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Journal of Scientific & Industrial Research

Vol. 63, March 2004, pp 276-282






Physicochemical characterization and applications of naphtha
S C Pandey, D K Ralli, A K Saxena and W K Alamkhan
Process & Products Control Laboratory, Uran Plant, Oil and Natural Gas Corporation, Uran 400 702, District Raigad
Received: 28 July 2003; accepted: 27 November 2003
The present work aims at comprehensive evaluation of naphtha quality at physicochemical levels along with its
applications. The study monitors the changes in the quality parameters by drawing samples from the storage tanks at Uran
plant as well as at Indian Oil Tanking Limited (IOTL) terminal. Group characteristic assigns this LAN group1 category. It is
observed that this LAN possesses high paraffin, low aromatic content, no olefins, and metallic constituents in a fraction of a
ppm. The presence of metals in minute concentrations may not cause significant corrosion problems, catalytic poisoning, ash
formation and any adverse impact on the quality of the product. Sulphur content is as low as 22ppm. Very small quantity of
residue left on evaporation (4.18 mg/100mL) indicates lesser coke forming and carbon depositing propensity. Preponderance
of paraffins renders faint odor to the product. Water whiteness of naphtha results owing to low concentration of aromatics.
Saybolt colour indices towards the brightest end of the scale (+28 to +30) show high degree of freedom from contamination
and cleanness of the product. High heating value, and C/H ratio indicate its hydrogen richness hence, it becomes suitable for
many hydrogen dependent processes. Average value of Reid Vapor Pressure (at 37.8
o
C) at the level of 10.2 psia makes it
safer for handling, storage and processing.
Keywords: Physicochemical characterization, Characterization, Naphtha, Hydrogen dependent processes
IPC: Int Cl.
7
: C 10 G 45/08

Introduction
Naphtha is a generic term applied to refined,
partly refined or unrefined petroleum products and
liquid products of natural gas which distill below
240
o
C; the volatile fraction of the petroleum, which is
used as a solvent or as a precursor to gasoline. In fact,
not less than 10 per cent of material should distil
below 75
o
C; not less than 95 per cent of the material
should distil below 240
o
C under standard distillation
conditions
1
.Naphtha contains varying amounts of its
constituents viz., paraffins, naphthenes, aromatics and
olefins in different proportions in addition to potential
isomers of paraffin that exist in naphtha boiling
range. Naphtha resembles gasoline in terms of boiling
range and carbon number, being a precursor to
gasoline. Naphtha is used as automotive fuel, engine
fuel, and jet-B (naphtha type). Broadly, naphtha is
classified as Light Naphtha and Heavy Naphtha.
Light naphtha is used as rubber solvent, lacquer
diluent, while heavy naphtha finds its application as
varnish solvent, dyer
,
s naphtha, and cleaner
,
s naphtha.
Volatility, solvent properties (dissolving power),
purity and odor determine the suitability of naphtha
for a particular use. The use of naphtha as an
incendiary device in warfare, and as an illuminant
dates back to 1200 AD. Naphtha is characterized as
lean (high paraffin content) or rich (low paraffin
content). The rich naphtha with higher proportion of
naphthene content is easier to process in the
platforming unit. A rich naphthene charge produces
greater volumetric yield of reformate than does a lean
charge The wide range of naphtha available from
ordinary paraffinic straight run to highly aromatic
type and the varying degree of volatility offer
products suitable for many uses. Naphtha solvents
may belong to categories such as, special boiling
spirits having distillation range 30-165
o
C, white spirit
(mineral spirit) boiling within 150-210
o
C, and high
boiling petroleum fractions(160-325
o
C).In aromatic
complexes, naphtha is converted into basic
petrochemical intermediates: Benzene, toluene and
xylene (BTX). Petroleum naphtha is by far most
popular feedstock for aromatics production.
__________
* Author for correspondence
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277
The Uran Plant
Mumbai region of Oil and Natural Gas
Corporation is a prolific producer of hydrocarbons in
the country. Uran processing facilities were
established in 1981 along the eastern shore of
Bombay Harbor. This plant receives oil, gas, and
condensate from western offshore. The plant
possesses in-built capacity to handle 16 MMSCMD
of Gas, 20 MMT/y of crude oil and 1500 MT/d of
condensate. The extraction of natural gas liquid from
natural gas is achieved as a result of fractionation of
natural gas into hydrocarbon constituents. Gas
condensates contain relatively high amount of high
molecular weight liquid hydrocarbons. Uran plant
processes natural gas by using cryogenic technology
to produce liquefied petroleum gas, natural gasoline
liquid, low aromatic naphtha, propane, and ethane-
propane mixture. Typical composition of feed gas and
condensate is presented in Table 1. This plant is also
engaged in stabilization of crude oil prior to its
dispatch to refineries. Uran plant has ISO 9001:2000,
ISO 14001:1996 certification and achieved level-7 of
international safety rating system (ISRS).
Characterization Parameters
An accurate description of naphtha quality
requires its characterization at physical and chemical
levels. Prescribed sampling protocols form the basis
of sound analytical analysis. Preliminary and
comprehensive assays are combined together to
evaluate the quality of low aromatic naphtha (LAN)
employing the latest international standards.
Analytical Methods and Practices
Sampling Protocol
The correct sampling protocol is extremely
crucial for any product destined for analytical
evaluation as accuracy and precision of any analytical
technique hinges on representative sample. Because
of high standards set for naphtha, it is essential to
employ correct sampling technique. Samples are
required to be drawn in containers that are
scrupulously clean, and free from odor while ensuring
minimal disturbance to avoid loss of volatile
components. Samples are drawn in accordance with
upper third, middle third and lower third from the
bigger tanks at the premises of Indian Oil Tanking
Limited (IOTL), and tap sampling procedure is
followed for drawing samples from smaller tanks at
Uran plant as per method ASTM D-4057.

