Professional Documents
Culture Documents
@facebook: https://www.facebook.com/pages/Ebooks-Chemical-
Engineering/238197077030
@facebook: https://www.facebook.com/AllAboutChemcalEngineering
@facebook: https://www.facebook.com/groups/10436265147/
ADMIN:
I.W
<< If you like this Book, than support the author and BuY it >>
PETROLEUM REFINING
TECHNOLOGY
Dr.RAM PRASAD
B.E.(HO~S.),M.Tech., Ph.D.
ASSISTANT PROFESSOR
DEPARTMENT OF CHEMICAL
ENGINEERING HARCOURT BUTLER TECHNOLOGICALINSTITUTE,
KHANNA PUBLISHERS
Operational Office: 4575115, Onkar House, Room No. 3-4, Ground Floor,
Darya Ganj, New pelhi-110002
Phone: 23243042 Fax: 23243043
Despatch Office: 11, Community Centre, Ashok Vihar, Phase 2
Delhi-110052. Phone : 27224179
Regd. Office: 2-B, Nath Market, Nai Sarak, Delhi-110006.
Ph. 23912380
Published by :
Romesh Chander Khanna
for KHANNA PUBLISHERS
2-B, Nath Market, Nai Sarak -,*
Delhi- 110 006 (India) It givesme a great pleasure in presenting the book on "Petroleum RefiningTechnology'
.The relvant topics for working Chemical/Petroleurn Engineers in Petroleum-Refineries have.",,
been covered.
The first chapter gives an account of theories of oil and gas formahon, methods f o p ,
exploration and drilling for oil and gas. It highlights the development of petroleum refininB
industry in India. ,. <
The knowledgeof chemisty and compositionof crude oil isessentialin the selectionof the
Q All Riehfq,Regerv,ed , , refining processes. The characteristics, constituents and classification of crude coils have been.
discussed.in chapter 2.
This book orpart thereof cannot be tmnslated or reprodued i n any form (exceptfor review or
criticism) without the written permission of the Author and the Publishers. Indian crudes such as Bombay l-hgh,Assam are waxy in nature. These require sped;
method for transportation. The problems related to the handling of waxy crude oils and their
feasible solutions have heen discussed in chapter 3. --
Quality control of petroleum-productsisa necessity if the products are to give satisfactory
wrformance to the customers. Bureau of ,lndian~Standard; New Delhi sfandaLdizes ~rocedure
ind issues specifcationsfor eachpetroleumproducts.~efktion,methodandsignifi-eof the
various laboratory tests have been given in chapter 4.
Chapter 5discusses manufacture,properties and uses of petroleum products. Thischapter
First Edition covers LPG, naphtha, gasoline, kerosine, ATF, diesel fuel, fuel oil, hydrocarbon solvenk " '
Fifth Reprint :2008 lubricating oils, petroleum waxes, bitumen and petroleum coke.
Petroleum refining processes have been discussed in six chapter (611). Crude ou
distillation is the first unit in the refinery and carried out in two stages-atmosphericand vacuum,
Before discucssing these processes the removal of impurities by electrical desalting process ha,
Price :Rs. 185.00 been discussed.The influenceof the process variables on the opera tion of a fractionatingcolumn
?.*
and the scope for improvement have been discussed in Chapter 6.
Crude oil distilltion produces reside which is to be upgraded. Thennal conversio~~..
processes for this purpose include visbreaking and coking. These processes have been discussea
Computer Typeset and Figures designed by : in chapter 7. lh
Steps Computers, D-2/77, Dayd Pur, Delhi 110 094 Catalytic conversion processes use catalyst and either change carbon number or carbon/
Ph. 218-1367 hydrogen ratio. The most important processes include fluid catalyticcracking, catalytic reform- -
ing,hydrocracking,catalyticalkylation, isomerizsltion and polymeriza tion Catalytic isom& tion
neither changes carbon number nor carbon/hydrogen ratio. These processes have been dis-,.
cussed in chapter 8.
f
3 TRANSPORTATION OF WAXY CRUDE OILS 29-44
3.1 INTRODUCTION
3.2 PIPELINE TRANSPORTATION
3.3 WAXY CRUDE OILS
I 3.3.1 Definitions of Rheological Parameters
3.3.2 RheologicalClassification of Fluids
3.4 FLOW PROPERTIES OF WAXY CRUDE OILS
3.5 PUMPABILITY CHARACTERIS~CSOF WAXY CRUDE OILS
3.5.1 Temperature
3.5.2 Yield Stress-Model Pipeline Test
3.5.3 Flow at Restart
- - -
10 LUBE OIL MANUFACTURING PROCESSES 296-319 12 CORROSION CONTROL IN REFINING PROCESSES 328-338
10 1 INTRODUCTION 296 12.1 TYPES OF CORROSION
10.2 EVALUATION OF CRUDE OILS FOR LUBE OIL BASE STOCKS MANUFACTURE 296 12.2 FORMS OF CORROSION
2 PETROLEUMRERNlMp TECHNp4OQY
kfikwkr;~ x ~ t ~ ~ A ~ ~ o h ; ~ AND
R b REFINING
~ a r c n o ~
1.2 FORMATION OF OIL AND GAS
There are two theories of the genesis of petroleum: the organic theory and non-orgMc Owing to the presence of fault planes and fissures, a seepage of oil to ihe surface may take
theory. The former holds that petroleum is of an organic origin and is the currently place. The analysis of surface samples of soil, water and oil or gGy'in such cake$'; for
favoured proposal. It predicts limited reserves worldwide; moreover Indian reserves are detection of oil and gas is known as geochemical prospecting.
predicted as minimal. The latter maintains that it is of non-organic genesis, supposedly of Magnetic surveys are then done. Magnetometer survey is carried out either on the
primordial origin. On the basis of this theory, oil reserves would be much larger than those ground or from the air by air-borne magnetometer. It is based on the principle that the
predicted by the organic theory. India, oil-poor in the organictheory, is predicted to be oil-rich magnetic attraction on the surface depends on the magnetic intensities of the rocks and their
in the non-organic one. distance from the surface. It helps to delineate the nature and possible dip angle of the
The non-organic theory that was much prevalent earlier suggests that oil is formed subsurface rocks. Dip is the angle that a geological stratum makes with a horizontal plane
by the action 'of waikr on metallic caibides or by atmospheric radioactivity or by cosmic (the horizon): the inclination downward or upward of a stratum or bed. The same principle
radiation. ?he rme occurrence of oil in,meteorite~,igneous dykes and in petrozoic rocks can be applied to the measurement of the gravitational attraction at the surface by a
weighs in favour of the non-organic theory. gravimeter. These two methods together help in demarcating areas having thicker pile of
The organic theory which is the most prevalent today, suggests that the petroleum sediments with better chances of oil.
was formed from remains of plants and animals that died millions of years ago and accumu- The seismic method of oil and gas exploration involves generation of a series of shock
lated on ocean floors. Tiny, minute marine animals and plants comprising mainly algae, waves in the subsurface and picking up the reflected waves by sensitive geophones which
fungi, diatoms and foraminifera used to float on the surface of the sea and were abundant are laid along a line on the surface. The time taken for the return signifies the velocities
during the Mesozoic (about 225 million years back) and Cainozoic (about 65 million years through the subsurface rocks and these can be interpreted to assess the nature of rocks and
back) period. On the other hand, rock surface and land are continuously getting eroded. their angle of dip.
Broken pieces of material like sand, clay, lime are carried away by rain and subsequentJy The field studies are supported by an e q u d y elaborate testing of samples in the
depamted on beds of oceans. In millions of years the sediments pile up to a great height laboratory. Sophisticated modern equipment like Electron Microscope, Mass
(several thousands of metres) and subsequently, pressure and temperature continue tq rise Spectrograph, X-rays Chromatograph, Nuclear Magnetic Resonance (NMR),Spectroscopy,
in *ose rocks. Shells and skeletons of dead planktong, sponges and jelly fish sublime.on sea Infia-red, Ultra-violet and Differential Thermal Analysis (DTA) are indispensable aids. On
bed and subsequently get buried under the piling sediments. Aerobic bacteria present infie the basis of all these studies, the most suitable places where oil is likely ta be found is
ocean flgor and sediments act as scavengers and attack the organic patter. Some complex selected for drilling.
chemical bansformation takes place that is facilitated by the enormous overburdeq,:pres-
sure, rising temperature and the absence of oxidizing agent. The process continues 1 1~ Q L ~ NFOR
G OIL AND GAS
through various complicated stages and chemical reactionsforming fats, amino acids, lipids The drilling equipment (shown in Fig. 1.1)consists of a tall huge tower called 'derrick'
and finally into oil and gas. Oil is produced within the temperature range of anchored to the ground, engines, Qd pumps, water tanks, draw-works and many other
100-200DC. Source rock when subjected to greater overburden pressure and temperature modules. The travelling block is suspended from the crown block (a large pulley at the top of
beyond 160°C for a long period does not generate liquid oil but gas. the derrick). The swivel, attached by a large hook to the travelling block, can rotate freely,
and the kelly is fitted onto this. Rotary table at the centre of the derrick floor holds the kelly
Amongst the different sedimentary rocks like sandstones, shales, clays and limestones, (which has a square or hexagonal cross-section) and can be rotated at a desired speed by
the clays are more suitable for formation of oil and serve as 'source rocks'. With the piling
the engine. To begin drilling, the kelly is hauled up the derrick, its bottom is fitted with a
up of sediments, lower sediments get progressively compressed and the fluids in them are drill bit and lowered through the rotary table until that bit is resting on the earth. With the
squeezed out. Oil formed in the clay rises up or sideways and if the rock above is,like a starting of the engine, the rotary table rotates the kelly and the drill bit which is pressed
sandatme with pore spaceo, fissures and fractures, the oil tends to get accumulated in such hard against the earth by the weight of the drill string above, cuts and penetrates the rock
a reservoir, provided this upward and sideways migration is prevented by the intervention at the bottom.
of an impervious layer of rock known as cap rock from moving further. This layer traps the
Much of the success of drilling depends on the quality of mud which is a specially prepared
oil. In a normal oil pool gas remains at the top, oil below i t and water further below. These
slurry of water, various chemicals and adhesives like barytes, bentonites, xanthanite. It is
pools remain intad till disturbed by earth.
pumped through the drill column to carry out several important functions such as removing
cuttings to the surface, cooling the bit (heat generated is due to friction), lubricating the
1.3 OIL AND GAS EXPLORATION bit, providing buoyancy to the drill string to reduce the hook load, retaining the side wall of
Oil exploration is a complex process. It begins with prognostication and involves au the well from caving in, allowing to examine the hole by lowering' a variety of instruments
entire gamut of activities. m e hunt for the hydrocarbons is focused at the favourable and balancing the formation pressure that prevents the formation fluids from running into
or promising areas based on geological considerations. Geological survey aims at selection the well. With the increase in depth of the open hole, the side walls of the well tend to collapse.
'and mapping of such areas which satisfy the criteria of being sedimentary rocks preferably To avoid this, a casing pipe is introduced into the hole. The annular portion between the hole
of marine origin with the presence of anticline structures of Mesozoic (50 percent of oil and the casing pipe is cemented. M h e r drilling is carried out with smaller diameter bit, and
produced belongs to this era), Cainozic (40 percent of oil produced belongs to this era) and at a certain depth a smaller diameter casing is introduced and cemented in the same manner.
Paleozic (10 percent of oil produced belongs to this era) periods.
v
3
J
LC.
20"s
" W X
= Z m
9* - g
e,
= * 1k *gz$. c" z9E
clmem u m m
w,.CLg g 3 q
c
8 15."Fa; ZB
? r-$. g g"c$
1 8 - g $ g * C P gg - 0
P :&g m g s p
3 q
5: - i g s e . * , . g g 3
c a c 8 - s l$go"*g
0 m o -
C
"2 %Z " Z ~ E g g1 Eg. m5
r $ 3
1 -". a $8' 2. goR m3 kg,pg
< q U w
0 9 C w m E'mg g $$
@'" 2 B $6.;
3 u:gg gap
! $ a m ~ 3 , ~ e =
m q s $
e lat sr 1r n
Fr0 % C a w B r ,+
D a m ! $ 8 E&e:&g
u, ;ilc E e ~ s g8
E k " "
g a g $ 8.1.&
? ;1
ape 9 m m 0 E g
m
" g a
rEv-
8. 3m *g ga
B i.3 me, e
? E a r , 6.9.
1 €i = &g.gQ
ggf
4 . d
8 g B ogmi ak, p2
"9 ag e , - m
g: g
s:P 3 skg:g g gJ
B 0%
eng
z u -,
s't ID . OPg: P3 xgEi
ptliwUk, .:: .;,
'' ; ~ t o ~ A n o ~ ; ~ ~ bAND
~ uRERNING
cno~
&:'A
pores. Second limitation is,$hat,the advapcing. water f q n t :bypaqsessjgpif~qt.~rt$n?~~of the pipe and abandon t h e lfield. It is beWr ts use EOR meth6da after primary recovery.
the reservoir due to difficult :wellplacements and wexpe+g:.,geologi+ c d g u r a t i ~ n s . It is imperative that proper assessment of EOR potential in the country is required for making
This lack of a perfect!sweep efficiency is responsible for leavingbehind crude oil'$ -!as not recovery plans. The successful application of any EOR process depends on its viability. The
reached by water.flood. ,. price of oil is the most important factor for how much will be produced and when. Gas
Anumber of methodsltechniques are employed to recqver the rem&ing oil. The diffkrent injection may not find wideapplication in India. It is true that natural gas or associated gas,
techniques may be ,broadly classified into three categories: propane, enriched gas and lean gas are available in India. But the pressure required to liquefy
the gas is high and it may not suit the shallow Indian reservoirs. So is the case with air and
( a )Miscible/immiscible displacement process nitrogen gas injection. But in some reservoirs carbon dioxide could be injected. Again it
Miscible hydrocarbon displacement (LPG enriched gas & lean gas) depends on the availability of low cost carbon dioxide in plenty. It is estimated that about
o Carbon dioxide injection 4-6 million cubic feet of CO2 is required to recover a barrel of crude oil, Although thermal
Inert gas injection (Nitrogen, air, etc.) methods predominate as most successful EOR processes, they may not be applicable on a
large scale in India. Depq of the Indian reservoir and API values of 28 - 45 restrict the
( b )Thermal recovery processes injection of steam or hot water for additional recovery because of apparently unattractive
Steam stimulatibn cost benefit ratio. Of course in Western sector it may be successful in some reservoirs. In-situ
Steam flooding (including hot water) combustion is the most difficult method to predict properly. Moreover, it is economical
In-situ combustion and successful in heavy oil recovery only. It appears that the chemical flooding viz.
polymer flooding or surfactant-polymer flooding may prove successful in India. For
alkaline flooding, acid number of the crude must be high which is not so with Indian crudes.
(c) Chemical flooding processes Polymer flooding method may become more popular in India not only for its easy handling but
Suifactant$olyrnei injection also for the economic returns. Surfactant/polymer flooding is required to be assessed
Polymer injection properly, particularly the non-compatible nature of surfadant to various monovalent and
Alkaline flooding bivalent metal ions and in Indian reservoimkhese metals are plenty.
The production of crude oil in India is given in Table 1.1.From a meagre 0.5 million
Selection of a suitable EOR method requires a careful analysis of reservoir tonnes of oil produced from one of the oldest oilfields in the world-Digboi in Assam, the
configuration and the oil properties. Trapping and release of fluids from porous media is indigenous crude production is expected to go up to 44.45 MMTPA (million metric tonnes
a complex phenomena. For a spe.cific system, trapping behaviour is controlled by Ci), the pore *r d u r n ) by the turn of the century. Till 1947, India used to produce around 0.5 to 1.0
geometry of rock matrix, (ii) fluid-rock properties, in particular, wettability and (iii) MMTPA of crude oil from Digboi and Naharkatia fields of Assam. After independence in
fluid-fluid i n t e r a ~ o n sincluding viscosity, rock density difference, interfacial tension 1947, two public sector companie~wete formed by Government of India, namely Oil &
and, partition coefficient. The general properties of pore system, its shape, size and Natural Gas Commission (ONGC)and Oil India Limited (OIL)to explore and produco oil and
distribution in the rock plays an important role in trapping of oil. It is established that (1) liatural gas in India from both onshore and offshore fields. Up to 1960, India was
Trapping of fluids occurs in unique and reproducible patterns which are controlled by practically depending on imported crude oil.
capillary forces, (2) Nearly complete networks of interconnected equal size pores exist ONGC first struck oil in Cambay in 1958-59 and in Ankaleahwar fields (Gujarat)in 1960,
throughout the pore size distribution, (3).individual pores have good accessibility with followed by oil finds in other pmta of Gujarat such as Nawagam, Ahmedabad, Mehsana,
adjacent pores, thereby allowing alternate paths of flow around igolated immobile phases, (4) Gandhar, Kalol, Tapti basin, 'etc. Biggest oil field struck by ONGC was Bombay High
Fluids can be trapped at pore constrictions for all degrees of wetting. Non-wetting offihore fielda in Arabian sea in 1974. In 1976, ONGC found a large sour gas r e s e ~ o i at r
pqases are trapped in discontinuous masses whose lengths are largely determined by South Bassein, south of Bombay High offshore fields. Also, gadoil was found in smaller
interfacial tension and potential gradient. For selection of suitable EOR methods quantities a t Heera, Panna, Ratna and Neelam offshore fielda in Arabian sea.
laboratory investigation under simulated conditions of reservoir are necessary. Mathemati-
cal models (3 phase, 3 dimension) are used to analyze the reservoir geometry. The past Crude production in the country has been going through fluctuating fortunes. From a
performance of the reservoir is matched to predict the performance of reservoir under high of 34.09 million tomeu in 1989-90, it dipped to 26.95 million tomes in 1992-93 and
different operating conditions. Based on these modelling studies, the most suitable EOR stayed a t that level in the following year also. But in the past couple of years there has been
methoais selected for maximum~productionof the oil in place. a recovery and the crude production was 33.865 million tomes in 1997-98. The offshore
In India, the increase in crude oil production is not significant during the last 4 5 reserves account for about 63 percent of total oil produced in the country. This reveals how
years. No new oil fields with substantial reserve is discovered. The percentage of poor the country is in on shore oil reserves and how much it is dependent on Bombay High.
primary recovery in the total oilgroduction is gradually decreasing. Rate of production from The production of natural gas in the country is currently about 74 million standard cubic
Bombay High is reported to have already shown the declining trend. Some of the old oil metres per day and the total gas availability for sale is about 61 million standard cubic metres
fields of Assam and Gujarat under prevailing price structure have already reached their per day.
economic limit. On economic terms, both ONGC and OIL may prefer to plug the well, pull
~FTR[31;ELlM,~ERPTORATION~~ODUCTION
AND REFINING a r9
*AOC,Digboi was taken over by the government in October 1981 and merged with IOC
Table 1.4 Consumption of Petroleum Products in India
The refinery production and consumptionof petdeqm+productsi s giyen$Tables 1.3-1.4. (In Thousand Tonnes)
In In$a the consumption of light.and heavy distillateshave beensfagnatkdgver t$epe.eod of
last Siie years. How+, the demand foi midd1,e ,&atjljates'ia'~'&ei$big's@ong'50 h$
.ip
r e c k t times. In order to meet :the' increasing d.em?d for, middle disFla%s:!60-65%),'the
second& and tertiary processink f@$ilities' . becoming$& bf1;1.bd.y~
. &e yelink$
. . cpmplqxts.
