
ratio
n of
the
pum
ps
with
low
flow
. If
th
e re
star
t flo
w r
ates
do
not
mee
t th
e pu
mp
requ
irem
ents
, gp
ecia
l pu
mps
wit
h ap
- pr
opri
ate
char
acte
rist
ics h
igh
hea
d, lo
w fl
ow) h
ave
to b
e us
ed fo
r res
tart
of t
he p
ipel
ine.
3.5.
4.E
ffec
tive
Pip
elin
e V
isco
sity
Fo
r det
erm
inin
g pr
essu
re g
radi
ents
in th
e pi
pelin
e, e
ffec
tive p
umpi
ng v
isco
sitie
s ha
ve to
be
det
erm
ined
. Usi
ng th
ese
visc
ositi
es, t
he c
onve
ntio
nal f
orm
ulae
can
be
used
for c
alcu
latio
n of
pre
ssur
e dm
p.
The
effe
ctiv
e pip
elin
e vi
scos
ity fo
r cal
cula
ting
fric
tiona
l pre
ssur
e dr
op a
t var
ious
flow
rate
s an
d te
mpe
ratu
res
can
be p
redi
cted
by
rota
tion
al v
isco
met
er te
sts.
Due
to w
ax c
ryst
alli
zati
on
at lo
w te
mpe
ratu
re, t
he c
onve
ntio
nal c
apill
ary
tube
vis
com
eter
s can
not b
e us
ed. M
oreo
ver,
for
non-
New
toni
an fl
uids
vis
cosi
ty is
dep
ende
nt o
n sh
ear r
ate.
For
this
ser
vice
as
also
for
othe
r sl
un
y se
rvic
es, r
otat
iona
l vis
com
eter
s ar
e us
ed. T
he s
ampl
e is
take
n in
a d
oubl
e w
de
d c
up
(a re
frig
eran
t flo
wid
in b
etw
een
the
two
wal
ls).
The
out
er c
ylin
der i
s ro
tate
d by
a v
aria
ble
spee
d m
otor
. The
&er
cy
linde
r is s
uspe
nded
from
a to
rsio
n w
ire
cons
istin
g of
a s
tain
less
stee
l tu
be, t
he
defl
ectio
n be
ing
mea
sure
d by
a b
alan
ced
poin
ter.
The
rpm
of
the
oute
r cy
linde
r m
ultip
lied
by t
he i
nstr
umen
t co
nsta
nt g
ives
the
she
ar r
ate.
The
def
lect
ion
read
ing
of t
he
poin
ter m
ultip
lied
by a
noth
er in
stru
men
t con
stan
t giv
es sh
ear s
tres
s. T
he ra
tio
of s
hear
str
ess
to s
hear
rat
e gi
ves
the
visc
osity
of t
he fl
uid.
W
hen
the
oil i
s at
such
a te
mpe
ratu
re th
at fl
ow is
non
-New
toni
an, t
he R
eyno
lds n
umbe
r is
a f
unct
ion
of v
isco
sity
whi
ch it
self
is
a fu
nctio
n of
the
eff
ectiv
e rat
e,of
she
ar. T
here
fore
, an
inte
rmed
iate
cal
cula
tion
is re
quir
ed to
arr
ive a
t the
app
ropr
iate
pip
elin
e vis
cosi
ty fo
r cal
cula
t-
ing
pres
sure
dro
ps.
Vis
cosi
ty of
the
oil
to b
e pi
pelin
ed is
det
erm
ined
at v
ario
us te
mpe
ratu
re a
nd ra
te o
f she
ar
by r
otat
iona
l vi
scom
eter
s. T
hese
are
use
d to
plo
t-vi
scos
ity v
ersu
s te
mpe
ratu
re c
urve
s fo
r va
riou
s rat
e of
she
ar. T
his
plot
can
be
used
to d
eter
min
e th
e te
mpe
ratu
re be
low
whi
ch th
e oi
l will b
ehav
e as
non
-New
toni
an fl
uid.
It i
s req
uire
d to
find
the
effe
ctiv
e vis
cros
ities
of t
he o
il fo
r pu
mpi
ng a
t'dif
fere
nt f
low
rat
es a
t var
ious
tem
pera
ture
s.
The
fis
t ste
p is
to u
se th
e pl
ot o
f vis
cosi
ty v
ersu
s te
mpe
ratu
re-a
nd p
lot c
urve
s of
vis
cosi
ty
vers
us ra
te o
f she
ar fo
r dif
fere
nt te
mpe
ratu
res.
TRAS
PORT
ATIO
N O
F WAX
Y CR
UDE
OIL
S
The
.sec
ond
step
is t
o pl
ot c
urve
s of
vis
cosi
ty v
ersu
s ra
te o
f sh
ear
for
diff
eren
t pip
elin
e th
roug
hput
as f
ollo
ws:
Fo
r a
give
n flo
w r
ate,
an
equi
vale
nt s
hear
rat
e is
det
erm
ined
by
Eq.
3.3
. Ass
umin
$ th
e va
lue
for v
isco
sity
, the
Rey
nold
s nu
mbe
r is
cal
cula
ted.
If t
he fl
ow is
in tu
rbul
ent r
egio
n, th
e co
rrec
tion
fact
or f
or r
ate
of s
hear
is re
ad f
rom
the
plot
of t
he c
orre
ctio
n fa
ctor
for s
hear
rate
ve
rsus
Rey
nold
s num
ber.
Usi
ng th
is fa
ctor
the
effe
ctiv
e rat
e of
she
ar is
obt
aine
d. B
y re
peat
ing
this
for d
iffe
rent
val
ues
of v
isco
sity
, a c
urve
of v
isco
sity
ver
sus e
ffec
tive r
ate
of s
hear
for a
flow
ra
te c
an b
e su
peri
mpo
sed
on th
e pl
ot o
f vis
cosi
ty v
ersu
s rat
e of
she
ar fo
r var
ious
tem
pera
ture
. T
he in
ters
ectio
n of
the
cons
tant
thro
ughp
ut c
urve
s with
the c
onst
ant t
empe
ratu
recu
rves
$ves
th
e ap
prop
riat
e vi
scos
ities
to
be u
sed
for
thes
e co
nditi
ons.
An
eff
ectiv
e vi
scos
ity v
ersu
s te
mpe
ratu
re c
urve
can
be
plot
ted
for
the
vari
ous
Chr
ough
puts
. As
men
tione
d ea
rlie
r, u
sing
th
ese
valu
es o
f eff
ectiv
e vis
cosi
ty, p
ress
ure
drop
s in
the
vari
ous s
ectio
ns of
the
pipe
line
can
be
calc
ulat
ed.
3.6
ME
THO
DS
FO
R P
IPE
LIN
E T
RA
NS
PO
RTA
TIO
N O
F W
AXY
CR
UD
E O
ILS
O
ne o
f the
follo
win
g m
etho
ds fo
r pip
elin
ing
wax
y cr
ude
oils
may
be
cons
ider
ed:
(a)
Sele
ct p
umps
to al
low
a p
aral
leY
seri
es ar
rang
emen
t, w
hich
coul
d tra
nspo
rt a
t slo
wer
ra
teg
and
high
er p
ress
ures
whe
n re
quir
ed. T
he p
ipin
g co
uld
be m
anif
old
so t
hat
para
llel
arr
ange
men
t wou
ld b
e ac
com
mod
ated
by r
epos
ition
ing
of v
alve
s to
hand
le
high
er fl
ow r
ates
. (b
) U
se o
f sep
arat
e lo
w fl
ow, h
igh
head
pum
ps fo
r res
tart
ing.
S
ide
trap
s at
freq
uent
inte
rval
? to
allo
w s
hort
s6&
ons
to b
e st
arte
d se
para
tely
. R
ever
se p
umpi
ng to
cre
ate
back
and
fort
h pu
mpi
ng se
quen
ce w
hich
pro
hibi
ts s
tati
c co
ol d
own.
U
se o
f pou
r poi
nt d
epre
ssan
ts/f
low
impr
over
s.
Add
ing
hydr
ocar
bon
dilu
ent s
uch
as a
less
wax
y cr
ude
or li
ght d
istil
late
. Iq
ject
ion
of w
ater
to fo
rm a
laye
r bet
wee
n pi
pe w
all a
nd c
rude
. M
ixin
g w
ater
wit
h cr
ude
to fo
rm a
n em
ulsi
on.
Dis
plac
emen
t with
wat
er o
r lig
ht h
ydro
carb
on li
quid
in ca
se of
shu
tdow
n of
pip
elin
e.
Sep
arat
ion
at h
ighe
r tha
n no
rmal
pre
ssur
e to
allo
w a
s muc
h ga
s and
ligh
t hyd
roca
r-
bons
as p
ossi
ble t
o re
mai
n in
the
crud
e.
Con
ditio
ning
the
crud
e be
fore
pip
elin
ing
to c
hang
e th
e w
ax c
ryst
al s
truc
ture
and
re
duce
pou
r poi
nt a
nd v
isco
sity
. F
urth
er s
ub-d
ivis
ion
of p
ipel
ine
into
sm
alle
r se
gmen
t or
redu
cing
bat
ch l
engt
h of
w
axy
md
e to
incr
ease
max
imum
she
ar s
tres
s av
aila
ble.
C
ombi
natio
n of
the
abo
ve m
etho
ds.
Pipe
linin
g th
e cr
ude
as an
oil i
n w
ater
(O
m) e
mul
sion
redu
ces t
he fl
ow p
rope
rtie
s to
nea
rly
the
visc
osity
of th
e co
ntin
uous
wat
er p
hase
. An
ON
emul
sion
pip
elin
e han
dlin
g 40
000
barr
els
of o
il pe
r da
y (2
65 m
3 h-
l) o
f 70
vol.%
crud
e oi
l has
bee
n op
erat
ing
in K
alim
anta
n (B
orne
o) in
In
done
sia
sinc
e 19
62. B
lend
ing
wit
h a
less
wax
y cr
ude
oil
or d
isti
llat
e im
prov
es th
e flo
w
prop
erti
es b
y al
teri
ng t
he w
ax s
olub
ility
rel
atio
nshi
ps.
Bot
h of
the
se m
etho
ds h
ave
the
disa
dvan
tage
of r
educ
ing
the
crud
e oi
l car
ryin
g ca
paci
ty of
the
pip
elin
e. N
ote
that
sepa
rati
on
at th
e w
ell h
ead
to in
clud
e m
ore
cond
ensa
te in
the
crud
epjl
(if
avai
labl
e) h
as th
e sa
me
effe
ct
I as d
ilutio
n. T
here
is o
ne in
tere
stin
g ca
se o
f a s
hear
and
te~
per
atu
re trea
tmen
t bei
ng u
sed to
I fa
vour
ably
alt
er th
e flo
w p
rope
rtie
s of
wax
y cr
ude
oils
in (A
ssam
(In
dia)
. Mor
e re
cent
ly, p
our
i
Page 26
40 PETR
OLEU
M R
EFIN
ING
TECH
NO
LOG
Y
point depressantdflow im
provers have been developed that, in small concentration, affect the
crystal growth, and as a result im
prove the flow properties.
Of the various m
ethods developed, the use of pour point depressantdtlow im
provers is found to be m
ore attractive. The m
ain attraction of this method is its relative cheapnees and
variability of dosage with respect to the tem
perature and desired viscosity requirements.
3.6.1 Use of P
ou
r Po
int D
epressantslFlow
Imp
rov
ers (
The injection of pour point depressantfflow
improver additives appears to hold the greatest
promise of achieving the desired overall objectives of operational safety and operating
economy. N
ow im
provers should have the capacity to reduce the pour point, viscosity and yield stress under dynam
ic conditions; and restart the pum
ping after a shutdown w
ith the available shew
stress. C
hemically pour point depressantshlow
improvers are ashless polym
eric additives which
when added into the crude oil at 300-600 ppm
level reduce the pour point and viswsity of the
crude oil. Polymeric m
aterials.widely used as pour point depressantdflow
improvers are (a)
alkyl acrylate polymers and cdpolym
ers, (b) ole
h alkyl m
aleate copolymers, (c) vinyl ester
polymers and copolym
ers, and (dl alkylated polystyrene. Norm
ally, the average molecular
weight of the com
mercial available pour point depressants for crude oils is betw
een 2000 to 20000.
Various flow
improvers developed at R
RL
, Jorhat (India) are SWA
T-104, SW
AT
-106, FIR1 and FIR
I-B. T
hese are polymerdcopolym
ers, easily soluble in crude oil around 4M5O
C and
non-corrosive. They are used in pipelining crudes of B
ombay H
igh and Asssm
(India).
3.6.2 Mechanism
of Flo
w Im
pro
vem
ent
When a w
axy crude oil is cooled below its cloud point, the w
ax crystals form and begin to
agglomerate and w
ith further temperature reduction crystal agglom
eration reaches a point at w
hich a gel structure is formed below
the pour point due to interlocking of the growidg crystals
and dependent on constituents like resins, asphaltenes, asphalts, paraffin and microcrystal-
line waxes, etc., their m
olecular weight, structure and quantity and also on the rate of cooling
and degree of agitation during cooling. When the additives or flow
improvers are added, they
alter the wax crystal size and shape in som
e manner and prevent the tendency to interlock.
l'he'flow
improvers or pour point depressants act by retarding the grow
th of the wax crystals
in the XY crystallographic plane, thereby producing sm
aller crystals of higher volume/surface
ratio. It appears that the flow im
provers cocrystallize with the grow
ing wax crystal, leading
to the formation of a fault in the otherw
ise compact regular w
ax crystal and resulting in dim
inished gel strength, so that by coating on to a grow
ing wax crystal the flow
improvers
reduce the tendency of wax crystals to interlock.
3.6.3 Po
int of A
dditive Injectio
n
As a general rule, the additives should be injected into the crude above or around its cloud point and also at a tem
perature of some 20°C
above the pour point of the additive. The additive
pour point could be depressed considerably by cutting (diluting) the basic component w
ith kerosine, or arom
atic solvents. The preferred location of iqjection should be at a point w
here N
o heating of the oil is required (utilize the heat of formation)
Subsequent external application of heat can be avoided or minim
ised. T
he maxim
um benefit can be derived in the system
downstream
.
TRA
SP
OR
TATIO
N'O
F WA
XY CR
UD
E OILS
41
All of the above considerations point to additive injection into the crude stream
at well
head.
3.6.4 Po
ur P
oin
t Reduction b
y A
dditives P
our point measurem
ents on crude oils have been used to detect low tem
perature handling problem
s. How
ever, as mentioned already, they do not necessarily predict the field perfor-
mance. Pour point can at best be used for prelim
inary screening of various additives for their potency w
ith a particular crude oil. T
hese studies were carried out in the Salaya-K
oyali-Mathura crude pipeline by O
il &
Natural G
as Com
mission, India. T
he line was originally designed for transportation of low
pour point M
iddle East crude oils (L
ight Arabian and N
orth Rum
aila). With the discavery of
the B
ombay H
igh crude oil, it was decided to process this crude too at these refineries. E
fforts w
ere made to find a suitable solution to the problem
of pipeline transportation of this high pour point (30°C
) Bom
bay High crude oil to these refm
eries during winter. It w
as reported by m
odel pipeline tests that the line will not be able to take a restart after cooling statically to
low w
inter temperature of around 16O
C.
A num
ber of flow im
prover additives were tested for their effectiveness on B
ombay H
igh crude. b
orn
preliminary tests, Shell-sw
im-5T
and Esso Paradyne-80 w
ere reported to be the m
ost effective additives in lowering pour point. F
urther tests by rotational viscometers
indicated that, for similar level of dosage, both effective viscosity and yield stress w
ere reported to be low
er in case of Shell-swim
-ST as com
pared to Esso Paradyne-80. It w
as therefore concluded th
at shell-swim
-5T is superior to E
sso Paradyne-80. Subsequently, Shell-swim
-5T
was used for transportation of the B
ombay H
igh crude to Uran term
inal through the subm
arine pipeline from the production platform
. Extensive studies w
ere subsequently done at IIP
, Dehradun and G
ujarat Refinery to determ
ine the optimum
doping conditions for Shell-sw
im-5T
in Bom
bay High crude. k
om
these.studies the optimum
doping levels were
reported to be 250-300ppm of the Shell-sw
im-5T
. The effect of doping temperature on the pour
point was reported to be negligible.
3.6.5 Effect of F
low Im
pro
vers on Y
ield Stress a
nd
Viscosity
Significant reduction in yield stress and effective viscosities can be achieved by doping w
axy crude oils with flow
improvers. T
he following results w
ere reported for the effect of Shell-sw
im-5T
(flow im
prover) on Bom
bay High crude oil.
I
These results show
significant reduction in yield stress with 250 ppm
doping. Further
improvem
ent with higher doping levels is, how
ever, marginal. In fact in som
e cases the trend I 1
was reported to be reversed w
ith higher doping levels, as shown below
by the following m
odel pipeline tests conducted by O
NG
C.
Viscosity @
160C
CP
'45.0 45.0 42.4 41.0
Doping level
PPm
Nil
250 300
400
Yield stress @ 160 C
dyneslcm2
330.0 62.5 62.5 45.8
Page 27
42
PETR
OLE
UM R
WN
INQ
TEC
HNO
LOG
Y . -
I 1u
.I.
I 58
9 at
45
dyne
dcm
2 10
00
27.5
96
6 at
45 d
ynes
/cm
2 H
ence
, opt
imum
dop
ing
leve
ls b
y ex
tens
ive l
abor
ator
y st
udie
s mus
t be
dete
rmin
ed b
efor
e st
arti
ng a
dditi
ve in
ject
ion.
1
pin
t DeP
res-
sa
nt in
Bom
bay
Hig
h CNde
Nil
I
400
750
3.6.6
Inco
rpor
atio
n of
Low
Po
ur
Po
int C
rude
s in
Waxy C
rud
es
Aa m
entio
ned
earl
ier,
this
can
be
one
of t
he p
roba
ble
solu
tions
to p
ipel
ine
tran
spor
tati
on
prob
lem
s of w
ary
crud
es p
rovi
ded
the
low
pour
pin
t cm
de is
eas
ily a
vaila
ble f
or b
lend
ing
and
. no
pro
blem
s ar
e ex
pect
ed to
be
enco
unte
red
in p
roce
ssin
g th
e cm
de b
lend
as
far
aa p
rodu
ct
spec
ific
atio
ns ar
e co
ncer
ned.
