4 PETROLEUM REflNlNG TECHNOLOGY

7. M. N. Sunil Kumar, Reviews on polymeric and copolymeric pour point depressants

for waxy crude oil, The Institute Of Petroleum, 0ct.-Dec., pp. 47-71 (1989).
8. B. Smith, Steps for finding crude properties, The Oil and Gas J., Vol. 77, No. 23, pp.
150-152 (1979).
9. L. T. Wardhaugh and D.V. Boger, Measurement of the unique flow properties of
waxy crude oils, Chem. Engg. Res. Des., Vol. 65, pp. 74-83 (1987). QUALITY CONTROL OF
10. B. Smith, Heat transfer explored in pipelining high-pour-point crude oil, The Oil and
Gas J., Vol. 77, NO.25, pp.110-lll(1979).
PETROLEUM PRODUCTS
11. B. Smith, Restart of heavy crude lines probed, The Oil and Gas J., Vo1.77, No. 27,
pp. 105-106 (1979).
12. B. Smith, Design of heavy crude facilities explored, The Oil and Gas J., Vol. 77, No.
29, pp. 69-70 (1979).
13. B.M.A. Rao, S.P. Mahajan and K.C.Khilar, A model on the breakdown of crude oil
gel, The Can. J. Of Chem. Engg., Vol. 63, No. 1, pp. 170-172 (1985).
14. T.Viswanathan and KC. Khilar, Hydrodynamically induced gel breakdown in pipes,
~ O D U C T I O N
The Can. J. Of Chem. Engg., Vol. 67, No. 3, pp. 353-360 (1989). Qunlity control of petrolcum products 1s ;I n(bc(bssilq.il't hc protlucls ilrt! to give sillisii~ctory
15. 3. Sestak, M.E. Charles, M.G. Cawkwell and M. Houska, Start-up of gelled crude oil pedormance to the customcra. Keeping in view 11~.ascli~in(~ss of mlch prlxluct. fi)r sp(*(:ilic
pipelines, Journal Of Pipelines, Vol. 6, No.1, pp. 15-24 (1987). purpose, standnrd urganisations have t n f L r l md\v)(lsol'trsl.~and s~cciticdinnc.Bur\.;iu I*
16. M.G. Cawkwell and M.E.Charles, An improved model for start-up of pipelines Indim Standard @IS), New Delhi is onc sc~chor~;rnis;~lion in lndia which stantlnrdihcs
containing gelled crude oil, Journal of Pipelines, Vol. 7, NO. 1, pp. 41-52, (1987). procedures and issues specilations. 111stiluteof Pctroleun~(ll').1J.K and Anlvrican S(aic1y
17. A. Majeed, B.Bringeda1 and S. Overa, Model calculates wax deposition for N. Sea for Testing & Materials (ASl"l'), U.S.A. ;IIX thc other two i ~ ~ ~ ~ ) organisiltions
o r l i ~ ~ ~ t wllosc'
oils, The Oil Gas J , Vol. 88, No. 25, pp. 63-69 (June 18,1990). methods and specifications are widely followed. Apart from BIS sl)ccifications, I!cntral Board
18. R.A. Vora and D.P. Bharambe, Polymeric flow improvers, Indian J. Techol., Vol. Of Revenue, New I)elhi has certain othcr specifications tbr the purpoxc ol'cxcisc Ic!vy. Some of
31, No. 9, pp. 633-635 (1993). the important limits set by them are for carbon residue, flame height,fli~sh[mint. a ~ visajsity.~ d
19. L.T. Wardhaugh and D.V. Boger, Flow characteristics of waxy crude oils :Applica-
tion to pipeline design, AIChE J., Vol. 37, No. 6, p. 871 (1991). 4.2 CLASSIFICATION OF LABORATORY TESTS
20. J.A. Svendsun, Mathematical modelling of wax deposition in oil pipeline systems, Most of the laboratory tests can be broadly classified into seven groups 11;lst:tl 011 t11('
AIChE J., Vol. 39, NO.8, pp. 1377-1388 (1993). followingcharacteristics:
21. T.F. Al-Fariss, Effect of wax on oil behaviour, Indian Chemical Engineer, Vol. .=I, Volatility
NO.2, pp. 8-12 (1990). Combustion
22. G.P.van Engelen, C.L. Kaul, B. Vos and H.P. Aranha, Study of flow improvers for e Viscosity and consistency
transportation of Bombay High crude oil through submarine pipelines, Journal of e Melting point
Pet. Tech., Vol. 33, No. 12, pp. 2539-2544 (1981). e Oxidation
23. T.R. Sifferman, Flow properties of difficult-to-handle waxycrude oils, Journal of Pet.
Corrosion and protection
Tech., Vol. 31, No. 8, pp. 1042-1050(1979).
24. C.A. Irani and J. Zajac, Handling of high pour point west African crude oils, Journal
of Pet. Tech., Vol. 34, No. 2, pp. 289-298 (1982).
25. R.N. Tuttle, High-pour-point and asphaltic crude oils and condensates, Journal of
Pet. Tech., Vol. 35, No. 7, pp. 1192-1196(1983).
! e Miscellaneous tests
Volatility is the major dcterminant ofthc tendency of a hydrocarbon to produce polontially
ex~losivevapours. I t is also critically important to an cmgine's start and warm-up. Volatility
is gssessed by the following tests:
(a) Distillation
26. E.D. Burger, T.K. Perkins and J.H. Striegler, Studies on wax deposition in t h e h a n s
Alaska Pipeline, Journal of Pet. Tech., Vol. 33, No. 6, pp. 1075-1086(1981). (b) Vapour pressure
27. C. Chang, D.V. Boger and Q.D. Nguyen, TLEyielding of waxy crude oils, Ind. Eng* (c) Flash point and fire point
Chem. Res., Vol. 37, No. 4, pp. 1551-1559 (1992). The combustion properties of petroleum products are evaluated by the following tests:
(a) Antiknock quality-Octane number, Performance number
(b) Ignition quality-Cetane number, Aniline point, Diesel index, Calculated cetanc index
I
(c) Calorific value