Group Characteristics

The selection of distillation characteristic at
atmospheric pressure has an important bearing on
safety and performance of fuels (ASTM D86, IP123,
ISO: 3405). The boiling range provides information
on composition and behavior during storage and use.
On the basis of group characteristics LAN produced
at Uran plant falls under group1 category (Table 2).
The conditions required for sampling, preparation of
apparatus, and conditions to be maintained during
test procedure for group1 naphtha are shown in
Table 3.
Table 1 Typical composition of feed gas and condensate
Feed gas Condensate
Component Feed gas1 Feed gas2 Component N-paraffins Iso-paraffins Naphthenes Aromatics
mol per cent (Volume per cent)
C1 83.67 83.63 C1
C2 8.18 8.14 C2 0.12
C3 5.09 5.15 C3 2.10
IC4 0.97 0.98 C4 7.12 2.59
NC4 1.19 1.15 C5 11.91 8.38 2.41
IC5 0.24 0.23 C6 8.70 9.61 11.68 7.65
NC5 0.21 0.22 C7 3.71 2.47 9.72 3.99
C6+ 0.10 0.11 C8 1.34 0.71 2.84 1.94
N2 0.35 0.39 C9 0.07

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Physicochemical Characteristics
Density
Density is an important parameter as it is the
main basis of sale transactions. Usually a hydrometer
(ASTM D1298; IP-160) or more modern digital
densitometer (ASTM D-4052 or D-5002) is used for
determination of density. However, ASTM D1298 is
the most commonly used method.
Composition
Adsorption chromatography ASTM D1319:
IP156 gives first level of composition information as
group-totals in terms of volume per cent of saturates,
olefins, and aromatics in materials that boil below
315
o
C. Naphtha composition, however, is monitored
mainly by gas chromatography. Although most of the
methods have been developed for gasoline, yet the
applicability of these methods for naphtha is sound. A
detailed analysis of petroleum naphtha can be carried
out by capillary gas chromatography (ASTM D5134).
A flame ionization detector detects the eluted
components.
Residue on Evaporation
The carbon residue is a property that can be
related with several other properties of petroleum. It
presents an indication of volatility and coke forming
propensity. Petroleum products are mixture of many
compounds that differ widely in their physical and
chemical properties. Some of them may be vaporized
in the absence of air at atmospheric pressure without
leaving any appreciable residue: other non-volatile
compounds leave carbonaceous residue when
destructively distilled. Methods ASTM D189, IP13
and ASTM D524, IP14 are used to determine carbon
residue in relatively non-volatile portions of
petroleum and petroleum products. Another common
method to determine carbon residue, and to assess the
propensity to form deposits is ASTM D1353. Carbon
depositing characteristics of fuels are used in certain
types of oil burning equipments and internal
combustion engine.
Odor and Colour
Naphtha is required to have a low level of odor to
meet the specifications for use. In general the
paraffinic hydrocarbons possess the mildest odor, and
the aromatics the strongest. The odor level is related
to chemical character and volatility of constituents.
Naphtha containing higher aromatic fractions may be
pale yellow. Usually, naphtha is colourless (water
white). Method ASTM D156, IP17 provides a rapid
method of checking the degree of freedom of
Table 2 Group characteristics of naphtha
Sample
characteristic
Group 0 Group 1 Group2 Group3 Group 4
Distillate type Natural gasoline
Vapour pressure
at 37.8
o
C (psi)
9.5 <9.5 <9.5 <9.5
Distillation IBP
o
C
EP
o
C


250

250
100
>250
>100
>250
Table 3 Group 1 naphtha sampling, apparatus, and test procedure conditions
Description Condition Description Condition
Temperature of sample bottle,
o
C <10 Bath temperature,
o
C 0 -1
Temperature of stored sample,
o
C <10 Temperature of bath around receiving cylinder,
o
C 13 - 18
Flask, mL 125
Thermometer 7C(7F)
Time from first application of heat to IBP, min 5 - 10
Flask temp. at start of test,
o
C 13 18 Time from IBP to 5 per cent recovered, s 60 100
Rate of condensation from 5 per cent recovered to 5mL in
flask, mL/min
4 5
Receiving cylinder and 100 ml charge,
o
C 13 18
Time recorded from 5 mL residue to end point, min 5max

