Indian Journal of Chemical Technology

Vol. 4, November 1997, pp. 259-276

Bitumen quality and manufacturing processes-Past and present

technological status
Himmat Singh & Pankaj Kumar Jain
Indian Institute of Petroleum, Dehradun 248 005, India
Received 11 April 1997; accepted 18 September 1997

Bitumens for road paving applications are derived from refming of crude oils. Their quality
depends upon the nature and origin of crude and processing scheme. Bitumen manufacture since the late
eighties has undergone significant changes, basically due to better understanding of chemistry of
hydrocarbons constituting the feedstocks, processing chemistry and final bitumen through the use of
advanced analytical techniques and understanding of the mechanism of aggregate interaction. In view of
this, there are fast developments in the technology of bitumen making, some of which are: (i) detailed
characterisation of feedstocks and fluxes, (ii) better understanding of the role of different types of
constituting hydrocarbons on performance properties, (iii) upgradation of process technology, based on
reaction kinetics, (iv) multigrading concept to have bitumen with low temperature susceptibility and
acceptable performance level in extreme climatic conditions, and (v) use of unconventional (non-
bitumen bearing) crudes in making bitumen. The present review examines some of the above on going
developments for their application in improving quality and technology of bitumen making.

Historically bitumen/asphalt was the first
petroleum product used by human being as an
adhesive and water proofing material by the
civilizations along the Euphrates river as early as
3800 B.CI. It is further believed that soft bitumen
'.vas used extensively in the preservation of
Egyptian mummies2 as well. Many theories have
been advanced concerning origin and formation of
petroleum and native bitumen3.4. Red Wood's
suggested that bitumens are of inorganic origin.
Lucas and Maberry2 however believed in an
organic origin of bitumen as later confirmed by
Peckham4 who showed that bitumen was a product
of distillation. Modem theories are also in favour
of the organic origin.
The use of bitumen for walls and pavement
surfaces in ancient days has been well
authenticated by excavations and inscriptions on
vases and tablets of different periodss,s.
Considerable research has been carried out to
determine whether bitumen was used in any way
on old roads so that one can bridge the enormous
gap in time between its use in ancient days and the
present. Little information has come to ~ight,
although one reference of considerable interest and
importance is worth recording. Abraham9 has
elaborated on this aspect using road construction
history ofPerulOl1
Bitumen and Highways - Prehistoric
In order to form some idea of the reasons why a
bituminous material was ever used on a road it is
desirable to very briefly review highway
conditions prevailing before and after the coming
of the automobile. The roads/highways of
preautomobile period (around the turn of present
century) were mainly of stone or gravel, or of such
other materials as would compact and support the
loads transported. Those were demanded by
.farmers, the postal service, and the people living
outside cities as improved means for travel. The
birth of automobile thereafter is considered more
responsible for the development of use of bitumen
than any other agency12.
Bitumen base crude oils were plentiful in many
southern sections of California, USA and its use
soon spread to all parts of the west and, as its
beneficial effect became known, to the eastern part
of the country. No specifications were then in
existence. The cutback bitumen had not been
developed, and the methods of application were
indeed crude. Engineers therefore, experimented