Onc
e ag
ain
Be
exam
ple
of S
alay
a-K
oyal
i-M
athu
ra pi
pelin
e ca
n be
cite
d he
re. T
he G
ujar
at s
pd M
athu
ra re
fine
ries
fed
by this p
ipel
ine (
Guj
arat
part
ly) are to
p
mn
n p
artl
y B
omba
y H
igh
crud
e an
d pa
rtly
low
pou
r po
int
Mid
dle
Eas
t cr
ude.
A s
mal
l pe
rcen
tage
of tbP
Mid
dle
Eas
t cm
de m
ixed
wit
h B
omba
y H
igh
cmde
will
not
res
ult io a
ny
seri
ous
proc
essi
ng p
robl
ems.
The
rep
orte
d re
sult
s of
lab
orat
oq s
tudi
es o
n bl
ends
of M
iddl
e E
ut c
rude
wit
h B
omba
y Hig
h m
de
indi
cate
that
the
inco
rpor
atio
n of B
asra
h cm
de in
dop
ed
Bom
bay
Hig
h cm
de s
how
s no
furt
her r
educ
tion
in p
our p
oint
. Ib
iq co
uld
be d
ue to
redu
ctio
n in p
erce
ntag
e of
n-p
arfi
ns
whe
n B
asra
h cm
de is
mix
ed, t
he e
ffec
t of p
our p
oint
dep
re~
sant
be
ing
mor
e pr
edom
inan
t on
n-pa
raff
ins
as c
ompa
red
to ia
o-pa
rafi
ins.
How
ever
, a s
igni
fica
nt
redu
ctio
n in
the
yiel
d st
ress
of t
he b
lend
is re
port
ed, a
s sho
wn
belo
w.
due to co
ngea
ling a
t 18O
C.
21.2
43
5 at
45
dyne
s/cm
2 o
n n
I
100%
Bom
hnv Hioh
Yie
ld s
tres
s at
1 kc, dy
tws~
cm~
Vis
cosi
ty at
16°
C a
t flo
w d
eueI
op.
men
t, cP
The
dop
ing
tem
pera
ture
is
quite
impo
rtan
t as
far
as y
ield
str
esse
s ar
e co
ncer
ned.
The
bl
ends
of B
asra
h w
ith
Bom
bay
Hig
h cr
ude
dope
d at
50°
C is
repo
rted
to g
ive
bett
er r
esul
ts a
s co
mpa
red
to t
empe
ratu
re o
f 30
°C.
Thi
s is
sh
ow
by
the
follo
win
g ex
peri
men
tal
resu
lts
repo
rted
.
Tes
t was
aba
ndon
ed a
s oil
coul
d no
t be
trans
ferr
ed to
mod
el p
ipel
ine
- -
/ .
--I-.
100%
Bom
bay
Hig
h w
ith 2
50 pp
m o
f pou
r poi
nt d
epre
ssan
t 90
% B
omba
y H
igh
+ 10
% B
asra
h w
ith 2
50 p
pm p
our p
oint
de
~res
aant
.
Cru
de bl
end
.
330.
0
62.5
J
5.0
Yield
stre
ss a
t 16"
C, d
ynes
/cm
2 1
90%
Bom
bay
Hig
h + 1
0% B
asra
h w
ith 2
50 pp
m p
our
poin
t de
pres
sant
TRA
SPO
RTA
TIO
N O
F W
AXY
CRUD
E O
ILS
90%
Bom
bay
Hig
h + 1
0% B
asra
1 .
- po
int
depr
essa
nt
3.6.
7 C
rud
e O
il C
ondi
tion
ing
This p
roce
ss i
s de
velo
ped
by O
il In
dia
Lim
ited.
The
cru
de o
il co
nditi
onin
g is
a u
niqu
e pr
oces
s in
whi
ch th
e cm
de o
il is
firs
t hea
ted
to m
elt a
nd d
isso
lve t
he w
ax in
it. T
here
afte
r, o
n dy
nam
ic co
olin
g an
d w
brkb
g tb
ug
h th
e p
mp
the
crud
e oi
l is
subj
ecte
d to
sta
tic
cool
ing
at
a pr
edet
erm
hed
rate
. T
he r
esul
t is
the
con
ditio
ned
crud
e oi
l w
hich
has
muc
h im
prov
ed
phys
ical
pro
pert
ies
than
the
virg
in c
rude
oil.
The
con
ditio
ned
crud
e oi
l rem
ains
flui
d at
muc
h lo
wer
tem
pera
ture
and
pos
sess
es s
atis
fact
my
phys
ical
pro
pert
ies
so fa
r as
tran
spor
tati
on o
f cr
ude
oil t
hrou
gh t
he p
ipel
ine
to re
fine
ries
dur
ing
the
win
ter m
onU
s is
con
cern
ed. This
has
been
em
ploy
ed fo
r tra
nspo
rtin
g wary c
rude
oils
from
Ass
am (I
ndia
).
I, t
he a
ctua
l pro
cess
the
cru
de o
il is
hea
ted
to a
tem
pera
ture
of
lCO
°C i
n tu
be h
eate
r.
Bef
ore
ente
ring
into
the
tube
hea
ter,
the
cru
de o
il pa
sses
thr
ough
hea
t ex
chan
ger
and
exch
ange
s he
at w
ith
the
outg
oing
oil
from
the
hea
ter,
bri
ngin
g do
wn
its
tem
pera
ture
to
65O
C by
dyn
amic
cool
ing.
The
crud
e oi
l at 6
5OC
is s
tare
d in
a ta
nk fr
om w
here
it p
asse
s th
mug
h a
pum
p to
sta
tic
cool
ing
vess
els,
com
mon
ly c
alle
d co
nditi
onin
g ve
ssel
s, T
hese
ves
sels
are
es
sent
ially
she
U a
ndtu
be h
eat e
xcha
nger
d'in
whi
ch c
rude
oil
is ta
ken
in th
e sh
ell s
ide
and
cool
ing
wat
er is
pas
sed
thro
ugh
tube
s. T
he c
on&
onin
g ve
ssel
s fo
llow
a b
atch
tim
e cy
cle
of
208
min
utes
to a
chie
ve c
oalin
g of
cru
de o
il &
om 6
5OC to l8
.S0C
(th
is in
clud
es h
~&
g
tim
e of
cm
de oi
l and
its
empt
ying
out
tim
e al
so).
The
cool
irig o
f the
crud
e oil
in th
e co
ndit
iohg
vess
els
is e
ffec
ted
by c
ircu
latin
g w
atet
s, n
amel
y in
tem
edia
te a
nd re
lrig
erat
ed w
ater
s. I
nter
med
iate
w
ater
is
mai
ntai
ned
in a
clo
sed
circ
uit t
hrou
gh a
pum
p an
d he
at e
xcha
nger
in w
hich
coo
ling
med
ium
ia tbs
cool
ing
wat
er. T
he re
frig
erat
ed w
atu
is a
lso
mai
ntai
ned
in a
clo
sed
circ
uit
tho
ug
h a
pum
p an
d ab
sorp
tion
refr
iger
atio
n m
achi
ne. T
he c
ir
~t
w
ater
whi
le f
loin
g p
aat
evap
orat
or c
ham
ber o
f abs
orpt
ion
refi
gera
tion
mac
hioe
th
ou
gh
tube
bun
dles
get
s ch
illed
. h
the
tem
pera
ture
of c
rude
oil
is br
ough
t dow
n to
the
desi
red
leve
l of 1
8 - 2
g°C
, the
cmde
oi
l fro
m c
ondi
tioni
ng ve
ssel
s is
empt
ied
out a
utom
atic
ally
into c
ondi
tione
d oi
l sto
rage
tank
s.
The co
nditi
oned
oil
from
thes
e ta
nks
flow
s pi
pelin
e pum
ps th
roug
h a
boos
ter p
ump
and
this
5.0
25.0
5.0
25.0
po
int d
epre
ssan
t
E
50°C
Dop
ing
5.0
.---
- --
--
com
plet
es th
e pr
oces
s of
con
ditio
ning
.
90%
Bom
bay
Hig
h + 1
0% B
asra
h w
ith
300
ppm
pou
r I
5.0
I 25
.0
poin
t dep
ress
ant
I 90
% B
omba
y H
igh
+ 10
% B
asra
t po
int d
epre
ssan
t I
I E
3O0C
) Dop
ing
25.0
I 50
°CD
opin
g I
1
K. W
. won
, The
hody
nam
ics
for s
olid
solu
tion
- liqui
d - v
apor
equi
libri
a : W
ax p
hase
fo
rmat
ion from h
eavy
hyd
roca
rbon
mixtures, F
luid
Pha
se E
quili
bria
, Vol
. 30,
pp.
26
5-27
9 (19
86).
2. J.H. H
anse
n, A
. F
rede
nslu
nd,
K.S
.Ped
erse
n an
d H
.P.
Ron
ning
sen,
A t
her-
m
odvn
amic
mod
el fo
r pre
dict
ing
wax
form
atio
n in
cru
de o
ils, A
IChE
J, V
ol. 3
4, NO.
) 30
°C)D
opin
g
--- -
-"
12, p
p. 1
937-
1942
(1.9
88).
3.
S. ~angul~,Ftheological~arameteraand
so
lu
ti
o~
em
s
of w
axy
cmde
oil,
UR
Jh v
ol. 2
6, N
o. 2
, pp.
33-
34 (1
989)
. 4
P. D
atta
, H
. Dub
ey a
nd K
.L.P
ate1
, Pip
elin
e tr
ansp
orta
tion
of w
axy
crud
e oi
l fro
m
the
oil f
ield
s, C
hem
ical
Eng
inee
ring
Wor
ld, V
ol. X
W, p
p. 4
3-45
(199
0).,
5 R
. Pra
sad.
Waxy
crud
e oi
ls, I
n PI
PIN
G D
ESI
GN
HA
ND
BO
OK
J.J
. Mck
etta
, Ed.
. 1
-. -.
Mar
cel ~
ikk
er,i
l99
2).
6.
S
. Nai
k, C
.K P
atha
k, a
nd V
.P. S
harm
a, E
ffec
te of
ou
r pin
t de
p"es
sant
8 on
WaX
Y In
dian
cru
de o
il, IE
(1) J
., V
ol. 6
9, P
art
CH
2, p
p 60
-63,
(198
9).
Page 28
4 PETR
OLEU
M R
EflN
lNG
TECH
NO
LOG
Y
7. M
. N. S
unil Kum
ar, Review
s on polymeric and copolym
eric pour point depressants for w
axy crude oil, The Institute O
f Petroleum
, 0ct.-Dec., pp. 47-71 (1989).
8. B
. Sm
ith, Steps for finding crude properties, T
he Oil and G
as J., Vol. 77, N
o. 23, pp. 150-152 (1979).
9. L
. T. W
ardhaugh and D.V
. Boger, M
easurement of the unique flow
properties of w
axy crude oils, Chem
. Engg. R
es. Des., V
ol. 65, pp. 74-83 (1987). 10.
B. S
mith, H
eat transfer explored in pipelining high-pour-point crude oil, The O
il and G
as J., Vol. 77, N
O. 25, pp.110-lll(1979).
11. B
. Sm
ith, Restart of heavy crude lines probed, T
he Oil and G
as J., Vo1.77, N
o. 27, pp. 105-106 (1979).
12. B
. Sm
ith, Design of heavy crude facilities explored, T
he Oil and G
as J., Vol. 77, N
o. 29, pp. 69-70 (1979).
13. B
.M.A
. Rao, S.P. M
ahajan and K.C
.Khilar, A
model on the breakdow
n of crude oil gel, T
he Can. J. O
f Chem
. Engg., V
ol. 63, No. 1, pp. 170-172 (1985).
14. T
.Visw
anathan and KC
. Khilar, H
ydrodynamically induced gel breakdow
n in pipes, T
he Can. J. O
f Chem
. Engg., V
ol. 67, No. 3, pp. 353-360 (1989).
15. 3. S
estak, M.E. C
harles, M.G
. Caw
kwell and M
. Houska, S
tart-up of gelled crude oil pipelines, Journal O
f Pipelines, Vol. 6, N
o.1, pp. 15-24 (1987). 16.
M.G
. Caw
kwell and M
.E.C
harles, An im
proved model for start-up of pipelines
containing gelled crude oil, Journal of Pipelines, Vol. 7, N
O. 1, pp. 41-52, (1987).
17. A
. Majeed, B
.Bringeda1 and S
. Overa, M
odel calculates wax deposition for N
. Sea
oils, The O
il Gas J, V
ol. 88, No. 25, pp. 63-69 (June 18,1990).
18. R
.A. V
ora and D.P. B
harambe, Polym
eric flow im
provers, Indian J. Techol., V
ol. 31, N
o. 9, pp. 633-635 (1993). 19.
L.T
. Wardhaugh and D
.V. B
oger, Flow characteristics of w
axy crude oils : Applica-
tion to pipeline design, AIC
hE J., V
ol. 37, No. 6, p. 871 (1991).
20. J.A
. Svendsun, M
athematical m
odelling of wax deposition in oil pipeline system
s, A
IChE
J., Vol. 39, N
O. 8, pp. 1377-1388 (1993).
21. T
.F. Al-Fariss, E
ffect of wax on oil behaviour, Indian C
hemical E
ngineer, Vol. .=I,
NO
. 2, pp. 8-12 (1990). 22.
G.P.van E
ngelen, C.L
. Kaul, B. V
os and H.P. A
ranha, Study of flow
improvers for
transportation of Bom
bay High crude oil through subm
arine pipelines, Journal of P
et. Tech., V
ol. 33, No. 12, pp. 2539-2544 (1981).
23. T
.R. S
ifferman, Flow
properties of difficult-to-handle waxycrude oils, Journal of P
et. T
ech., Vol. 31, N
o. 8, pp. 1042-1050 (1979). 24.
C.A
. Irani and J. Zajac, H
andling of high pour point west A
frican crude oils, Journal of P
et. Tech., V
ol. 34, No. 2, pp. 289-298 (1982).
25. R
.N. T
uttle, High-pour-point and asphaltic crude oils and condensates, Journal of
Pet. T
ech., Vol. 35, N
o. 7, pp. 1192-1196 (1983). 26.
E.D
. Burger, T.K
. Perkins and J.H
. Striegler, S
tudies on wax deposition in th
eh
an
s A
laska Pipeline, Journal of Pet. T
ech., Vol. 33, N
o. 6, pp. 1075-1086 (1981). 27.
C. C
hang, D.V
. Boger and Q
.D. N
guyen, TLE yielding of waxy crude oils, Ind. E
ng* C
hem. R
es., Vol. 37, N
o. 4, pp. 1551-1559 (1992).
QU
ALIT
Y C
ON
TR
OL O
F
PE
TR
OLE
UM
PR
OD
UC
TS
~O
DU
CT
IO
N
Qunlity control of petrolcum
products 1s ;I n(bc(bssilq. il't hc protlucls ilrt! to give sillisii~ctory
pedormance to the custom
cra. Keeping in view
11
~. ascli~
in(~
ss of m
lch prlxluct. fi)r sp(*(:ilic purpose, standnrd urganisations have tn
fLrl m
d\v)(ls ol'trsl.~ and s~
cciticdin
nc. Bur\.;iu I
*
Ind
im S
tandard @IS
), New
Delhi is onc sc~
ch or~;rnis;~
lion in lndia w
hich stantlnrdihcs procedures and issues specilations. 111stilute of P
ctroleun~(ll'). 1J.K
and Anlvrican S(aic1y
for Testing &
Materials (A
Sl"l'), U
.S.A.
;IIX thc other tw
o i~
~~
~)
or
li
~~
~t
organisiltions w
llosc' m
ethods and specifications are widely follow
ed. Apart from
BIS
sl)ccifications, I!cntral Board
Of R
evenue, New
I)elhi has certain othcr specifications tbr the purpoxc ol'cxcisc Ic!vy. Some of
the important lim
its set by them are for carbon residue, flam
e height,fli~sh [m
int. a~
~d
visajsity.
4.2 CLA
SS
IFICA
TION
OF LA
BO
RA
TOR
Y TES
TS
Most of the laboratory tests can be broadly classified into seven groups 11;lst:tl 0
11 t11('
following characteristics: V
olatility C
ombustion
e V
iscosity and con
sistency
e
Melting point
e
Oxidation
Corrosion and protection
! e
Miscellaneous tests
Volatility is the m
ajor dcterminant ofthc tendency of a hydrocarbon to produce polontially
ex~
losiv
e vapours. It is also critically important to an cm
gine's start and warm
-up. Volatility
is gssessed by the follow
ing tests: (a) D
istillation (b) V
apour pressure (c) F
lash point and fire point T
he combustion properties of petroleum
products are evaluated by the following tests:
(a) Antiknock quality-O
ctane number, Perform
ance number
(b) Ignition quality-Cetane num
ber, Aniline point, D
iesel index, Calculated cetanc index
I I (c) C
alorific value (d
) Burning quality-Sm
oke point, Char value
I
Page 29
46
PETR
OLEU
M R
EFlM
lNG
TECH
NQLQ
GY
The
det
erm
inat
ion
of v
isco
sity
and
con
sist
ency
of
petr
oleu
m p
rodu
cts is
done
by
the
follo
win
g te
sts:
(Q
) K
inem
atic
vis
cosi
ty (R
edw
ood,
Say
bolt
, Eng
ler)
(b
) Vis
cosi
ty in
dex
(c) P
enet
rati
on te
sts
The
tes
ts d
esig
ned
to a
scer
tain
the
tend
ency
of
cert
ain
petr
oleu
m p
rodu
cts
to m
elt
or
liqu
efy,
,to s
olid
ify
or to
pre
cipi
tate
wax
-lik
e m
ater
ials
are
: (a
)'k8
ezin
g P
oint
(b
) Clo
ud p
oint
and
pou
r po
int
(c) D
rop
poin
t of g
reas
e (d
) Mel
ting
and
set
ting
poi
nt o
f wax
(e
l Sof
teni
ng p
oint
of b
itum
en
Met
hods
hav
e be
en d
evis
ed f
or t
he e
valu
atio
n of
sto
rage
sta
bili
ty a
nd r
esis
tanc
e to
ox
idat
ion
for g
asol
ine
and
avia
tion
turb
ine
fuel
. The
se in
clud
e:
(a) I
nduc
tion
per
iod
of g
asol
ine
(b) T
herm
al s
tabi
lity
of J
et fu
els
(c) G
um c
onte
nt
Mos
t cru
de o
ils a
re c
orro
sive
to g
reat
er o
r les
ser e
xten
t, fr
eque
ntly
due
to th
e pr
esen
ce o
f su
lphu
r co
mpo
unds
, org
anic
aci
ds (
mai
nly
naph
then
ic a
cids
) and
trac
es o
f br
ine.