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279
contamination. Saybolt colour of a clear petroleum
liquid is measured on a scale of 16 (darkest) to +30
(lightest).The sample is viewed through a length of
column. Visually it is matched with one of the
appropriate glass standards.
Volatility/Distribution of Boiling Range
Volatility or distribution of boiling range has
been an important aspect of product specification in
petroleum industry. It is a primary characteristic, and
is indicative of tendency of liquid fuel to vaporize,
and the ease with which material can be refined. This
characteristic has an important bearing on the safety
and the performance, especially in the case of fuels
and solvents. Volatility is an important property for
coating applications. It is critically important for
automotive fuels, and gasoline affecting start/
warming up, and tendency to form vapor lock at high
temperatures, and high altitudes or both. The
distillation data consisting of initial temperature, final
temperature along with sufficient temperature and
volume observations can provide useful information
on volatility.
Reid Vapor Pressure
Vapor pressure is an important physical property
of volatile liquids, having critical implications on
safety of operations of equipment and handling. Reid
vapor pressure (RVP) is an indirect measure of
evaporation rate of such liquids. It is also used in
regulations relating to emission and air quality
control. RVP of petroleum and petroleum products is
determined by using method ASTM D323, IP69, ISO
3007. Procedure A of this method is applicable for
petroleum products having RVP below 180Kpa
(26psi).
Sulphur Content
Impurities, other than hydrocarbons, are of
concern in petroleum industry. Quality of many
petroleum products is related to the amount of
sulphur. For example, many catalytic processes are
sensitive to sulphur contaminant. Sulphur compounds
contribute to corrosion of refinery equipment and
poisoning of catalyst, cause corrosiveness in refined
products, and they contribute to environmental
pollution as a result of combustion of such fuel
products. Sulphur is present in petroleum as
sulphides, thiophenes, benzothiophenes, and
dibenzothiophenes. A series of methods are utilized
to determine trace concentration of sulphur. Method
ASTM D4294, IP336, ISO 4785 utilizes energy
dispersive x-ray fluorescence spectrometry for
determination of sulphur in naphtha as well as in
other fuels.
Metallic Constituents
Petroleum contains metallic constituents but they
may also get incorporated during recovery,
transportation, and storage. Range of principal
trace elements found in petroleum is mentioned in
Table 4.
Even trace of these metals can be deleterious in
refinery as they can cause corrosion, catalytic
poisoning, and affect the quality of refined product.
Nickel and vanadium along with iron and sodium
(from brines) are the major metallic constituents. The
presence of even small amounts of iron, copper,
nickel and vanadium in the charging stocks for
catalytic cracking affect the activity of the catalyst
and result in increased gas and coke formation and
reduced yield of gasoline. In oil-fired gas turbines the
presence of metallic constituents, particularly V may
lead to ash deposits on the turbine rotors, thus
reducing clearances and disturbing their balance. The
ash resulting from combustion of fuels containing
sodium and specially V reacts with refractory furnace
linings to lower their fusions and so cause their
deterioration. Metals can be determined by A A
Spectrophotometry (ASTM D-5863, IP285, IP288,
IP465), wavelength dispersive X-ray fluorescence
spectrometry and inductively coupled plasma
emission spectrometry (ASTM D5185).
Table 4 Principal trace elements in petroleum (ppm)
(Source: Applied energy technology series by Mushrush and Speight)