260 INDIAN 1. CHEM. TECHNOL., NOVEMBER
with other types of construction using this
promising material. Many references to its
successful use can be found in reports of State
Highway Departments13 of USA. In addition to the
use of liquid bitumens for dust elimination,
numerous experiments were conducted, in many
states, using mixes of stone and heated bitumen as
binders. The processing and placing of road mixes
of sand, gravel, or stone were all done by
manually, a method inefficient and costly (A
practice followed in our country even today).
Highway engineers felt need of mechanised system
to mix bitumen with aggregate, spread and
consolidate the mixture to the proper grade and
camber.
The introduction of cut back bitumen in the
early 1930' s was largely res}Jonsible for the
development of road machines to incorporate
bitumen with the aggregates. The self operated
spreading machine come into general use in the
early 1930's replacing all hand spreading on major
projects. Further developments of hot mix plants
are probably responsible for the excellent
performance of sheet bitumen and bituminous
concrete pavements than any other mechanical
device. The importance of the machinery required
and the proper handling of the mix therefore
assumes great significance as the very success of a
pavement is largely dependent on the machinery
used. The percentage of bitumen in the mix as a
binder usually varies from 3 to 10% as compared
to 90% and above of aggregate depending upon the
requirement of traffic and specifications.
Bitumen Quality Aspects
In view of huge expenditure involved in the
construction of new roads and maintenance of the
existing road network, the quality considerations
of bitumen have become a subject ofinterese4. The
bitumen quality varies with the variation in crude
oil source and refining process, which often cause
considerable' distress to road pavement. Bitumen
obtained from refineries, though meet the existing
specifications'5 but do not give required inservice
performance under the prevailing heavy traffic and
environmental conditions thus indicating
deficiencies in the specifications itself. It is
desirable that the specifications should enable the
engmeers to select a bitumen on the basis of
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1997
performance required under the current and also
under the projected traffic and environmental
conditionsl6. The daily and seasonal variations in
temperature and traffic loadings besides changes in
original properties during construction and
inservice aging makes the task of designer more
difficult to select an appropriate binding material.
The quality of bitumen is judged'7 by : (i) its
flow properties at different temperatures, (ii)
chemical composition, (iii) resistance to change in
flow properties during inservice aging and climatic
variations. The compositional changes during
aging and corresponding effect on flow can help
explain serviceability of bituminous roads. Hence,
quality of a bitumen to achieve performance levels
required by present and projected traffic loadings
and environmental exposures prevailing in
practically world over can be controlled by a set of
specifications based on valid relationship between
its properties, mix properties and field
performance 18. Hence, as a result of increased
traffic loading conditions, variations in nature of
crudes and developed quality consciousness among
highway engineers, recent trends all over the world
are to move from a simple to performance base
specifications'9. Since an approach allows field
engineers to match materials to desired levels of
pavement serviceability and to tailor the choice of
bituminous binder and bitumen - aggregate
mixtures to alleviate or minimize specific road
distress associated with bitumen characteristics20.
Besides taking care of key performance factors, the
specifications should also enable the control of (i)
constructability and (ii) safety aspect involved in
'Ill
bituminous road construction.
A performance based specification may be
defined 17 as "the limi ts and requirements
developed from an extensive data base related to
performance based tests by means of well
established performance prediction models, which
have been validated by correlation within place
field performance data". In the 4th Eurobitume
Conference held at Madrid, Spain, Shell Research
Laboratories Amsterdam presented Qualagon21
concept for performance based specifications. This
concept consist of 9 tests that includes 6 tests on
bitumen and 3 tests on bituminous mixtures which
cover the following three key performance
elements:
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 SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING
Cohesion - Low temperature ductility
Adhesion - Retain Marshall stability
Durability - Rolling thin film oven test
The background philosophy of quality polygon
for performance emanates from the fact that by
proper choice of feedstock and processing
conditions, the bitumen may be produced with
right balance in properties, i.e.,
A balance in molecular weight distribution.
A balance in chemical composition.
A balance in physical properties.
In case the properties of the bitUmenprepared from
any crude/feedstock does not fall within the
preferred limits of qualagon they are brought
within the area by altering the process conditions.
These liinits are however not used as pass/fail
criteria.
According to Strategic Highway Research
Programme IS (SHRP) concept of specifications, it
should be based on a set of validated relationship
between, bitumen properties, mixture properties
and pavement performance factors that establish
acceptable response to changes during construction
and inservice aging. SHRP specifications are
presented in Table 1. It is reported that moisture
sensitivity and adhesion can be controlled by
specifying limits of strength of the bitumen
aggregate bond in blister test. Fatigue cracking can
be controlled by specifying limits in repeated
bending beam test. Details of both the tests are
given under SHRP specifications IS.
Summary of specifications representing
American view point is as follows :
Average 7 days maximum pavement
temperature.
Minimum pavement design temperature.
Flash point.
Maximum viscosity at 135C.
Dynamic shear (G* Sin 8)
Physical hardening index.
Rolling thin film oven test residue
Mass loss
Dynamic shear (G*Sin 8).
A tripartite group of lIP, IOC R&D Centre and
CRRI has also worked into the prevailing BIS
bitumen specifications1s in our country. The group
PROCESSES 261