The
refo
re,
test
met
hods
hav
e be
en d
esig
ned
to e
valu
ate
the
corr
osiv
e po
teqt
iali
ties
of
the
petr
oleu
m
prod
ucts
whi
ch a
re o
btai
ned
by p
roce
ssin
g of
cru
de o
ils. T
he fo
llow
ing
met
hods
are
ava
ilab
le:
(a) T
otal
sul
phur
(b
) Aci
dity
and
alk
alin
ity
(c) C
oppe
r-st
rip
corr
osio
n te
st
(dl S
ilve
r-st
rip
corr
osio
n te
st fo
r Avi
atio
n T
urbi
ne F
uels
T
he m
isce
Jlan
eous
test
s in
clud
e:
(a) A
sh
(b) C
arbo
n re
sidu
e (c
) C
olou
r (d
) Den
sity
.and
%pe
cifi
c gra
vity
(e
l Gas
ckp
mat
ogra
phy
of p
etro
leum
gas
es a
nd li
quid
s (f
) Ref
ract
ive
inde
x of
hyd
roca
rbon
liqu
ids
(g) L
ead
in g
asol
ine
(h) W
ater
sep
arom
eter
ind
ex (m
odif
ied)
(WSI
M)
(i) D
ucti
lity
T
he d
efin
itio
n, m
etho
d an
d si
gnif
ican
ce o
f tes
ts m
enti
oned
abo
ve a
re g
iven
bel
ow.
4.3
DIS
TILL
ATI
ON
T
he l
abor
ator
y di
stil
lati
on t
est
com
pris
es a
sim
ple
proc
ess
in w
hich
100 m
l sa
mpl
e is
va
pori
sed
in a
sui
tabl
y de
sign
ed f
lask
fit
ted
wit
h a
ther
mom
eter
, an
d co
nden
sed
in a
n
ice-
cool
ed tu
be a
nd c
olle
cted
in a
mea
suri
ng c
ylin
der.
Whe
reas
an
indi
vidu
al h
ydro
carb
on
wou
ld e
xhib
it a
sin
gle
boil
ing
poin
t, co
mm
erci
al fu
el b
lend
s boi
l ove
r a ra
nge
of te
mpe
ratu
res.
C
orre
spon
ding
rea
ding
s of
vap
our
tem
pera
ture
and
con
dens
ate
reco
vere
d ar
e m
ade
at
pres
crib
ed i
nter
vals
and
th
e re
sult
s ar
e pl
otte
d in
the
form
of
dist
illa
tion
cw
e. T
he in
itia
l bo
iling
poi
nt (
IBP
) is
tak
en a
s th
e te
mpe
ratu
re o
bser
ved
at t
he f
all
of t
he
firs
t dr
op o
f co
nden
sate
, and
the
fin
al b
oilin
g po
int
(FB
P) a
s th
e m
axim
um te
mpe
ratu
re r
each
ed d
urin
g
QUA
LITY
CON
TROL
OF
PETR
OLEU
M P
RODU
CTS
the
test
. Due
to s
mal
l los
ses
of v
apou
r a
t th
e co
nnec
tions
and
open
ings
in th
e ap
para
tus
and
the
resi
due
rem
aini
ng i
n th
e fl
ask
on c
ompf
etio
n of
the
tes
t, t
he t
otal
rec
over
y do
es not
gene
rall
y ex
ceed
abo
ut 9
7 pe
rcen
t. A
max
imum
dis
till
atio
n te
mpe
ratu
re li
mit
of 3
70%
has
to
be s
et, o
ther
wis
e th
e he
avie
r hy
droc
arbo
n m
olec
ules
are
liab
le t
o su
ffer
from
cra
ckin
g in
to
ligh
ter m
olec
ules
cau
sing
the
dist
illa
tion
cha
ract
eris
tics
to ch
ange
dur
ingt
heir
mea
sure
men
t.
Thu
s fi
els h
eavi
er th
an g
as o
ils c
anno
t be
test
ed c
ompl
etel
y fo
r dis
till
atio
n be
havi
our.
T
he d
isti
llat
ion
char
acte
rist
ics
give
a b
road
ind
icat
ion
of f
uel t
ype.
Bei
ng a
mea
sure
d
vola
tili
ty,
they
det
erm
ine
the
syst
em o
f fu
el m
eter
ing
requ
ired
(w
ick
feed
, car
bura
tion
or
atom
izat
ion)
, and
are
indi
cati
ve o
f the
vap
oris
atio
n be
havi
our o
f fue
ls in
sto
rage
(vap
our l
oss
and
vapo
ur lo
ck),
and
in p
isto
n-en
gine
man
ifol
ds (u
nifo
rmit
y of d
istr
ibut
ion
to c
ylin
ders
). T
he
exte
nt o
f th
e di
stil
lati
on r
ange
for
any
giv
en f
uel i
s re
pres
enta
tive
of
the
avai
labi
lity
of
that
fu
el fr
om th
e pa
rent
cru
de o
il. F
or a
fue
l wit
h a
high
dem
and,
the
aim
of t
he s
uppl
ier w
ill b
e to
ext
end
the
dist
illa
tion
ran
ge a
s fa
r as
pra
ctic
able
. How
ever
, due
to t
he in
terr
elat
ions
hip
betw
een
prop
erti
es a
nd th
e as
soci
ated
pro
blem
s, m
inim
um a
nd m
axim
um li
mit
s, re
spec
tive
ly,
may
nee
d to
be
set f
or th
e in
itia
l and
fina
l boi
ling
poin
ts.
The
sig
nifi
canc
e of t
his t
est v
arie
s fr
om p
rodu
ct to
pro
duct
. In
case
of c
rude
oil,
the
AST
M
dist
illa
tion
dat
a gi
ve s
ome
idea
of t
he f
rwti
ons
that
cou
ld b
e co
llect
ed b
elow
300
°C. I
f it
is a
tr
ue
boil
kg p
oint
(T
.B.P
.) di
stil
lati
on, t
he T
BP
cur
ve re
veal
s a
lot o
f ch
arac
teri
stic
s th
at a
re
usef
ul fo
r th
e de
sign
of t
he re
fine
ry. T
he 10
vol.%
of d
isti
llat
ion
for m
otor
spi
rit i
s an
indi
cati
on
of t
he
ease
wit
h w
hich
th
e en
gine
can
be
star
ted.
Too
hig
h a
FB
P w
ill c
ause
cra
nkca
se o
il di
luti
on.
4.4
VA
PO
UR
PR
ES
SU
RE
V
apou
r pr
essu
re o
f a
liqu
id f
uel
may
be
defi
ned
as th
e pr
essu
re e
xert
ed b
y th
e va
pour
ab
ove
the
free
sur
face
of
the
liqu
id a
t th
e gi
ven
tem
pera
ture
. F
or v
olat
ile,
non
visc
ous
petr
oleu
m p
rodu
cts,
it i
s de
term
ined
by
Rei
d m
etho
d. T
his
is th
e pr
essu
re e
xert
ed b
y va
poll
r w
hen
it is
in e
quil
ibri
um w
ith
the
liqu
id u
nder
the
cond
ition
s of
test
. For
liqu
efie
d pe
trol
eum
ga
s, th
e pr
oced
ure
is d
iffe
rent
and
the
dete
rmin
atio
n sh
ould
be
done
at 6
5%.
The
con
diti
ons
unde
r w
hich
vap
our
pres
sure
s ar
e de
term
ined
giv
e re
sult
s w
hich
are
not
true
bec
ause
of t
he '
air w
hich
is in
vari
ably
pre
sent
in a
ppar
atus
. ne
true
vap
our p
ress
ure
is h
ighe
r tha
n th
e R
eid
vapo
ur p
ress
ure
by a
bout
5 to
9 p
erce
nt b
ut th
is re
lati
onsh
ip v
arie
s w
idel
y.
The
sta
ndar
d R
eid
appa
ratu
s co
nsis
ts o
f a
fuel
cha
mbe
r co
mec
tea
to a
n a
ir c
ham
ber
of
four
tim
es v
olum
e, a
nd f
itte
d w
ith
a pr
essu
re g
auge
. T
his
test
is
impo
rtan
t wit
h x-on,
vzan
.oort,p
zur&
&jg-
the
gdso
line
*t
yp
es
of
sto
rage
tank
s em
ploy
ed a
nd th
e st
arti
ng c
hara
cter
isti
cs o
f mot
or h
els.
Hig
h va
pour
pre
ssur
e en
tail
s lo
ss o
f th
e ~
rod
uct
in s
tora
ge a
nd t
rans
port
atio
n. I
n ca
se o
f m
otor
sp
irit
, it m
ay c
ause
vap
our
lock
in th
e ga
soli
ne e
ngin
es.
4.5
FLA
SH
PO
INT
AN
D F
IRE
PO
INT
Fla
sh p
oint
and
fir
e po
int
can
be t
aken
as
indi
rect
mea
sure
- of
th
e pr
oduc
t.
The
flas
h po
int i
s th
e lo
wes
t tem
pera
ture
at w
hich
app
lica
tion
of t
est f
lam
e ca
uses
the
vapo
ur
abov
e th
e oi
l to
igni
te. T
he f
ire
poin
t is
the
low
est t
empe
ratw
e a
t whi
ch th
e oi
l ign
ites
and
co
ntin
ues
to b
urn
for
5 se
cond
. T
he d
eter
min
atio
n of
fla
sh p
oint
of p
etro
leum
pro
duct
s co
nsis
ts o
f hea
ting
a g
iven
vol
ume
of l
iqui
d at
a s
tand
ard
rate
of t
empe
ratu
re r
ise
unti
l vap
our
is p
rodu
ced
to s
uch
a de
gree
as
to g
ive
a fl
amm
able
mix
ture
wit
h ai
r in
an en
clos
ed sp
ace
(i.e
. clo
sed
flas
h po
int t
emp
erat
ye)
or
wit
h ai
r in
an
ope
n cu
p (i
.e. t
he
high
er o
pen
flas
h po
int
tem
pera
ture
), ig
niti
on r
esu
ltin
g
Page 30
- -
I Q
UALITY CO
NTR
OL O
F PETRO
LEUM
PRO
DU
CTS
49 48
PETRO
LEUM
REFIN
ING
TE~HN
O)~~&
~
tiom the applicalion of'a sm
all flame. A
t firc point, not only will the vapour-air m
ixture'fir)8h but the liquid w
ill continue to burn. A
bcl apparatus is used for determiningthc closed cup flash point of' petroleum
products h
;tvin
~ tlash points betw
een 19°C and 49°C
. Pcnsky-Martens ap
~aratu
ais used for deteym
in- in
g the flash point of fuel oils and lubricating oh
, bitumcn other than cutback bitum
en having ;I ilaxh point :~br>vc
49OC. C
lcvcland appariltus is used for determining the flash and fire points
of pctroleun~ products cxccpt l'uucl oils and those products having an open cup flash point below
79°C.
Ylirsh p
un
t measurcs thc tcntlcncy of the fuel to form
a flamm
able mixture w
ith air under conlrollcd laboratory conditions. T
his is tho only propcrty that must be considered in assessing
the ovcrull tlamm
ability l~azartl of a m
ntcrial. It is used in shipping and safety regulations thnldcfinc flttm
mable and com
bustible n~uterials. Petroleum
products having low flash points
irrlb ~~o
tential
to fire hazards. Flash point can indicate the possible presence of highly volatile ant1 tlan~
n~ablo
materials in rclativoly nonvolatile or nonflam
mnble m
akrial.
4.6 OC
TAN
E N
UM
BE
R
This is an
important test for m
easuring the antiknock quality of the gasoline (petrol or m
otor spirit). The knocking of the m
otor fuelsis compared using blends of reference fuels. T
he standard reference fuel8 used foroctanenum
bers below 100areiso-octiineand norm
al hep
twe
which arc assigned valuerr of100 and 0, respectively, on the octane num
ber scale. The octane
number of thc fucl is defined atl the volum
e percentage ofiso-octane t2,2,4-trimethyl pentane)
in a blcnd with n-heplanc w
hich is equal to the test fuel in knockintensity under standardised and closely controllcd conditions of test in a single-cylinder, variable cbm
pression ratio enbines, know
n as CF
li cnginerr. Thus, a fuel of 87 octane num
ber has a CFR
engihe perform
ance matching that obtainable w
ith a blend of 87 volume percent iso-octane and 13
volume percent n-heptane. T
hc rating can be done by either Research m
cthod or Motor m
ethod. T
he differences in the two m
ethods are as follows:
Octane num
bcr rcquirc~ncnts of gasoline engines depend on their com
pression ratio. If the fuel m
eets the minim
um requirem
ents in respect of octane number it ensures trouble B
ee ol~cration. Apart fiom
being a nuisance, the knocking in an engine may result in loss of energy
:~n
d at tim
es may cause severe dam
age to the engine.
4.7 PE
RFO
RM
AN
CE
NU
MB
ER
This is used to estim
ate knoekihg characteristics of aviation gasolines of octane number
highcr than 100. The standard reference fuels for knock ratings above 100 octane num
ber are iso-octane and its blends w
ith tetraethyl lead (TE
L). T
he ratings of aviation gasoline above 100 octane num
ber are normally expressed as perform
ance number.
The perform
ance number scale is based on engine pow
er output. The perform
ance number
of an aviation fuel represents approximately the m
aximum
knock-free power output. T
he
onrformance num
ber shows the percentage increase in aipcrafi engine pow
er for addition of r-------
TE
L to iso-octane and is given by
Performance num
ber - 100) O
ctane number =
100 + ( 3
-
On the perform
ance number scale, 100 octane num
ber equals 100 performance num
ber. T
he ratings of aviation gasoline above 100 octane number can be done by
(a) Aviation m
ethod (lean mixture rating);
(b) Supercharge method (rich m
ixture rating); and (c) xie ended m
otor method.
In aviation m
ethod, the rating is done at 1200 rpm
by comparing the com
bustion chamber
temperature for the fuel w
ith those of the blends of known perform
ance number. T
his lean m
ixture rating gives us an idea of the availability of knock limited pow
er in spark ignition type aircraft engines w
hen the aircraft is under cruising conditions. In supercharge m
ethod, the rating is done at 1800 rp
m by com
paring the ho
ck
limited
power of the fuel w
ith those for blends of iso-octane and isooctane plus TE
L. T
his is done at constant com
pression ratio by measuring indicated m
ean effective pressure at enough points
to define the mixture response curves for the sam
ple and the reference fuels. When the knock
limited pow
er for the sample is bracketed betw
een those for two adjacent reference fuels, the
rating is cakulated by interpolation. The rich m
ixture rating indicates the avd
abzty
of b
oc
k
limited pow
er when the plane is under take-off conditions.
In extended motor m
ethod, the rating is done in a C
FR engine norm
ally used for rating of m
otor gasolines by motor m
ethod (rpm=9O
O). T
he knocking intensity of the fuel is bracketed betw
een reference fuel prepared from iso-octane and T
EL
and the performance num
ber is calculated by interpolation.
4.8 CE
TAN
E N
UM
BE
R
Cetane num
ber is related to the ignition delay of a fuel in a diesel engine, i.e. how
rapidly
to lower cetane num
bers. C
etane number of diesel fuels is determ
ined in a single cylinder CFR
engine by comparing
the ignition delay characteristics of the diesel fuels w
ith that of reference blends of known
,,
cetane number. C
etane number of a diesel fuel is defined as the w
hole number nearest to the
value determined by calculation from
the percentage by volume of norm
al cetane in a blend w
ith hep
tametw
nonane which m
atches thdignition quality of the test fuel when com
pared bv this m
ethod..The m
atching blend percentages to the fiist decim
al are inserted in the follow
ing equation to obtain the cetane number:
Cetane num
ber = %
n-cetane + 0.15 (% heptam
ethyl nonane) ... (4.2)
The shorter the ignition delay period, higher is the cetm
e number of the fuel.
Cetane num
ber is the index of ignition quality of a fuel. High cetane num
ber fuels will
facilitate easy starting of compression ignition engines, particularly in cold w
eathers, and faster w
arm up. T
hese also result in increased engine efficiency and pow
er output, reduced
Page 31
exha
ust s
mok
e and
odo
ur a
nd c
ombu
stio
n noi
se. I
n th
e ab
senc
eoft
este
n&e,
the
dieg
el in
dex
or th
e ca
lcul
ated
cet
ane
inde
x w
ill g
ive
an a
ppro
xim
ate i
dea
ofth
e ig
nitio
fi q
uai*
of
thef
dcl.
C
etan
e nu
mbe
r can
als
o be
rou
ghly
ass
esse
d by
th
e fo
rmul
a:
Cet
ane
Num
ber =
0.72
x D
iese
l Ind
ex +
10
... (4
.3)
4.9
AN
ILIN
E POINT
Ani
line
is a
poo
r so
lven
t for
ali
phat
ic h
ydro
carb
ons a
nd e
xcel
lent
one
for
arom
atic
s. T
his
prop
ertg
is u
sed
in t
he
anil
ine
poin
t tes
t. A
nili
ne p
oint
of a
n oi
l is
the
et
ur
e
&
l&
f&
J-
aW
-.
. .
Equ
al v
olum
es o
f the
sam
ple
and
anil
ine
(5 m
l eac
h) a
re h
eate
d or
coo
led
wit
h st
irri
ng in
a j
acke
ted
test
tube
and
tem
pera
ture
at w
hich
com
plet
e m
isci
bilit
y oc
curs
is n
oted
. H
igh
anil
ine
poin
t ind
icat
es th
at th
e fu
el is
hig
hly
para
ffm
ic a
nd n
ence
has
a h
igh
dies
el
mde
x an
d ve
ry g
ood
igni
tion
qua
lity
. In
cas
e pf
ar~
maG
c&he
-mila
nilh
e poin
t is
low
ue
.. ._
+,-.- "
~.rrc
.-.n
--
i-oor.
4.10
DIE
SE
L IN
DEX
D
iese
l ind
ex is
an
indi
cati
on o
f the
igni
tion
qua
lity
of a
die
sel f
uel.