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
- -
48 PETROLEUMREFINING T E ~ H N O ) ~ ~ & ~
tiom the applicalion of'a small flame. At firc point, not only will the vapour-air mixture'fir)8h
but the liquid will continue to burn.
Abcl apparatus is used for determiningthc closed cup flash point of' petroleum products
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
;I ilaxh point :~br>vc 49OC. Clcvcland appariltus is used for determining the flash and fire points
of pctroleun~products cxccpt l'uucl oils and those products having an open cup flash point below
79°C.
Ylirsh p u n t measurcs thc tcntlcncy of the fuel to form a flammable mixture with air under
conlrollcd laboratory conditions. This is tho only propcrty that must be considered in assessing
the ovcrull tlammability l~azartlof a mntcrial. I t is used in shipping and safety regulations
thnldcfinc flttmmable and combustible n~uterials.Petroleum products having low flash points
irrlb~~otential to fire hazards. Flash point can indicate the possible presence of highly volatile
ant1 tlan~n~ablo materials in rclativoly nonvolatile or nonflammnble makrial.
4.6 OCTANE NUMBER
This is a n important test for measuring the antiknock quality of the gasoline (petrol or
motor spirit). The knocking of the motor fuelsis compared using blends of reference fuels. The
standard reference fuel8 used foroctanenumbers below 100areiso-octiineand normal heptwe
which arc assigned valuerr of100 and 0, respectively, on the octane number scale. The octane
number of thc fucl is defined atl the volume percentage ofiso-octane t2,2,4-trimethyl pentane)
in a blcnd with n-heplanc which is equal to the test fuel in knockintensity under standardised
and closely controllcd conditions of test in a single-cylinder, variable cbmpression ratio
enbines, known as CFli cnginerr. Thus, a fuel of 87 octane number has a CFR engihe
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.
The differences in the two methods are as follows:
Octane numbcr rcquirc~ncntsof gasoline engines depend on their compression ratio. If the
fuel meets the minimum requirements in respect of octane number it ensures trouble Bee
ol~cration.Apart fiom being a nuisance, the knocking in an engine may result in loss of energy
: ~ n da t times may cause severe damage to the engine.
4.7 PERFORMANCE NUMBER
This is used to estimate knoekihg characteristics of aviation gasolines of octane number
highcr than 100. The standard reference fuels for knock ratings above 100 octane number are
iso-octane and its blends with tetraethyl lead (TEL). The ratings of aviation gasoline above
100 octane number are normally expressed as performance number.
The performance number scale is based on engine power output. The performance number
of an aviation fuel represents approximately the maximum knock-free power output. The
I QUALITY CONTROL OF PETROLEUMPRODUCTS
onrformance number shows the percentage increase in aipcrafi engine power for addition of
49
r-------
TEL to iso-octane and is given by
Performance number - 100)
Octane number = 100 + ( -
3
On the performance number scale, 100 octane number equals 100 performance number.
The ratings of aviation gasoline above 100 octane number can be done by
(a)Aviation method (lean mixture rating);
( b )Supercharge method (rich mixture rating); and
(c) xie ended motor method.
I n aviation method, the rating is done a t 1200 rpm by comparing the combustion chamber
temperature for the fuel with those of the blends of known performance number. This lean
mixture rating gives us an idea of the availability of knock limited power in spark ignition
type aircraft engines when the aircraft is under cruising conditions.
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
constant compression ratio by measuring indicated mean effective pressure a t enough points
to define the mixture response curves for the sample and the reference fuels. When the knock
limited power for the sample is bracketed between those for two adjacent reference fuels, the
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
limited power when the plane is under take-off conditions.
In extended motor method, the rating is done in a CFR engine normally used for rating of
motor gasolines by motor method (rpm=9OO). The knocking intensity of the fuel is bracketed
between reference fuel prepared from iso-octane and TEL and the performance number is
calculated by interpolation.
4.8 CETANE NUMBER
Cetane number is related to the ignition delay of a fuel in a diesel engine, i.e. how rapidly
to lower cetane numbers.
Cetane number of diesel fuels is determined in a single cylinder CFR engine by comparing
the ignition delay characteristics of the diesel fuels with that of reference blends of known ,,
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
with h e p t a m e t w nonane which matches thdignition quality of the test fuel when compared
bv this method..The matching blend percentages to the fiist decimal are inserted in the
following equation to obtain the cetane number:
Cetane number = % n-cetane + 0.15 (% heptamethyl nonane) ... (4.2)
The shorter the ignition delay period, higher is the cetme number of the fuel.
Cetane number is the index of ignition quality of a fuel. High cetane number fuels will
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