' . . .. ..
.::...., '
H 4 t o pmqesscrud? bib,?= gpttihgg+temati&awti6n:L d$&l?*%~+&<~j$?s ki+
efficienqies.'@e n,eedto co'nv* bottomcif:?+eb,arrelil:iii$ocleiitofuel
couM 'increase i h e r e f i n e ~
as~~mes,si~ific.mtim~;twce, ipIn,$a p@icul,+lyj@ 09pool 4aficit,c?nt$etddb$lwh a&d
India costiflues to dep,pnd feafly on impoited crude 'oil. '&e.,e$sting refineries skbuld
therefore upgrade,t&eirtechnologies, o p ~ i z e s n e r g y : c @ s ~ p*dt i ~fmpro+e&fficiencyof
furnaces and process equipmeritsto kclude the f1exib;iQt.yt;d p+c&g the broad spect,mm . . .c ~ d e
oil.
.. 1.S. Abbas, p e noxi-orgapic theory of the genesis of petroleum, Current Science, Vol. 71,
NO,9, ppF877-684 (1996X,
"
2. P. Dutia, The oil refining industry in India, Chemical Industry Digest, pp. 103-110
(hhrch 1997).
3. A. Borthakur, K.V. Rao and B. Subrahmanyam, Recent trends in enhanced oil recovery
by chemical methods, Chemical Engineering World, Vol. XXXII,No. 4, pp. 83-86 (1997).
4. A.X'~r0r.a:Status. &projectionsin the oil refining sector, Chem. Engg. Progress, Vol.
XXXE.N,o. 4, pp. 87-88 (1997).
-
CRUDE OlLS CHEMISTRY AND COMPOSITION
5. Aqonymous. India still lagging potential as major player on worid energy markets, Oil &
Gas J., pp. 19-22 (Feb. 12,1996).
2.1 INTRODUCTION
Petroleum, etymologically, means rock oil. It is natural organic material composed
principally of hydrocarbons which occur in the gaseous or liquid state in geological traps. The
liquid ,part obtained after the removal of dissolved gas is commonly referred fto as crude
petroleum or crude oil or simply crude.
Crude oil o c m in many different parts of the world, and its structure and composition
variestaccording to its source to such an extent that each producing area, and field, and
reseryoir bears its own profile just as individually as finger prints identify man.
!
pressure. The kinematic viscosities vary from 0.7 to 1300 cSt a t 37.8"C; the bulk of the values
being in the range of 2.3-23 cSt.
In terms of elements, crude oils are composed principally of carbon and hydrogen. Of the
other elements present, sulphur, nitrogen and oxygen appear as heteroatoms in hydrocarbon
I derivatives, some of which occur as petroporphyrins, i.e. complexes involving traces of metals
I (mainly vanadium and nickel). Carbonthydrogen ratio is usually between 6 and 8. A wide range
I of metallic elements have been found, generelly as traces, in the small amount of ash obtained
by burning many crude oils. The elemental composition of crude oils is given in Table 2.2.
!
G
16 PETROLEUM REFININGTECHNOLQGY
suth as metals, mostly in -small quantities-some contained in water impuritieg and some :;:<.Th& w&&p, &#b&ted .with ?oil:ma.gas & c c u m y l ~ t ~$8: o :usually
n~ - jn&&$aljris~lifiB)i and
existing as complexes in the hydrocarbon phase. appears Mmany fnstmces to' be modified$eaWater,tkepnncipa1:diKere'nc~s~bei~ a'deficiency
in sulphates, relatively less magnesium and commonly.,greaterconcentration than normal sea
Table 2.1 Typical Properties of Crude Oils water. Traces of hydrocarbons andorgrtllic acids are pksent.
2.3.1 Hydrocarbons
Hydrocarbons are compounds composed solely of hydrogen (H) and carbon (C). The main
types of hydrocarbons present in crude oils are alkanes, cycloalkanes, arenes and hybrids
involving combination of these types. They range widely in boiling point, and many cannot be
distilled under atmospheric pressure without breakdown.
Alkanes.These are open-chain saturated hydrocarbons. They are also known asparaffins.
They can be divided into two types:
Straight chain alkanes - x~ormal
Branched chain alkanes - iso or neo
When carbon atoms are connected in a straight chain, they are known as straight chain
alkanes. When carbon atoms are connected in a branched fashion,they are known as branched
chain alkanes. '
'
Alkanes have a general formula Cn H2n + 2, where n is the number of carbon atoms. The
names ofthe alkanes end in -me. The first four alkanes have specialnames (methane, ethane,
propane, butane) related to their histories
H H H H H H H H H H
I I I I 1 I I I I I I,
H-C-H H-C-C-H H-C-C-C-H H-C-C-C-C-H
I I I I l l I I I I
H H H H H H H H H H
methane ethane propane butane
15. ( ~ econtent,
h wt. % ( - ( 0.0047 ( 0.006 ( 0.004 1 - ,tif
16. (KUOP ( 12.0 1 11.8 1 11.7 ( - From pentane (C5 Hlz) onwards, Latin or Greek numerals are used to reveal the number
of carbon atoms per molecule. A few examples are given below:
Table 2.2 Elemental composition of crude oils
CH3 - CHz - CHZ- CHZ- CH3 CH3 - CHz - CHz - CHz - CH2 - CHz - CHz - CH3
n-pentane n-octane ,
- Element Amount, w f 8
C 83.9-86.8 From butane (C4Hio) onwards, alkanes may exist in two or more forms (isomers)differing
H 11.0-14.0 in structure. For example, butane may exist in two forms as follows:
S 0.06-8.00
N 0.02-1.70
n-butane I
---- 0 0.08-1.82 cH3
--- Metals 0.0-0.14 isobutane
Ill
, , ~ m & ~ , . p e ! m n ~ ~ i n ~ b t ' ; s....~ ~- ...~ ~ ; d i i ~ b ~ ~ b ~ ~5 ~,: 3F.j ~ ~ I w
ine f B h ~ i i ~ ~ ~ O ~ ~ ' b ~ f i v ~ ~ t i ' 6 ~ . ~di.;~!
,;
The moat common mononuclear ammatics found in crude oils,are toluene and m-xylene.
The possible constituents of crude oils. include polynuclear species containing up to a t least
eight condensed rings. Many polycyclic aromatic hydrocarbons present in petroleum are
carcinogens.
Alkenes. ,These are openchain unsaturated hydrocarbons,c o n w g a carbon-cirbon
d&&rh:!b. 7 ona; T
' ~tgn&~ the
~ : , chbbn-h,+ddi6h
~ pr!op,c~~hk.xrPi.it:~'d 'driabsgj,cli,c
..I .......f......
*em rs o C ~ Wl ~ l
m4;'th
*t{a%ahe;.
*e., we .' '.. iS( ; .GoS
CiH,, , e i e l y i:A,
fe :
pF&, .Ad$&.& 6 4 ?',le;&:,6f
eak.e)i :, ,an.d,,:& ?-1;'d;a:vi8r
.$&.&;::hd& $
,p&
*ivLfds&dtutai,is&h&&:&po8diti1;,d'e ped&g,,od ,&ei'&Pti:bh' s;i hl,&Ij:6$d
within the basic hainmu.&
, for =hpr8', . ~ 6 : i t i ~ g h c ~ w & ' b ~ & n nljre~ ~ 6 . a ~
expected, as follows:
p,@adlene . . . . . ! .:; : . l;'3-butadl@ne: ,:&penWeriw
:I -..:. .I3,
;b'he~ttiine
H H H H ,. ! : .: :'
t ':. ' .
.. ; , ,<, ;,! 2
H H H H . . . ; ;, ,!. .'; ; ; . < !.:. v. ' .' ,
I l l 1 I I I I A l ~ e e ~ ~ e e . a r e o p e n - c h a i n ~ h y d r o e a rcboo~ntsa h i n onecarbon-ctybon
g triple bond.
C=C-C-C-H H-C-C=C-C-H The fin&.member:o$thi~~s~eesi~acetylene, Cfia,:wbich,appe~~8;injexten44 f o h ' l a as:the
I I linear molecule: H-CGH. Additional members of the alkyne seriea:.comphe,-open-chain
H H
but-2-ene molecules somewhat similar to the higher alkenes but with each double bond replaced by a
t r i ~ l ebond. The.IWAC system of nomenclature.ri~pliesthroughout t h e series as with the
The number indicates the number of the first of the doubly bonded carbon atoms, alcenes, but t h e des&tem treats tho!~~htah&abers. as d&vativee,:of acetylene. Thus, .I:
numbered from the end nearer the double bond. In addition, the typical side-chain isoniei is for example,. H.arnWfijjcbuld . be d e s d & d !& .&itherbut-l--ge' b i s&ylacetylene. The ,
' I
C=C
.. , .-8 , : .; ,. Cycloalkanoarenes. These, also called naphthenoaromatics, are mixed polycyclic
' I
H3C H
hydrocarbons and possess structures involvingfusion of aromatic with alicyclic rings, and may
carry aliphatic side chains. These h y $ ~ ~ & ~ ~ ; ~ Q appearing
u$ in the kerosine fraction,
...
-
I . I increasing in concentration in the higher-boiling dbtillaticn fractions and residues. Bicyclic
isobutene (2methylpropene)
~?!p~t$enp~~m~$c.. $nee.tu.prn~ti-~ r h g . &dfpop alicxy&c).ingee.?:p.$+in and..theic,alkyl
The two possible geometrical isomers of but-2-me are the foliowing: 4$vativ$ 3;" r'la!jiy$~.+&dadt' .9,keroeifte..apd:h& gas ,oi4,
. . ......<... ..... ,Ew , . -pl of+ , C:Q ~ P O ~ W &
7 L.
present
. . . giyen.belpw :
are. ...
: . . I. . . . . .
H-C-CH3 CHR-C-H . . > . . .
... . . .
. . . .
These isomers are classified by the Latin preiixes cis (on this side) and trans (across) i.,. ! : ., . .
indicating the relative locations of the two end methyl groups. Coneequeptly, there are four I n ~ a n O ' ( ~ ~ " ,'::o"~ . . . I .k(~ln.~Cio,H,2).. .. ...,,. . .. .
- ..
isomeric butenesin all. (1,2, 3, Ctetrahydmnaphaalene)
d '
2.3.2 Non-Hydrocarbons CH3 CHSCHCH3
I I
Crude oils contain appreciable amounts of organic compounds with structures incorporat- CH3 CH3
(CHI CHdz S
ing one or more (the same or different) atoms of sulphur, nitrogen, or oxygen in addition to 3-thiap'entane 2,4-dlmethyl-3thiipentane
carbon and hydrogen and some of these are associated with metals such an vanadium and (dlethyl sulphlde) (dhwrwyl sulphide)
nickel, i.e. they are organometallic in nature. A
Sulphur compounds. Sulphikr'is th8 mast.abundant atomic constituent of &de oils,
otherthan carbon and hydrogen. One of the origins of sulphur compo.ydsin the c v d e oils is -
~~&~~tcird:kulphiw~h-*~i;it .dtigs;siie$.bf&e.filarit
and'mirriLl $&&;ns'd;po&ted,&
.;<, :<,.. , .,< .,,! m ~ h e x a n a m w p h l d e )
geological beds. The other origin is the biogenic reduction ~f'"dil$h'&.~'&de oil* "&-y As in the case of thiols, the sulphides are generally very malodouroue.
considerably i n their sulphur content ranging from a few hundredths by weight to as ;puch Afew low molecular weight disulphides (dithiaabnw) have also beenshownto be present
#rceht OT sdbhdi. ~ u l b h u ycokedf of 13.95% foddd $ d a d p o i n t (inetah State in in crude&.The accurrence of disulphides in;prudeoile may be owing to the secondary reaction
. I :.. record&
Ui$.;Aj?.is #e,&ghkst . sulphur cdptent of any cqde:oil.. . .,.. I'. .
'. . . , *
of thiols with tln olriaant such as air or free sulphur. Organic disulphides are isologs of the
The * u l p h ~com~~unds~'~re'se'nt in c k d e oils can' be dividedlinto thiolq, &on& and organic peroxides, ROOR, but are much morestable. Examplea are given below:
.
Wlphides and thiophenes. (': i- @-
. .
" >.,v.-
.?C,.. .. I ..
~.
in low concentration, however, and they are often used as odourants iii LPQThe ibwer thibls
are the inost malodourous..One part in 50 million of ethanethiol can be detected in air by the
human nose. The odour is strong at 0.6 ppm arid distinct at 0.03-0.07 ppm. In high concentra-
tions, the odour ohanges to something like that of chloroform.
Thiols are stronger acids than alcohols, and use is made of this to remove low molecular Thiophene and its alk$ dNvativee are n o ~ y , r ~ l a t i v ~ I y . sconstituents
c~ce of crude
weight thiols from light gasolines with caustic soda solution. Hydroprocessingtechniques are oils, but condensed system-benzothiophenes, dibenzothiophenes, and higher polycyclics (e.g.
employed to desulphurise other oil fractions and here combined sulphur is eliminated as benibnaphth~thio~henes) are impartant component8ofall high aulphur crudes. Thiophene
hydrogen sulphide from all type of-compoundcontaining this heteroatom. derivatives are p d c u l a r l y abundant in erude oils containing high proportions ofmmatics,
resins and asphaltenes.
syao~spaaj jo d0n)Fse nam se .-a 'leaq ag!aads 'queqsuoa blpad-bq!soasr~ 'ququo3 uaSorp6q
s-e qans savadord i a q o pue d0nx u a a w q pado~a~ap suo!+81auoa Lxequaura~duroaaqq
u! saq lo33ej a w j o etlaqnJasn u y u r a q , 'uo!qaeq a w u! suoqieaolplCqjoadLq ~ep!+%d re jo
aaueu!uropa~da w q e 3 ! p ~03 pasn aq trea suogaeq wna~oqadjo donxjo sanIea aq? ' m u
0'11 - 0'6 sa!lamoxv
0'zT - 0.11 sauayqqd8~
O'ET - 9'ZT sugsisd
910aplu3 JO uo!pa&ssa13 j o - p o q l a ~ go
d npamg
~ Sn p.g e l q ~ ~
~ P a q d ~ g ~?F
q EI!O;aP!v
. 30 uoRe~J!$m % ?I.! W+:(PUO!TW. Xaq, s y ~ ~ ? ~ , ? ~ , ; ~ ~ ) , j o ~ ~ & y e @
? K J ! ? ~R
~ SY
~ Wp a s ~ w .ys a u ! m ~ n e a m psn<eyqs39*np3033a ~I!Q,a p r u ~ j o , ~ w p ~ m ~ ~ ~ 1 r 3 ~ a ~
2.4.2 Correla$inqJn~@xi .. : .,;:,
. . - ~c~oe~ F index
p ((311, developed by US Bureav of ~ i n e s is, Biven by the following
empiiiical eqfiation:;
,.
11 ., ..,.
: ..,
.
: ,:I.,: ;
..
,u
, i',.
require fiequent.piggingtokeep the wax accumulation manageable. Apigging operation often to be the:waxy. Such a,classificatioo~wasbased-on the wax content.oEthe,cmdeaad itspour
rattires significant amounts of costly offshore man-hours. Taking into consideration all the point; The,characteristics of some of these crudes are given in-Table3:l. In-contrast,mos$of
&o-economic aspects additive treatment is reported to be the most suitable method for the the MiddleEast crude oils have a pour pointbelow 0 OC and wax contentless than 7wt.kand
t k w o r t a t i o n of waxy crude oil, which can depress the pour point and improve the flow therefore pose no problems in pipeline transportation even at low temperatures.
characteristics at low temperatures.
,\,
Waxy crude oils exhibit non-Newtonian behaviour a t temperatures below about 10°C
above the pour point. The wax can crystallize as the crude is cooled to form gel or a partial gel.
~.$+~P~~~U~~'~R~NSPORTATION Under static conditions a rigid gel is formed, but if the crude is cooled while in motion, the
For the transportation of large quantities of crude oils, pipelines are the most economic apparent viscosity will increase but the material remains fluid: Therefore, the rheological
means. Under safety aspects, transportation by pipeline guarantees the best protection for the properties are functions of temperature, shear rate, shear stress and past history. Problems
environment. Further, there is no handling of other traffic and no disturbance by noise or air in pumping these crudes will occur if the temperature drops and the fluid becomes non-New-
pollution. A continuous supply to the refineries is normally assured and this is not endangered tonian and if gel formation occurs after a shutdown. The pipeline facility must be designed to
by weather conditions such as fog, icy roads, or traffic conditionsalong inland waterways, such recover from these problems or prevent them. A realistic approach should be developed based
as high or low water level, ice, etc. upon an extensive evaluation of the rheological behaviour of the crude oil under representative
However, each pipeline system requires very high investment which should be used most temperature and shear conditions. The two rheological parameters of which knowledge is
economically. The most economical and efficient operation of a pipeline could be reached by indispensable for transporting waxy crude oil through pipeline are viscosity and yield stress.
maintaining a continuous constant flow rate without any interruption. Also, ip respect of a Before we go further into rhealogical behaviour of the crude oils, a few relevant terms that will
reliable and continuous supply to the refineries, a steady-state throughput, with some seasonal be frequently used are defined below.
fluctuations due to market requirements, should be envisaged. Otherwise, additional storage
volume has to be provided for large quantities of crude oil and this would be very expensive. able 3.1 Characteristics of Waxy Crude Oils
Interruptions by shutdown of a pipeline are by no means desirable. However, a shutdown
may occur due to the following operational reasons:
(a)There ia an inadequate stock of oil in the terrnind. This could be caused by distribution
in tanker schedules, for instance, due to weather conditions.