Elements Cu Ca Mg Ba Sr Zn Hg Ce B Al
Range 0.2-12.0 1.0-2.5 1.0-2.5 0.001-0.10 0.001-0.10 0.5-1.0 0.03-0.10 0.001-0.6 0.001-0.10 0.5-1.0
Elements Ga Ti Zr Si Sn Pb V Fe Co Ni
Range 0.001-0.10 0.001-0.40 0.001-0.40 0.10-5.0 0.10-0.30 0.001-0.2 5.0-1500 0.04-120 0.001-12.0 3.0-120

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Thermal Property (Heating Value)
Calorific value or heat of combustion is a direct
measure of fuel energy content and is determined as
per method ASTM D-240, IP12. In the case of non-
availability of experimental determination, it can be
estimated satisfactorily, using ASTM D-6446. An
alternative criterion of energy content is the aniline
gravity product (AGP), which is related to calorific
value (ASTM D1405, IP193). In another method
(ASTM D3338 or IS 1448) the heat of combustion is
calculated from the fuel density, the 10 per cent, 50
per cent and 90 per cent distillation temperature and
the aromatic content. However the method ASTM
D240 is preferred.
Product Specifications
Specifications of LAN and test methods followed
at Uran plant are mentioned in Table 5.
Results and Discussion
Natural gasoline liquids produced from two LPG
plants and condensate fractionation unit are blended
to obtain final product Low aromatic naphtha.
Quality parameters are evaluated at in-process stage
as well as prior to dispatch. Batch samples of naphtha
were drawn from tanks at Uran Plant and IOTL as per
procedure laid down in method ASTM D4057.
Naphtha from Uran plant is assigned Group-1
category on the basis of Group characteristics and all
experimental conditions are set for this particular
group.Density of LAN has been monitored at plant
level as well as for tanks at IOTL (sold parcels) to
observe the general trend of density variation. It
varies between 0.6749-0.6838 g/mL, and 0.6785 -
0.6822 g/mL for plant tanks and IOTL tanks,
respectively. Density profile vis--vis FBP is
presented in Figure 1. Specification of the product
permits variation limit between 0.67-0.69 g/mL.
Compositional Information in the Form of Group
Type Totals have been deduced by chromatographic
method. The results indicate the paraffinic nature
(>77 per cent v/v) with low aromatic content ( 7.3
per cent v/v). Concentration of naphthenes ranges
between 14.29 - 15.55 per cent vol (Table 6). This
naphtha may be characterized as lean. Average values
of paraffins, isoparaffins, naphthenes, and aromatics
are reflective of types by carbon number (Table 7).
Dominance of paraffins in the chemical composition
renders LAN very mild odor. Very small amount of
carbon residue as low as 0.8 mg/100mL to a max of
7.60 mg/100mL against prescribed limit of 50
mg/100mL left after evaporation shows high
volatility, little coke forming propensity, and carbon
depositing characteristics.
Owing to low aromatic and high paraffinic
content the colour of naphtha is similar to water.
Saybolt colour index of samples of plant tanks
(average +27) and of IOTL tanks (average +29)
shows fairly high degree of freedom from
contaminants and fares well against the stipulated
limit (+25 min). Volatility is assessed on the basis of
distillation data. Average IBP, and temperatures (
o
C)
Table 5 Test methods and specifications of low aromatic
naphtha
Characteristic Test method Specification
Paraffins ASTM D5134 75 per cent by vol.
(Min)
Aromatics ASTM D5134 10 per cent by vol
(Max)
Olefins ASTM D5134 1 per cent by vol (Max)
Naphthenes ASTM D5134 Balance
Lead ASTM D5185 250 ppb (Max)
Sulphur ASTM D4294 250 ppm (Max)
RVP at 37.8
o
C ASTM D 323 12 psi (Max)
Color saybolt ASTM D156 +25 (Min)
Residue on
Evaporation
ASTM D 1353 50 mg/100ml (Max)
Density at 15 0c ASTM D1298 Min 0.67-0.69 g/mL
Max
IBP ASTM D 86 35
o
C (Min.)
FBP ASTM D 86 150
o
C (Max)
Calorific value IS 1448 P:7 As observed
C:H ratio ASTM D 3343 As observed
Iso : N-paraffin ratio Calculated As observed