4.15 VISCOSITY Table 4.1 Instrument Constant Values

Kinematic viscosity is defined ris the mearidre of the r e d s t h i &to gravity flow of a fluid,
the pressure head being proportional to the density. The time of flow of a fixed volume of fluid
is directly proportional to its kinematic viscosity. The unit of kinematic viscosi$ is, cm2/s or
Stoke. The unit most usually used in measurement of the kinematic viscosity of ~etioleum
fuels is the centistoke (cSt) which is Stoke.
Dynamic viscosity, also known as absolute viscosity, is the ratio of applied shear stress to
rate of shear and thus a measure of the resistance of a fluid to flow. The unit of dynamic
viscosity is gm1cm.s or Poise. Dynamic viscosity may be obtained from kinematic viscosity by
I
multiplying it by the density of the fluid at the temperature at which measurement was made.
1
'1
I
Kinematic viscosity may be measured as an absolute property of the fuel, or alternately
as a conventional property that is'dependent on the instrument and the method used. Both
approaches depend on the efflux time of a given volume of sample flowing under its own head
through a restriction. This follows because the force acting the laminar (low speed) flow of a
fluid through a restriction is approximately proportional to the dynamic viscosity, whereas
the force promoting the flow is that due to gravity, and is proportional to the density of the
I fluid. Hence the time taken for the gravity flow of a given volume of sample through a
restriction is approximately proportional to the kinematic viscosity. 4.1 6 VISCOSITY INDEX
, Viscosity index (VI)is the most widely used way of characterizing the effect of change of
The conventional methods, which are generally simpler but less accurate, are represented i