(b) There are no delivery requirements by the refineries fed by pipeline. This could be
caused by disruption in operations sf one or more of the processing units of the refineries, for
instance, due to equipment breakdown.
(c) A pressure test for leakage control of the pipeline has to be performed.
( d ) Repair, maintenance work on the pipeline system including pumps is required.
(e) The pipeline might be shutdown automatically by exceeding the operational safety
limits.
These shutdowns are not expected to last longer than 3-4 day. Under extreme conditions
one could think of extraordinary long shutdowns. The reasons might be government action,
I
I
3.3.1 Definitions of Rheological Parameters
earthquake, strike, war, etc. However, under normal conditions, they are'not expected. SHear stress. Consider the steady flow of a fluid in a horizontal pipe of circular cross-sec-
I n e n transporting waxy crude oils, these operational points of view'are of considerable tion. The fluid flows with an average velocity of U in apipe of inside diameter D. The pressure
importance. difference between two points 1 and 2, separated by a distance of L is (Pi - P2).
q e decrease in pressure in the fluid reflects the applied force causing the fluid to flow
3.3 WAXY CRUDE OlLS and if the flow is steady (i.e. no change in the flow and hence velocity), this force must be
The crude oils pumped in pipelines up to the early sixties generally showed normal counter-balanced by a shear force of equal magnitude at the wall of the pipe. If r, is the shear
characteristics in respect of pumping conditions such as viscosity'and low pour point. nowever, stress at the pipe wall, then force acting on the fluid at the wall must be - 71 DL rw.The
the opening up of remote oil fields in North Africa and India in the 1960's to exploit the low negative sign indicates that this force acts in a direction opposite to the direction of flow. The
sulphur (but waxy) crudes in these locations, and the need to pump tKese oils through the force acting upon the fluid due to pressure difference is (Pi - P2). In steady state (no
much colder pipelines has led'oil producers to study the pumpability of waxy crudes at 1
temperatures below the pour point limit. The advantages of these crude'oils in respect of high
reserves, low sulphur content, good distillate product yield and its low dscous flow under fair
1 acceleration), the sum of these two forces is zero. Therefo;e, w6 can write
temperature conditions are, however, partly compensated by the disadvantage of high wax
content, which results in a high pour point and under certain conditions of low temperatures
could create operational difficulties after a long-term shutdown of the pipeline. Worldwide,
one can distinguish about 1500 varieties of crude oil of which 10 to 20 percent are considered
I /
s e*@&ioh bP"dti%n~losd.-~rbin
~ e a n of E1$,3j1, itfdlfowru that.avddab1e~hear'strgSs~or a ,For laminar flow in pipes, friction loss ie given by
particular pipeline depends,on the leligtbd the line between twa,pump stations! and the &. -(PI
= -P2) 32 p U
pressure difference. The availdble sheatj $tress can<be1 increased by increasing the initial /
L o2
pressure, PI, and/or, reducing the section length of pipe, L. An example of calcu\ati~nof which can be rearranged in the form
available shear 'stress is given,below. -
[(PI P2)DI4LI -- TW
'= (8UD) -(8UD)
STATION : VIRAMGAN TO ABU ROAD Therefore, for laminar flow, . .
SVatic head at Viramgan Rate of shear = 8U/D J3.3)
Static head dt";sb'u Road
and for turbulent flow,
Pump puction Rate of shear = (SU/D) Cr *..(3.4)
Differentialheaq of each of the pumpa at rated flow
where Cri3 correction factor which depends upon Reynolds number.
Two pumps willtbe operated in series.
Ressure drop ah Abu Road
Yield stress. It measures the ability of fluid to restart its flow aRer shutdown of the
transportation system. The yield stress of an oil, at a given temperature is defined as the shear
Resdure dtop in the liile stress required to initiate flow. It can thus be directly compared with theshear stress available
or allowable in a pipeline. The yield stress of waxy crudes ie influenced by-ite temperature
Density of crude at pumping temperature history, shear history, aging and composition.
:. Pressure drop
3.3.2 Rheological Classification of Fluids
There exists a rate of shear and shear stress at each point in a flowingfluid. In determining
Inside diameter of line the rheology of fluids, any one of the following b a i c behaviour patterns (fluid types) may be
Line length found upon agitation of the fluid a t constant temperature.
Newtonian fluids.A Newtonian fluid is one whose visco~itya t a given temperature ie
Shear strees
independent of the rate of shear. There is a linear rdationship between the shear streas and
the rate of shear for a Newtonian fluid. The viscosity of a Newtonian fluid a t a given
= 0.000339 psi temperature is constant regardless of the velocity, previous agitation or shearing of the fluid.
= 23.4 dynes/m2
If the available shear stress is equal to or more than the.
overcome the shear streas at the.innersqfape of the pjpe, $hen tbe,flow 3 forcp peeded to
l$e initiated.
Shear rate. consider two p&allq;lplanes of area A, separated by &:d~erqntiai&jtance
dr. The space between the two planes is filled with a fluid. The lower plane is fixed. A small
P Fluids
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 wall and the flGd, the fluid adjacent to the upper plane or wall &q also
have a velocity dU in the direction of the applied force and the fluid next to the lower plane or Purely viscour flddr
whll will have a zero velocity. Thus, a unifoy velocity gradient of magnitude dU/&ris set up
in the fluid since the shear force F is uniform across the distance dr;The velbcity gradient,
dU/cir, is commonly referred to as the rate of shear. The shear force per unit area, F/A, is called
P
the shear stress.
Time dependent
Viscosity. It measures 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. Viscosity, p, can be defined as the ratio of the shear
stress to the rate of shear.
I
Flg. 3.1 RheologlcalclasslficaUon of lulds.
I
-
I
Figure 3.2show8 thevariation of viscosity with shear rate for different types of fluid. Curve
number 1 is typical of the response of a Newtonian fluid. A Bingham-plastic fluid is charac-
terized by a flow curve 2 which is a straight line having an intercept b on the shear stress
axis. The stress is called the yield stress which must be exceeded for flow to commence. The
Shear rate -
flow behaviour is described by an equation fig. 3.2 Typical non-~ewtionionfluids.
for a statically cooled pipeline (the fluid was above the pour point while flowing and allowed
.,-.-, to cool during shutdown of the pipeline) than for one that has been dynamically cooled (the
With pseudoplastic behaviour, the fluid displays increasing viscosity with decreasing fluid was already below pour point when pipeline was sl~utdown),i.e. the cooling occurred due
--
shear rate. This means that there is a non-hear relationship between shear stress and shear to the flow of the crude in the pipeline.
rate. Curve number 3 represents pseudoplastic behaviour. Dilatent beheviour is depicted by
curve number 4. 3.4. FLOW PROPERTIES OF WAXY CRUDE OILS
Most waxy crude oil gels exhibit thixotropic or occasionally rheopectic behaviour. When a The viscosity of crude oil is perhaps it. most important physical property. For most crudes,
waxy crude oil is allowed to cool below its pour point under static condition in a pipeline, the at sufficientlyhigh temperature, the viscosityat a given temperahue is constant and the crude,
paraffins will crystallize causing the entire mass of crude to gel. To initiate flow again, a finite although chemicallyverymmpl?~,is a simple N e v is reduced,
pressure is required. For waxy crudes, yield stress is an inverse function of temperature and however, the flow properties of a crude oil can readily change
increases with decreasing temperature. With the crude oil that is below its pour point, the wax very complex flow b e h a w due to the crystallization of
crystal structures in the oil start to breakdown as flow begins. This breakdown depends both of asphaltenes. The waxes basically consist of
on the time and rate of shear. form an interlocking structure of plates, needle or malformed ~ s t a l sThese. crystals Can
Start up pressure depends to a large extent on whether the oil is cooled under static or entrap the oil into a gel-like struehue that is capable of forming thick deposits in pipes and
dynamic condition. For instance, the additional restart pressure will be substantially higher
TRASPORTATION OFWAXY CRUDE OILS
Correlation of the model pipeline test results for actual pipeline d e s i p ie tlormally based The .second step is to plot curves of viscosity versus rate of shear for different pipeline
on the previous experience. Some of these correlations are developed by the designers by pilot throughput as follows:
plant tests simulating the field conditions in a test loop. For a given flow rate, an equivalent shear rate is determined by Eq. 3.3. Assumin$ the
A general equation for calculating restart r e q ~ r e m e for
h a cooled line is value for viscosity, the Reynolds number is calculated. If the flow is in turbulent region, the
correction factor for rate of shear is read from the plot of the correction factor for shear rate
p=-YLC versus Reynolds number. Using this factor the effective rate of shear is obtained. By repeating
A ...(3.6)
where P is the pressure required, Y is the yield stress of gelled crude (thitr value must be this for different values of viscosity, a curve of viscosity versus effective rate of shear for a flow
determined in laboratory tests and is different for static and dynamic cooling), L is the line rate can be superimposed on the plot of viscosity versus rate of shear for various temperature.
length, C is the circumference of inside pipe wall and A is the cross sectional area of pipe. The intersection of the constant throughput curves with the constant temperaturecurves$ves
the appropriate viscosities to be used for these conditions. An effective viscosity versus
temperature curve can be plotted for the various Chroughputs.As mentioned earlier, using
3.5.3 Flow a t Restart kc these values of effectiveviscosity, pressure drops in the various sections of the pipeline can be
At the time of restart of the pipeline because of very high viscosity,the flow rate is ejrpected calculated.
to be low. This, however, depends on available shear stress as compared to thejrield stress. In
any case, the minimum flow conditioris of the pumps have to be investigated. If a pump is 3.6 METHODS FOR PIPELINE TRANSPORTATION OF WAXY CRUDE OILS
operated at a very low flow rate, additional wear due to unbalanced flow is expected. Further,
One of the following methods for pipelining waxy crude oils may be considered:
due to the poor efficiency,the oil will be heated and, after a short while, the allowable maximum
temperature will be exceeded. This limits the allowable time for the operation of the pumps (a) Select pumps to allow a paralleYseries arrangement, whichcouldtransport at slower
with low flow. rateg and higher pressures when required. The piping could be manifold so that
parallel arrangement would be accommodated by repositioning of valves to handle
If the restart flow rates do not meet the pump requirements, gpecial pumps with ap- higher flow rates.
propriate characteristics h i g h head, low flow) have to be used for restart of the pipeline.
(b) Use of separate low flow, high head pumps for restarting.
Side traps at frequent interval? to allow short s6&ons to be started separately.
3.5.4.Effective Pipeline Viscosity
Reverse pumping to create back and forth pumping sequence which prohibits static
For determining pressure gradients in the pipeline, effective pumping viscosities have to cool down.
be determined. Using these viscosities, the conventional formulae can be used for calculation
Use of pour point depressants/flow improvers.
of pressure dmp.
Adding hydrocarbon diluent such as a less waxy crude or light distillate.
The effective pipeline viscosity for calculating frictional pressure drop at various flow rates
and temperatures can be predicted by rotational viscometer tests. Due to wax crystallization Iqjection of water to form a layer between pipe wall and crude.
at low temperature, the conventional capillary tube viscometers cannot be used. Moreover, for Mixing water with crude to form an emulsion.
non-Newtonian fluids viscosity is dependent on shear rate. For this service as also for other Displacement with water or light hydrocarbonliquid in case of shutdown of pipeline.
sluny services, rotational viscometers are used. The sample is taken in a double w d e d cup Separation at higher than normal pressure to allow as much gas and light hydrocar-
(a refrigerant flowid in between the two walls). The outer cylinder is rotated by a variable bons as possible to remain in the crude.
speed motor. The &er cylinder is suspended from a torsion wire consisting of a stainless steel Conditioning the crude before pipelining to change the wax crystal structure and
tube, the deflection being measured by a balanced pointer. The rpm of the outer cylinder reduce pour point and viscosity.
multiplied by the instrument constant gives the shear rate. The deflection reading of the Further sub-division of pipeline into smaller segment or reducing batch length of
pointer multiplied by another instrument constant gives shear stress. The ratio of shear stress waxy m d e to increase maximum shear stress available.
to shear rate gives the viscosity of the fluid. Combination of the above methods.
When the oil is at such a temperature that flow is non-Newtonian, the Reynolds number
is a function of viscosity which itself is a function of the effective rate,of shear. Therefore, an Pipelining the crude as an oil in water (Om) emulsion reduces the flow properties to nearly
intermediate calculation is required to arrive at the appropriate pipeline viscosity for calculat- the viscosity of the continuous water phase. An O N emulsion pipeline handling 40000 barrels
ing pressure drops. of oil per day (265 m3 h-l) of 70 vol.% crude oil has been operating in Kalimantan (Borneo) in
Viscosity of the oil to be pipelined is determined at various temperature and rate of shear Indonesia since 1962. Blending with a less waxy crude oil or distillate improves the flow
by rotational viscometers. These are used to plot-viscosity versus temperature curves for properties by altering the wax solubility relationships. Both of these methods have the
various rate of shear. This plot can be used to determine the temperature below which the oil disadvantage of reducing the crude oil carrying capacity of the pipeline. Note that separation
will behave as non-Newtonian fluid. It is required to find the effective viscrosities of the oil for at the well head to include more condensate in the crudepjl (if available) has the same effect
pumping at'different flow rates a t various temperatures. I as dilution. There is one interesting case of a shear and t e ~ p e r a t u r treatment
e being used to
The f i s t step is to use the plot of viscosity versus temperature-and plot curves of viscosity I favourably alter the flow properties of waxy crude oils in (Assam (India). More recently, pour
i
versus rate of shear for different temperatures.
40 PETROLEUMREFININGTECHNOLOGY 41
TRASPORTATION'OFWAXY CRUDE OILS
point depressantdflow improvers have been developed that, in small concentration, affect the All of the above considerations point to additive injection into the crude stream at well
crystal growth, and as a result improve the flow properties. head.
Of the various methods developed, the use of pour point depressantdtlow improvers is
found to be more attractive. The main attraction of this method is its relative cheapnees and 3.6.4 P o u r Point Reduction b y Additives
variability of dosage with respect to the temperature and desired viscosity requirements. Pour point measurements on crude oils have been used to detect low temperature handling
problems. However, as mentioned already, they do not necessarily predict the field perfor-
3.6.1 Use of P o u r Point DepressantslFlow Improvers mance. Pour point can at best be used for preliminary screening of various additives for their
( The injection of pour point depressantfflowimprover additives appears to hold the greatest potency with a particular crude oil.
promise of achieving the desired overall objectives of operational safety and operating These studies were carried out in the Salaya-Koyali-Mathura crude pipeline by Oil &
economy. Now improvers should have the capacity to Natural Gas Commission, India. The line was originally designed for transportation of low
reduce the pour point, viscosity and yield stress under dynamic conditions; and pour point Middle East crude oils (Light Arabian and North Rumaila). With the discavery of
restart the pumping after a shutdown with the available shew stress. the Bombay High crude oil, it was decided to process this crude too at these refineries. Efforts
Chemically pour point depressantshlow improvers are ashless polymeric additives which were made to find a suitable solution to the problem of pipeline transportation of this high
when added into the crude oil a t 300-600 ppm level reduce the pour point and viswsity of the pour point (30°C) Bombay High crude oil to these refmeries during winter. It was reported by
crude oil. Polymeric materials.widely used as pour point depressantdflow improvers are (a) model pipeline tests that the line will not be able to take a restart after cooling statically to
alkyl acrylate polymers and cdpolymers, (b) o l e h alkyl maleate copolymers, (c) vinyl ester
polymers and copolymers, and (dl alkylated polystyrene. Normally, the average molecular low winter temperature of around 16OC.
weight of the commercial available pour point depressants for crude oils is between 2000 to A number of flow improver additives were tested for their effectiveness on Bombay High
20000. crude. born preliminary tests, Shell-swim-5Tand Esso Paradyne-80 were reported to be the
most effective additives in lowering pour point. Further tests by rotational viscometers
Various flowimprovers developed a t RRL, Jorhat (India) are SWAT-104, SWAT-106, FIR1
indicated that, for similar level of dosage, both effective viscosity and yield stress were reported
and FIRI-B. These are polymerdcopolymers,easily soluble in crude oil around 4M5OC and to be lower in case of Shell-swim-ST as compared to Esso Paradyne-80. It was therefore
non-corrosive. They are used in pipelining crudes of Bombay High and Asssm (India). concluded that shell-swim-5T is superior to Esso Paradyne-80. Subsequently, Shell-swim-5T
was used for transportation of the Bombay High crude to Uran terminal through the
3.6.2 Mechanism of Flow Improvement submarine pipeline from the production platform. Extensive studies were subsequently done
When a waxy crude oil is cooled below its cloud point, the wax crystals form and begin to at IIP, Dehradun and Gujarat Refinery to determine the optimum doping conditions for
agglomerate and with further temperature reduction crystal agglomerationreaches a point a t Shell-swim-5T in Bombay High crude. k o m these.studies the optimum doping levels were
which a gel structure is formed below the pour point due to interlocking of the growidg crystals reported to be 250-300ppm of the Shell-swim-5T.The effect of doping temperature on the pour
and dependent on constituents like resins, asphaltenes, asphalts, paraffin and microcrystal- point was reported to be negligible.
line waxes, etc., their molecular 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 3.6.5 Effect of Flow Improvers on Yield Stress a n d Viscosity
alter the wax crystal size and shape in some manner and prevent the tendency to interlock. Significant reduction in yield stress and effective viscosities can be achieved by doping
l'he'flow improvers or pour point depressants act by retarding the growth of the wax crystals waxy crude oils with flow improvers. The following results were reported for the effect of
in the XY crystallographic plane, thereby producing smaller crystals of higher volume/surface Shell-swim-5T (flow improver) on Bombay High crude oil.
ratio. It appears that the flow improvers cocrystallizewith the growing wax crystal, leading
to the formation of a fault in the otherwise compact regular wax crystal and resulting in
diminished gel strength, so that by coating on to a growing wax crystal the flow improvers Doping level Yield stress @ 160 C Viscosity @ 160C
reduce the tendency of wax crystals to interlock. PPm dyneslcm2 CP
Nil 330.0 '45.0
3.6.3 Point of Additive Injection 62.5 45.0
250
As a general rule, the additives should be injected into the crude above or around its cloud 42.4
300 62.5
point and also a t a temperature of some 20°C above the pour point of the additive. The additive
400 45.8 41.0
pour point could be depressed considerably by cutting (diluting) the basic component with
kerosine, or aromatic solvents. The preferred location of iqjection should be a t a point where I
No heating of the oil is required (utilize the heat of formation) These results show significant reduction in yield stress with 250 ppm doping. Further
Subsequent external application of heat can be avoided or minimised. I improvement with higher doping levels is, however, marginal. In fact in some cases the trend
The maximum benefit can be derived in the system downstream. 1 was reported to be reversed with higher doping levels, as shown below by the following model
pipeline tests conducted by ONGC.