Thi
s is
dct
emin
ed b
y ca
lcul
atio
n fr
om th
e sp
ecif
ic g
ravi
ty a
nd th
e an
ilin
e po
int o
f th
e sa
mpl
e. A
lthou
gh it
is o
fthe
sa
me
orde
r as
the
ceta
ne n
umbe
r, i
t may
dif
fer
wid
ely
from
th
e ce
tme
num
ber.
Hig
her t
he
dies
el in
dex,
bet
ter
is th
e ig
niti
on q
uali
ty o
f th
e di
esel
ie
l. It
is n
orm
ally
use
d aa
a g
uide
to
igni
tion
qua
lity
of t
he d
iese
l fue
l in
the
abse
nce
of t
est e
ngin
e fo
r the
dir
ect m
easu
rem
ent
of
ceta
ne n
umbe
r.
The
die
sel i
ndex
is c
alcu
late
d as
follo
ws:
(a)
Die
sel i
ndex
= A
nilin
e po
int,
OF
x OA
PI
100
... (4.
4)
(b)
Die
sel i
ndex
= A
nili
ne g
ravi
ty c
onst
ant
100
... (4
.5)
(c)
Die
sel i
ndex
= C
etan
e nu
mbe
r - 10
0.
72
J4.6
)
4.1 1
CA
LCU
LATE
D C
ETA
NE
IND
EX
Cal
cula
ted
Cet
ane
Inde
x (C
CI)
is b
ased
on
spec
ific
gra
vity
and
the
10 p
erce
nt, 5
0 pe
rcen
t an
d 90
per
cent
dis
till
atio
n te
mpe
ratu
res
of t
he fu
els a
nd it
giv
es n
umbe
rs th
at c
orre
late
wit
h th
e en
gine
-tes
ting
met
hod.
The
rela
tion
ship
is
give
n Ly
the
follo
win
g fo
ur-v
aria
ble
equa
tion
: C
CI =
45.
2 +
0.08
92 T
ION
+ (0
.131
+0.9
01B
) T~
ON
+
(0.0
523 -
0.4
28
)Tg
o~
+ 0.
0004
9 [(
T~
oN
)~
- (T
~o
N)~
] + 10
7B + 6
0~
~
J4.6
) w
here
T
ION
= T
i0 - 21
5 , O
C
Tlo
= 1
0 pe
rcen
t dis
till
atio
n te
mpe
ratu
re,
OC
T~
ON
= Tm -
260,
OC
Tso
= 5
0 pe
rcen
t dis
till
atio
n te
mpe
ratu
re,
OC
T~
ON
=
2'90
-
310
OC
T90
= 9
0 pr
ecen
t dis
till
atio
n te
mpe
ratu
re, "C
B =
- 3
.5(G-O.85) -
1
G =
spec
ific
gra
vity
at
15O
C
QU
AM
Y C
ON
TRO
L O
F PE
TRO
LEU
M P
RO
DU
CTS
38
Thirr
CCI ia
use
ful f
or e
stim
atin
g ce
tane
num
bers
whe
n a
test
eng
ine
is n
ot a
vail
able
for
dire
ct m
easu
rem
ent,
and
it m
ay be
con
veni
ently
empl
oyed
for e
stim
atin
g ce
tane
num
ber w
hen
the
quan
tity
of s
ampl
e av
aila
ble i
s too
smal
l for
an
engi
ne ra
ting
.
CAL
ORIFI
C VA
LUE
Thi
s is
the
quan
tity
of h
eat r
elea
sed
per u
nit q
uant
ity
of fu
el, w
hen
it is
bur
ned
com
plet
ely
wit
h ox
ygen
and
the
prod
ucts
of c
ombu
stio
n re
turn
ed to
am
bien
t tem
pera
ture
. Thi
s qu
anti
ty
of h
eat w
ill in
clud
e th
e he
at o
f con
dens
atio
n (l
aten
t hea
t) o
f th
e w
ater
vap
our f
orm
ed b
y th
e co
mbu
stio
n of
the
hyd
roge
n in
the
fuel
, as i
t coo
ls to
am
bien
t con
ditio
ns. I
t is
calle
d th
e '@
ca
lori
fic
valu
e" o
r "h
i~h
er calo
rifi
c ya
lue"
. -
Mos
t hzt
ing
app
lica
tion
s can
not r
ecov
er th
e he
at o
f the
wat
er v
apou
r; it
sim
ply
esca
pes
wit
h th
e va
poui
out
of
the
chim
ney.
The
pot
enti
al h
eat
cont
ent
is t
here
fore
mor
e ne
arly
in
dica
ted
by s
ubtr
acti
ng th
is la
tent
hea
t fro
m th
e gr
oss c
alor
ific
val
ue, a
nd th
e re
sult
ant v
alue
is
cal
led
the
net c
alor
ific
val
ue, o
r low
er c
alor
ific
val
ue.
A w
eigh
ed q
uant
ity
of t
he s
ampl
e is
bur
ned
in a
bom
b ca
lori
met
er u
nder
con
trol
led
cond
ition
s. T
he c
alor
ific
val
ue i
s ca
lcul
ated
fro
m t
he w
eigh
t of
the
sam
ple
and
the
rise
in
tem
pera
ture
. It c
an a
lso
be c
alcu
late
d fr
om th
e fo
rmul
ae
Cal
orif
ic v
alue
= 1
2400
- 21
00 p
2 J4
.7)
in w
hich
cal
orif
ic v
alue
is in
caY
gm a
nd p
is d
ensi
ty a
t 15
OC
in g
m/c
rn3.
Cal
orif
ic v
alue
is
a m
easu
re o
f th
e en
ergy
ava
ilab
le in
a f
uel.
Thu
s a
know
ledg
e of
the
ca
lori
fic
valu
e of
the
fuel
, and
the
effi
cien
cy of
the
hea
ting
equ
ipm
ent,
is e
ssen
tial
to c
ompa
re
the
mer
its
and
runn
ing
cost
s of d
iffe
rent
fuel
s and
ene
rgy
cost
s. I
t is
a cr
itic
al p
rope
rty
of f
uel
inte
nded
for
use
in w
eigh
t-lim
ited
vehi
cles
.
4.13
SM
OK
E P
OlN
T Sm
oke
poin
t is
the
max
imum
fla
me
heig
ht i
n m
m a
t w
hich
the
fue
l will
bum w
itho
ut
smok
ing
*hen
det
erm
ined
in a
sm
oke
poin
t app
arat
us u
nder
spe
cifi
ed c
ondi
tions
. Sm
oke
poin
t app
arat
us c
ompr
ises
four
mai
n pa
rts-
lam
p bo
dy, c
andl
e so
cket
, can
dle
and
stan
d. T
he la
mp
body
wit
h ch
imne
y is
fitt
ed o
n th
e in
side
wit
h a
polis
hed
blac
k en
grav
ed sc
ale
whi
ch is
mar
ked
in w
hite
. A g
alle
ry is
secu
red
in th
e lo
wer
par
t of t
he b
ody.
The
can
dle
sock
et
asse
mbl
y is
des
igne
d to
giv
e a
smoo
th ri
se a
nd fa
ll o
ver t
he to
tal d
ista
nce
of t
rave
l. To
ens
ure
inte
rcha
ngea
bili
ty t
he c
andl
e is
fin
ishe
d to c
lose
tole
ranc
es. T
he a
ssem
bly
is m
ount
ed o
n a
stan
d. T
he s
ampl
e is
bur
ned
in a
sta
ndar
d la
mp
wit
h a
spec
ifie
d w
ick
for
five
min
utes
. The
he
ight
of t
he
flam
e is
read
whe
n it
leav
es n
o sm
oky
tail
. This is
an
impo
rtan
t tes
t for
eva
luat
ion
of il
lum
inat
ing
oils
(ker
osin
es) f
or th
eir
abil
ity
to
bum
wit
hout
pro
duci
ng s
mok
e an
d th
e as
sess
men
t of
the
burn
ing
qual
ity
of a
viat
ion
fuel
s.
Hig
her
the
smok
e po
int
bett
er i
s its
dom
estic
use
. It
als
o se
rves
as
a gu
ide
to a
sses
s th
e ar
omat
ic c
onte
nt o
f ker
osin
es.
4.14
CH
AR
VA
LUE
T
he a
mou
nt a
nd n
atur
e of
the
dep
osits
(ch
ar)
prod
uced
on
a w
ick
duri
ng c
ombu
stio
n de
pend
on
the
hydr
ocar
bon
com
posi
tion
of t
he fu
el a
nd a
lso
on th
e de
sign
of t
he a
ppli
ance
s in
'whi
ch it
is u
sed.
Cha
r oc
curs
as
a re
sult
of t
he b
reak
dow
n an
d de
com
posi
tion
of t
he k
eros
ine
unde
r the
loca
l con
ditio
ns ex
isti
ng at
the
wic
k su
rfac
e, a
nd th
ese
cond
itio
ns w
ill a
lso
dete
rmin
e w
hat p
ropo
rtio
n of
the
dec
ompo
sed
prod
ucts
rem
ains
on
the
wic
k.
Page 32
52 PETR
OLEU
M R
EFIN
ING
TEC
HN
OLO
GY
4.15 VIS
CO
SITY
K
inematic viscosity is defined ris the m
earidre of the red
sthi&
to gravity flow of a fluid,
the pressure head being proportional to the density. The tim
e of flow of a fixed volum
e of fluid is directly proportional to its kinem
atic viscosity. The unit of kinem
atic viscosi$ is, cm
2/s or Stoke. T
he unit most usually used in m
easurement of the kinem
atic viscosity of ~etio
leum
fuels is the centistoke (cSt) w
hich is Stoke.
Dynam
ic viscosity, also known as absolute viscosity, is the ratio of applied shear stress to
rate of shear and thus a measure of the resistance of a fluid to flow
. The unit of dynam
ic viscosity is gm
1cm.s or Poise. D
ynamic viscosity m
ay be obtained from kinem
atic viscosity by I
multiplying it by the density of the fluid at the tem
perature at which m
easurement w
as made.
1 K
inematic viscosity m
ay be measured as an absolute property of the fuel, or alternately
I as a conventional property th
at is'dependent on the instrument and the m
ethod used. Both
' approaches depend on the efflux tim
e of a given volume of sam
ple flowing under its ow
n head 1
through a restriction. This follow
s because the force acting the laminar (low
speed) flow of a
fluid through a restriction is approximately proportional to the dynam
ic viscosity, whereas
the force promoting the flow
is that due to gravity, and is proportional to the density of the I
fluid. Hence the tim
e taken for the gravity flow of a given volum
e of sample through a
restriction is approximately proportional to the kinem
atic viscosity. ,
The conventional m
ethods, which are generally sim
pler but less accurate, are represented by the R
edwood instrum
ent in the UK
, Saybolt in the USA
and Engler in continental E
urope. T
hey each comprise a sam
ple cup fitted with a standard-sized oriiice in the base and
I surrounded by a w
aterjacket containing a heating device. When the tem
perature reaches the test level, the orifice is unsealed and the tim
e of flow is determ
ined for the given volume of
sample. T
he result is reported as Redw
ood or Saybolt universal second or as Engler degree,
given by the efflux time ratio for the sam
ple and for water. W
hen the efflux time exceeds a
specified maxim
um-for exam
ple 2000 s-due to high viscosity, use is made of a R
edwood N
o. 2, or a Saybolt Furol (fuel and road oils) instrum
ent, incorporating a larger diameter orifice.
The absolute determ
ination of kinematic viscosity'generally em
ploys a glass U-tube
viscometer w
ith a capillary tube built into one leg. The length-diam
eter ratio is such that end effects are negligible and the precision is therefore higher. T
he instrument is suspended
vertically in a thermostatically controlled w
ater bath, and the time is m
easured for a given volum
e of sample to flow
do
ug
h the capillary. T
his measured tim
e period is inserted into an \
equation to give a direct measure of the kinem
atic viscosity in centistokes. v
=A
t-B/t
... (4.8) w
here A
= instrum
ent calibration constant; B
= instrum
ent type constant, depending on the capillary diameter;
and t =
efflux time, s (E
ngler degree for Engler viscom
eter)
Table 4.1 gives the values of A
and B for R
edwood, Saybolt and E
ngler viscometers.
Viscosity is an im
portant characteristic of a fuel and it is used for the pump design. Pum
p clearance are aG
usted according to the viscssity and if it is out of the range, it will result in pum
p seizer. Pump operation of an engjne depends on the proper visesity of the liquid fuel.
The viscosity of liquid fuel is im
portant to its flow through pipelines, injector nozzles, and
orifices, and for atomization of fuel in the cylinder.
OU
AU
TY C
ON
TRO
L OF P
ETR
OLE
UM
PRO
DU
CTS
Tab
le 4.1 Instru
men
t Co
nstan
t Values
4.1 6 VIS
CO
SITY
IND
EX
V
iscosity index (VI) is the most w
idely used way of characterizing the effect of change of
i
temperature on the viscosity of any oil. Proposed by D
ean and Davis, viscosity index is an
empirical concept based on the behaviour of m
ineral oils. In this concept, an oil whose viscosity
,
changes rapidly with change in tem
perature has a low V
I. An oil w
ith a minim
um change in
. viscosityw
ith change in temperature has a highV
I. In this system, P
ennsylvanian (paraffinic) oils of a selected type w
hich show a desirable, relatively sm
all change of viscosity with change
in temperature, w
ere assigned a VI of 100, w
hile selected Texas C
oastal oils showing less
desirable viscosity-temperature characteristics w
ere assigned a VI of O
.VI is governed by the
type of hydrocarbons in the oil. D
ean and Davis prepared tables giving the kinem
atic viscosities at 40°C
and 100°C of the
Texas C
oastal oils (L) and the Pennsylvanian oils (H
I. The values of kinem
atic viscosities of L
and H are given in T
able 4.2. The V
I of an oil can be calculated from the equation
v1
=L
-Ux
10
0
L-H
where
U =
kinematic viscosity at 40°C
of the oil whose V
I is to calculated
L =
kinematic viscosity at 40°C
of an oil of 0 VI
H =
kinematic viscosity at 40°C
of an oil of 100 VI
.17 PE
NE
TRA
TION
TES
TS
Several standard grades of bitumen are com
lqercially available, which are norm
ally ssified into different grades by p
en
etr
atio
np
e sam
ple of bitumen is plzced in a
. , suitable container and brought to a tem
perature of 25OC in a w
ater bath. The w
eighted needle is brought to the surface.and at the end of 5 seconds interval, the penetration
the needle into the bitum
en, in units of UlO
mm
is te
~v
on
'
ofthe b$
The penetration at 25O
C and the softening point, or penetrations at tw
o di erent tem
pera- tures (for exam
ple, 25OC and 10°C
) can be used to define the extent to which the consistency
of a bitumen changes w
ith temperature. T
his an important characteristics for bitupens, and
determines th
e type of bitumen used for a particular application. V
arious factors have beexi 1
Page 33
used
to
defin
e te
mpe
ratu
re 'd
epen
denc
e. T
he m
ost
com
mon
l~ us
ed f
acto
r,.h
owev
er, i
s th
e Pe
netr
atio
n In
dex
(PI)
, whi
ch is
def
ined
as f
ollo
ws :
Tab
le 4
.2 V
alu
es o
f H. L
and D
for
Kin
emat
ic V
isco
sity
at
100
OC
(H =
Kin
emat
ic v
isco
sity
at 4
0°C
of
an o
il o
f 10
0 V
I, cS
t,
, .
L =
Kin
emat
ic v
isco
sity
at 4
0 OC
of
an
oil
of
0 V
I, cS
t)
QU
AU
TYC
ON
TRO
L OF
PETR
OLE
UM P
RODU
CTS
55
Page 34
56 P
ETR
OLE
UM
REFIN
ING
TEFH
NO
LQG
Y
QU
ALITY
CO
NTR
OL O
F PE
TRO
LEU
M P
RO
DU
CTS
57
Page 35
log
(800
) - log
(PE
N 25
°C) -
20 - P
I 1
TR
B - 2
5 - [
i?G
x] [SO
] w
here
TR
B is
the
rin
g an
d ba
ll so
ften
ing
poin
t of
the
bit
umen
in
"C.
etra
tion
of
a -?
I
bitu
men
at t
he s
ofte
ning
poi
nt te
mpe
ratu
re is
abo
ut 8
00. B
itum
ens l
ess
n fe
cted
by
tem
pera
- '
I
ture
cha
nge h
ave
posi
tive v
alue
s of P
I and
thos
e ?o
re a
ffec
ted
by te
mpe
ratu
re ch
ange
neg
ativ
'e
4'@
valu
es.
I
4.18
FR
EE
ZIN
G P
OlN
T F
reez
ing
poin
t is
the
tem
pera
ture
at w
hich
cry
stal
s of
hyd
roca
rbon
s fo
rmed
on
cool
ing
disa
ppea
r w
hen
tem
pera
ture
of f
uel i
s al
low
ed to
rise
. T
his m
etho
d co
vers
a p
roce
dure
for t
he
dete
ctio
n of
sepa
rate
d so
lids i
n av
iati
on re
cipr
ocat
- in
g en
gine
and
turb
ine
engi
ne fu
els a
t any
tem
pera
ture
like
ly to
be
enco
unte
red
duri
ng fl
ight
r
or o
n th
e gr
ound
.
4.19
CLO
UD
PO
lNT
AN
D P
OU
R P
OlN
T --
Clo
ud p
oint
of
petr
oleu
m p
rodu
cts
is th
e te
mpe
ratu
re a
t w
hich
a c
loud
or
haze
of
wax
cr
ysta
ls a
ppea
rs a
t the
bot
tom
of t
he te
st ja
r w
hen
the
oil i
s coo
led
unde
r pre
scri
bed c
ondi
tions
. It
is g
ener
ally
det
erm
ined
for p
rodu
cts
that
are
tran
spar
ent
in a
43-
mm
thic
k la
yer a
nd h
ave
clou
d po
ints
bel
ow 4
9°C
. T
he c
old
filt
er p
lugg
ing
poin
t tes
t is
used
to d
eter
min
e th
e ex
tent
to w
hich
die
sel f
uel o
r ga
s oi
l will f
low
, eve
n th
ough
the
tem
pera
ture
is b
elow
th
at a
t whi
ch w
ax c
ryst
als
norm
ally
ap
pear
, i.e
. cl
oud
poin
t. C
loud
poi
nt g
ives
a ro
ugh
idea
of th
e te
mpe
ratu
re ab
ove w
hich
the
oil c
an be
saf
ely h
andl
ed
wit
hout
any
fear
of c
onge
alin
g or
fil
ter
clog
ging
. P
our
poin
t is
the
low
est
tem
pera
ture
exp
ress
ed in
mul
tipl
e of
3°C a
t w
hich
the
oil
is
obse
rved
to fl
ow w
hen
cool
ed a
nd e
xam
ined
und
er p
resc
ribe
d co
nditi
ons.