by the Redwood instrument in the UK, Saybolt in the USA and Engler in continental Europe.
They each comprise a sample cup fitted with a standard-sized oriiice in the base and
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
sample. The result is reported as Redwood or Saybolt universal second or as Engler degree,
given by the efflux time ratio for the sample and for water. When the efflux time exceeds a
specified maximum-for example 2000 s-due to high viscosity, use is made of a Redwood No. 2,
or a Saybolt Furol (fuel and road oils) instrument, incorporating a larger diameter orifice.
The absolute determination of kinematic viscosity'generally employs a glass U-tube
viscometer with a capillary tube built into one leg. The length-diameter ratio is such that end
effects are negligible and the precision is therefore higher. The instrument is suspended
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
\ L-H
equation to give a direct measure of the kinematic viscosity in centistokes.
v=At-B/t ...(4.8)
where A = instrument calibration constant;
B = instrument type constant, depending on the capillary diameter;
and
t = efflux time, s (Engler degree for Engler viscometer)
Table 4.1 gives the values of A and B for Redwood, Saybolt and Engler viscometers.
Viscosity is an important characteristic of a fuel and it is used for the pump design. Pump
clearance are aGusted according to the viscssity and if i t is out of the range, it will result in
pump seizer. Pump operation of an engjne depends on the proper visesity of the liquid fuel.
The viscosity of liquid fuel is important to its flow through pipelines, injector nozzles, and
orifices, and for atomization of fuel in the cylinder.
temperature on the viscosity of any oil. Proposed by Dean and Davis, viscosity index is an
empirical concept based on the behaviour of mineral oils. In this concept, an oil whose viscosity
.,
viscositywith change in temperature has a highVI. In this system, Pennsylvanian (paraffinic)
oils of a selected type which show a desirable, relatively small change of viscosity with change
in temperature, were assigned a VI of 100, while selected Texas Coastal oils showing less
desirable viscosity-temperature characteristics were assigned a VI of O.VI is governed by the
type of hydrocarbons in the oil.
Dean and Davis prepared tables giving the kinematic viscosities a t 40°C and 100°C of the
Texas Coastal oils (L) and the Pennsylvanian oils (HI. The values of kinematic viscosities of
L and H are given in Table 4.2. The VI of an oil can be calculated from the equation
v1=L-Ux100
where U = kinematic viscosity at 40°C of the oil whose VI is to calculated
L = kinematic viscosity at 40°C of an oil of 0 VI
H = kinematic viscosity at 40°C of an oil of 100 VI
.17 PENETRATIONTESTS
Several standard grades of bitumen are comlqercially available, which are normally
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 .,
suitable container and brought to a temperature of 25OC in a water bath. The weighted needle
is brought to the surface.and at the end of 5 seconds interval, the penetration the needle
into the bitumen, in units of UlO mm is t e ~ v o nofthe ' b $
The penetration at 25OC and the softening point, or penetrations a t two di erent tempera-
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

used to define temperature 'dependence. The most commonl~used factor,.however, is the

Penetration Index (PI),which is defined as follows :

Table 4.2 Values of H. L and D for Kinematic Viscosity at 100 O

C
(H = Kinematic viscosity at 40°C of an oil of 100 VI, cSt,
, . L = Kinematic viscosity at 40 OC of an oil of 0 VI, cSt)
56 PETROLEUMREFININGTEFHNOLQGY QUALITY CONTROL OF PETROLEUMPRODUCTS 57
 grease' of an hknown formulation. It cannot be used to measure the upper operating
temperature limit for a grease.