42
PETROLEUMRWNINQ TECHNOLOGY
. - TRASPORTATIONOF WAXY CRUDE OILS
pintDePres- Yield stress at 1kc,d y t w s ~ c m ~ Viscosity at 16°C at flow deueIop.
sant in Bombay High 3.6.7 Crude Oil Conditioning
CNde ment, cP This process is developed by Oil India Limited. The crude oil conditioning is a unique
Nil Test was process in which the cmde oil is first heated to melt and dissolve the wax in it. Thereafter, on
I
- abandoned
- as oil could not be transferred to model pipeline
dynamic cooling and wbrkbg t b u g h the p m p the crude oil is subjected to static cooling at
due to congealingat 18OC.
400 a predetermhed rate. The result is the conditioned crude oil which has much improved
21.2 435 at 45 dynes/cm2 physical properties than the virgin crude oil. The conditioned crude oil remains fluid at much
750 on n I
I 1u.I.
I 589 at 45 dynedcm2 lower temperature and possesses satisfactmy physical properties so far as transportation of
1000 27.5 966 at 45 dynes/cm2 crude oil through the pipeline to refineries during the winter monUs is concerned. This has
Hence, optimum doping levels by extensive laboratory studies must be determined before been employed for transporting wary crude oils from Assam (India).
starting additive injection. I,the actual process the crude oil is heated to a temperature of lCO°C in tube heater.
1 Before entering into the tube heater, the crude oil passes through heat exchanger and
3.6.6 Incorporation of Low Pour Point Crudes i n Waxy Crudes exchanges heat with the outgoing oil from the heater, bringing down its temperature to
Aa mentioned earlier, this can be one of the probable solutions to pipeline transportation 65OC by dynamic cooling.The crude oil at 65OC is stared in a tank from where it passes thmugh
problems of wary crudes provided the lowpour p i n t cmde is easily available for blending and . a pump to static cooling vessels, commonly called conditioning vessels, These vessels are
no problems are expected to be encountered in processing the cmde blend as far aa product essentially sheU andtube heat exchangerd'in which crude oil is taken in the shell side and
specificationsare concerned. Once again B e example of Salaya-Koyali-Mathurapipeline can cooling water is passed through tubes. The con&oning vessels follow a batch time cycle of
be cited here. The Gujarat spd Mathura refineries fed by thispipeline (Gujaratpartly) are to 208 minutes to achieve coaling of crude oil &om 65OC to l8.S0C (this includes h ~ & time g of
p m n n partly Bombay High crude and partly low pour point Middle East crude. A small cmde oil and its emptying outtime also). The coolirigof the crude oil in the conditiohg vessels
percentage of tbP Middle East cmde mixed with Bombay High cmde will not result io any is effected by circulating watets, namely intemediate and relrigerated waters. Intermediate
serious processing problems. The reported results of laboratoq studies on blends of Middle water is maintained in a closed circuit through a pump and heat exchanger in which cooling
E u t crude with Bombay High m d e indicate that the incorporation of Basrah cmde in doped medium ia tbs cooling water. The refrigerated w a t u is also maintained in a closed circuit
Bombay High cmde shows no further reduction in pour point. I b i q could be due to reduction though a pump and absorption refrigeration machine. The c i r ~water t while f l o i n g paat
in percentage of n-parfins when Basrah cmde is mixed, the effect of pour point depre~sant evaporator chamber of absorption refigeration machioe though tube bundles gets chilled.
being more predominant on n-paraffins as compared to iao-parafiins. However, a significant
h the temperature of crude oilis brought down to the desired level of 18 - 2g°C, the cmde
reduction in the yield stress of the blend is reported, as shown below.
oil from conditioningvessels is emptied out automatically into conditioned oil storage tanks.
T h e conditioned
.---- ---- oil from these tanks flows pipeline pumps through a booster pump and this
completes the process of conditioning.
100%Bomhnv -
Hioh
-I-.
330.0
100% Bombay High with 250 ppm of pour point depressant
62.5 J
/ . 90% Bombay High + 10% Basrah with 250 ppm pour point
de~resaant. 5.0
The doping temperature is quite important as far as yield stresses are concerned. The
-
1 K. W. won, Thehodynamics for solid solution liquid - vapor equilibria :Wax phase
formation from heavy hydrocarbon mixtures, Fluid Phase Equilibria, Vol. 30, pp.
blends of Basrah with Bombay High crude doped at 50°C is reported to give better results as 265-279 (1986).
compared to temperature of 30°C. This is s h o w by the following experimental results 2. J.H.Hansen, A. Fredenslund, K.S.Pedersen and H.P. Ronningsen, A ther-
reported. modvnamic
--- - -" model for predicting wax formation in crude oils, AIChE J, Vol. 34, NO.
12, pp. 1937-1942(1.988).
3. S. ~angul~,Ftheological~arameteraand s o l u t i o ~ e m s
Crude blend .
I
Yield stress at 16"C, dynes/cm2
1 4
of waxy cmde oil, URJh vol. 26, No. 2, pp. 33-34 (1989).
P. Datta, H. Dubey and K.L.Pate1, Pipeline transportation of waxy crude oil from
90% Bombay High + 10% Basra1 . - 250 ppm pour
Basrah with I
50°CDoping
50°C Doping
5.0
) 30°C)Doping
3O0C)Doping
25.0
1 the oil fields, Chemical Engineering World, Vol. XW, pp. 43-45 (1990).,
point depressant 5-. R. Prasad. Waxy crude oils, In PIPING DESIGN HANDBOOK J.J. Mcketta, Ed..
-.
90% Bombay High + 10% Basrah with 300 ppm pour Marcel ~ikker,il992).
point depressant
90% Bombay High + 10% Basrat
I 5.0
I 25.0
25.0
I 6. S. Naik, C.K Pathak, and V.P. Sharma, Effecte of our p i n t dep"essant8 on WaXY
Indian crude oil, IE(1) J., Vol. 69, Part CH2, p p 60-63, (1989).
point depressant 5.0 25.0
I I
E
4 PETROLEUM REflNlNG TECHNOLOGY
I
I
( d )Burning quality-Smoke point, Char value
46 PETROLEUM REFlMlNGTECHNQLQGY
QUALITY CONTROL OF PETROLEUM PRODUCTS
The determination of viscosity and consistency of petroleum products is done by the
following tests: the test. Due to small losses of vapour a t the connections and openings in the apparatus and
(Q) Kinematic viscosity (Redwood, Saybolt, Engler) the residue remaining in the flask on compfetion of the test, the total recovery does not
(b)Viscosity index generally exceed about 97 percent. A maximum distillation temperature limit of 370% has to
(c) Penetration tests be set, otherwise the heavier hydrocarbon molecules are liable to suffer from cracking into
The tests designed to ascertain the tendency of certain petroleum products to melt or lighter molecules causing the distillation characteristics to change duringtheir measurement.
liquefy,,tosolidify or to precipitate wax-like materials are: Thus fiels heavier than gas oils cannot be tested completely for distillation behaviour.
(a)'k8ezing Point The distillation characteristics give a broad indication of fuel type. Being a measure d
(b) Cloud point and pour point volatility, they determine the system of fuel metering required (wick feed, carburation or
(c) Drop point of grease atomization), and are indicative of the vaporisation behaviour of fuels instorage (vapour loss
(d) Melting and setting point of wax and vapour lock), and in piston-engine manifolds (uniformity of distribution to cylinders). The
(el Softening point of bitumen extent of the distillation range for any given fuel is representative of the availability of that
Methods have been devised for the evaluation of storage stability and resistance to fuel from the parent crude oil. For a fuel with a high demand, the aim of the supplier will be
to extend the distillation range as far as practicable. However, due to the interrelationship
oxidation for gasoline and aviation turbine fuel. These include:
between properties and the associated problems, minimum and maximum limits, respectively,
(a) Induction period of gasoline may need to be set for the initial and final boiling points.
( b )Thermal stability of Jet fuels The significance of this test varies from product to product. In case of crude oil, the ASTM
(c) Gum content
distillation data give some idea of the frwtions that could be collected below 300°C. If it is a
Most crude oils are corrosive to greater or lesser extent, frequently due to the presence of true boilkg point (T.B.P.) distillation, the TBP curve reveals a lot of characteristics that are
sulphur compounds, organic acids (mainly naphthenic acids) and traces of brine. Therefore,
useful for the design of the refinery. The 10vol.% of distillation for motor spirit is an indication
test methods have been designed to evaluate the corrosive poteqtialities of the petroleum
of the ease with which the engine can be started. Too high a FBP will cause crankcase oil
products which are obtained by processing of crude oils. The following methods are available: dilution.
(a) Total sulphur
(b) Acidity and alkalinity 4.4 VAPOUR PRESSURE
(c)Copper-strip corrosion test Vapour pressure of a liquid fuel may be defined as the pressure exerted by the vapour
(dl Silver-strip corrosion test for Aviation Turbine Fuels above the free surface of the liquid at the given temperature. For volatile, nonviscous
The misceJlaneous tests include: petroleum products, it is determined by Reid method. This is the pressure exerted by vapollr
(a) Ash when it is in equilibrium with the liquid under the conditions of test. For liquefied petroleum
(b) Carbon residue gas, the procedure is different and the determination should be done at 65%. The conditions
(c) Colour under which vapour pressures are determined give results which are not true because of the '
(d) Density.and%pecific gravity air which is invariably present in apparatus. n e true vapour pressure is higher than the Reid
(el Gas ckpmatography of petroleum gases and liquids vapour pressure by about 5 to 9 percent but this relationship varies widely.
(f) Refractive index of hydrocarbon liquids The standard Reid apparatus consists of a fuel chamber comectea to an air chamber of
(g) Lead in gasoline four times volume, and fitted with a pressure gauge.
(h)Water separometer index (modified)(WSIM) This test is important with,no-x vzan.oort,pzur&&jg-the gdsoline
( i ) Ductility *types of storage tanks employed and the starting characteristics of motor hels. High
The definition, method and significance of tests mentioned above are given below. vapour pressure entails loss of the ~ r o d u cin
t storage and transportation. In case of motor
spirit, it may cause vapour lock in the gasoline engines.
4.3 DISTILLATION
The laboratory distillation test comprises a simple process in which 100 ml sample is 4.5 FLASH POINT AND FIRE POINT
vaporised in a suitably designed flask fitted with a thermometer, and condensed in an Flash point and fire point can be taken as indirect measure- of the product.
ice-cooled tube and collected in a measuring cylinder. Whereas an individual hydrocarbon The flash point is the lowest temperature at which application of test flame causes the vapour
would exhibit a single boiling point, commercial fuel blends boil over a range of temperatures. above the oil to ignite. The fire point is the lowest temperatwe a t which the oil ignites and
Corresponding readings of vapour temperature and condensate recovered are made at continues to burn for 5 second.
prescribed intervals and the results are plotted in the form of distillation c w e . The initial The determination of flash point of petroleum products consists of heating a given volume
boiling point (IBP) is taken as the temperature observed at the fall of the first drop of of liquid at a standard rate of temperature rise until vapour is produced to such a degree as
condensate, and the final boiling point (FBP) as the maximum temperature reached during to give a flammable mixture with air in an enclosed space (i.e. closed flash point temperatye)
or with air in an open cup (i.e. the higher open flash point temperature), ignition resulting
- -
onrformance number shows the percentage increase in aipcrafi engine power for addition of
49
tiom the applicalion of'a small flame. At firc point, not only will the vapour-air mixture'fir)8h r-------
but the liquid will continue to burn. TEL to iso-octane and is given by
Performance number - 100)
Abcl apparatus is used for determiningthc closed cup flash point of' petroleum products Octane number = 100 + ( -
3
h ; t v i n ~tlash points between 19°C and 49°C. Pcnsky-Martens a p ~ a r a t u a iused
s for deteymin-
ing the flash point of fuel oils and lubricating o h , bitumcn other than cutback bitumen having On the performance number scale, 100 octane number equals 100 performance number.
;I ilaxh point :~br>vc 49OC. Clcvcland appariltus is used for determining the flash and fire points The ratings of aviation gasoline above 100 octane number can be done by
of pctroleun~products cxccpt l'uucl oils and those products having an open cup flash point below (a)Aviation method (lean mixture rating);
79°C. ( b )Supercharge method (rich mixture rating); and
Ylirsh p u n t measurcs thc tcntlcncy of the fuel to form a flammable mixture with air under (c) xie ended motor method.
conlrollcd laboratory conditions. This is tho only propcrty that must be considered in assessing I n aviation method, the rating is done a t 1200 rpm by comparing the combustion chamber
the ovcrull tlammability l~azartlof a mntcrial. I t is used in shipping and safety regulations temperature for the fuel with those of the blends of known performance number. This lean
thnldcfinc flttmmable and combustible n~uterials.Petroleum products having low flash points mixture rating gives us an idea of the availability of knock limited power in spark ignition
irrlb~~otential to fire hazards. Flash point can indicate the possible presence of highly volatile type aircraft engines when the aircraft is under cruising conditions.
ant1 tlan~n~ablo materials in rclativoly nonvolatile or nonflammnble makrial. In supercharge method, the rating is done a t 1800 rpm by comparing the h o c k limited
power of the fuel with those for blends of iso-octane and isooctane plus TEL. This is done a t
4.6 OCTANE NUMBER constant compression ratio by measuring indicated mean effective pressure a t enough points
This is a n important test for measuring the antiknock quality of the gasoline (petrol or to define the mixture response curves for the sample and the reference fuels. When the knock
motor spirit). The knocking of the motor fuelsis compared using blends of reference fuels. The limited power for the sample is bracketed between those for two adjacent reference fuels, the
standard reference fuel8 used foroctanenumbers below 100areiso-octiineand normal heptwe rating is cakulated by interpolation. The rich mixture rating indicates the a v d a b z t y o f b o c k
which arc assigned valuerr of100 and 0, respectively, on the octane number scale. The octane limited power when the plane is under take-off conditions.
number of thc fucl is defined atl the volume percentage ofiso-octane t2,2,4-trimethyl pentane) In extended motor method, the rating is done in a CFR engine normally used for rating of
in a blcnd with n-heplanc which is equal to the test fuel in knockintensity under standardised motor gasolines by motor method (rpm=9OO). The knocking intensity of the fuel is bracketed
and closely controllcd conditions of test in a single-cylinder, variable cbmpression ratio between reference fuel prepared from iso-octane and TEL and the performance number is
enbines, known as CFli cnginerr. Thus, a fuel of 87 octane number has a CFR engihe calculated by interpolation.
performance matching that obtainable with a blend of 87 volume percent iso-octane and 13
volume percent n-heptane. Thc rating can be done by either Research mcthod or Motor method. 4.8 CETANE NUMBER
The differences in the two methods are as follows: Cetane number is related to the ignition delay of a fuel in a diesel engine, i.e. how rapidly
Octane numbcr rcquirc~ncntsof gasoline engines depend on their compression ratio. If the to lower cetane numbers.
fuel meets the minimum requirements in respect of octane number it ensures trouble Bee Cetane number of diesel fuels is determined in a single cylinder CFR engine by comparing
ol~cration.Apart fiom being a nuisance, the knocking in an engine may result in loss of energy the ignition delay characteristics of the diesel fuels with that of reference blends of known ,,
: ~ n da t times may cause severe damage to the engine. cetane number. Cetane number of a diesel fuel is defined as the whole number nearest to the
value determined by calculation from the percentage by volume of normal cetane in a blend
4.7 PERFORMANCE NUMBER with h e p t a m e t w nonane which matches thdignition quality of the test fuel when compared
This is used to estimate knoekihg characteristics of aviation gasolines of octane number bv this method..The matching blend percentages to the fiist decimal are inserted in the
highcr than 100. The standard reference fuels for knock ratings above 100 octane number are following equation to obtain the cetane number:
iso-octane and its blends with tetraethyl lead (TEL). The ratings of aviation gasoline above Cetane number = % n-cetane + 0.15 (% heptamethyl nonane) ... (4.2)
100 octane number are normally expressed as performance number. The shorter the ignition delay period, higher is the cetme number of the fuel.
The performance number scale is based on engine power output. The performance number Cetane number is the index of ignition quality of a fuel. High cetane number fuels will
of an aviation fuel represents approximately the maximum knock-free power output. The facilitate easy starting of compression ignition engines, particularly in cold weathers, and
faster warm up. These also result in increased engine efficiency and power output, reduced
Q U A M Y CONTROL OF PETROLEUMPRODUCTS 38
exhaust smoke and odour and combustionnoise. In the absenceoftesten&e,the diegel index
or the calculated cetane index will give an approximate idea ofthe ignitiofi quai* ofthefdcl. Thirr CCI ia useful for estimating cetane numbers when a test engine is not available for
Cetane number can also be roughly assessed by the formula: direct measurement, and it may be convenientlyemployed for estimating cetane number when
Cetane Number = 0.72 x Diesel Index + 10 the quantity of sample available is too small for an engine rating.