P
our p
oint
is a
wel
l-es
tabl
ishe
d te
st to
est
imat
e th
e te
mpe
ratu
re a
t whi
ch a
sam
ple
of o
il be
com
es s
uffi
cien
tly
solid
to p
reve
nt i
ts m
ovem
ent b
y pu
mpi
ng. T
he p
our p
oint
tem
pera
ture
de
pend
s to
a la
rge
exte
nt o
n th
e th
erm
al h
isto
ry of
the
sam
ple.
Als
o, th
e po
ur p
oint
indi
cate
s th
e w
axy
natu
re o
f the
oils
.
4.20
DR
OP
PO
lNT
OF
GR
EA
SE
T
he s
tand
ard
drop
poi
nt te
sts
ind
ikte
that
the
tem
pera
ture
at w
hich
the
thic
kene
r is
so
solu
ble
in t
he b
ase
oil t
hat
th
e gr
ease
bec
omes
sub
stan
tial
ly f
luid
. Cla
y an
d dy
e th
icke
ned
grea
ses h
ave
no m
easu
rabl
e dr
op p
oint
s.
The
dro
p po
int
can
be u
sed
to a
sses
s w
heth
er a
gre
ase
of kn
own
form
ulat
ion
has
been
pr
oper
ly m
ade
or t
o ob
tain
an
indi
cati
on o
f the
type
of
thic
kene
r w
hich
has
bee
n us
ed i
n a
grea
se' o
f an
hk
no
wn
for
mul
atio
n. I
t ca
nnot
be
used
to
mea
sure
the
upp
er o
pera
ting
te
mpe
ratu
re li
mit
for a
gre
ase.
42
1 M
ELT
ING
AN
D S
Ell
lNG
PO
lNT
OF
WA
X T
he c
oolin
g cu
rve
met
hod
is u
sed
to d
eter
min
e th
e se
ttin
g po
int o
f wax
es. M
olte
n w
ax is
al
low
ed to
cool
in a
spe
cifi
ed a
ppar
atus
and
the
tem
pera
ture
is re
cord
ed a
t fre
quen
t int
erva
ls
The
poi
nt a
t whi
ch th
e te
mpe
ratu
re r
emai
ns w
ithi
n a
rang
e of
O.l°
C f
or o
ne m
inut
e is
take
n as
the
sett
ing
poin
t. T
his
met
hod
is n
ot s
uita
ble
for m
icro
crys
tall
ine o
r in
term
edia
te w
axes
, or
ble
nds
of p
araf
fin
wax
es w
ith
thes
e or
any
add
itiv
es.
The
con
geal
ing
poin
t of
a pe
trol
eum
wax
or p
etro
latu
m i
s de
term
ined
by
appl
ying
a d
rop
of m
olte
n w
ax to
a th
erm
omet
er b
ulb,
and
not
ing
the
tem
pera
ture
at w
hich
it c
onge
als w
hen
the
ther
mom
eter
is ro
tate
d un
der s
tand
ardi
sed
cool
ing
cond
itio
ns. T
his
met
hod
is su
itab
le fo
r al
l wax
es.
The
dro
p m
elti
ng p
oint
of w
ax o
r pet
rola
tum
is
dete
rmin
ed b
y re
cord
ing
the
tem
pera
ture
at
whi
ch a
dro
p of
the
sam
ple f
alls
from
the
bulb
of a
ther
mom
eter
whe
n he
ated
und
er s
tand
ard
cond
ition
s.
The
se a
re c
onsi
dere
d to
be
suit
able
for
che
ckin
g th
e co
nsta
nt q
uali
ty o
f w
ax o
utpu
t in
re
fine
ries
.
4.22
SO
FTE
NIN
G P
OlN
T O
F B
ITU
ME
N
Bit
umin
ous m
ater
ials
do
not c
hang
e fr
om th
e so
lid s
tate
to th
e li
quid
sta
te a
t any
def
init
e te
mpe
ratu
re, b
ut g
radu
ally
bec
ome
soft
er a
nd le
ss v
isco
us a
s th
e te
mpe
ratu
re ri
ses.
For
this
re
ason
, the
det
erm
inat
ion
of th
e so
fbni
ng p
oint
mus
t be
mad
e by
a fi
xed
arbi
trar
y, a
nd c
lose
ly
poin
t is d
efm
ed a
s the
tem
pera
ture
at w
hich
a s
ubst
ance
att
ains
a p
arti
cula
r un
der
spec
ifie
d co
nditi
ons o
f tes
A
ste
el b
all o
f spe
cifi
ed w
eigh
t is
plac
ed
upon
a d
isc
of s
ampl
e co
ntai
ned
wit
hin
a m
etal
d
ng o
f spe
cifi
ed d
imen
sion
s. T
he a
ssem
bly
is
heat
ed a
t a c
onst
ant r
ate
anct
the
tem
pera
ture
at w
hich
the
sam
ple
beco
mes
sof
t eno
ugh
to
allo
w th
e ba
ll, e
nvel
oped
in a
bit
umen
, to
fall
-d di
stan
ce is
take
n as
the
soft
enin
g
-2 T
he r
ing
and
ball
test
for
sof
teni
ng p
oint
mea
sure
s th
e te
mpe
ratu
re i
n OC
at
whi
ch a
st
anda
rd d
isc
of b
itum
en c
onfi
ned
in a
met
al ri
ng s
ofte
ns to
such
an
exte
nt, w
hen
heat
ed a
t a
rkte
if 5
"~/m
inut
e, th
at it
def
orm
s und
er th
e lo
adin
g im
pose
d by
a s
mal
l ste
el b
all w
hich
fall
s a
dist
ance
of 2
.54
cm.
The
det
erm
inat
ion
of th
e so
ften
ing
poin
t of b
itum
en is
rega
rded
by
som
e as
an
indi
catio
n of
visc
osity
, alt
houg
h fr
om th
e po
int o
f vie
w o
f th
e ap
plic
atio
n of
bit
umen
its
use
is li
mit
ed to
th
at o
f its
titl
e. T
he s
ofte
ning
poin
t is
used
in th
e de
sign
atio
n of
har
d bi
tum
ens
and
oxid
ized
bi
tum
ens.
4.23
IN
DU
CTI
ON
PE
RIO
D O
F G
AS
OLI
NE
In
duct
ion
peri
od o
f ga
solin
e is
the
tim
e el
apse
d be
twee
n th
e pl
acin
g of
the
bom
b in
the
bath
and
bre
ak p
oint
at
100°
C. B
reak
poi
nt i
s th
e po
int i
n th
e pr
essu
re-t
ime
CUN
e th
at is
pr
eced
ed b
y a
pres
sure
dro
p of
exa
ctly
2 p
si w
ithi
n 15
min
ute
and
succ
eede
d by
a d
rop
of n
ot
less
than
2 p
si in
the
next
15
min
ute.
F
ifty
mil
lili
tre
of t
he sa
mpl
e is
encl
osed
in a
bom
b w
ith
oxyg
en a
t 100
psi
and
hea
ted
in a
w
ater
bat
h at
100
°C. T
he p
ress
ure
is th
en re
cord
ed e
ithe
r on
a ch
art o
r rea
d ev
ery
15 m
inut
es
Page 36
60 PETR
OLEU
M REFIN
ING
~TECH
NO
LOG
Y
The test is continued until th
e break point is reached. The test result is reported as induction
period in minute.
This test is conducted to assess the stability of gasoline in storage. T
his test indicates the presence,of unsaturated hydrocarbons in the fuel and hence its gum
forming tendency. H
igher the induction period, better is the storage stability of the fuel. A
n induction period of 360 m
inute under laboratory conditions ensures storage stability of at least six month. H
owever,
this correlation may vary w
ith different gasolines under different conditions.
4.24 THE
RM
AL S
TAB
ILITY O
F JET FU
ELS
Jet fuel therm
al oxidation tester (JFT
OT
) is used to measure the high tem
perature stability of gas turbine fuels. T
his subjects the test fuel to conditions which can be related to
those occumng in gas turbine engine fuel system
s. The fuel is pum
ped at a fixed volumetric
flow rate through a heater after w
hichit enters thestainless steel filter whert! fuel degradation
products may becom
e trapped. The apparatus requires 600 m
l of test fuel for a 2.5 hour test. T
he essential data derived are the amount of deposits on an alum
inium heater tube, and the
rate of plugging of filter located just downstream
of the heater tube. In the JF
TO
T a charge is placed in a reservoir and the w
hole system is pressurized to 3.45
MPa w
ith nitrogen. This ensures a single-phase reaction in the heated section. T
he fuel passes from
the reservoir through a 0.45 micron filter, to rem
ove trace particulate matter, and into
the reactor section, where it passes upw
ards in an annular space over iy
aluminium
tube and out via a 17 m
icron stainless steel filter through a heat exchanger, to cool it, and back to the top of the reservoir. T
he used and unused fuel in the reservoir are separated by a floating piston. T
he fuel is rated by a visual tube rating or by placing the tube in a Tube D
eposit Rater.
In this the tube is rotated at a constant speed and its surface scanned by two light sources
reflecting off the tube on to a photocell. The photocell gives a signal to a m
eter. Also, the
differential pressure across the 17 micron filter is m
easured. T
he test results are indicative of fuel performance during gas turbine operation and can
be used to assess the level of deposits that can form w
hen liquid fuel contacts a heated surface.
4.25 GU
M C
ON
TEN
T T
he gum com
pounds which can be present or produced in the fuel are classified into tw
o types for test evaluation. E
xistent gum m
ay be already formed in the fuel and can be deposited
from solution as the fuel evaporates. P
otential gum m
ay be formed under extended storage
conditions during which unstable hydrocarbons are thereby polym
erized and oxidized to form
gums. E
xistent gum is the am
ount of nonvolatile heptane insoluble residue left when the sam
ple is evaporated in a jet of hot air at 160°C
. For jet fuels, the evaporation is camed
out in a jet of superheated steam
at 232OC
. P
otential gum is the am
ount of gum form
ed afier the sample is aged in an oxidation
stability bath and evaporated under specified conditions. G
um is alw
ays troublesome in any fuel and it m
ay cause piston ring sticking and deposits on engines. T
he amount of gum
points to the presence of olefins which have very poor storage
stability. The existent gum
test is claimed to m
easure the amount of gum
or gum-form
ing com
pounds existing in the fuel, while the potential gum
test attempts to predict the tendency
to form gum
on storage and use. These gum
tests are usually used as refinery control methods.
1 Q
UA
LITY CO
NTR
OLO
F PETRO
LEUM
PRO
DU
CTS
g1
4.26 TOTA
L SU
LPH
UR
.:
. T
his is determined by lam
p method or w
ickbold procedure for volatile petroleum P
roducts and by bom
b method for heavier products. S
ulphur in the sample is oxidized by com
bustion ,
and is estimated volum
etrically after absorption in Hz02 or by gravim
etric methods after
converting into barium sulphate.
Sulphur com
pounds pose a dual problem: they not only cause environm
ental pollution from
their combustion products, but these products are also naturally corrosive and cause
1 severe physical problem
s to engine parts. A know
ledge of the sulphur content of petroleum
" products is therefore of im
portance to both refiner and user. I 1
dc
lD
IT
Y AN
D A
LK
AL
iNln
I I
New
and used petroleum products m
ay contain acidic constituents present as additives or 1
as degradation products, such as oxidation products, formed during service. T
otal acidity is a I I
measure of the com
bined organic and inorganic acidity. T
he acids in the sample are extracted in neutral alcohol andthen titrated against standard
alcoholic potassium hydroxide under hot conditions.
Total acidity is an
indication of the corrosive properties of the product. Inorganic acidity is a m
easureof the m
ineral acid present. Organic acidity is obtained by deducting th
e inorganic acidity from
the total acidity.
ER
-STR
IP C
OR
RO
SIO
N TE
ST
products contain sulphur compounds, m
ost of which are rem
oved during I
refining; Of th
e sulphbr compounds rem
aining in the petroleum product, how
ever, some can
have a corroding effect on various metals. T
his corrosivity is not necessarily directly related to the total sulphur content. T
he effect can vary according to other chemicals and types of
sulphur compounds present.
A cleaned and sm
oothly ~o
li$h
ed copper strip is irnm
erse&&
hsm@
&
which is then
mam
tained at the specified tem
perature for the specified length of time. T
his strip is removed
1 L
am
pl
e,
washed w
ith aromatic and sulphur free petfoleum
spirit and examined for
evidence of etching, pitting or discolouration. It is then compared w
ith FT
M copper-strip
corrosion stand
kd
colour code. Th_e class%cation cbde indkates th
at the num
bers 1,2
,3 and
4 designate slight tarnish,'moderate tarnish, dark tarnish m
d corrosion,kespectively. S
ub-- scripts-a-e describe a standard colour reproduction'in th
e standard chart. For exam
ple, the classification code la
indicates slight tarnish with a light orange colour.
C~
his
test serves as a m
easure of possible difficulties with copper, brass, or bronze parts of
the fuel systems. 7
4.29 SILV
ER
-STR
IP C
OR
RO
SIO
N TE
ST FO
R A
VIA
TION
TUR
BIN
E FU
ELS
A
Polished silver strip is completely im
mersed in A
viation Turbine F
uel at 45 f 1°C
for a period of 16 hour. A
t the enctof this period, the silver strip is removed from
the sam
ple, washed
and evaluated for corrosion against the set of standard. S
ince some parts of the fuel pum
ps in aircraft are made of silver, th
e corrosive tendency of the h
e1 for silver assum
es special significance. The cum
ulative effect of corrosion on such a vital com
ponent in the aircraft is hazardous.
Page 37
_? 4.
30 A
SH
-h
~ji{
:!:*
;:~ :p
>5
~z
:~
y~
~;
c~
~~
~~
~
.b,,:
;.7!t$
; j
!;,;: .,:
,.t;.3
: ...
<..
, :, ..
. ..
. .
.,&h.
@n!
~es
ult f
r0.p
oi1
,wat
er-s
olpb
le m
etal
lic
cqp
ou
nd
s, o
r ex
tran
eous
sol
ids,
suc
h as
di
&qj
&+s
$,~.
:~~:
~.
. ,
. ..
'A k
qo
m'p
~,o
gn
$:.
qf
3ai
ble
is
igni
ted
and
the
ca
rbo
na
~io
~s
resi
due
I&€
ib
. he
ated
..
to
I
800°
C i
n a
muf
fle h
rnac
e, co
oled
and
wei
ghed
as
ash.
A
b~
wle
dg
e, of t
he
amou
nt o
f a
prod
uct's
ash
for
min
g m
ater
ial
can
prov
ide
info
rmat
ion
on
whe
them
the-
prod
uct i
s su
itab
le fo
r use
in
a gi
ven
appl
icat
ion.
wr
bo
n
resi
due
can
be d
efin
ed a
s th
e am
ount
of c
arbo
n re
sidu
e le
ft a
fter
eva
pora
tion
and
I
pyro
lysi
s of a
n oi
l and
is in
tend
ed to
pro
vide
som
e in
dica
tion
of re
lati
ve c
oke
form
ing
tend
ency
. E
ithe
r C
orir
adso
n m
etho
d or
Ram
sbot
tom
met
hod
can
be u
sed
to d
eter
min
e th
e ca
rbon
re
sidu
e of
pet
role
um p
rodu
cts.
onra
dson
Met
hod
quan
tity
of s
ampl
e is
pla
ced
in a
cru
cibl
e an
d su
bjec
ted
to d
estr
ucti
ve d
isti
ll$-
ti
on.
The
res
idue
und
ergo
es c
rack
ing
and
coki
ng r
eact
ions
dur
ing'
fixe
d pe
riod
of
seve
re
heat
ing.
At t
he
end
of t
he
spec
ifie
d he
atin
g pe
riod
, the
cru
cibl
e co
ntai
ning
the
carb
onac
eous
re
sidu
e is
, coo
led
in a
des
icca
tor
and
wei
ghed
. T
he r
esid
ue r
emai
ning
is
calc
ulat
ed a
s th
e 'p
erce
ntag
e of
th
e or
igin
al s
ampl
e an
d re
port
ed a
s co
nrad
son
carb
orl r
esid
u 3
Met
hod
e sa
mpl
e S
ter
bein
g w
eigh
ed i
nto
a sp
ecia
l gla
ss b
ulb
havi
ng a
cap
illa
ry o
peni
ng i
s 'p
lack
d. in
"& m
etd
furn
ace
mai
ntai
hed
at 5
50°C
for 2
0 i I'
min
ute.
The
sam
plei
e th
us
quic
kly
'1 hea
tedy
to th
e po
int,
atw
hic
h a
ll v
olat
ile
Mat
ter i
~ev
apo
rate
d ou
t of t
he
bulb
wit
h or
wit
hout
de
com
posi
tion
whi
le th
e he
avie
r res
idue
rem
aini
ng in
the
bulb
und
ergo
es c
rack
ing
and
cqki
ng
reac
tion
s. A
ftek
a sp
ecif
ied 2
0 m
inat
e he
atin
gper
iod,
the
bulb
is re
mov
ed fr
om th
e ba
th, c
oole
d in
a d
esic
cato
r an
d ag
ain
wei
ghed
. The
resi
due
rem
aini
ng is
cal
cula
ted
as th
e pe
rcen
tage
of
the
orig
inal
em
pie
and
repo
rted
as
ram
sbot
tom
car
bon
resi
du
C?+
on
;&du
e gi
ves
a m
easu
re o
f of
a f
uel
oil w
hen
h$at
ed i
n a
buI6
und
er p
resc
ribe
d co
ndit
ions
. W
hile
not
dir
ectl
y co
rrel
atin
g w
ith
engi
ne
depo
sits
, *s
prop
erty
is c
onsi
dere
d as
an
app
roxi
mat
ion.
For
exa
mpl
e, c
arbo
n re
sidu
e va
lue
of d
ie&
h
e1
cori
elat
es w
ith
the
amo
un
t of
carb
onac
eous
dep
mit
s th
e fu
el w
ill f
orm
.& t
he
com
bust
ion
cham
ber
of t
he
engi
ne. T
he e
xpec
ted
carb
on d
epos
its
in th
e co
mbu
stio
n ch
ambe
r is
gre
ater
for
hig
her
valu
e of
th
e ca
rbon
res
idue
. C
arbo
n re
sidu
e is
als
o us
ed i
n de
sign
ca
lcul
atio
n of
ves
sels
.