Figure 1 FBP vs density profilofLAN
PANDEY et al.: APPLICATIONS OF NAPHTHA





281
corresponding to 5, 10, 20, 30, 40, 50, 60, 70, 80, 90,
95 per cent, respectively, whereas recovery and FBP
are 37, 43, 45, 47, 50, 52, 56, 61, 68, 78, 92, 111 and
134, respectively. Distillation curve is presented in
Figure 2.
Reid vapor pressure at 37.8
o
C varies from 10.2 -
11 psi and from 10.0 - 10.5 psi for the plant storage,
and IOTL tanks respectively. This meets well the
prescribed specification limits of 12 psi.
Naphtha produced at Uran Plant contains sulphur
20-100 ppm only (below 45 ppm in most of the
cases). Hence, it is quite safe to use this LAN as fuel
without any hazardous effects. Mercury, arsenic, lead,
sodium, potassium, vanadium, zinc, nickel, and
calcium were monitored for four months for assessing
the level of these metals in the LAN (Table 8). Out of
these, mercury and arsenic are <0.1 ppb, sodium 0.12
ppm, potassium 0.02 ppm, zinc 0.06 ppm, nickel
0.006 ppm, calcium 0.25 ppm, and vanadium with nil
values. Lead was observed in the range of 16-100
ppb. Hence, metallic constituents are present at a
level of fraction of a ppm, which indicates that any
deleterious effect in terms of corrosion, catalytic
poisoning, ash residue or any adverse effect on the
product quality due to the presence of metallic
constituents is insignificant in this naphtha.
Table 6 Assessment of LAN quality
(Source: IOTL terminal)
Characteristic Unit Min. Max. Average
Paraffins Per cent v/v 77.61 79.12 78.21
Aromatics Per cent v/v 6.59 7.30 6.83
Naphthenes Per cent v/v 14.29 15.55 15.00
Lead Ppb 16.00 110.00 66.27
Sulphur Ppm 22.00 100.00 51.18
RVP at 37.8 0c Psi 10.00 10.50 10.18
Color Saybolt Saybolt unit 28 30 29
ROE* mg/100mL 0.80 7.60 4.18
Density at 15 0c g/mL 0.6785 0.6817 0.6802
IBP
o
C 37.00 42.00 39.18
FBP
o
C 129.00 137.00 132.64
Calorific value K cal/ Kg 11420 11430 11423
*ROE stands for residue on evaporation
Table 7 Types by carbon number
Average volume per cent Carbon no.
Aromatics Isoparaffins Naphthenes Normal
paraffins
4 - - - 0.39
5 - 23.01 0.84 25.69
6 4.46 12.15 7.94 8.64
7 1.88 3.18 5.39 2.58
8 0.44 1.05 1.00 0.66
9 - 0.31 0.23 0.16
Total 6.78 39.70 15.40 38.12