421 MELTING AND SElllNG POlNT OF WAX

The cooling curve method is used to determine the setting point of waxes. Molten wax is
allowed to cool in a specified apparatus and the temperature is recorded at frequent intervals
The point at which the temperature remains within a range of O.l°C for one minute is taken
as the setting point. This method is not suitable for microcrystalline or intermediate waxes,
or blends of paraffin waxes with these or any additives.
log (800) - log (PEN25°C) - 20 - PI 1 The congealing point of a petroleum wax or petrolatum is determined by applying a drop
-
TRB 25 - [i?Gx][SO] of molten wax to a thermometer bulb, and noting the temperature at which it congeals when
where TRBis the ring and ball softening point of the bitumen in "C. etration of a
I the thermometer is rotated under standardised cooling conditions.This method is suitable for
-?
bitumenat the softening point temperature is about 800. Bitumens less n fected by tempera-
ture change have positive values of PI and those ?ore affected by temperature change negativ'e
'
4@
'
I all waxes.
The drop melting point of wax or petrolatum is determined by recording the temperature
values. at which a drop of the sample falls from the bulb of a thermometer when heated under standard
I conditions.
4.18 FREEZING POlNT These are considered to be suitable for checking the constant quality of wax output in
Freezing point is the temperature at which crystals of hydrocarbons formed on cooling refineries.
disappear when temperature of fuel is allowed to rise.
This method covers a procedure for the detection of separated solids in aviation reciprocat- 4.22 SOFTENING POlNT OF BITUMEN
ing engine and turbine engine fuels at any temperature likely to be encountered during flight Bituminous materials do not change from the solid state to the liquid state at any definite
r or on the ground. temperature, but gradually become softer and less viscous as the temperature rises. For this
reason, the determination of the sofbning point must be made by a fixed arbitrary, and closely
4.19 CLOUD POlNT AND POUR POlNT -- point is defmed as the temperature at which a substance attains a particular
Cloud point of petroleum products is the temperature at which a cloud or haze of wax
crystals appears at the bottom of the test jar when the oil is cooled under prescribed conditions.
It is generally determined for products that are transparent in a 43-mm thick layer and have
cloud points below 49°C.
d
under specified conditions of tes A steel ball of specified weight is placed
upon a disc of sample contained within a metal ng of specified dimensions. The assembly is
heated at a constant rate anct the temperature at which the sample becomes soft enough to
allow the ball, enveloped in a bitumen, to falld - distance is taken as the softening
The cold filter plugging point test is used to determine the extent to which diesel fuel or
gas oil will flow, even though the temperature is below that at which wax crystals normally -
2 The ring and ball test for softening point measures the temperature in OC at which a
appear, i.e. cloud point.
standard disc of bitumen confined in a metal ring softens to such an extent, when heated at a
Cloud point gives a rough idea of the temperature above which the oil can be safely handled
without any fear of congealing or filter clogging. rkteif 5"~/minute,that it deforms under the loading imposed by a small steel ball which falls
a distance of 2.54 cm.
Pour point is the lowest temperature expressed in multiple of 3°C at which the oil is The determination of the softening point of bitumen is regarded by some as an indication
observed to flow when cooled and examined under prescribed conditions.
of viscosity, although from the point of view of the application of bitumen its use is limited to
Pour point is a well-established test to estimate the temperature at which a sample of oil that of its title. The softening point is used in the designation of hard bitumens and oxidized
becomes sufficiently solid to prevent its movement by pumping. The pour point temperature bitumens.
depends to a large extent on the thermal history of the sample. Also, the pour point indicates
the waxy nature of the oils.
4.23 INDUCTION PERIOD OF GASOLINE
Induction period of gasoline is the time elapsed between the placing of the bomb in the
4.20 DROP POlNT OF GREASE
bath and break point at 100°C. Break point is the point in the pressure-time CUNe that is
The standard drop point tests indikte that the temperature at which the thickener is so
preceded by a pressure drop of exactly 2 psi within 15 minute and succeeded by a drop of not
soluble in the base oil that the grease becomes substantially fluid. Clay and dye thickened less than 2 psi in the next 15 minute.
greases have no measurable drop points.
Fifty millilitre of the sample is enclosed in a bomb with oxygen a t 100 psi and heated in a
The drop point can be used to assess whether a grease of known formulation has been
properly made or to obtain an indication of the type of thickener which has been used in a water bath at 100°C. The pressure is then recorded either on a chart or read every 15 minutes
60 PETROLEUMREFINING~TECHNOLOGY
The test is continued until the break point is reached. The test result is reported as induction
period in minute.
This test is conducted to assess the stability of gasoline in storage. This test indicates the
presence,of unsaturated hydrocarbons in the fuel and hence its gum forming tendency. Higher
the induction period, better is the storage stability of the fuel. An induction period of 360
minute under laboratory conditions ensures storage stability of at least six month. However,
this correlation may vary with different gasolines under different conditions.
4.24 THERMAL STABILITY OF JET FUELS
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
flow rate through a heater after whichit enters thestainless steel filter whert! fuel degradation