4.32
CO
LOU
R
Col
ouri
s an
indi
cati
on o
f the
deg
ree
of r
efin
ing
of th
e pr
oduc
ts. V
ario
us te
st m
etho
ds u
sed
for t
he
mea
sure
men
t of
col
our o
f pet
role
um p
rodu
cts
alon
g w
ith
thei
r m
ain
item
s eq
uipm
ent
and
prod
uct
appl
icat
ion
rang
e ar
e gi
ven
in T
able
4.3
.
4.33
DE
NS
ITY
AN
D S
PE
ClF
lC G
RA
VIT
Y
Den
sity
of a
flui
d is
its m
ass
per
unit
vol
ume.
It i
s m
easu
red
over
a ra
nge
of t
empe
ratu
res.
us
uall
y fo
r con
veni
ence
at t
he te
mpe
ratu
re a
t whi
ch th
e fu
el is
to b
e st
ored
.
Tab
le 4
.3 C
olou
rMea
sure
men
t met
hod
s,
,,. .
. ,
<, ,;
,,il
5
..;.,,
:<,<
%
*,(
...(,
....
-,
.rll..-..
.~..
. I I.
-. :.-;
i
.!l:.,
,.:.
... , , : .
- .
' . I
. . ' .
. .
.
.,
.
Spe
cifi
c gra
vity
is th
e ra
tio
ofth
eden
sity
ofa
flu
idto
that
ofw
ater
at th
e sa
me t
empe
ratu
re.
The
tem
pera
ture
usu
ally
spe
cifi
ed is
15.
56O
C. I
n th
e U
SA, s
peci
fic
grav
ity
of a
n o
il is
oft
en
-e,~
~e
ss
ed
as
deg
rees
kP1. A
PI g
ravi
ty is
an
arbi
trar
y fi
gure
rel
ated
to
the
spec
ific
gra
vity
of
jytr
oleu
m p
rodu
cts
in a
ccor
danc
e w
ith
the
form
ula:
Nam
e Sa
ybol
t chr
omom
eter
ASTM C
olou
r .
Col
our o
f dye
d av
iatio
n ga
solin
e C
olou
r by
the
Lovi
bond
tin
tom
eter
?, .
? ,
Deg
rees
API
=
141.
5 -
131.
5 Sp
ecif
ic G
ravi
ty a
t 15
.56°
C11
5.56
0C
. .(4.11)
The
spe
cifi
c.gr
avit
y is
an
indi
cati
on o
f th
ety
pe
of h
ydro
carb
on p
rese
nt,
bein
g hi
ghes
t for
ar
omat
ics
and
low
est f
or p
araf
fins
. The
API
gra
vity
rev
erse
s th
is r
elat
ions
hip.
-
The
mos
t acc
urat
e m
etho
d of
det
erm
inin
g th
e sp
ecif
ic gr
avit
y of
an
oil
is to
wei
gh a
kno
wn
volu
me
in a
spe
cifi
c-gr
avit
y bo
ttle
at
15.5
6OC
. A c
orre
ctio
n m
ay b
e ap
plie
d by
mea
suri
ng th
e 's
peci
fic
grav
ity
at s
ome
conv
enti
onal
tem
pera
ture
nea
r 15
OC
and
addi
ng o
r su
btra
ctin
g 0.
0006
3 pe
r OC ab
ove
or b
elow
15O
C.
' A
noth
er m
etho
d fo
r de
term
inin
g th
e sp
ecif
ic g
ravi
ty o
f th
e oi
l is
by
mea
ns o
f a
set
of hy
drbm
eter
s. A
hyd
rom
eter
is p
lace
d in
the
6il
sam
ple
at 1
5.56
OC
and
all
owed
to c
ome
to re
st.
The
spe
cifi
c gra
vity
is s
how
n on
the
sca
le a
t the
poi
nt c
oinc
iden
t wit
h th
e su
rfac
e of
the
oil.
A
ccur
ate
dete
rmin
atio
ns o
f th
e de
nsit
y, s
peci
fic
grav
ity
and
AP
I gr
alii
ty-o
f pe
trol
eum
pr
oduc
ts a
re n
eces
sary
for
th
e co
nver
sion
of
mea
sure
d vo
lum
es t
o vo
lum
es a
t st
anda
rd
tem
pera
ture
of
lb.5
6OC
. Whe
n th
e vo
lum
e of
oil
is k
now
n, i
ts m
ass
can
be c
alcu
late
d. T
hese
fa
ctor
s go
vern
the
qua
lity
of
cmde
pet
role
um.
The
se p
rope
rtie
s, h
owev
er,
are
unce
rtai
n
Mai
n eq
ucpm
ent
Chr
omom
eter
Cal
orim
eter
Col
our c
ompa
rato
r
Lovi
bond
tint
omet
er
indi
cati
ons o
f fue
l qua
lity
, unl
ess
corr
elat
ed w
ith
othe
r A
corr
elat
ion
of fu
el d
ensi
ty
wit
h pa
rtic
ulat
e em
issi
ons
indi
cate
s inc
reas
ing
part
icul
ate
emis
sion
s wit
h in
crea
sihg
dens
ity.
4.34
GA
S C
HR
OM
ATO
GR
AP
HY
OF
PE
TRO
LEU
M G
AS
ES
AN
D L
IQU
IDS
fi
mea
sure
d vo
lum
e of
the
gas
sam
ple
is in
trod
uced
into
a c
hrom
atog
raph
ic c
olum
n an
d tr
ansp
orte
d th
roug
h th
e co
lum
n, t
he s
ampl
e is
spl
it i
nto
vari
ous
com
pone
nts,
eit
her
by
adso
rpti
on o
r pa
rtit
ion,
dep
endi
ng o
n th
e co
lum
n pa
ckin
g. T
he c
ompo
siti
on o
f th
e sa
mpl
e is
de
term
ined
from
the
chro
mat
ogra
ms b
y m
easu
ring
the
area
und
er th
e pe
aks.
An
iden
tifi
cati
on
of t
he
com
pone
nts
is d
one
by n
otin
g th
e el
utio
n ti
me.
-
.
Col
our s
cale
I +3
0 to
- 16
Oto
8
Perm
anen
t col
our g
lass
di
sc
Col
our s
tand
ards
of d
if-
fere
nt ra
ting
for r
ed, y
el-
low
, blu
e an
d ne
utra
l tin
t
I 4.
35 R
EF
RA
CTI
VE
IND
EX
OF
HY
DR
OC
AR
BO
N L
IQU
IDS
R
efra
ctiv
e in
dex
is d
efin
ed a
s th
e ra
tio
of t
he
velo
city
of
ligh
t (of
spe
cifi
ed w
avel
ent$
) in
t ai
r to
its
velo
city
in th
e su
bsta
nce
unde
r ex
amin
atio
n. I
t may
als
o be
def
ined
as
the
sine
of t
he
-
-
App
lt'ca
tlon
-
Whi
te
prod
ucts
pe
trole
um
Hea
vy p
etro
leum
pr
oduc
ts, l
ubri
catin
g oi
ls D
yed
avia
tion
gaso
line
A11
petro
leum
pro
duct
s ex
cept
bla
ck o
ils a
nd
bitu
men
s -J
Page 38
64 P
ETR
OLE
UM
RE
FININ
G TE
CH
NO
LOG
Y
angle of incidence divided by sine of the angle of refradion, as light passes from air into the
substance. The refractive index of liquids varies inversely w
ith both wavelength and tem
pera- ture. R
efractive intercept is calculated by
Refractive intercept
= n - ' 2
... (4.12) w
here ri is the refractive index at 20°C and p is the density at 20°C, gm
/cm3.
' ~
i~h
the
ne
content in naphthas can be easily calculated by know
ing the refractive index
and density of the saturates fractions as determined by the refractive intercept m
ethod. There
is a relation between the m
olecular weight, arom
atics and refractive index of hydrocarbons and hence the determ
ination of refractive index gives an indication of the content of aromatics
in the hydrocarbon fractions.
4.36 LEA
D IN
GA
SO
LINE
T
he lead alkyl is converted to lead chloride and extracted from the gasoline by refluxing
with concentrated hydrochloric acid. T
he acid extract is evaporated to dryness. Any organic
material present is rem
oved by oxidation w
ith nitric acid and the lead is determined
gravimetrically as lead chrom
ate. The m
ethod covers the gravim
etric determination of th
e total lead content of gasoline and other volatile distillates blended w
ith lead alkyls (tetraethyl lead or tetram
ethyl lead, etc.). !
Tetraethyl lead is added in gasoline to im
prove the octane number but it is highly
poisonous. Hence, its concentration in gasoline is restricted and its handling is done w
ith utm
ost precaution.
4.37 WA
TER S
EP
AR
OM
ETE
R IN
DE
X (M
OD
IFIED
) (WS
IM)
This is carried out w
ith a water separom
eter. It~m
easures the water separation charac-
teristics of fuels expressed in terms of W
SIM.
An em
ulsion of water and fuel is prepared and passed through a cell containing a
standardized 'fibreglass' coalescer.~The effluent from
the cell is examined for entrained w
ater by light transm
ission. A num
erical scale (0-100) rates the case with w
hich the fuel releases gxpu!sified w
ater. :,,W
SIM
is a measure of fuel cleanliness relative to its freedom
from surfactant m
aterials. I
A higher W
SIM rating indicates th
at the fuel is cleaner relative to surfactant materials.
4.38 DU
CT
lLlP
l -7
Bitum
inous surfaces exposed to varying temperature conditions undergo a great deal of
elrpansion and contraction. Therefore an im
portant characteristic of the Kinder is its ductility
and the degree of ductility h
as an effect on the cracking of bituminous surfaces caused by traffic
stress. The ductility of bitum
en is expressed as the distance in centimeter to w
fich a standard briquette can be elongated before the thread form
ed breaks under the specified conditions. A
molten bitum
en sample is poured into a standard m
ould, allowed to coal to
room
temperature and then placed in a w
ater bath so that the briquette can be brought to test
temperature before m
ounting in the testing machine. D
uctility testing machine consists of a
moving carriage m
oving over a lead screw. A
n electricmotor driven reduction gear unit ensures
smooth constant speed and continuous operation. T
he temperature is controlled therm
o- statically.
Bitum
en having high ductility may be m
ore temperature susceptible.
. :&
,tfYiiii iiFY
B,'C!'C!E Td'(jr:&,M6i;.4*c$i
. .'" ";"i;
:.,< '.,
, .,;ii>.5 $
,~
'., +: ,! :..1<.<7 <
. .,:,,, ;!!,:,:l:.ji:.: .
.,
., I,.'
L!
tgffl,. bj2~?y8> .:sj...tis:
,(, j+
xp
,..d, )&
.,JA
~~
~. u::.
*,:a,
...... %+;*:: ig
~jk
::~~
'Y$<.T, t:F* 1
% ,
,~
ri
t&
~~
~:
3 : , , .
he
fi+
. p7$~c5$~+5~~9~@~~$l~~.tPo . +
.
;; z., .ji .!,_
_ f g&$rakf
it.. - ' &&&!
li&t, K
p$$&Pi.
ons denved from. fieirol'eum
wh
l~h
mi? : .,$>,..
t6mp
&f&
@
..... :;.:.I $
d&
T~
$~
h~
~<
,~
~
bu
t condensed to th
e Iiquidtitst.eatnmbievt
,
by aP$ffclAbhfsprri:da@
&O
$!!
B'&B&~~&Kxh~~~~@&~~~~<$&&t~&&4&eY
are .,. Ir4:.
! , :,$tored :
~d
tfa
na
p6
~d
&
liiji$duids.bnder prasw
e. p hey are sold .a pm
pane or butane or undr :i~~f;'e'~~ideTame~sU~~~~S.~n~~ne,
~b
~~
t:
~~
~,
.H
p.
.~
~~
i~
J~
di
~.
,
. . .
..
.., .,
' ' ?"
\.... -:,<,.-; .
;. . ...;....
:.>,:
,?..! i!.
..
..
..
.
., ,.. 6;:$.i'embairt2bn%
it I;~pG
:. ; ... :
, .
..
.
. .-
, ,
. .,.I>'!>
,
,, , , ~
,~
~,
~,
,u
s~
al
l~
m
iihk
s of saturated and unsaturated hydrocar-
.!bdtS
gl$ be:cy
and
~r~
~&
-f,p~-~
h'sis~
af.o*?r rn0fe of fie foll&
ghydrocarbons: - ..
ho
pb
e(C3
Hsj
, ...L
.,
' * Propylene (C
3H6)
..... ......... .........
0' . n-butane &
!jH$) '.
..,. 1~0-6uta" gq10j
. :
..
.
. ,i
. ~
Butylene (C
4Hs)
~races'to
smnli auantiti&
s of one or more of th
e follow&
g hydrocarbons may. also be presen..
Ethane (C
zH6)
Ethylene (C
zH4)
I
- - P
enbane (c5H12)
Pentene (C
sHlo) )
ii\)
. ,i) ~
PG
separated from
heavier hydrocarbons by r straight distillation process contains only
the saturated hydrocarbons wliereas Z
PGaobtained from
conversion processes such as tht m
acatalytic cracking,
,:< ., ;'
reforming ,c: . and
~ hydm
cracking contains unsaturated hy
dro
cmtio
~
. . as
@li+.
I : Bulleau of Tndian811Standarde-4BIS) have categoised L
PG
as under: , . (A
) C
omm
ercid bu
tme
k a-hydm
carbon-product -
.
composed re dom
inantly of butane i-
butyleneb or th
eir mixtures.
(I%)' C
om
me~
ciak butaneapropane m
ixture - a hydrocarbon ~
rod
uc
t composr '
predominantly of a
mixture of butanes andlor butylenes w
ith propane and
J~1 propylene.
' (C) C
omm
ercial propane- a hydqocarbon product com
posed predorninandflfproph- . propylene or their m
ixture. > T
he requirements of L
PG are ev
en in T
able 5.1. LPG produced at Indian refinen
conforms to grade B
.
Page 40
1d'fldi~~Mtkl~ie~h8'c~fig1(~~~)
uiifir the Yeed~&
sfi&\ffb$W
"hi'&xddp
&-fed C
Q~
~~
~U
OU
B\
~
to the reactor tower, fm
m w
hich, at thetsamet&
e,kk8alyhtia k&5&
jw1@h&
nf to a regenerator w
here coke deposited on the catalys6is burnt &~
~h
'&n
tka
dffl~
$o
h~
the
reactor is fractionated in m
ain fractionating column into so called light en
dq
;mf~
dk
b&
t~late
and heavy fraction#. Uncondensed overhead gases and catalytically crao
k&
iqg
~el~
e are
routed for LPG recovery. The uncondensed gases are com
pressed, moledaq~pha&
$&uqces-
sively to two absorbers w
hich employ cracked gasoline and light cycle oil respectively as
absorbents to increase hgbt ~?
~r
~~
~v
ew
~,
~~
hg
as
ol
ip
e
fmm
absmber is45tfi8p&
,d, off its
lighter ends in a stripperjl'he stripped g~sol$ne
kfed
to a debpta?iger ~
~l
~~
,~
~b
,&
~i
ac
ke
d
LPG
is taken as overhead producp. LP
qq
4:yerhead product from debptahipfr ,$oJu+n is
treated further to conform to required specikations.
. t
f,"
-.
Coker gases are com
pressed in two stage com
pressor and routed to the bloi~&$$&
k~~orber ~
$@
df
?~
~;
$?
~~
~
is used, as absorbing medium
. Gases from
ap$tha a sorber to
are P
er a sqrbe y coker'kerpsi$,
~L%
"kerosifib kord kerdsine a!sor~&
% d
~~
~R
~k
'&
the
;&a
i,
t<
\2
a
, , ,,,
mw$$a$tidnating,k71mnnb,!the ,ckkii;~*li8?%
ighte'rrehds (C
1 and-cijkre s,thr&qdff G
od
' ?,'
/ '
rich nab
hk
a in a $lp
$y
r ?ndtc$&et'riom
stri$eP$re
??<kd back. to naih
t& &
$?$erfto
recover back QqC
4s. St$&r
&dfd&
~"&n~&
$'n ,,) .,.,,,,! j
g "' ~39
~1
~a
@l.$
~~
h$
~,$
9
V"t
P$
2v
th~
~a
in
1 debutanise; w
liCrbiW
G is iuihii?iw
n %om
bp an&
't"hb"lfi&d c6ke'r liaphthd
6&d&
. 1
bPG
tmatm
ent. M
ost of straigh
tan L
PG produced from
Gulf cm
des reguires only caustic w
8s)rasthb mercaptaii le*elik below
-5q ppm. C
austic wash alb&
doeanat bring down
I the percaptan content-of L
PG in respect of,A
ghajari ?rude and-he-e M
erox treatment
(extractive type) is nwessary. S
traight-run LPG
produced fro~&$&
...d& is B
enGraily
sweet but requires m
ildpcaustic wash. ,
-
Likew
ise cracEed LJ'G
produced from pro&
ssing of Indian cFdeL idj;' lres -- caustic -
wash.
Cracked L
PG from
F~
C'
unit processing feedstock from ~
ul
f
nuddk'irei$Ares am
ine wash for,
H2S rem
oval follwed by M
erox treatment. T
he Mem
x process is one of oxidation of the m
edaptans with ail. in ~kaIjne'r+
$$m
in tffe pre$& of~~el~t6d1i~&n'&&$d~fi&
i$t&
&.
r,
n'
'
The m
ercaptans are converted to di~
~lp
hk
des w
hidi ire &&
ively odod~
1dd~ddn~
ko~&
'ive com
pounds. A sm
all amount m
ay remain in the treated L
PG but the bulk is transferred w
ith the caustic to a'regeneratorw
here sodium
m$rcaptanine ik'conveited B
diluphide oil and N
aOH
is regenerated. The insoluble disulphide oil is rem
oved thereby reducing the total s~
@tiu
r. Q
dourisation. Since LPG
is used as domestic fuel the chances of fire in confined locations
Ii b
ec
oi ,?rgein the case 0Ia:cidental
leakage. Beingagas this sh?uld betm
ost easily detectable by sm
ell alone. Since constituents of LPG
do not have any characteristic o&ur,'it;s
cimb;on
practice to deliberately mix highly odoriferous additives in LP
G to ilnpart a distinct odour.