... (4.3)
4.9 ANILINE POINT CALORIFIC VALUE
This is the quantity of heat released per unit quantity of fuel, when it is burned completely
Aniline is a poor solvent for aliphatic hydrocarbons and excellent one for aromatics. This
propertg is used in the aniline point test. Aniline point of an oil is the e t u r e & with oxygen and the products of combustion returned to ambient temperature. This quantity
of heat will include the heat of condensation (latent heat) of the water vapour formed by the
l & f & J - a W - . .. combustion of the hydrogen in the fuel, as it cools to ambient conditions. It is called the @
'
Equal volumes of the sample and aniline (5 ml each) are heated or cooled with stirring in
a jacketed test tube and temperature at which complete miscibility occurs is noted. -
calorific value" or "hi~hercalorific yalue".
Most h z t i n g applications cannot recover the heat of the water vapour; it simply escapes
High aniline point indicates that the fuel is highly paraffmic and nence has a high diesel with the vapoui out of the chimney. The potential heat content is therefore more nearly
mdex and very good ignition quality. In case pf ar~maGc&he-milanilhe point is low u e
.ro-i . ._+,-.-" ~.rrc.-.n--
indicated by subtracting this latent heat from the gross calorific value, and the resultant value
is called the net calorific value, or lower calorific value.
A weighed quantity of the sample is burned in a bomb calorimeter under controlled
4.10 DIESEL INDEX conditions. The calorific value is calculated from the weight of the sample and the rise in
Diesel index is an indication of the ignition quality of a diesel fuel. This is dctemined by temperature. I t can also be calculated from the formulae
calculation from the specific gravity and the aniline point of the sample. Although it is ofthe Calorific value = 12400- 2100 p2 J4.7)
same order as the cetane number, it may differ widely from the cetme number. Higher the
diesel index, better is the ignition quality of the diesel i e l . It is normally used aa a guide to in which calorific value is in caYgm and p is density at 15OC in gm/crn3.
ignition quality of the diesel fuel in the absence of test engine for the direct measurement of
cetane number. Calorific value is a measure of the energy available in a fuel. Thus a knowledge of the
The diesel index is calculated as follows: calorific value of the fuel, and the efficiency of the heating equipment, is essential to compare
the merits and running costs of different fuels and energy costs. It is a critical property of fuel
(a) Diesel index = Aniline point, OF x OAPI intended for use in weight-limited vehicles.
100 ...(4.4)
(b) Diesel index = Aniline gravity constant
4.13 SMOKE POlNT
100 ...(4.5)
(c) Diesel index = Cetane number 10 - Smoke point is the maximum flame height in mm at which the fuel will b u m without
smoking *hen determined in a smoke point apparatus under specified conditions.
0.72 J4.6)
Smoke point apparatus comprises four main parts-lamp body, candle socket, candle and
4.1 1 CALCULATED CETANE INDEX stand. The lamp body with chimney is fitted on the inside with a polished black engraved scale
Calculated Cetane Index (CCI) is based on specific gravity and the 10 percent, 50 percent which is marked in white. A gallery is secured in the lower part of the body. The candle socket
and 90 percent distillation temperatures of the fuels and it gives numbers that correlate with assembly is designed to give a smooth rise and fall over the total distance of travel. To ensure
the engine-testing method. The relationship is given Ly the following four-variable equation: interchangeability the candle is finished to close tolerances. The assembly is mounted on a
stand. The sample is burned in a standard lamp with a specified wick for five minutes. The
CCI = 45.2 + 0.0892 TION+ (0.131+0.901B)T ~ O+N(0.0523 - 0.428)Tgo~ + height of the flame is read when it leaves no smoky tail.
- (T~oN)~]
0.00049 [(T~oN)~ + 107B+ 6 0 ~ ~ J4.6)
This is an important test for evaluation of illuminating oils (kerosines) for their ability to
where bum without producing smoke and the assessment of the burning quality of aviation fuels.
TION= Ti0 - 215 ,OC Higher the smoke point better is its domestic use. I t also serves as a guide to assess the
Tlo = 10 percent distillation temperature, OC aromatic content of kerosines.
T ~ O=NTm - 260, OC
4.14 CHAR VALUE
Tso = 50 percent distillation temperature, OC
The amount and nature of the deposits (char) produced on a wick during combustion
T ~ O=N2'90 - 310 OC depend on the hydrocarbon composition of the fuel and also on the design of the appliances in
T90 = 90 precent distillation temperature, "C 'which it is used. Char occurs as a result of the breakdown and decomposition of the kerosine
B = - 3.5(G-O.85) - 1 under the local conditions existing at the wick surface, and these conditions will also determine
what proportion of the decomposed products remains on the wick.
G = specific gravity at 15OC
52 PETROLEUM REFININGTECHNOLOGY OUAUTY CONTROL OF PETROLEUMPRODUCTS
by the Redwood instrument in the UK, Saybolt in the USA and Engler in continental Europe. temperature on the viscosity of any oil. Proposed by Dean and Davis, viscosity index is an
They each comprise a sample cup fitted with a standard-sized oriiice in the base and empirical concept based on the behaviour of mineral oils. In this concept, an oil whose viscosity
I changes rapidly with change in temperature has a low VI. An oil with a minimum change in
.,
surrounded by a waterjacket containing a heating device. When the temperature reaches the
test level, the orifice is unsealed and the time of flow is determined for the given volume of viscositywith change in temperature has a highVI. In this system, Pennsylvanian (paraffinic)
sample. The result is reported as Redwood or Saybolt universal second or as Engler degree, oils of a selected type which show a desirable, relatively small change of viscosity with change
given by the efflux time ratio for the sample and for water. When the efflux time exceeds a in temperature, were assigned a VI of 100, while selected Texas Coastal oils showing less
specified maximum-for example 2000 s-due to high viscosity, use is made of a Redwood No. 2, desirable viscosity-temperature characteristics were assigned a VI of O.VI is governed by the
or a Saybolt Furol (fuel and road oils) instrument, incorporating a larger diameter orifice. type of hydrocarbons in the oil.
The absolute determination of kinematic viscosity'generally employs a glass U-tube Dean and Davis prepared tables giving the kinematic viscosities a t 40°C and 100°C of the
viscometer with a capillary tube built into one leg. The length-diameter ratio is such that end Texas Coastal oils (L) and the Pennsylvanian oils (HI. The values of kinematic viscosities of
effects are negligible and the precision is therefore higher. The instrument is suspended L and H are given in Table 4.2. The VI of an oil can be calculated from the equation
vertically in a thermostatically controlled water bath, and the time is measured for a given
volume of sample to flow d o u g h the capillary. This measured time period is inserted into an v1=L-Ux100
\ L-H
equation to give a direct measure of the kinematic viscosity in centistokes.
where U = kinematic viscosity at 40°C of the oil whose VI is to calculated
v=At-B/t ...(4.8) L = kinematic viscosity at 40°C of an oil of 0 VI
where A = instrument calibration constant;
B = instrument type constant, depending on the capillary diameter; H = kinematic viscosity at 40°C of an oil of 100 VI
and
t = efflux time, s (Engler degree for Engler viscometer) .17 PENETRATIONTESTS
Several standard grades of bitumen are comlqercially available, which are normally
Table 4.1 gives the values of A and B for Redwood, Saybolt and Engler viscometers. ssified into different grades by p e n e t r a t i o n p e sample of bitumen is plzced in a .,
Viscosity is an important characteristic of a fuel and it is used for the pump design. Pump suitable container and brought to a temperature of 25OC in a water bath. The weighted needle
clearance are aGusted according to the viscssity and if i t is out of the range, it will result in is brought to the surface.and at the end of 5 seconds interval, the penetration the needle
pump seizer. Pump operation of an engjne depends on the proper visesity of the liquid fuel. into the bitumen, in units of UlO mm is t e ~ v o nofthe ' b $
The viscosity of liquid fuel is important to its flow through pipelines, injector nozzles, and The penetration at 25OC and the softening point, or penetrations a t two di erent tempera-
orifices, and for atomization of fuel in the cylinder. tures (for example, 25OC and 10°C) can be used to define the extent to which the consistency
of a bitumen changes with temperature. This an important characteristics for bitupens, and
1
determines the type of bitumen used for a particular application. Various factors have beexi
QUAUTYCONTROLOF PETROLEUMPRODUCTS 55
The test is continued until the break point is reached. The test result is reported as induction 4.26 TOTAL SULPHUR
period in minute. This is determined by lamp method or wickbold procedure for volatile petroleum Products
This test is conducted to assess the stability of gasoline in storage. This test indicates the and by bomb method for heavier products. Sulphur in the sample is oxidized by combustion ,
presence,of unsaturated hydrocarbons in the fuel and hence its gum forming tendency. Higher and is estimated volumetrically after absorption in Hz02 or by gravimetric methods after
the induction period, better is the storage stability of the fuel. An induction period of 360 converting into barium sulphate.
minute under laboratory conditions ensures storage stability of at least six month. However, Sulphur compounds pose a dual problem: they not only cause environmental pollution
this correlation may vary with different gasolines under different conditions.
"
1 from their combustion products, but these products are also naturally corrosive and cause
severe physical problems to engine parts. A knowledge of the sulphur content of petroleum
4.24 THERMAL STABILITY OF JET FUELS products is therefore of importance to both refiner and user.
I
Jet fuel thermal oxidation tester (JFTOT) is used to measure the high temperature
stability of gas turbine fuels. This subjects the test fuel to conditions which can be related to
those occumng in gas turbine engine fuel systems. The fuel is pumped at a fixed volumetric
1
I
d c l D I T Y AND ALKALiNln
New and used petroleum products may contain acidic constituents present as additives or
I
flow rate through a heater after whichit enters thestainless steel filter whert! fuel degradation 1 as degradation products, such as oxidation products, formed during service. Total acidity is a
products may become trapped. The apparatus requires 600 ml of test fuel for a 2.5 hour test. I
I
measure of the combined organic and inorganic acidity.
The essential data derived are the amount of deposits on an aluminium heater tube, and the The acids in the sample are extracted in neutral alcohol andthen titrated against standard
rate of plugging of filter located just downstream of the heater tube. alcoholic potassium hydroxide under hot conditions.
In the JFTOT a charge is placed in a reservoir and the whole system is pressurized to 3.45 Total acidity is an indication of the corrosive properties of the product. Inorganic acidity
MPa with nitrogen. This ensures a single-phasereaction in the heated section. The fuel passes is a measureof the mineral acid present. Organic acidity is obtained by deducting the inorganic
from the reservoir through a 0.45 micron filter, to remove trace particulate matter, and into acidity from the total acidity.
the reactor section, where it passes upwards in an annular space over iyaluminium tube and
out via a 17 micron stainless steel filter through a heat exchanger, to cool it, and back to the
ER-STRIP CORROSION TEST
top of the reservoir. The used and unused fuel in the reservoir are separated by a floating
piston. The fuel is rated by a visual tube rating or by placing the tube in a Tube Deposit Rater. products contain sulphur compounds, most of which are removed during
I refining; Of the sulphbr compounds remaining in the petroleum product, however, some can
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 meter. Also, the have a corroding effect on various metals. This corrosivity is not necessarily directly related
differential pressure across the 17 micron filter is measured. to the total sulphur content. The effect can vary according to other chemicals and types of
sulphur compounds present.
The test results are indicative of fuel performance during gas turbine operation and can
be used to assess the level of deposits that can form when liquid fuel contacts a heated surface. A cleaned and smoothly ~oli$hedcopper strip is irnmerse&&hsm@& which is then
mamtained at the specified temperature for the specified length of time. This strip is removed
4.25 GUM CONTENT
The gum compounds which can be present or produced in the fuel are classified into two
1 L a m p l e , washed with aromatic and sulphur free petfoleum spirit and examined for
evidence of etching, pitting or discolouration. It is then compared with F T M copper-strip
corrosion standkd colour code. Th_eclass%cation cbde indkates that the numbers 1 , 2 , 3 and
types for test evaluation. Existent gum may be already formed in the fuel and can be deposited 4 designate slight tarnish,'moderate tarnish, dark tarnish m d corrosion,kespectively. Sub--
from solution as the fuel evaporates. Potential gum may be formed under extended storage scripts-a-e describe a standard colour reproduction'in the standard chart. For example, the
conditions during which unstable hydrocarbonsare thereby polymerized and oxidized to form classification code l a indicates slight tarnish with a light orange colour.
gums.
C ~ h itest
s serves as a measure of possible difficulties with copper, brass, or bronze parts of
Existent gum is the amount of nonvolatileheptane insoluble residue left when the sample the fuel systems.
is evaporated in a jet of hot air at 160°C. For jet fuels, the evaporation is camed out in a jet 7
of superheated steam at 232OC. 4.29 SILVER-STRIP CORROSION TEST FOR AVIATION TURBINE FUELS
Potential gum is the amount of gum formed afier the sample is aged in an oxidation
A Polished silver strip is completely immersed in Aviation Turbine Fuel at 45 f 1°C for a
stability bath and evaporated under specified conditions.
period of 16hour. At the enctof this period, the silver strip is removed from the sample, washed
Gum is always troublesome in any fuel and it may cause piston ring sticking and deposits and evaluated for corrosion against the set of standard.
on engines. The amount of gum points to the presence of olefins which have very poor storage
stability. The existent gum test is claimed to measure the amount of gum or gum-forming Since some parts of the fuel pumps in aircraft are made of silver, the corrosive tendency
compounds existing in the fuel, while the potential gum test attempts to predict the tendency of the he1 for silver assumes special significance.The cumulative effect of corrosion on such
to form gum on storage and use. These gum tests are usually used as refinery control methods. a vital component in the aircraft is hazardous.
_? 4.30 ASH -h~ji{:!:*;:~
: p > 5 ~ z :.b,,:;.7!t$;
~ y ~j !;,;~
: ;.,:,.t;.3:
<..
. .
... c ,~:.., ~ ~ ~. ~.. ~ Table 4.3 ColourMeasurementmethods, ,,. . .,
.,&h.@n!~esultfr0.p oi1,water-solpble metallic cqpounds, or extraneous solids, such as <, ,;,,il5 ..;.,,:<,<
.rll..-..
% * , ( ...(,....
. ~ . .. I I. -. :.-;- , .!l:.,,.:. ...
i . - . .
, ,: ' I.. . ' . . . . , .
di&qj&+s$,~.:~~:~.
. , . .. - -
'A kqom'p~,ogn$:.qf 3aible is ignited and the c a r b o n a ~ i oresidue
~s I&€ib
. heated
.. to Name Main equcpment Colour scale Applt'catlon -
I
I
800°C in a muffle hrnace, cooled and weighed as ash. Saybolt chromometer Chromometer +30to - 16 White
products
petroleum
A b ~ w l e d g eof, the amount of a product's ash forming material can provide information
ASTM Colour . Calorimeter Oto8 Heavy petroleum
on whethemthe-product is suitable for use in a given application. products, lubricating oils
Colour of dyed aviation Colour comparator Permanent colour glass Dyed aviation gasoline
gasoline disc
w r b o n residue can be defined as the amount of carbon residue left after evaporation and Colour by the Lovibond Lovibond tintometer Colour standards of dif- A11 petroleum products
I
pyrolysis of an oil and is intended to provide some indication of relative coke forming tendency. tintometer ferent rating for red, yel- except black oils and
Either Coriradson method or Ramsbottom method can be used to determine the carbon low, blue and neutral tint bitumens -J
residue of petroleum products.
Specific gravity is the ratio ofthedensity ofafluidtothatofwaterat the same temperature.
onradson Method The temperature usually specified is 15.56OC. In the USA, specific gravity of an oil is often
quantity of sample is placed in a crucible and subjected to destructive distill$- e ddegrees kP1.API gravity is an arbitrary figure related to the specific gravity of
- e , ~ ~ e s s as
tion. The residue undergoes cracking and coking reactions during' fixed period of severe jytroleum products in accordance with the formula:
heating. At the end of the specified heating period, the crucible containing the carbonaceous . , 141.5
?, ?
Degrees API = - 131.5
residue is, cooled in a desiccator and weighed. The residue remaining is calculated as the Specific Gravity at 15.56°C115.560C . .(4.11)
'percentage of the original sample and reported as conradson carborl residu
3 The specific.gravity is an indication of thetype of hydrocarbon present, being highest for
Method aromatics and lowest for paraffins. The API gravity reverses this relationship. -
e sample S t e r being weighed into a special glass bulb having a capillary opening is The most accurate method of determining the specificgravity of an oil is to weigh a known
'plackd. in"&metdfurnace maintaihed a t 550°C for 20 i I'minute. Thesampleie thus quickly volume in a specific-gravity bottle at 15.56OC. A correction may be applied by measuring the
'1heatedytothe point, atwhich all volatile Matter i~evaporatedout of the bulb with or without 'specific gravity at some conventional temperature near 15OC and adding or subtracting
decompositionwhile the heavier residue remaining in the bulb undergoes cracking and cqking 0.00063 per O C above or below 15OC.
reactions. Aftek a specified 20 minate heatingperiod, the bulb is removed from the bath, cooled ' Another method for determining the specific gravity of the oil is by means of a set of
in a desiccator and again weighed. The residue remaining is calculated as the percentage of
the original e m p i e and reported as ramsbottom carbon residu hydrbmeters. A hydrometer is placed in the 6il sample at 15.56OC and allowed to come to rest.
of a fuel oil when The specific gravity is shown on the scale at the point coincident with the surface of the oil.
C?+on ;&due gives a measure of
h$ated in a buI6 under prescribed conditions. While not directly correlating with engine Accurate determinations of the density, specific gravity and API graliity-of petroleum
deposits, *s property is considered as an approximation. For example, carbon residue value products are necessary for the conversion of measured volumes to volumes a t standard
of die& h e 1 corielates with the amount of carbonaceous depmits the fuel will form.& the temperature of lb.56OC. When the volume of oil is known, its mass can be calculated. These
combustion chamber of the engine. The expected carbon deposits in the combustion chamber factors govern the quality of cmde petroleum. These properties, however, are uncertain
is greater for higher value of the carbon residue. Carbon residue is also used in design indications of fuel quality, unless correlated with other A correlation of fuel density
calculation of vessels. with particulate emissions indicates increasing particulate emissions with increasihgdensity.