products may become trapped. The apparatus requires 600 ml of test fuel for a 2.5 hour test.
The essential data derived are the amount of deposits on an aluminium heater tube, and the
rate of plugging of filter located just downstream of the heater tube.
In the JFTOT a charge is placed in a reservoir and the whole system is pressurized to 3.45
MPa with nitrogen. This ensures a single-phasereaction in the heated section. The fuel passes
from the reservoir through a 0.45 micron filter, to remove trace particulate matter, and into
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
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.
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
differential pressure across the 17 micron filter is measured.
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.
4.25 GUM CONTENT
The gum compounds which can be present or produced in the fuel are classified into two
types for test evaluation. Existent gum may be already formed in the fuel and can be deposited
from solution as the fuel evaporates. Potential gum may be formed under extended storage
conditions during which unstable hydrocarbonsare thereby polymerized and oxidized to form
gums.
Existent gum is the amount of nonvolatileheptane insoluble residue left when the sample
is evaporated in a jet of hot air at 160°C. For jet fuels, the evaporation is camed out in a jet
of superheated steam at 232OC.
Potential gum is the amount of gum formed afier the sample is aged in an oxidation
stability bath and evaporated under specified conditions.
Gum is always troublesome in any fuel and it may cause piston ring sticking and deposits
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
compounds existing in the fuel, while the potential gum test attempts to predict the tendency
to form gum on storage and use. These gum tests are usually used as refinery control methods.
1 QUALITY CONTROLOF PETROLEUM PRODUCTS
.: .
g1
4.26 TOTAL SULPHUR
This is determined by lamp method or wickbold procedure for volatile petroleum Products
and by bomb method for heavier products. Sulphur in the sample is oxidized by combustion ,
and is estimated volumetrically after absorption in Hz02 or by gravimetric methods after
converting into barium sulphate.
Sulphur compounds pose a dual problem: they not only cause environmental pollution
"
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
products is therefore of importance to both refiner and user.
I
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
1 as degradation products, such as oxidation products, formed during service. Total acidity is a
I
I
measure of the combined organic and inorganic acidity.
The acids in the sample are extracted in neutral alcohol andthen titrated against standard
alcoholic potassium hydroxide under hot conditions.
Total acidity is an indication of the corrosive properties of the product. Inorganic acidity
is a measureof the mineral acid present. Organic acidity is obtained by deducting the inorganic
acidity from the total acidity.
ER-STRIP CORROSION TEST
products contain sulphur compounds, most of which are removed during
I refining; Of the sulphbr compounds remaining in the petroleum product, however, some can
have a corroding effect on various metals. This corrosivity is not necessarily directly related
to the total sulphur content. The effect can vary according to other chemicals and types of
sulphur compounds present.
A cleaned and smoothly ~oli$hedcopper strip is irnmerse&&hsm@& which is then
mamtained at the specified temperature for the specified length of time. This strip is removed
1 L a m p l e , washed with aromatic and sulphur free petfoleum spirit and examined for
evidence of etching, pitting or discolouration. It is then compared with F T M copper-strip
corrosion standkd colour code. Th_eclass%cation cbde indkates that the numbers 1 , 2 , 3 and
4 designate slight tarnish,'moderate tarnish, dark tarnish m d corrosion,kespectively. Sub--
scripts-a-e describe a standard colour reproduction'in the standard chart. For example, the
classification code l a indicates slight tarnish with a light orange colour.
C ~ h itest
s serves as a measure of possible difficulties with copper, brass, or bronze parts of
the fuel systems.
7
4.29 SILVER-STRIP CORROSION TEST FOR AVIATION TURBINE FUELS
A Polished silver strip is completely immersed in Aviation Turbine Fuel at 45 f 1°C for a
period of 16hour. At the enctof this period, the silver strip is removed from the sample, washed
and evaluated for corrosion against the set of standard.
Since some parts of the fuel pumps in aircraft are made of silver, the corrosive tendency
of the he1 for silver assumes special significance.The cumulative effect of corrosion on such
a vital component in the aircraft is hazardous.
_? 4.30 ASH -h~ji{:!:*;:~
: p > 5 ~ z :.b,,:;.7!t$;
~ 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.

4.32 COLOUR 4.34 GAS CHROMATOGRAPHY OF PETROLEUM GASES AND LIQUIDS

Colouris an indication of the degree of refining of the products. Various test methods used
for the measurement of colour of petroleum products along with their main items equipment
and product application range are given in Table 4.3.
4.33 DENSITY AND SPEClFlC GRAVITY
fi measured volume of the gas sample is introduced into a chromatographic column and
transported through the column, the sample is split into various components, either by
adsorption or partition, depending on the column packing. The composition of the sample is
determined from the chromatograms by measuring the area under the peaks. An identification
of the components is done by noting the elution time. - .

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.

4.36 LEAD IN GASOLINE

_
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!.
. . . . . . .

4.37 WATER SEPAROMETER INDEX (MODIFIED) (WSIM)

6;:$.i'embairt2bn% :..
itI;~pG ;...
.,.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.