Most com
monly used substances are low
molervlar w
eight organif thfols (mtb$ahlf&
':d; have an pbnoxous odour in concentrated form
and serve as-effective 40
ur m
arkersin dilutqt form
(ppm levels). Som
e compounds of this type are ethyl and $tbb$l m
ercaptans. ~~
~$
8$
ts
t
made-D
octor negative and then ethyl mercaptan (about 50 ppm
) is usually added.
i -5J.4
Uses of L
PG
I
.&pG
isbwed aq
a domestic fuel, 8
fuel for internal copbustion engine anQa feydstopk for
themanufacture of various chem
icals and olefins (by pyrolysis.). LPG
supplied for,dbmestic
PU
YY
~S
~~
is ysually, a m
ixture of propane and butane, butanes predominating in w
armer
countries and propane being in greater proportion in colder countries. LPG
' has many
industrial applications. It is used for portable blow-lam
ps, soldering, brazing, welding, anneal-
SU-+& jfl r-
;
vv
h
hg
and hardening, steel;utting e
tc
h f
ue
for in
com
bus$on .<
ed&es,
it is e&em
ely .
- good, but it has yet ta leco
mep
op
ul~
. I
I A
1 I
\." -
, ik
5,2 NA
PH
THA
S
, N
aphtha is a nam
e give? td light hydrocarbons bgilin&$he:ge.gasoline range. It is
at light distillate obtaine4,frop refipwg of crude:~
il. ye
bo~lingfiiages of various types of
) -,
naphthas produced include: C5 - 85OC. C
s - 11
8C
, C5 - 140°d, CS
; ~~
OO
C,
C
5 - 17
50
~
and C
5 - 200°C. In these iiitial boilink point (IB
P) is co
ns
tsn
t.~~
t~~
-bo
ilin~
ranges can be
60 - 85Oc, 85 - llo0C
, p+
llp - 140",~. w
as
are u
suall~
classified as light.hterm
e&ate
and heavy naphthas. Itthh
aph
tha fraction ~
ls
be1ovk1000($,
it ii,"c1bsified as lgh
t naphtha. H
~~~ naphgaboils above 150°C. For ..
A
interniediate naphtha ~k
b@
%$
&~
~g
<?
ies
between
Ti
)O
PC
.
'v
I - .;
4 '3
.L
*
_I__
1 3:
5.2.1 M
ethod. of ~
*a
ctm
&o
~~
a*
hth
g~
!
'' '
I ki
Naphtha is prod&
ed by atm~
sfiheric distillation of cmds bil?&
s./s &
e+straight-run
naphtha. Several c~
nversion processes such ad visdre&jng$?uid
c tal* c
rnf~
ng
, hydm
cracling, cokingalso ? roduce llqp
hth
j. TE
ssb @ b
d2d
crgcked 'pa!hth&.
The im
portant chatacterjstics of t%aphthi?ractions 6
~ d
ae
ren
tl@b
~a
re gv
en
h Table
5.3. The proper qualitypf naphtha f
o~
the petrochem
ic$ an
d
fe&lher inapm
can be -
achieved by dearomatising the naphtha w
ith or without reform
ing openh;ams
~g
or
to extrac-
tion Of arom
atics. Higharom
ptic naphtha is not gly.s;auisapce @ k
sp
mndsbies, but also consum
es &a
en
erfl in thd cracking operafions$ithout P
ing
my
useful ~rd
uc
ts. S
O, it
produces more coke and increases the dow
ntime in both the patm
ehemica1 p
d fertilizer
industries. On the other h
aid, the eyiracted arom
atic fraction can:be used in thq
aou
facture
of synthetic fibres.
,&&2 C
omposition of N
aph
thas
$pbl"" is a complex m
ixture of hydrocarbons. Its mm
positiopdep&ds
o&+e
crude oil .
proce sed and the conversion.proce~g employed. For the com
position oq
ba
ph
v, tw
o types of analyses aie usually carried out. T
hese are: ~
vd
rocarb
on
type analysis Individual com
ponent wise analysis 1
he hydrocarbontype~alysis de
term~n~~thepercenta~~of
~~
@m
s,
olefi&
naphthenes .
and aromatics. G
fferent tj$es of c
o~
po
~n
da
found inpaphtba fracti~
nsfm
vv
uses are
' given in T
able 5.b The approxim
at& cdrbon dum
ber range of the pr
dd
u~
is slap 8
ven
in the sam
e table. In Table 5.5, a sum
man, of quality+
of the naphtha-fiqctions porn various ,
' indigenous and certain im
p~
rted and w
orldWidqyailable cm
de);&h
respecQ9 the para!-
' '
fidnaphthendar~m
atic c~n
tents ofq
eir na$hth@fracG
ons $re given. The v
qu
e indicated 1s ,
for the full ranggnaphthd (C5 - 140°C
). ~h
~h
yd
rocarb
on
type com
position of naphthas fionl --
Indian crudes is @en
in Table 5.6 for boiling ranges of 60 - 85O
C, 110 - l2O
0C, 120 - 130"~
' and 130 - 14o0C
:
2 3
Uses of N
aph
thas
J.
The m
ajor end-uses of naphthas are listed in T
able 5.7. The use of naphthas in fefl-
and petrochemical industries and as gasoline is discussed below
.
Page 42
Table 5.6 Hydrocarbon Type Composition of ~ a ~ h t h a s from Some Indian Crudes
a b l e 5.7 Mqjor End-Use* of Naphthas
1~ Toluene - Solvent, high-octaneasol~ne component, chemical i n t e r m c d i a t e , e - , r
Xylenees - ~ r - o l i n e component, lacquer and enameis, chemical inteimediate
v m 2 0
- C
- . . .
2 E Zc
. .
. ~ e i v y n&ht;kab. :
. - .'
. ,, . - . . . . . . . ;.
Type of naphtha Light riaphthas
~ntehediatenaphth&- '
., . , , . (h) Olefins -and'$iole&s .. '
. . - . . . . . . . . . ., *. . . . . . . . . . . . . ( i j~mm(inia probuc&n . . . . .- . . . . . . . . - ..,
:.
p . , . .
:, . . . . . -. . . . . . -' , t.
.~. -..> . .
>. - -- - (a) V h f & ~ ( ~ a r n i s h &;nuf&ture:and pi$&inaphtha : ~:- r:. . . . . . . . . . : .: . . . . r . . . . . - .: , .. ,.. , .,,. ~. . . . . . . . . . . (6 ~ h i n n e r for paint& va&ishes,jacquPs ... ' i, :. . . . . . ' . . . . . .
. ., . . > . > . . . . . . . . (=) s toddad ~ulvefit?&ecib &l&&&foi\:dijc& m$ng'*idk::. ' . . . . . , .- . .<- . .* . . , ,
.. . - . . . (d) Mineral ~ p i r i t s - ~ G n n & foF~8ifitg- c d ? ~ ~ j ~ ~ ~ ~ ~ t i < e s&.itu@ 'I.. ::
End'uses . . . . . . (a) Gas making;gasoline
(6) Special ias&:ne ? . . . . ..- .,.. i:
(6) &ation g&lineji. . ,.. - . . . i b ) hiotor &asoliie :6 *,. .-: . . ~ 6 . -. . fd ) ~omm&ia@olv~nts-~ubber, lacquer &id pesticide diluents -
. . . . . . . . . .
lie) ~ e n z e n e - ~i%h-o&ne'gasoliee cbmjmnhnt; solver$, petrochemical manufacture; . '
?z
. . ,L :.
Page 44
.,-
~:~
@0
0m
bu
6tio
n~
qlix
alb
&~
s$i~
:~~
@
~~
ai
~y
~h
~:
sp
&i
gn
it
i~
~@
gj
n~
&m&
mw
,
On en&
nd
des&
ad
~~~4~~lihr~~,~~idBa1iCbnilitMn.8~~e~'~in~dfRdra.~xCf;;g~~~ p~~g~p~~~dklpa~o&h~~~bii.&i~~~~,
"nfi~a1~khe:gasP1i~a&ii&bs8;.~~&;r~e .Y
er
ef
js&
i~te
~p
a~
r~
o
au
ge
&b
~~
h6
~r
d~
g~
fthB
fl~~
,&&
U1
~s
&,a
$~
~~
~~
&ih
: '
grmssurc
in the end gas zone, w
hich is thatpart:of the p
solin
sair mix
turew
her~
the flam
e h@ m
tye
t reached. T
h@lscmoseh~PLpe~~~~p~~$u~a~~tb~~~&~~~.~n~~~~~~~th6~~&sbli~e~t0
undergoprc+m
e reactions: A
mongst-them
yn preflamepriducts are the:highly tem
perature ,\',,:.:,.xTl. .,;: ,i:
~
e~
~~
t~
ve
~~
~"
d~
~~
~d
'~
f~
~~
~&
~~
$~
&~
~$
,rtain
c.itical t~&
b~
~:e
~fi~
~h
tratio
n,
the end:gas w
in';pontaneo";,$ ;ini&
:.y2i;;k
..t:ii >.:"
,.,: ";.:'. e arrival pf the flam
e fr~n
teman
atin~
from
.the sparking
plug: this causes detonation or' knocking. If, on the other hand, th
e flame fm
nt
end sasE
one before the @
$d U
P of th$@
$&fi,
t&reshold:per6~ideconcentrati~n,~~ co@
JJ&ion
of the gasoline-air m
~x
ture \?fiI.k-be.w
~t&jut kbock.
;;. .:!,
, ::,~
s:5
,,:<L
3
- .
..
,. ,
.t .:;.,,
, ,'<
::!%:-,..I;
! :<,,
. .
..
..
..
.
..
..
..
..
,
.,
,
..
..
...
.
. .
. "
:
. .
~ig
bre
5.1 i
~h'dia~~~ii:6f~~.dt~~ir!a~1~dj~~il1,ati~n
CU
rye ffp ga890na 6nd.itagw
jR~anC
e "ark-W
ition engine perfor&
&i.
Thy fiont-end (0 to2
0 perbent e
~a
~o
ra
fa
dj
~~
~~
~e
'~
~~
~1
d
stb
ing
and& bl)trQ~l.$as9&-p~,~k,qr~~~r~sti~s
ofn
f"ll-bbili,ngg9$~~~$,.$&$f~&b the k
id
range (2O'toso'p&
ic$nt eva
p~
ate
a)i$
~ic
&~
~v
e
orddve&,ifity
a$:&,,+;$;f&;h.. .
':: : :,
:-. ;
.-: ,
:. ..;. .:;:: :,4
! .:
. . .
%,~
Y~
~R
oT
@@
~
Fig. 5.1 Typical distillation curve for gasoline.
The phenom
enon of preignition is encountered in gasoline engines. The deposits in the
combustion cham
ber are supposed to be resppnsible far hot spots which are responsible for
preignition. Som
e of these deposits arise from tail ends of fuel and lube oil aaum
ulating,in the com
bustion chamber. T
hese form carbonaceous deposits w
hich may trap lead salts also.
The build u
p of such deposits affects th
e octane requirement of the engine. W
hen lead halides or sulphates get deposited on the spark plug they cause low
shu
nt resistance (short circuiting).
1 (H
eavy ends contamination
1 ...
...... Preform
ed gum i~
pu
rities ' . I
.... .
. ,,
Pobr cold starting Im
proper volathiti coir&b%
r ; . , r:
' .: l" '
i:. ,
Water contam
ination i
..
-~
.~
~:
.~
;i
:~
~.
f~
..
: :
Hot fuel problem
s .Im
proper-volotilityeontro1.-- ~
e~
~~
~d
~.
~~
~,
~~
~~
~~
~~
~
: ; ::
Carburetor1
High
Pcrformqi:,&
g ~
!$.$
~~
fco!$
$~
~
impurities
,; :, , i. &.: .,.: :
inauction system fouling
-----I
- .~
- .
.
.,.. Soluble m
etal :
cpetaminants
&wr.m
ntdminatiU
I'i . " ..
..
..
..
.
Filter plugging ;
.. ,
. @ifi,:(~!$P
m)iC
,o~ta&nation ,.,,..,,
...._..... ,.:,
-I
2,. . ., ,
~,fg
h,~
~o
~i$
ic
content Spark plug fouling
XV
;~
.
~i
J
. . ,,
.
. . /v
olatility
ch
aracteristice The volatility of gasoline affectsth
a Q~
&~
~$
~
af the ecengine is
a number of w
ays, which ~
rea
ey
$~
,o~
-,~g
r~n
g,
r$p:;!f w
arm;yf3
vapour lock, . .
carburetor icing and crankcase dil~
tion
r(~,&
,~~
,~$
i~n
of t
he,.~~p~.e.~Iub~.~.a~~~~g.~.oil
with the
higher boiling constituents of the gasoline): The fuel m
ust be sufficiently volatilc to give easy starting, rapid w
arm-up, and a
~e
q~
gte
~g
ap
ori~
tion
fo
r pro
qr ,d.E
$.ribution bctyeen* the
cylinders; Conversely, it m
ust n~
t
b:b'&'"ol&
ti~&tli~t ',kipour losses fibm
the'fud @hk are
!,
.exccssivear that-vapouris forme&
i-t@ ffibf%
fic causing vapouf'#&k'rnich
dj%&
&d
the '
'.
flow of fuel to th
e carburetor. To som
&&
kf'6fil%hcse co
nflic
ti~@
ii~l~
~&
cn
ts can;6?ibet by
usin
ga nibre volatile gasoline in w
intcr than in summ
er, bu
t some dcgrce of com
pfomise is
,, .
..
.
.<'i. :...
.... .
- .... '.
/:.:..l.:. ......
'
ob
vi~
usl~
~~
ec
essa
r~.
J o
xid
ation
Sta
bilit~
or gasolines. ~hi~d~pg~d~stori\ge!g~s:o!irlps
undf.pg~~
&a)y. but
pro
gressiv
e oxidatibn dcterioration. Thc rcsult of' this is form
ation of n~
n-v
da
t~!~
~~
,mm
y
residues. If present in the gasolincs, th
c gumm
y residucs can causc multiplc G
ouble, such as deposit form
ation in thc carburctor parts,p&pPr&~,~ifA1d~o.f$~~t~jpluIji$~p&~p-+i~
the s.m
A~
~p
iwyh
$r.. ~
y~
~~
~l
~~
~c
ci
fi
L~
~l
~~
~~
,r
p~
c~
it
i~
~~
~b
~~
~~
i,
~~
i~
,y
f~
~~
~j
$~
~~
~~
~~
~~
~~
~~
tian&
&p
:q~
qq
~"
r~.;o
&g
~?
.pp
cscnt.
jn.;;tk f4&lj(erjst~nt
gum);. ~8fi$a~EFia!bFF:y~~r:$~~~~$:"t
proccdur* arc used to dcterm
lnc thc tendency of w
m f~r,@ati~~~~~~~~~~~~~;fpp&~f!fi\~@~~:
..il3g;(+m&
qna~ion :is! due: tp;.o~iPativ.c. #g&g@
ti~g~$$lyfqc\ j ~fi~$~#~~~$k~.fif&pf~$~~.~'~~~ ?@
;irr,d~~ +
gk
os4
datip
a 0nc.c initiate?. $Pp-941~?~~?~~9f!~4f0~73~~3~%k~~fir0$css1ve chain reaction. T
he primary products of auto-oxidation are hydibpcroxidcgl:T
,,~.~
$ecompose
+ &~
~~
~r
$,
~f
~a
~~
~f
o~
mi
~~
m~
re
free .rad
ic:?1,~
,1~
~~
i~g
, P F~,$~.'F!J:~C$?
tpP
P~
!?$
~$
~I~
&~
9
f~
~r
i~
m~
re
~h
y~
ro
p~
r~
~i
de
s~
~
a-$&~<~&lz&;:!6 guh .rm
ati1onn, ,a
~.F
B~
P[s4
~~
@&
y~~
~ti'Jr.I;:2
$~
I rpc I: ,?.j...,.....G
. e
.~
SO
~~
~<
S
... am$n&$Fgo$?by+&! aiC
!?$i$
)it :$%
"., to p
dfo
rmatio
n duridg++&
i~&.uiatea
also ui;aerpo &~
~:;x
l~t~
ori~
~~
g%
+$
$$
!..~
' ''
'.
Most petrole"?
products a& $u$ceptible to deterioration~
n ~f
~~
ft
,,
$:
~
\!dir $*pi?
composition an
&~
h2
~~
&$
2~
c&.o
f~m
21
1
. . am
aun
ts of nitrogen, sulphbr, organla hld
S-%
d%
~g
~~
. ,
.c
. .
;, :. ,,;: : :
Page 45
. .
,:j:
~~
06
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s~
~~
~
uvqq
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qvlu
alls
a!m
ouoa
a pu
s ~v
a!qa
e~d ai
om B
slua
sa~d
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amoq
'sa~
g!pp
v
JO
.aq3
4 su
p! 3
0 io
~q
uo
~
.mar
, 4 B
UE
~q
a~
nq
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a
103
Laua
~uaq
aw
uo v
ag
a p
qm
w
s..
sp
4~
p~
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au!p
ssD
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n-u
~~
sfi au
gua
Su
~~
np
L
[~s[
na!w
d SU
!~[B
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uana
pus
Sy
uu
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au@
pa~q
snol
q,o)
lnsa
r s!
q& .
~oqu
nqrB
a ag)
u!q
$+
aZ
aq
UV
J 1!
8 q
a~
y
aqq mq em
qs\o
w
1un3
~id
maq
lua!
qms
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Page 46
. .
!. , ,
! i I D
etergen
ts. ..,,,.+
. . . The
,,. . control of deposit build-up in carburetor; fuel, injection equipm
ent and
,
inlet system.canbffer significant perform
ance benefits. These include:
. ,)
,
I ta?$Zd&ced exhaust:eniissions,
:,:: .
. :..,
,..!.,.- ,xi; .
. ~
.
,,
(bl !mp=$$id fuel e~
on
c&~
, I
(c) Improved-vehicle d
riv'eab
i~it~
, and
(d) R
educed maintenance costs.
i / T
he use of.;low levels of carburetor detergents typically am
ides; fatty amines and im
- idazolines can,give good control of carburetor deposits.