I
Density of a fluid is its mass per unit volume. It is measured over a range of temperatures.
usually for convenience a t the temperature at which the fuel is to be stored. 4.35 REFRACTIVE INDEX OF HYDROCARBON LIQUIDS
Refractive index is defined as the ratio of the velocity of light (of specified wavelent$) in
t
air to its velocity in the substance under examination. It may also be defined as the sine of the
64 PETROLEUMREFINING TECHNOLOGY
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 with both wavelength and tempera-
ture. Refractive intercept is calculated by
'
Refractive intercept = n - 2 ...(4.12)
where ri is the refractive index at 20°C and p is the density at 20°C,gm/cm3.
' ~ i ~ h t h e content
ne in naphthas can be easily calculated by knowing the refractive index
and density of the saturates fractions as determined by the refractive intercept method. There
is a relation between the molecular weight, aromatics and refractive index of hydrocarbons
and hence the determination of refractive index gives an indication of the content of aromatics
in the hydrocarbon fractions.
_
The lead alkyl is converted to lead chloride and extracted from the gasoline by refluxing
.
with concentrated hydrochloric acid. The acid extract is evaporated to dryness. Any organic :&,tfYiiiiiiFYB,'C!'C!E
Td'(jr:&,M6i;.4*c$i .'"
. <,.: '., .,;ii>.5 '., +: .,:,,,;!!,:,:l:.ji:.:
,! :..1<.<7<. ., I,.'
g&$rakf
";"i; , $ , ~
material present is removed by oxidation with nitric acid and the lead is determined bj2~?y8>.:sj...tis: j+xp,..d,) & . , J A ~ ~ ~u::.
. , ~ r i t & ~ ~ ~
...... %+;*::i g ~ j k : 'Y$<.T,
. . ,
: ~ ~t:F* 1% ,
z.,
tgffl,. ,(,
3:&&&!.....
*,:a,
p7$~c5$~+5~~9~@~~$l~~.tPo
L!
gravimetrically as lead chromate. The method covers the gravimetric determination of the , hefi+.
, .
li&t, $Kp$$&Pi.
d & T ons
~ denved
$ ~ h from.
. + .;
; .ji
, ~ ~whl~h
~ fieirol'eum
.!,_
to the m i? f it..
,
-'
total lead content of gasoline and other volatile distillates blended with lead alkyls (tetraethyl : .,$>,..
t6mp&f&@ :;.:.I ~ but condensed
< Iiquidtitst.eatnmbievt
lead or tetramethyl lead, etc.). ! by aP$ffclAbhfsprri:da@&O $!! B ' & B & ~ ~ & K x h ~ ~ ~ ~ @ & ~ ~ ~ ~ < $ & & t ~ & &4&eY
are
Tetraethyl lead is added in gasoline to improve the octane number but it is highly .,. Ir4:. ! ,
:,$tored : ~ tfanap6~d
d &liiji$duids.bnder praswe. p hey are sold .apmpane or butane or undr
poisonous. Hence, its concentration in gasoline is restricted and its handling is done with :i~~f;'e'~~ideTame~sU~~~~S.~n~~ne,
..
~ b ~ ~ t : ~ ~ ~ , . H p. .. . . ~, ~ ~ i ~ J ~ d i ~ .
utmost precaution. .., ,. ' ' ?"
\.... -:,<,.-;. ;. ....;.... :.>,:
,?..! i!.
. . . . . . .
This is carried out with a water separometer. It~measuresthe water separation charac- ,, ,, ~
.!bdtSgl$
, ~ ~ , ~ , , mu i i h k
s s of ~saturated
be:cyand ~r~~&-f,p~-~h'sis~ af.o*?r rn0fe of fie foll&ghydrocarbons:
a and
l unsaturated
l ~ hydrocar- - ..
teristics of fuels expressed in terms of WSIM.
' * Propylene (C3H6)
An emulsion of water and fuel is prepared and passed through a cell containing a h o p b e.........
. . . . ., . . . . . . . . .
(C3Hsj
.
0' . n-butane &!jH$) gq10j
...L.,
standardized 'fibreglass' coalescer.~Theeffluent from the cell is examined for entrained water . . . ..,. '. . 1~0-6uta"
~ . :
,
i
by light transmission. A numerical scale (0-100) rates the case with which the fuel releases Butylene (C4Hs)
gxpu!sified water. ~races'tosmnli auantiti&sof one or more of the follow&g hydrocarbons may. also be presen..
:,,WSIMis a measure of fuel cleanliness relative to its freedom from surfactant materials. Ethane (CzH6) Ethylene (CzH4) I
I
A higher WSIM rating indicates that the fuel is cleaner relative to surfactant materials. -- Penbane (c5H12) Pentene (CsHlo) )ii . \)
4.38 DUCTlLlPl ,i)~ P separated G from heavier hydrocarbons by r straight distillation process contains only
-7 the saturated hydrocarbons wliereas ZPGaobtained from conversion processes such as tht
Bituminous surfaces exposed to varying temperature conditions undergo a great deal of
macatalytic cracking, , c :.and hydmcracking contains unsaturated hydrocmtio~
,:< ., ;' reforming ~ . . as
elrpansion and contraction. Therefore an important characteristic of the Kinder is its ductility
and the degree of ductility has an effect on the cracking of bituminous surfaces caused by traffic
@li+.
I : Bulleau of Tndian811Standarde-4BIS)have categoised
LPG as under:
stress. The ductility of bitumen is expressed as the distance in centimeter to wfich a standard .(A) - .
Commercid b u t m e k a-hydmcarbon-product composed re dominantly of butane
,
briquette can be elongated before the thread formed breaks under the specified conditions.
A molten bitumen sample is poured into a standard mould, allowed to coal to room i- butyleneb or their mixtures.
temperature and then placed in a water bath so that the briquette can be brought to test (I%)' Comme~ciakbutaneapropane mixture - a hydrocarbon ~ r o d u c tcomposr '
temperature before mounting in the testing machine. Ductility testing machine consists of a predominantly of a mixture of butanes andlor butylenes with propane andJ~1
propylene.
moving carriage moving over a lead screw.An electricmotor driven reduction gear unit ensures
smooth constant speed and continuous operation. The temperature is controlled thermo- ' (C) Commercial propane- a hydqocarbon product composed predorninandflfproph-
propylene or their mixture. > .
statically.
The requirements of LPG are e v e n in Table 5.1. LPG produced at Indian refinen
Bitumen having high ductility may be more temperature susceptible. conforms to grade B.
1d'fldi~~Mtkl~ie~h8'c~fig1(~~~) uiifir the Yeed~&sfi&\ffb$W"hi'&xddp &-fed SU-+& j f l r- ; h
and heavy fraction#. Uncondensed overhead gases and catalytically c r a o k & i q g ~ e l ~are e
-
-
I
"
.\ , ik
routed for LPG recovery. The uncondensed gases are compressed, moledaq~pha&$&uqces-
sively to two absorbers which employ cracked gasoline and light cycle oil respectively as 5,2 NAPHTHAS
, Naphtha is a name give? td light hydrocarbons bgilin&$he:ge.gasoline range. I t is
absorbents to increase hgbt ~ ? ~ r ~ ~ ~ v e w ~ , ~ ~ fmm h g aabsmber
s o l i p is45tfi8p&,d,
e off its
lighter ends in a stripperjl'he stripped g~sol$ne kfedto a debpta?iger ~ ~ l ~ ~ , ~ ~ b , & ~ i a c k e datlight distillate obtaine4,frop -, )
refipwg of crude:~il.y e bo~lingfiiagesof various types of
LPG is taken as overhead producp. L P q q 4:yerhead product from debptahipfr ,$oJu+n is naphthas produced include: C5 - -
85OC. Cs 118C, C5 140°d, CS; -
~ ~ O O C C5
, 1 7 5 0 and
~
treated further to conform to required specikations.
-.
. tf,"
C5 - 200°C. In these iiitial boilink point (IBP) is c o n s t s n t . ~ ~ t ~ ~ - b oranges
i l i n ~can be
Coker gases are compressed in two stage compressor and routed to the bloi~&$$&k~~orber 60 - 85Oc, 85 - llo0C, p + l l p - 140",~.w a s are u s u a l l ~classified a s light.hterme&ate
~ $ @ d f ? ~ ~ ;is $used, ? ~as~absorbing
~ medium. Gases from ap$tha a sorber to are and heavy naphthas. I t t h h a p h t h a fraction ~ lbe1ovk1000($,
s it ii,"c1bsified as l g h t naphtha.
;&aer a sqrbe, ,,,y coker'kerpsi$, ~L%"kerosifibkord kerdsine a!sor~& % d ~ ~ ~ R the
i , t < \ 2 a,
mw$$a$tidnating,k71mnnb,!the ,ckkii;~*li8?%ighte'rrehds
P
(C1 and-cijkre s,thr&qdffG o d
~k'& H~~~ naphgaboils above 150°C. .
For A
4
'v
' 3
I- .;
interniediate naphtha ~ k b @ % $ & ~ ~ g < ? ibetween
*
es
3:
_I__ '
1 recover back QqC4s. St$&r .,.,,,,!
,,) n j g "~' V"t
&dfd&~"&n~&$' 3 9 ~ 1 ~ a @ l . $ ~ ~ h $ ~ P, $$92 v t h ~ ~ a i n
debutanise; wliCrbiWG is iuihii?iwn %om bpan&'t"hb"lfi&d c6ke'r liaphthd 5 .2.1 Method. of ~ * a c t m & o ~ ~ a * h t h g ~'' !
I
ki
1
6&d&. Naphtha is prod&ed by atm~sfihericdistillation of cmds bil?&s./s &e+straight-run
bPG
caustic tmatment.
w8s)rasthb Most of le*elik
mercaptaii s t r a i gbelow-5q
h t a n LPGppm.produced
CausticfromwashGulf
alb&cmdes
doeanat reguires only
bring down naphtha. Several c~nversionprocesses such ad visdre&jng$?uid c tal* crnf~ng,
the percaptan content-of LPG in respect of,Aghajari ?rude and-he-e Merox treatment hydmcracling, cokingalso ?roduce llqphthj. TEssb @ bd2d crgcked 'pa!hth&.
I
(extractive type) is nwessary. Straight-run LPG produced fro~&$&...d& is BenGraily The important chatacterjsticsof t%aphthi?ractions6~ d a e r e n t l @ b ~ a r eg v e n h Table -
5.3. The proper qualitypf naphtha f o the ~ petrochemic$ and fe&lher inapm can be
sweet but requires mildpcausticwash. , -
Likewise cracEed LJ'G produced from pro&ssing of Indian cFdeL
Cracked LPG from F ~ Cunit ' processing feedstock from ~ u l nuddk'irei$Ares
f
idj;' lres
-- caustic
-
amine wash for,
wash.
achieved by dearomatising the naphtha with or without reforming openh;ams ~ g otor extrac-
tion Ofaromatics. Higharomptic naphtha is not gly.s;auisapce @ k s p mndsbies, but also
H2S removal follwed by Merox treatment. The Memx process is one of oxidation of the consumes &a enerfl in thd cracking operafions$ithout P i n g m y useful ~ r d u c t s .SO, it
medaptans with ail. in ~kaIjne'r+$$m in tffe pre$& of~~el~t6d1i~&n'&&$d~fi& i$t&&. produces more coke and increases the downtime in both the patmehemica1 p d fertilizer
The mercaptans are converted to di~~lphkdes whidi i r e &&ively odod~1dd~ddn~ko~&'ive
r , n ''
industries. On the other haid, the eyiracted aromatic fraction can:be used in thqaoufacture
compounds. A small amount may remain in the treated LPG but the bulk is transferred with of synthetic fibres.
the caustic to a'regeneratorwhere sodium m$rcaptanine ik'conveited B diluphide oil and
NaOH is regenerated. The insoluble disulphide oil is removed thereby reducing the total ,&&2 Composition of Naphthas
s~@tiur. $pbl"" is a complex mixture of hydrocarbons. Its mmpositiopdep&ds o&+e crude oil
.
Ii Qdourisation. Since LPG is used as domestic fuel the chances of fire in confined locations
b e c o i ,?rgein the case 0Ia:cidental leakage. Beingagas this sh?uld betmost easily detectable
proce sed and the conversion.proce~gemployed. For the composition o q b a p h v , two types
of analyses a i e usually carried out. These are:
by smell alone. Since constituents of LPG do not have any characteristic o&ur,'it;s cimb;on ~vdrocarbontype analysis
practice to deliberately mix highly odoriferous additives in LPG to ilnpart a distinct odour.
Most commonly used substances are low molervlar weight organif thfols (mtb$ahlf&':d;
Individual component wise analysis 1
he hydrocarbontype~alysisdeterm~n~~thepercenta~~of ~ ~ @ m olefi&naphthenes
s ,
.
have an pbnoxous odour in concentrated form and serve as-effective4 0 u r markersin dilutqt and aromatics. Gfferent tj$es of c o ~ p o ~ n found d a inpaphtba fracti~nsfmv v uses are
form (ppm levels). Some compounds of this type are ethyl and $tbb$l mercaptans. ~ ~ ~ $ 8 $ t s t ' given in Table 5.bThe approximat&cdrbon dumber range of the p r d d u is ~ slap 8 v e n in the
made-Doctor negative and then ethyl mercaptan (about 50 ppm) is usually added. same table. In Table 5.5, a summan, of quality+of the naphtha-fiqctions porn various ,
' indigenous and certain imp~rtedand worldWidqyailable cmde);&h respecQ9 the para!- ' ,
i -5J.4 Uses of LPG ' fidnaphthendar~maticc~ntentso f q e i r na$hth@fracGons $re given. The vque indicated 1s
I
.&pGisbwedaofq avarious
domestic fuel, 8 fuel for the full ranggnaphthd (C5 - 140°C). -- ~ h ~ h y d r o c a r b type
o n composition of naphthas fionl
andfor internal copbustionLPG engine anQa feydstopk for
themanufacture
P U Y Y ~ S is~ysually,
~
chemicals olefins (by pyrolysis.). supplied
a mixture of propane and butane, butanes predominating in warmer
for,dbmestic
-
Indian crudes is @en in Table 5.6 for boiling ranges of 60 85OC, 110 l2O0C, 120 130"~' - -
countries and propane being in greater proportion in colder countries. LPG' has many and 130 - 14o0C:
industrial applications. It is used for portable blow-lamps, soldering, brazing, welding, anneal-
J.
2 3 Uses of Naphthas
The major end-uses of naphthas are listed in Table 5.7. The use of naphthas in fefl-
and petrochemical industries and as gasoline is discussed below.
I.
a:: 5 :
Table 5.6 Hydrocarbon Type Composition of ~ a ~ h t hfrom
a s Some Indian Crudes
... &
;. (d) Mineral ~ p i r i t s - ~ G n nfoF~8ifitg- c d ? ~ ~ j ~ ~s&.itu@ ~ ~ 'I.. ~ ..t :: i . -< . . e .
. . . . . . . . . .
.,-
sasEone before the @$d UPof th$@$&fi, t&reshold:per6~ideconcentrati~n,~~ co@JJ&ion end i:. ,
Water contamination . :
i . . - ~ . ~ ~ : . ~ ; i : ~ ~ . f ~:
-
of the gasoline-air m ~,x. ,t u r \?fiI.k-be.w~t&jut
~ i g b r 5.1
e
.:;.,, ,
........
, !. <
:,, ,
,'<::!%:-,..I;
kbock.
. .
e i~h'dia~~~ii:6f~~.dt~~ir!a~1~dj~~il1,ati~n
. .. ..
. . . . .. . .. . ..
" :
. . .t.
.
. .
Hot fuel
Carburetor1
problems .Improper-volotilityeontro1.--
~
High
e
Pcrformqi:,&g
~ ~: ;
or gasolines. ~hi~d~pg~d~stori\ge!g~s:o!irlps
J o x i d a t i o n Stabilit~ undf.pg~~&a)y.but
progressive oxidatibn dcterioration. Thc rcsult of' this is formation of n ~ n - v d a t ~ ! ~ ~ ~ , m m y
residues. If present in the gasolincs, thc gummy residucs can causc multiplc Gouble, such as
deposit formation in thc carburctor parts,p&pPr&~,~ifA1d~o.f$~~t~jpluIji$~p&~p-+i~ the
s . m A ~ ~ p i w y h $~r .y. ~ ~ ~ ~ l ~ ~ ~ c c i f i L ~ ~ l ~ ~ ~ ~ , r p ~ c
tian&&p :q~qq~"r~.;o&g~?.ppcscnt. jn.;;tk f4&lj(erjst~nt
gum);. ~8fi$a~EFia!bFF:y~~r:$~~~~$
proccdur* arc used to dctermlnc thc tendency of w m f ~ r , @ a t i ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ; f p p & ~
..il3g;(+m&qna~ion :is! due:tp;.o~iPativ.c. #g&g@ti~g~$$lyfqc\ j ~ f i ~ $ ~ # ~ ~ ~ $ k ~ . f i f &
%,~Y~~RoT@@~
? @ ; i r r , d ~+~g k o s 4 d a t i p a0nc.c initiate?. $Pp-941~?~~?~~9f!~4f0~73~~3~%k~~fir0$cs
Fig. 5.1 Typical distillationcurve for gasoline. chain reaction. The primary products of auto-oxidation are hydibpcroxidcgl:T ,,~.~$ecompose
the combustion chamber. These form carbonaceous deposits which may trap lead salts also. Most petrole"? products a& $u$ceptible to deterioration~n~ f ~ ~ f t , d!,\ri $ : $*pi? ~
The build up of such deposits affects the octane requirement of the engine. When lead halides composition a n & ~ h 2 ~ ~ & $ 2.~. c & . o famaunts
~ m 2 1 1 of nitrogen, sulphbr, organla . . h l ;d S:;, - %:d: % ~ g ~ ~ .
, :.
, . c
or sulphates get deposited on the spark plug they cause low shunt resistance (short circuiting).