Figure 2 Distillation curve of LAN
Table 8 Monitoring of LAN quality at Uran plant during
December 2002-March 2003
Source Unit Min Max Average
Mercury ppb <0.1 <0.1 <0.1
Arsenic ppb <0.1 <0.1 <0.1
Sodium ppm 0.11 0.12 0.12
Potassium ppm 0.01 0.02 0.02
Vanadium ppm nil nil nil
Zinc ppm 0.054 0.096 0.067
Nickel ppm 0.005 0.007 0.006
Calcium ppm 0.24 0.27 0.25
Gross calorific
value
k cal/Kg 11420 11450 11436
Net calorific
value
K cal/Kg 10610 10635 10624
C/H Ratio 5.28 5.35 5.32

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Calculated value of gross calorific value ranges
from 11420-11450 kcal/kg, while the net calorific
value varies from 10610 kcal/kg -10635 kcal/kg for
LAN samples drawn from tanks at Uran. For sold
parcels ex-IOTL the gross calorific value ranges
between 11420 - 11430 kcal/kg.
Carbon-Hydrogen ratio of LAN lies between
5.28:1 and 5.35:1. Because of this characteristic,
naphtha may be used as a feedstock for many
hydrogen dependent processes like hydro-cracking,
sulphur removal, nitrogen removal and olefins
removal. The demand for hydrogen is increasing over
last several decades, which is utilized for conversion
of petroleum to match changes in product slate.
Conclusions
Studies conducted on samples from plant storage
tanks and IOTL tanks corroborate each other.
Enormous database provides finer compositional
details of the product and it may serve as a good pool
of information for buyers in national and international
markets. LAN produced at Uran plant is low boiling
light naphtha beonging to group-I category on the
basis of distillation characteristics. Predominance of
paraffins makes it lean naphtha, hence it has a good
market potential. All the quality parameters, as
demanded by market forces, fall well within required
limits.
In addition to monitoring quality parameters,
metallic constituents, heating values and C/H ratio
have been evaluated on a continual basis. It is
observed that it contains low level of metallic
constituents, high calorific value and C/H ratio, and
sulphur content as low as 22 ppm. Hydrogen richness
of this LAN may render it suitable as feedstock for
hydrogen dependent processes. Minute level of
carbon residue shows lesser coke forming and carbon
depositing propensity. Colour indices towards
brightest side of scale are indicative of freedom from
contaminants. Low RVP makes it safe for storage,
handling, and processing.
Acknowledgements
The authors are grateful to Shri M L Panwar,
Group General Manager-Head Uran Plant and Shri
K Raman, Dy General Manager-Operations Manager
for permission and guidance to carry out the study.
Our thanks are also due to Shri R Kher, Chief
Engineer (P) for his valuable suggestions.
Bibliography
1 Handbook of petroleum product analysis, by James G
Speight (John Wiley & Sons Inc, New Jersey, USA) 2002.
2 Petroleum refining processes, by James G Speight and Baki
Ozum (Marcel Dekker Inc, New York, USA) 2002
3 Modern petroleum technology, edited by Alan G Lucas (The
Institute of Petroleum) 2001
4 The Institute of Petroleum Standard Methods, 2003 and
Annual book of ASTM Standards, 2000
5 Ralli D K, Pandey S C, Saxena A K and Alamkhan W K,
Impact of quality management system on product quality at
ONGC, Uran, J Sci Ind Res, 62 (2003) 1001-7.









* Author for correspondence