Co
mb
ustio
n im
prover*. A range of additives for com
bustion improvem
ent have been used. T
hese intluae: (a) ha
d ap
preciytoyi such as tertiary but$
acetate which w
ere effective at extonding th
e anti-knock effectiveness of leqd alkyls a
t high additive concentraticins. (b),;Q
epgs~,m
bdifiprs sy
ch a
s the phosphorus and, b
p~
n,co
mp
bu
nd
s extensively used to .
. increase the g1oW
:point of engine deposits. "
. , : ,
(c) 'me
catalytic approach where the ?atalyst is added to th
e fuel which ;:: ,appeaia ,
! ,. 4.,,
to
. be
increasingly considered. .
..
5k
;~
ew
Gaso1ine!Blendinggc~mpopent8 ,
,, ,
. . . , . . ..
. . . .
. .:.
; I
. : .
.
. In recent tim
es, pollution, from autom
obileexhausts: has increased toalarm
ing~li.V
elsi S
tarting from A
pril 1, 1995, new
c~
rs
~~
old
in
four metropolitan cities of India, i.e. D
clhi, M
umbai, C
alcutta, Chennai are fitted w
ith a catalytic converter on their exhaust pipes. C
atalytic ,. .~
.! , . .
converter is an anti-~
llutiori'devicetittcdto the exhaustsygtcm o
f~e
h~
d&
~It~
~c
lps
prevent em
~ssio
~o
f'no
xio
us
gasds in
t~
th
e atmosphere. ~
t.is-tu~
ul:&
in.sh
a~e
&id. c0nipA
se.a hoiit?'jico~
lj.hetallic or ccrariii'cd'i'Sc coated With 'noble m
etals like pl~
tin~
'~&
hd
ipa
llad
ium
. ~
o!k
&F
ebl~
jAiy
Be'i6
ll~o
f~atatal~
~1
in
ii:lractibn which w
ridbis exhaust;eonponents ltke. carbbfit"m
onoxide and hydro'carbons Bafrn
~ess~
by
converting. th
cmin
to carbon. dioxide 'and,
wat'e%
:Thcse inetals are spread over a Inrgb su
rfaccto proddeihbim
atc.wntact betw
een exhaust gases and catalysts.C
atalytje corivdrtcrs nie rcquirgd.::to sim
ultnne&sly
:remove
tdfg~0Eeil'pal~utants,~rc6ist.'Cahlyst:poisoning bycontam'irrants;md:~~tJlo~g~~~~Ofa.a.~two
t~e
~~
of.~
a~
~~
ytit~
co
nv
er
tcr
s. T
wo-w
ay systems using.plabinum
and
:pallad
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leavingnitrogen oxidcs unchwgd.:~he~latt'cr.,is
o%idf~
ed-th,rm&
h..air,: pum
p; Threc-w
ay catalytin
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ms. O
qplpy plati~m
Gip
all~diY
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rhodium to rem
ove all thrcepollu~ananb simu
ltnn
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oly
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-i.n-,thegawli~~:issj~ju~ious tha..honeycom
b disc of the:co
nu
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eta
l.~,in
,~h
~d
~@
~~
a",r+
uc~s its potency; . . .,. ,'... .. . , .
. ..
-Bheiaquirem
ent olp
rod
~cin
g unleaded gasoline w
ill result in octane s$ortages qt m
any m
anufacturing sites.!The use of oxygenates in gasolines is m
ade for raising thc gasolinq pool
volume and its octane level, especially in
the critical front-end ran* The excellent bym
ing properties of oxygenated com
pounds result in increased op
erating
cficicncy of. the engines, thus com
pensating for the loww
calorific vrlucs of the oxygcnatw
. Simultaneously, 11.w
er
Page 47
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Page 48
PETRO
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slnte*and w
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gas (LPG
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(CN
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Me of LPG
ad hlel for spark-@ition
inbines has already &ehvsk&
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,fd'm:
advantages of fiPG over liquid fuels include the follow
ing: I
I i
pr
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, 4
x1
3.jr
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mixes.m
ore readily *i$X air.
(b) ' It
be used at somew
hat leaner~air/fuel ratios. '
(c) fi @
ves lower em
isSi0ns ofpollutants ?carbon monoxide and unburnt hy&
wapbo&
). (d
) . It reduces cqybustion chamber dehsits.
k) It had excellent ;in'ti-hoi~+iforriizince, providid unsaturates are
excessive proportians. $
,!* ,.. s..,
(f) It is resistant to preignition.
I ,
ti
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It gives excellent cold-start and wa
h-u
p p&
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fie use O
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PG
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Khg 2 h+ber of d$hanM
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e include tde follbw
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fyithstat;@d, hu& hjgh,
pressure. r
c>
\
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tank is quite bulky. (c)
The perform
ance O~
LP
G
in tenns ~f em
isyions, d ecoriim
Y myis depe*degt on
(7 its com
position. The W
C.4 ratio
and the level of Lnsatw
ates strbngly Y$jlence
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tion show that fn. a
Weh
Page 49
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Page 50
uth
er extra t' Q
ce qes for the sep atipn of arom
atics ad
on
-
o atics use solvents
with m
uch highBr'?fk'B
$$biiie$ ~H&"~%B~~$'~I~~W&~BQ&S#~~'~~G"&Q~~~
very in that rafthates
with very low
, as well as extracts w
ith very high arpm
atics contentr can be - -
. . - -.
made, O
f the processes ayaJpRIe? th
e Shell%.ulfi&
e extra<$i<<
pG
e&
i. w
ide$ u
bd
, especial1y.for the extractionbf..~ arom
atics from hydrocarbon m
irtlires hu
or
e piqduc-
tion of low-arom
atic!solvents. . - +irrq
;:ltnz.~-t, -
.-
%
- ,
4 : 1
L,,
5.5 AV
IATIO
N TU
RB
INE
FUE
LSA
A
potentialfuel for'the gas turbine engines usedin alcr~Fe~tlir~s8highl~~mdstabi1itY, high heat content, low
vapour pressure, good combustion charakt+
ris$di zodd kis-ty- tem
perature relationship, hi&, density, high specific heat, a
u#
Jo
~t
~7
#y
~g
~+
~q
dl
in
g
charac$ngtics. T
he combustion properties of aviation turbine fiiet (A
gJilfi~
yti~
ela
fi controlled using several of the follow
ing five tests: smoke point, lu
mid
~m
eta
~u
~b
er.
aromatics content, aniline point.and m
avitv. ,.
I lr
7
- -
$.
, T
he heat of combustion ishorm
ally ,calculated f~~~-,-@j9aP~t~ad@g~tYYY
&)ely
hvb basic types ofAT
Fs, the k~
msin
e type and Ue
wide-cut$;
,$jnek&,a$hgm
ira\18ed w
orldwide+ T
he kerosine typ
~
"of AT
F is a much m
odikC&f@
R@+;&
l&iTR~gpr
kernsin; oeginally used in gas fY
rbine engines, whilst th
e mde-cdF
ap m
y ~JJ
AT
is a w
ider bGiling range fuel in
cl~d
ibd
somegasoline fraction. h
$8&&
:idird$e+ r eeia'Ij?ed
fuel grades are required for limited m
ilitary use, as irl su~db!oriid aFr$r'affv ' tk ?'-;' '"'
The properties that control A
TF quality are listed in T
able 5.14. ~o
hb
&fi$
g'*
&alit~
relates those properties w
hich directly affect the ability of a fuel to ignite properly. With g
~s
turbine engines, the volatility factor assures delivery of fuel~ta~b~e+tb~bi~e~~hb;bpIe~~ith satisfacto
~ig
nitio
n and flam
e propagation characteristics. Ioturbin&engines, the L
iishd
uld
m
t allow deposit. to form
in fuel nozzles, fuel control systems, turbine blades, cpatings and
wale, all of w
hich will degrade perform
ance.
Page 51
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Page 52
.. .
. ,.,
.
The volatilityaf ATPa is contfdled to m
inimize the]oS8 off&
f&$
&$$&
uri;id
ed.&
,.raR
tanks due to boiling-off at high i1ditude8. Fop this
the
"&&
i&$ '#k;$Ji$he
.tn, ATF is desirable. D
istillatioq apeiifirntjon regu
ire~
at lest 20 vol,c r
&d
J$
e'&
~$
.~~
,&jt+
~T
he
20 prcen
t point control8 hvnt-e~d.w
]ati]ity, and ensures ~~
k&
:f~
&~
gjjj~
+~
a~
i~y
:$
~w
&
i ,i 001d atadbg and lim
it evaparaWon losses st high altitudes,,
I .
..
6
.,'
i .)
*uh-igniti?n of ATF can happen w
ith a algh
t leak of fu&'from
the engine .h&
&: ifter
~h~f!b~!A!::"~.f?p a h
e1 line fracture during aperation. T
~:
~~
&~
re
,f
W
BU$ .&i%
n ~
~c
~e
a~
~~
w
~ain
crease in vapour proe?U
n, &.the atm
Ospherii ~~eB
B,u
iB;i-a~'d
<~e.2fb-~yam
\1i ~rew
",""duel increa-
a,ldao tho ~u
t~-,g
njtio
n
tempe&
"&j
in;&&&, "",
'. ,
.
Therm
al prop
erties. Jet engines require the use of fuels which ha*L
owfreezin~poinh
, and m
aintain their flow properties. A
high degree of thermal stability of fuels is nqbirea t.a
Page 54
94 PETR
OLEU
M lil&
PN
MN
Bk
OQ
W '
A~
ty
pi
ca
la
~i
~i
~n
0*
b~
~~
li
~W
0~
~~
~i
;P
.4
~,
,
known
as conductivity unit @U). %
he .c.onduetivity of a fuel in a tank
~.b
emeagu
re4directly by
portable (.m&
te~
~:
~~
~~
r+
~fiifu
re
d~
' by.. M
aibak or Em
cee ~l
ec
t~
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~,
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;:
~?
~~
.~
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dem
ink' rdi~e~wa~~i~~~&&k~iNEysf'.~~~:
CU; T~
US
AT
E.
ha9:$~~w:10:~.~&td&bhvi$;,~he e
od
~~
tl~th
t4.&
e~
:~ffe
tttthe
:ra
tt khi&rthe!~habgedi~nv,are-
re~avedifibm~tli'e;fue1,'
that..is the-charge.relaxation. The tim
e taken
f~?lttl&.~cH
&if&
?ik~he .itel. $0. Qll from
.,a given valud~&
lh&h2I&
fl&iue~~(6he:.dud1'sS
half-walue.&
im'e.=
,tI/y =12/con~ctivity'~(C
U);.sec)i@
ves an
in
di~
~tio~
E.w
Beth
er.static charges.are.likely to..be'l$i~
iddy~$i??fibt;
Chargeq.:c,a.n.ac~um
ulat.e .
..
..
.
tola
~a
pp
,~ci~
bl,~
:eext~
rit:.~n
ly
if.thct. re1,mation: tim
~an
d.:~
he~
h.alf~
~aIu
e tim
e. aIe
...
..
..
..
..
.
higlxi,. r.;;r: l.; i;
.,,, mg. ~gefi~ation~~o~~static:electrical:~rges,in~handling,oE~~Fs
. ,
has.Iong:beenirecopnized a
s#~
~d
ti'all&
t;ph
~zd
~d
.~~
A
n~
mb
ero~
m~
~~
verig
g~
pu
rnp
jng
~.a
tes, line velocities, bottom
loading-(no .splash filling) and settling tifiidi'-~tiv8: b&
fi$g2!~'e'1?:ii~1y. adoptedby. the m
ajqr. oil cofhyl&
~le~
.iii:stahdaid; ptactid&
dor safe: handlin&.:df~thesq.pxod~ts.
:4s aw
additipna1;safety prg@
,ution a static dissipator g;rldit~ve.~a'~~beti'dd~d~.~~~~~~~~~~.ad$itiv~.
per_
mit~
A,f9
r,.u.~
~.
in ..:@@lD1.2494. specification :is. -~alledi;@~&~~an~~-~,@~~~addi~on?rate to -tharjfiiel~
B:Z
ippm
(rnaxilnuml..:T
he !amou?t o
fadd
iti~e ~r
ree~ui~~,de~e~~g~R~~~tk~16,&d~,~~{r
f<&p..ybi?h ..the
fuel was produced, since th
e additive ie$Giise'is' affeit5dX
y tFC vahatfoii hi th
6 th6m
ical ~
~,~
p.,i
o~
~~
f,t
R~
~M
1~
It i%
lts;yfd t4.q.djilpte 8,stati~ $
jq
~i
~a
t$
y'.$h,,@
$l.be,fol;q ,mq+
ing pltfi4dM
w& tqp!4+,fud..Thie,,k
done.(o ens~~e.,g@gw
$e .~~j~~~[~fl~fi~~~$q~~i~eeit,,3~eIfrleJi .
.::::S&qtjc dis?iea,Wr, d4iti~iti~~ln+the-~~~~~~t~~tio~;~~qf#)~~~~~
'p$p;:pJfi~$Ay&
hf b$ereaL
U~
bili$
91 ~*$.akive fitabili%~,of~t)sfupl.or it@
~w
by
gt
~~
~q
y~
~t
z~
~~
~~
~~
~~
&~
&
&t
in th
e additive
may
re4pc.e .tlle,kater seeqrom
kkr :ir!
~-
(~
p$
li~~
q~
~(
W.
......... 4
' 1:bx;&6<4t:;5 .
.. .
..
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.
P.?~!I~.s. ,. .
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.,
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,: .,:.i.<. . .
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-
!DIESEL FU
ELS . .-
..
..
..
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.
.I
<
! .:
:::~l,~
,:'a.+
::, <
,>
;.,, . ;
:~
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?,.
$, ?, ......
,f:
2,
.,,: .-.. ,,
kig
h speed d
ie~el toil (H
SJW
and, ligh~diesel;oil(ZW)~tiretpro~ur~:~~~~.Ogr .cow
tw.~ H~D
is:Wldely usedindiesel:engine f
~ra.uto~otjrr;e;.~.~~o~eS.,,a~~p~~~es;~o~~~~~~j~~~~~~~~ptjves.
Statjlonary. anti m
arine! diese1:engisas:as:. hsfa!J.ed
;iq n?;hips,or
.ugg$.f~r:;dec@yi$y ge,neratiqn
ompared ...b
:th
eIr~et,q
frwo
r~d
,. !~dia's,~eq~d[.~~;di~~~~f~~ls,is.
*, A
",..
rowhly sijr
gasqline. .~irlce s&rak
hk
ru~
~#
e:sel fj-$ctlpfiifo5;p, @~&
:5~.%!dq,?il;~.ifiW
Sd, 'varying am
duots.. @f selected: cracke,dddij;sti!l.akp : from
iconvqcsipn;. p$c@pee .'s~
c~
,,g~
,flqid
d
rata!@k crackipgV
.h~dr~cr,8cking, cykiqg areiw
d, t.o:incpqp$ t+e.y@
u.me ay.qjlabl.e:'for meeting
the growing dem
and of diesel fuels. .
. .:.: iT
k, P~
WX
!
~+
i~
,f
?~
t$
~~
pf
%
?$ern! f~f;..~?vp~;e.9,sio?~i,~tip,n~e&$~~~f aqy;qpl.ustion,
volatility .and.~ieanli,~~~fi.~$:b?~hi~ r~;@n~~!~d.,t~:ir~~~id~i~~~~
qq~,e:d
ef $'$y2,yl
th~(Bt
p~
tr
d
PF
~~
c,&
~
U@
Y a~c.li?@d:i~;~91)~~.~t{8,,$?~&~p9E~l$e.pd;,p.19
relates those properties which directly affect the abilitjr'dhi.~fud to
$;properly. ieiil f&
ls m
ust be suitable for handling by the injection equipment. T
he handlingialid storage charac- teristic is a function of volatility, fluidity, contam
i?a,ti,qn ddfin: yfinem
ent and product s
hi~
9~
t ?r!qovem
ent. The characteristic,of cl&
"filihebs du~n~liki~sk633f&.t~d~&&i~tikition. .
..
ti[ace:contam
lnation,dfid kh&&
gre$ :of +~
$i:$
n~
~~
tab;ili~
j;of
th
I;di-ti~ar;I'~
:fi~l:. ' .
: !::.: . . :
!~
ie
~~
l~
u;
~'
fo
~
automot+ (I&& begded
gbo;d igniti;niiuali+, o ensufe .. '... .$ d&
y staitirig aha
~u
l~liu
r co
nteit m
ust bk c;iti&
liy c6~&bll&'~6.iiii;ii&h&.eiivit~~~~fit~l
Poll,ution,C
ombsion, wear and
, .
.
Fig. 5.2. Typical oscilloscope traces forcompression ignition
Page 56
PETRO
LEUM
RfflN
lNa TEC
HN
OLO
QY
.... .-
. .,
.<.
and ' i!
.': !! .
!i ; r.: ;.: ,?
r,:fhtr'$
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3,
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. . .
(d) Nkdedin the es/tikation of &
ane index :
' .
! (:<
.. .
. .
, 'I
"' '
'
,&a; S
~@
cgravity (o) for t6e w
.nvira& ~
f~
e&
~~
ol
.d;
-
bv
~li,&
&,&
.
- .t
..!I.
temperature of 15'C
%i !
..?'!:;..
. .j
(b) Greater carbon depaits expected for higher values of m
'bn reeidue
11. Particulate (a
) Indicates the potential of emission of particulate m
atter m
atter I (b) C
o~taine prim
arily carbon particla (c) h
uh
na
oy
wt@h
te9
finned lu
ph
ase
&qg&
) 'pprtidm
: 'ab
f~~
rb
md
c~
9
pg
em
c m
at
ed
iq? en%
nme$t
u e
Ld
om
4-
cawe an ill e
ffa on hum
an health Exeasslve soot W
de
a m
wt clog the ex-
haust valves (
,
::-. 'r
72
. Aeh
(a') Resulte from
oil. water-s01"ble P
e~
rc
om
~~
or
-w
loG
&, such w
dirt and mat.
(6) Can be uaed to decide product's suitability fdr a given application 13. Sulphur
(a) Controlled to
. ' '
cornion, wear and tear
I1
(b) C
aueee environmental pollution from
their combustion p
du
ete I.. -
I
I I
~(c, ccirrosive in nature and causes p
hp
id problem
to en&e
parta 1
Particulate m
atter con* prim
arily carbonpartic1es. Carbonaceous prticuIa?s
that
fom
hm
gas-phase proceaaea are
generally referred to a. smt, an
d those th
at develop fmm
p
~m
lysia of liquid hydrocarbon fuels are generally referred to aa coke. B
ecause mo
t particu-
Page 57
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