,:j:
.. s~anoldux!uo!qsnqux03 (n q u a 2 ~ a q a a(a)
~ ~ 0 6uvqq&antqvlualls ~ s a!mouoaa
~ ~pus ~~va!qae~d
~ aiom B sluasa~d'~anamoq' s a ~ g ! p p v spunoduxoa %u!a!-!qw ( p ) 6 " T ~ W B a p la^ (3)
.aq3 4 s u p ! 30 i o ~ q u o.mar,
~ 4 BUE ~ q a ~ n q 103
~ e Laua~uaq
a a w uo v a g a pqmw
JO 9 w p u r 0 - 9 v (Q) "p"lod~oa J i ~ u y - 9 W ( a )
s . . s p 4 ~ p ~ 1 au!pssD
~~ . d n - u ~ ~ saugua
fi S u ~ ~ Ln [p~ s [ n a ! w dS U ! ~ [ Buana
~ S pus S y u u ~
au@pa~qsnolq,o)lnsar s!q& .~oqunqrBaag) u!q$+ a Z a q U V J 1!8 q a ~ aqq y m q emqs\ow :Molaq w qu!od m a p I e u o w u y m o y pag!sse[a aq us3 sau!loss2 u! pasn aah!q!ppnjo
1 u n 3 ~ i d m a qlua!qms do1 L l a ~ ! l ~ l pus
a l 4!p!m"'( @!qJ9 sUo!q!pUoa ' p u n '~0!$dLLms00~ lay sadLq a q ~ e l q p a suog!sodmoa p w ' s u o ! p u y 1 ! a v ' s a u ! ~ b h&i ~paen B ~ A ~ I J P B
; jo 6% mom^ .Lam Fa!uo,uoaa us u! s u o v u y a s a q v o q ?no Xuea sSi9!pps a u ! p s s s
assanu! PUB O ~ U lay/l!B
J qasdn usa s i q a m q ~ e aU! Uo!$BzIuoJ m s p r m o Q m o ~ S u p p g ~
, .apap!1La!pqp~o san!qsnuap a u ! u q p a u a ~ d o ~pus d au!arslp ava~&qqa
aqq a m aqaqq 30 UOQI~UOSv o w a u . U O ~ J B s!q3 quanad q pasn a m s ~ o q q ! q uao;)u&z~p ~
1sqar.u p m ' s U O ! ) ~ Buo!~vp!xo
~ aqq* a usa addoa s s ym.s p l a m y s p a g .aylos& aql
JO &!1enb aBv1qs a w uo rmga snouaqalap paaunouold v aney q pun03 uaaq ansq a q l o d a g
gtq Lnm qay? pug b e m qeqq q q a w jo q u n o m s aavq aqq JO amos .saoqs~~3sep pla~?
-
J.
-
[drf)aeila$se%qsnss [ d ~pea?
~e
uo!lv8vdO?l(q)
C . ::. .<,;:;i..? , : .
.
p a ! p ~aag uga~o
. . . . . . .33 3"'3
UO!V?J!UI(0)
. .
!. , ,
!i
I Detergents. ,,. . control of deposit build-up in carburetor; fuel, injection equipment and
. . , , , . + . . . The
, inlet system.canbffer significant performance benefits. These include: ., ) ,
I . .
ta?$Zd&ced exhaust:eniissions, :,:: . .. :..,
,, ,..!.,.- ,xi;
~
increasingly considered. . . .
5 k ; ~ e Gaso1ine!Blendinggc~mpopent8
w , ,, , . . ., . . .. .. .
. . .:. ; I . :
. . .
In recent times, pollution, from automobileexhausts: has increased toalarming~li.Velsi
Starting from April 1, 1995, new c ~ r s ~ ~ in o lfour
d metropolitan cities of India, i.e. Dclhi,
Mumbai, Calcutta, Chennai are fitted with a catalytic converter on their exhaust pipes.
,. .~.! , . . converter is an anti-~llutiori'devicetittcdto
Catalytic the exhaustsygtcm o f ~ e h ~ d & ~ I t ~ ~ c l p s
prevent em~ssio~of'noxious ~ atmosphere. ~ t . i s - t u ~ u l : & i n . s h&id.
gasds i n t the a ~ ec0nipAse.a
hoiit?'jico~lj.hetallicor ccrariii'cd'i'Sc coated With 'noble metals like p l ~ t i n ~ ' ~ & h d i p a l l a d i u m .
~o!k&Febl~jAiy B e ' i 6 l l ~ o f ~ a t a t a in l ~ ~ii:lractibn
1 which wridbis exhaust;eonponents ltke.
carbbfit"monoxideand hydro'carbons Bafrn~ess~by converting. thcminto carbon. dioxide 'and,
wat'e%:Thcse inetals are spread over a Inrgb surfaccto proddeihbimatc.wntact between
exhaust gases and catalysts.Catalytje corivdrtcrs n i e rcquirgd.::to simultnne&sly :remove
tdfg~0Eeil'pal~utants,~rc6ist.'Cahlyst:poisoning bycontam'irrants;md:~~tJlo~g~~~~Ofa.a.~two
t ~ e ~ ~ o f . ~ a ~ ~ ~ y t i t ~ c oTwo-way
n v e r t c systems
rs. using.plabinum and:palladi~,:.yhich.remove
o~'1~'c~~b~n~m~nbxideand~hydrdcnrbons~ leavingnitrogen oxidcs unchwgd.:~he~latt'cr.,is
o%idf~ed-th,rm&h..air,: pump; Threc-way catalytinysbms. Oqplpy plati~mGipall~diY$;!~ayd
rhodium to remove all thrcepollu~ananbsimultnne~uoly.,had-i.n-,thegawli~~:issj~ju~ious
tha..honeycomb disc of the:conu~rterand poisons the noble m e t a l . ~ , i n , ~ h ~a",r+uc~s d~@~~
its potency; . . .,. , ' . . ... .,. . ..
&$'~ed~dd~e~ha"~t:
, . (:,. &h5kiions, ,,.
...,. ..,. ! .
it
.
d ? ~ ~ i ~ . ~ p p r ?where.
, a c h thecatalyst
,. .
in addid b, the fuel which a p p e a r ~ t o
be
. . , '",.:". *. . . . ..
increasingly constdefid.
5 h ~ e Gasoline w - - . . . .-
BlendingComnonenta ,
Starting from April 1, 1995, new c&++"ild-?~ fo0.f metrepditan ci$cs of :Iodia, i.e. Dclhi,
Mumbai, Calcutta, Chennai are fitted with a catalytic convcrter on their exhaust pipes.
Cat&l@ideonwrter is an s"ti:p6llutibi d&ice fiftdiJ.td the eih.aust s y ~ ~ c ~ o f & e ~ . ~ ~ . ~ ~ ~ t . ! ~ c ] P S
$&&df , , . & ~ i ~ & n ~ o f n o ~ i o u s ' ~ a k ~ s & ' d p h e r & , ig,ahla$in ,shapL*.and
: ,.,!:: ', :'~m.p&ae:a.
,
BY?d?i!~d"'$h~iiQgh-oir.
dr~.~~o+wap nn~alladiynj~~~c,h.~mov~
t ~ 6 ~ , 6 ~ h ~ ~ i k ~ c ~ n ~ b r t '~jrbtemsusingpldinum
@ r ~ ~ ~ o x i d o ~ a . d ; ~ h y d r d ~ al cra W v i nnb~n i b m n oiidca h,nchq$.::T.he !l$t$.;ib
pump;:Thr&woy .catil@c systems, crnpluy , @ & i n . m J p d l a d i , pand ~
.
::;*5gjhflpltJ$&;mm.\,
,iofiw@ng 5 +.reen;
uf~cturqd by,fepentqt@n,9f,i!@fg:,
.,,.,?, ,., , i L '<. r. ,' .:: . , I :
ethanol by volume are sold in Sdhth kihxica 9.W~!>,
t;..
.
. :: ., ,. >,.:
tvra12~mduc,@.
.th
~''~$s$&>~.
%;RF~:
- . ., & J : ~ " .
rhodium to remove ill,thre6pollutdnts ~irnnltaneuusly;laad:inth~.g@ig~ia.ir\ju~iou~t'o,
' t i~e*~,&
$J&
$$f$
p p r t i q such.as better w a M
; 14biahi=gidsponent
@$?et$ .:. ~ . i ~ $ ~ ~ ? O .
.2kyz:55
. . 'pithout
. .. .
kh0nev-b discof the: conxocter, gndpoirma ,&henoble m a t n l s,. i f i 3 ~ h y ~ d ~ v j ~ ~
its pobnpy,;..:.-!.!;.: :.., . apdre$uces i o v m m & subsidies its price is currently u n a t t r a c ~ v e/nm*~,~$*tnes-:, ;; . ;. !,: , r::
. . .. ., ,
. -.
i"he&quiremnttor p.rod~cing:un'loaded~asolioe will re"$, i n &tqo s&~.a@ceqt many ..:. p#3B.,Lpia pro,du!e$,b~ ,a simp! , ~ ~ ~ ~ y ~ ,,, - ~ ~ a ~
"e~faetiatin~;sites:~The use of.ixygcnntcsin gasolincs is made for rai$.i.ng.ihc gaio~ind.. joo]
i~P'AfiI;hoi:~ltsbbutjli'ene
repre? nts a way,to use metbanpl
is available rn Feltber
t q r : gfrom
F o l mFCC *
? (fluid eiit&lpialytiscrackyg) o&-gples ar
. . volumeandits octane ,level, cspecialb in. tho critical front-end range. The r.&ell& bUrohg 3
. . Propertie? of oxygcnatcd compounds result in increased operating,cfficicney of thc 'on$nes, steamcrackers. ~~t the amount of isobutylene available fmm these sources Is very 'lrnlted'
. thus compensating for the lower ealoritir valucs of tho oxypcnates. ~ i ~ u i t ~ n e o ulbwcr sl~, ; The isobut.lene content in the c4fractions from steam cracker varies from 4' to 45.Prcent
P~
PETROLEUMR , - M ~ ~
. -1 .-.- ".
~ ~ ~ ~ f $ i bc%he f h ~ blehthig
%
~ & h tompbbnt~71tg
~
.:, L >tpr - ,?' s. * T~l,l:; 1 1 )
e x ~ e l ~ ~ t f ( t ~ $ d ~ ~ ~ bWtaiVdh a a t ~ &th
e r i no d ~odpatibilit~fpmb]emx It ean;bc blehded
a t ' t E P f ~ d W e ~ ~ a a liiixhire
dhe can\be handledy &$pod dist)ibukd via e$jtabli&e&
c h ~ ~ e l ~ ~ ~ U $ t h ~ ~ d h b t i o n ~wni et hc1s&r~st ha~~1 n o l ~is~eipeaialiy,atfractiue
~?,~~l for edgines i ~ c t u d f ~ . *, ,.. ,-. . <.
b ~ shortage
~ and
~ insufficient
~ e reforming r a p a ~ i t ~ ; ~ ~ e ( l oflMfJBE(in
iof~o~i~~ ,(4 cNqii lightyeigl$ gas with a hi$h @ition t e ,r.pidly*m dispew~@?~ntO p
cases appears favomble when compared with other octane enhancers. MTBE blending ~ k l l l .
l ;
. *..
? + ii&&pe&pb
, , , , ~t ~um&kerbp~f~tu~e;~&~r:waui:a,fi~GVG; - LJ.'d't" '
n o r m ~ ~ ~ r f ~ ~ ~~ b ~~ ~ e~r . s~~ c e~ ~ u ~~ t pgasoline e$ ~ & ~ Q ~N r ~ ,,b,~,,~,atm~s&p~g
u i ~ o ~ b ~i.. .l , , , .
i , , - ~ ;~ ~"dJ..7 4fl.fiI ' i d k , . , * r l r - ~bi,,:
o%%'i . L:J~. additive&jot
can be pmduced by catnh.hc reforming, with relatively less yield loss. MTBE to the extent of . e r &8NG +idiahqi.@~BD. rz;Ie"nc@iCSGineeds no. ,. dl<*'' Y
fighera*g $ i h h ~ s o m e i v h a t l ~ w eoctane
r val& ~ M T B E~ . AT M f u & ~ ~ ~ ~ ~IF,~y;@p
~ E~ , I,a s-(it a~slightly $ j &&ib(i&a&,qd'mdrgfggtlltzp:>~:~~
~ \ ~ $9 9" t " ~ ~ ""8w~.:)ii 74 [vb; .':cd "11flf4' ' "
With ~ ! i o f " h x z l r ~ ~ e p d s . Abi&;'&x~e~@Q$b ~ e ~ @ & o f & ~ ~ ~ ~ @ a d ~ r f $ t j ~ ~ l @ @ ~ & t r b I 'g,~ s ' d b ~ s n o t r ~ i W h w e
h p ~ l i h i ~- ~ ~ 48 ;m @ul #gcbrrgd iitasi&$@anc.
somed refmeries
as a t iab
- hao mems
t k eLbrqmndntbas2h
b cbemi&al ~ ? @ ; ~ ~ t ~ ~ i @ + & b ~ g ~ & .~i&j$%&kii<e@i4 .~dySgg ij61~1&$@ I 8@6&t+&4)5j f
6 1 2 2iY+%al *
1.. I
2 , '
IC4'
va -
l,x)fsv,,, *ne:t L 1,. !zLv
P
Sngineshave allongMe. ~ ~ ~ d $
+
:I!;~CI~,~;;xx d
a%!6e" aii Tn A SaT Qt ~ sift c ~ o &
~ ~ I no yi91 t r *
~ trr y ~k ' i~ u ~ @ ~
2 <
(.
-. , I I
5 - ~ ~ e m a t i ~ e i h l ~ a ~ & d 1 ~ 1
,
t -
, , I ~ ,
,
%~j&! m&hs6 br , d ~ ~ ~ i ~ f ~ $ $ ~ b ~ ~ ~ ~ i ~i jt #~ ~~ ha 1~ ~i ?+ $~ %~ tE:Y3 d' ~h 2&~ J & s t ~
:gad
I > 9
T h e m o 3 t + t e n t i @ a ~ t i v e gdaoline fuels for spark ignition engines, b o t h ~ f i o ~ l ~ d i ~ f :id?b&u#1$~&$~1,j "&&&~i,i1\; f@&S@~&~.ei~~ l~'@k%i&'b$~ f i i ? F ' i ' ' ! ' t
';l ~(l~.il.f;30"P!B&le'B1~iig6YY~!
*i';"i[j"'.,lJ.-., d U 17'4'; ' 0 7' Y U d f i ~ ! & l' '!' ~
5
slnte*and world enerWscenari0, areliquefied petkleum gas (LPG), c o m ~ r e s q e $ p p ~ $ ~ ~ ~
(CNG),p@ue18 and glyh$ls. - r . .
LPG. m e Me of LPG ad hlel for spark-@ition inbines has already &ehvsk&&k$h~' ,fd'm:
advantages of fiPG over liquid fuels include the following: I , I i p r i , 4x13.jr
-
~ b8a.q qtw9304d qqq~m 4,
I t 1, I - ,, , , ; .sau!saraq ~ n q d mqsg
C
s
L
q~p;fa
Brnn~wmpsm~iq1'6a~po~~~n n ~ e q a qu a % q p p a s t4pm0@03
e "spupodmb~
~ b p l s e P ~ ~ ~ l o ~ w a ~ s p e ~ uwu~a mq ~ q q~ ~~~n~usnp y~ ~ ~aqq
= mq
d apporp
~ ~ ' ~ @ Em ~ ~ ~~~F . 4A6 w 9 ~ @ 1 ~ ~ 1 ~ p t r o c PlW ~~ . J~~ ~
Bp ~~ q ~~.~~ ~D n~ ~
I O ~ ~ -
1 ~ $ ~ ~ f t r ~ f # ~ g ~ ~ LwwmcI:nmarappm $ ~ - @ ~ e 4 1 I ~I M~O ~o s p s ~ * ? u d q p ~ . p
' ~ W W W i ~ ~ ~ % ~ m ~ ~ W 3 ~mqd1n8 P ~ w~b f4l w~w pp a?q ,x~ o q ~@ayrwq
u a M g ~ ~ ~ ~ 6 * r n f h # p u r 9 p t ~aMU.pqB~ndgs
!aq B y$$i m q y e r q a g i i a q s q p
W!t33n@@' 3 5 i i W ~ W : k B~t~p IJepiro1ap
If "etrrpuiqdiuk~w~ 1 % ~ m n q ~ a q s m a ~ ~ ~ ~ ~ s
$ t W d s ~ ' ~ i t ta2~~d'.8'8e"@dp$p
@d~ UptU1eq$,~ q w ~ $ u o 3 ~ ~ ~ 7'sq~pemeaaq
1!wm &s&ti
~ ~ ~ f * ~ -9- 7 bayf pslly9q@qm ~ ~ ~! s o l a qm
~ q ~g ~ ~q ~ ~~
,t.jf)q,,: 2 cur, , . -, , ., 1\, :r. <,%"' 7
F~$'+bJd
02 U O ~ 2-q ' au!so~ay~o
B JraLe1 ~ o p qXs ~ A m LIa3 sad4
~ L1snonquoa
~
Jaw .Ia&'ii@ i58~iffffn#nPltf&dtlatto55 ~ 5 ~ & d h ~ P d &4'dkdd ~ t $ b'~6t.d %q$sa'$$t~~dh u n q
a&tq%a!~~~, ~~l~~'hpiw~wft~ql~.sw~*~ aqi+$&S asd6~%iq&@ri~kri1~~q
~ u a u t + % 3 &3!5 quapg)ns Bqaq a q s o ~ a q30 41J9810~ qua~aqtf! a q uo b1a~s r a u o d ~ ~
$ 1 ~,n'.~uC"!~e~~fi
I rrprri;p!c i.a z a i s : .r i;o..-..*:-ti.~i .-;*;.i . g i ~ z l ~ ~ $ ~ & w ~ & A
Jag!. 6 r d f i & k ~ 1 ) $ ~ % ~ ~ ~ ' ~ ~ & ~ f s%~U~bk$a@;a~kt$~!tadmq
5pa~qjd q!B@sea~aq
PUB fiif@ffi@%@36%& 'Q'd8$ks'wf~q&~q .!&i@~fb#'h o , ~ p z ~ f i & ' + \ ~ ~ + q ~ e
JO s&U6~~fi~@f~C&5'4k1r%b!$~'~ode~a aqq a s e a o q q h s s a a a u s! qf'nrwmq agsamop
u! p * d a ~ ~ $ g 0 ~ ~ 4 ~ t l 4 a t d % ! ~ ;anappe t ~ u ~ o& ~ p.L1arols
s u o o l sqsrodena a q s o ~ ~a n~ q
' s a l ~ ~ ~ a ~ s p ~ ~ ~ ~ q ~ ~ ~ w ~ ~ ~ ~ ~ ~ d 1 ~ !w pd~8oa W 5 j~! a~wam lq ~ ~ 4 d m a
L p a ~ m m ~ b g e x ~ ~ # ~ w U a t r ~ q doqs paaodxaw~pqq uaqm quapa autos oq a z o d s a aupofay
s + h a o l ~ r n m a 1 0 ~ 1i~wd!' a m u r . a r q a v q u r q u w o p q o!ar qaa.um ew q z pa q q
u a a oaq~x7pQaqw p m a n o d w o ~ 0aqq3u!aq 4 s s q 31 -aqswp!nbg aqq q quanq aq qortusa
au!so~ax? p g 0 9 b rR~ aBa~~-%v!l!oqt~w~~~!o
*ti .
~~
2 - 1
q p g o u~!qae,gaqe~~qs!l(anrssaupos@,
-
. , - - > r < ,'ti ,,.: - A + I 3fils~j~~e
.
*, :.'i~lf!q,
uther extra t' Qce qes for the sep atipn of aromatics a d o n - o atics use solvents
with much highBr'?fk'B$$biiie$ ~H&"~%B~~$'~I~~W&~BQ&S#~~'~~G"&Q~~~ very
in that rafthates with very low, as
-- ..--. well as extracts with very high arpmatics contentr can be
made, Of the processes ayaJpRIe? the Shell%.ulfi&e extra<$i<< p G e & i. wide$ u b d ,
extractionbf..~
especial1y.for the aromatics from hydrocarbon mirtlires h u o r e piqduc-
tion of low-aromatic!solvents. . -+irrq;:ltnz.~-t,
- . -%
- , 4 : 1
5.5 AVIATION TURBINE FUELSA L,,
&)ely
hvb basic types ofATFs, the k ~ m s i n etype and U e wide-cut$; ,$jnek&,a$hgmira\18ed
worldwide+ The kerosine t y p "of~ ATF is a much modikC&f@R@+;&l&iTR~gpr
kernsin; oeginally used in gas fYrbine engines, whilst the mde-cdFap my ~JJ AT is a
wider bGiling range fuel incl~dibdsomegasoline fraction. h $8&&:idird$e+ r eeia'Ij?ed
fuel grades are required for limited military use, as irl su~db!oriidaFr$r'affv ' tk ?'-;' '"'
The properties that control ATF quality are listed in Table 5.14. ~ohb&fi$g'*&alit~
relates those properties which 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~ignitionand flame propagation characteristics. Ioturbin&engines,the Liishduld
mt allow deposit. to form in fuel nozzles, fuel control systems, turbine blades, cpatings and
wale, all of which will degrade performance.
i 2 ,> + : , ., i . .;,; .c t ~ tbsq a ,n $ ~~f i :~& &j~-~ ~~5~
i ~ ~~~ ~ ~ g ; ~A $ ( q : a~3 u 8 m d~.E ' a. ( 1.~; w r i ' a ~
aqpelh " ~ l j ~ ~ ~ ~ ; r ~ ! ~ ~ . p ~ ~
1 a y i d[as~a@8~.ua3~55ga d a8u-n~p ~
i ~~a :d ~* ~a p o u f . ~ ~ 1.18.
Sassa48 p.uwaqquapun uo b L ~ d u o ~ r a : ~ 0 $ ppa a: z~~i s$I a n~3 A ~ a ~ ~ 1 d : ' a ~ P ~ . ~. ~ ~ I i r 4
~ q ~ ~ 4 3 ! u w q ~ ~ 1 6 : s ~ p u'angdps
s : u a ~ &'~uaS~~s~Q.uogrea~o
o saxqdtuma~uii3~0.ap~on~uou
'qq2fiwi;tel~oqow+~&g :!qje~i ,.'.am,
~ daq&'.;rnqIltis yqiqqnuug~,,: , + ~ ~ q ~ . ~ .imOi.
: u p .~ ~
. m
. . . .
~!~$~J~~U)~~W 3 I O ~~ W ~ ~W s.Wfl:uf
; ~ paw'qap p & i ~S~ p & ~ p~r ~ g e ~ $ ~ o ! p ~ a a ~ e a i f 5 ~
U? Lru!elu WJJO~ u n o d w uasOq!~ o~ 'pmporqu! uaeq wq qsa?uo)souo~d g s - r a n ~ as 'sdmnd
p n j alubsu! juasaid '<$pedi a ~ uo ~ uo*o-
s $+k,ji$$ l~clese cYbja)cld :b.- :qgsi
uO!sOuOa d%s-~addoJa nq ~aliu!l s p u n o d ~ r o ~ . g ~ ~ q ~ o ~iaq$o)oro@w
~ x a ~ d w ~ ad e a j a ~
',% T W O asl sIa1 4 m ~ d s ~ l a w ~ ~no o amq % j ; ~ s u o ! ) ~ ~ g ! a aad su .inopo alqeaases!p
Sq! 103 p w run!olpe3 pus iadd0J OT s s a u a ~ ~ s sii o atifij.
~ ~dflsagyads pa1lol)ooa s! m q d ~ r r ~ ~ .
*.c:?.:e'o Oq Pa?!uY s! ~ ~ J ~ Yq ~ I1Pu~ 0 "Alll02i.?lb ,>*:-
%~ .:~.@?q2r3~@a~oxd a q p w .UOR!SO~WO~
aqzft0.s p pi^ p b q $ ! ipalIoJ1uoa ~ ~ ,,. ... . . s! q u ? e d ua83i$ih p&;inqdlns 3o imoursiu .uasbo
u~3oaq!u'~nqd[nrilqm~?uoa~ ~ ~ ~ . j ~ ~~~ ~ : u ~ ~ ~u a & ~ ~ ~ du ~ q ~ ~ a ~aa~
r p X .Y ~- ~o o u ~
. u o g s n q u o ~ ~ oS@J&~JSB
,I~~ p,& iuyls*d
o a a ~ a aq ? a ~ a o u a ~ ~ s a ~ w n bs~mn&-p:~.9?~?ie~iEa~;~,.;&sr;@;~$~~,
asp* pa b + ~ JcJ?m?'lJ
.
v a ' ~ ! I F ~ wl ~ T! a ~ u d~p b .~[ o ~o~~q p ~~~ ~ u9 a a ~m s a~y..a r~~
qjIV& :, ilw
"
""
,2rrtsci -rut .Ti-:: . i11;7,c::
.~kp
arlr.
.WP$W~ .
P@uo al(l
~ ~ w
- ,
. . .
. - .
YaIy .4.!auqn[-.~opu@unr
''
~
.) *uh-igniti?n of ATF can happen with a alght leak of fu&'from the engine .h&&: ifter
~h~f!b~!A!::"~.f?pa he1 line fracture during aperation. T ~ : ~ ~ & ~ r BU$ e , f.&i%n
W
~ ~ cw ~~a i n ec r e a s in
e ~vapour
~ proe?Un,
~ &.the atmOspherii ~~eBB,uiB;i-a~'d<~e.2fb-~yam\1i
~rew",""duel increa- a,ldao tho ~ut~-,gnjtiontempe&"&j in;&&&, '.
"", , .
Thermal properties. Jet engines require the use of fuels which ha*Lowfreezin~poinh ,
and maintain their flow properties. A high degree of thermal stability of fuels is nqbirea t.a
94 PETROLEUM l i l & P N M N B k O Q W '
A ~ t y p i c a l a ~ i ~ i ~ n 0 * b ~ ~ ~ l i ~ Wknown 0 ~ ~ ~ ~ i ; P . 4 ~ , ,
as conductivity unit @U). %he.c.onduetivity of a fuel in a tank~.bemeagure4directlyby
portable ( . m & t e ~ ~ :~ ~ r + ~ f i i by..
f u rMaibak
e d ~ ' or Emcee ~ l e c t ~ r . ~ , ~ ~ ~ . ; : ~ ? ~ ~ . ~ ~ $ ~ { ~ ~ ~ ,
demink'r d i ~ e ~ w a ~ ~ i ~ ~ ~ & & k ~CU; i NT~USATE.
E y s f 'ha9:$~~w:10:~.~&td&bhvi$;,~he
.~~~:
e o d ~ ~ t l ~ t h t 4 . & e ~ : ~ f f e t t t t hkhi&rthe!~habgedi~nv,are-
e:ratt re~avedifibm~tli'e;fue1,'
that..isthe-charge.relaxation. The time taken f~?lttl&.~cH&if&?ik~he .itel.$0. Qll from.,agiven
valud~&lh&h2I&fl&iue~~(6he:.dud1'sS half-walue.&im'e.=,tI/y =12/con~ctivity'~(CU);.sec)i@ves an
indi~~tio~E.wBether.static charges.are.likely to..be'l$i~iddy~$i??fibt; Chargeq.:c,a.n.ac~umulat.e . . . . . .
t o l a ~ a p p , ~ c i ~ b l , ~ : e e x t ~ rif.thct.
i t : . ~re1,mation:
nly tim~and.:~he~h.alf~~aIue time. aIe. .higlxi,.
. . . . . . .r.;;r:
. . . l.; i;
>
,
!DIESELFUELS . .- . . . . .. . . .
. I .:<! . - . . ,?,.
:::~l,~,:'a.+::,;.,, . ;:~i.
<,> , ?, . . . . . . .,,: $, ,f:2,
..
' :
automot+
! ~ i e ~ ~ l ~ u ; ~ ' f o ~(I&& begded gbo;d igniti;niiuali+, o ensufe '.... $ d&y staitirig aha
~ u l ~ l i conteit
ur m u s t bk c;iti&liy c6~&bll&'~6.iiii;ii&h&.eiivit~~~~fit~l
Poll,ution,Combsion,wear and
,&a; S~@cgravity (o) for t6e w.nvira& ~ f ~ e & ~ ~ o l . db;v-~. l i -, & &
. . ! I,
.&
temperature of 15'C
.t
..?'!:;.. . .j
%i
!
(b) Greater carbon depaits expected for higher values of m'bn reeidue
11. Particulate (a) Indicates the potential of emission of particulate matter
matter
I (b) Co~taineprimarily carbon particla
(c) h u h n a o y w t @ h t e 9 finned l u p h a s e &qg&) 'pprtidm:
' a b f ~ ~mr b d c 9 p~ g e m c m a t e d iq? en%nme$t u e L d o m 4-
cawe an ill e f f a on human health Exeasslve soot W d e a m w t clog the ex-
haust valves ( ::-. 'r
,
I 1
I I
- I..
(b) Caueee environmental pollution from their combustion p d u e t e
~(c,ccirrosive in nature and causes p h p i d problem to en&e parta 1I
Particulate matter con* primarily carbonpartic1es. Carbonaceous prticuIa?s that
f o m h m gas-phase proceaaea a r e generally referred to a.smt, and those t h a t develop fmm
p~mlysiaof liquid hydrocarbon fuels a r e generally referred to aa coke. Because mot particu-
u ~ p q m j e@ua
? S q p w e u .@@~ ~ a ee¶3,4g e %p~*$q =*I!#
s)a~wqdvu 'a@~&"3?y? 41araua 1 ~ ~ 4 9 %
dmpp OJ 3 1 'QVa
mu inow!fi -3.i w F a z ~ ~d- ~ s h ! ~ ~ y v m q U O W ~ P ~ CJSJIP! q??.,&pw papm p mn e q mag qgauaq ~ ! m o u mw qy.
uo Supuidap % m o mn!L-Aprn V-!P I F ~ 4 ~ ~ f l f i ~ ? P ~ P P ~ 5 ~ ~ ~ w uo~mgpadsaaam q 4 p n b ~ ( I S Bepsrsdn
! :o!@F&pb€b
i I
, I < I ~ ~ . z $ ~ ~ M P I '-
- -
-.-.- L~UT,' W q b p ol ~[SP 8 uo 4 ~ q - u p ~ o g q ~ o
.
ap-d a u .a[qpeod tn3~ B P W ~ uIIOQ@@-l?%,1W" I W ~ ~ @!tl
~% q P @ q @ @ . . ! ~ m n b ~ ~ . P ~ ~ ~ a m ~ .p!r~?~P~d~qn
a A ! V ? 8. p q)psap- apuwd a;i&dm em&B
lwp1x0.31~a ~ r.UOPU-J
. l~
mppoled j q ~ ~ ~ + Q ~ ~ ~ p ~ ~ ~ % # ~ $ W ! W ,# l - & - ., - 3 !,I* 5 \ r-.,,
$9 ~098p*p
~ 4 9 p do *xge , e ~ ~LWqw,,, ~ . ? ~ - , -1. i ~ a m d q ( ad )~ py30i Slw~
o k W E *q: 9 % - & o a~w= wo .qsq!u I~JO-OS!apr qyi .apmnu sm 0-a
"gl~ o d a ph~jtij'iiak!'p4'Bespn~s'ermr%:[~n~JO UO!.~B~~PJ>Q!I~-PWW&~++PWF~R&??L.I~;, ?'-pb
.qld c 4 z e n ezw8s!wep m a m p $am1 .h.op p~!dQ,*swamaawo p m addm u?*% q + y a A m d q ""4~ b A W q O 4 01q!98Od 8! )! ' ~ E Z3Sw
aAF1?PPBP ~ Z ~ P ~ ~ b
Q 1 pWq amq
* a w uo gqpuadaa -qsqp
Lq eIaj lasap 30 u o g s ~ o u ~ apus
p UQg!80dTpp3ap 7r?bW~3%q!p a V hI I W ,P P . v I %yL!, r-
sin . h i O b * i ~,~OF)P% ~ Xppm aa u u o l d ~
' t
>.,. t i . - -L-!t r'>:' !
@q& l a & o i i anq) ,pm q a q 3d uoguppo
-
~ psaqr.baa lmu pue uo!eorro3 moq r n a @ w . ~ ~ ym~ o 1 7 . " a ? a r d - a y ) ~ e n L r p a a , y ? ~ ww>pm mv@fi)@@;B.i".g 9~ ~ P W XIFPwaJ
P pya.pmodmm am a a a o l d q am)aa
~ ~ f i ~ ; u o ~ ~ ~s
. qsa3u)rm
o x i m a w aarqlldw8m & ~ 1 ~ 1 0 j a ~ P u f WJIWt$Ysbp l p d ~ "4f!J!q8???P;~94? ' : ~ ~ o Iaq k 'mdo!s.)ma ~ ~m q~x a 6aahibd' a s ~ lu d o - ~2q.mp y
939" @now s3qpdyI pa7qd 0) .pmp.ru ~QAY!PPB ~ w ! g ~ ~ p r P ~ ~ ~ 0 . J @ 9 W g S 9 ~ n h ~ WQrSslPra e-90&?- ~~s Plm a p q q q 3 9 a 8apadard pq~1a.xw ~ ~ t l l l o)O~ aqmPa!
&
, . ~ n d : og T
~ oz ~ Lp ~s g Qe c ; l p $ u ~
.
Iasag 4p q q s u a g ~ w ~ n b p apyold
s ~ w a d v -map n raluou U Opw ~
Tp! pyi uO~@! Uo!s8a!dmm ~ W ~ a pl! m wyi ama ayq q q a r 1qqg, 8 p
~ m 5 ~ ~ .9~'s 3~ . F P~ P& ~@ ~- -~ ~ rwuanPJ -__,
~ A o I..&I,.
i8'+ni la'ig 9ald&iii'gnmaA _.
szaqm~q3uo!prlqmoa a q go s a j s p s a q daaq pmBq!lL6dap, am$%qua~e&W J ~ ! % W & ~ qaIdmm ~ u a n ~ k ~ ~ ~ ' ? % V~ O~- ~? ! ~ , ~Ilav~m ~ hW @&ag[ :ilwla
? ~ uo; wq
s 0 p ~ ~ a . psa3sj~m
m q w e m q a o p q w p s~e;~iX~qvCa'fj+?p~.~n,e;a@ d~qy- 3W.T9f"9
7gBrnmPw W W m d mS93-Pa'EI. .I1siJtr, u '~018sazdm03 A L,
!@
d k 6 ~ s . i t 4 ~ + & ~ aapun Kl!pwa~ q
.LI!SE? uom az!moqs pus dn Tazq q w ~ d I?v,apl q ayyr. sap!P!FWv!€!us @yYI?@&J 3Bq@*SdmgMl?89P+Jo aqma+WjQj?? %4!&&qpgyn
,q, a,w
1sap!m8Llod su. qans saA~:pps,,a?~;~m lwsadalp ' d o ~ a al a s ~ s,Ian3s Pvefioi
'aA~s*lsm s~~
u%"mPvL&?rnb I a F L ? . ? ~ ~ Vpm dWw
L~I cauo!auar S.I~Ya w a?wy~ m ? a q . ~ d ~ q:e~t-6:ap7 jaq w , ~ a:'+?F+@l@~t~
t 3 !,-#-?,rY ~ g ? ~l a~a ar~ (~~ a q
1 1 . 4 1 -- e~ar?g ~
~4 0a *=qa~ppw
~awa
;s7pudap PUB ~ ~ $ ~ ~ P , W Q . Q W J ~ W 1 r ?a ~, 2 R ? ~ ~ ? : vt- ci:itGul
, 'I I. < .
: s I ~ a n r , a 3 ~ . x ? . ~ J r e . uol)~$m~~~~. pB~&! ~q 1~ ~ B ,*.: I Bh;iIruj~ Y v
6 s a ~s !~~ q~a ms~ q u o ! s a r a ; p w ~ S p ~ d ~ ~iguJw al!bq!w
e ~ y o p o ~ X ~ , efxl~ s+ p
j .
r - t : t q m J a p aaqTmJ7paqqcLp&za~~<, ~1:) 1 . ~
u p q appold pus uolsuaq a3~)msanp'al 4 q a g d q ,dn ~ w ~ 4q@szada(i
~dn~lmir~rnodap 7 ~q7wp.'alal
1 eBPn1S