has evolved an elaborate approach/set .of
specifications22 to be followed at refineries during
manufacturing of bitumen and later for
performance during application.
Relationship between bitumen composition!
constitution and performance-Bitumens are
visco-elastic materials and their behaviour varies
from purely viscous to elastic, depending upon
time of loading and temperature. Viscosity of
paving bitumen therefore plays an important role
during bituminous road construction and
subsequent performance 17. During mixing,
compaction of bituminous mixes at high service
temperatures their properties can be expressed
through a stiffuess modules. The field performance
of bitumen is further linked with their chemical
compositions in terms of concentration of
asphaltenes and wax present.
Cerrone23 studied the influence of asphaltenes in
controlling the properties of paving grade bitumen.
With increase in percentage of asphaltenes, there is
a substantial change in the bitumen's colloidal
structure which tend to assume more and more the
configuration of a "Gel" type. At the same time
important properties of bitumen are altered in a
manner more favourable to their use. The altered
properties are thermal susceptibility and
rheological characteristics in general and the
mechanical and elastic properties in particular.
Asphaltenes theref6re constitute an important
element in estimating the commercial value of
bitumen. It is possible that a bitumen of specified
origin containing small quantity of asphaltene may
posses a structure and characteristics which are
more favourable than those of bitumen of another
type containing a higher percentage of asphaltene
constituents24 Asphalt Institute25, USA opined that
chemically asphaltenes are most complex fraction
of bitumen, they contain largest tendency to
interact and associate. Indonesian specification25
stipulate a range of 15-25% asphaltenes a:;..more
appropriate.
In petroleum industry paraffins (wax) is the
collective name given to a crystalline material with
melting point above 45C that is present in oil
products including bitumen. The melting point of
the paraffin increases with the increase in carbon
number of the paraffin chain and decreases when
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 SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING
structural variations are presehe6 The structure
(crystallinity and hardness) of paraffin wax, its
molecular weight, and its concentration all affect
bitumen performance in two ways : At low road
temperature (below 15C)paraffin crystallizes and
bitumen surfacings show sign of distress in the
form of fine hair cracks. At high road temperature
(above 60C) paraffin melts, act as a flux and the
bituminous surfacings start bleeding. The presence
of high paraffin content reduces the net bitumen
content in the surfacings and thus affects its
durability. Also presence of high paraffin content
in bitumen posses adhesive problems and affects
setting characteristics. Wax decreases the
penetration viscosity number (PVN) making
bitumen more susceptible to temperature changes.
The bitumen produced from indigenous crudes
particularly for special application in Assam region
at Digboi Refinerl7 contain paraffin wax as high
as ~ 8% while bitumen deri~d fromimported
crude the quantity of paraffin is below 4.5% at par
with the international standards..
The relationship between constitution and
rheology-Rheology is the science of deformation
and flow of matter. A body is said to be deformed
when application of appropriate loading system
alters its shape and size. Considerable evidence2829
exists that the stress versus strain characteristics of
the material comprising the structural section of
road pavements are stress dependent. Bitumen as
an integral constituent of road pavements, based on
its composition determines the resistance to flow
under various conditions of loading. Systematic
studies involving blending of saturates, aromatics,
resins and asphaltene fractions separated from
bitumen have demonstrated the dependence of
rheology on constituents30-33 By holding
asphaltene content constant, and varying the
concentration of other three fractions, it has been
demonstrated that (i)increasing aromatic content at
a constant saturate to resin ratio has little effect on
rheology, other than a marginal reduction in shear
susceptibility, (ii) maintaining a constant ratio of
resins to aromatics and increasing saturate contents
softens the bitumen and (iii) addition of resins
hardens the bitumen, reduces the penetration index
(PI) and shear susceptibility but increases the
viscosity.
PROCESSES 263
It has also been shown1718 that the rheological
properties of biturilel) depend strongly on the
asphaltene content. At constant temperature the
viscosity of the bitumen increases as the
concentration of the asphaltenes blended into the
parent malthenes is increased. The increase in
viscosity, however, is substantially high~r than.
would be expected if the asphaltenes. were
spherical, non-solvated entities. This' suggests that
the asphaltenes can interact with each other and/or
the solvating medium. Even in a dilute toluene
solution the viscosity increase observed when
increasing the asphaltene content corresponds to a
concentration of non-solvated sphere, some five
times higher than the amount of asphaltene used34
Bitumen asphaltenes are believed to be stacks of
plate - like sheets formed of aromatic/naphthenic
ring structures. The viscosity of a solution, in
particular a dilute solution, depends on the shape
of the asphaltene particles. Size is important only
if shape changes significantly as size increases. At
high temperatures the hydrogen bonds holding the
sheets/stacks together are broken, resulting in a
change in both the size and shape of the
asphaltenes. Dissociation of the asphaltene entities
continues until the limiting moiety, the unit sheet
of condensed aromatic and naphthenic rings, is
reached3s Consequently, viscosity falls as
temperature increases. However, as a hot bitumen
cools, associations between asphaltene occur to
produce extended sheets. These, in turn, interact
with other chemical types present (aromatics and
resins) as well as stacking together to form discrete
asphaltene particles. Thus property relationship of
late has become extremely important with the
introduction of multigrade concept in paving
bitumen as well.
Physico-chemical Methods for the Separation of
Bitumens
Developments in the past two decades in the
field of separation science and advances in
analytical techniques have provided better
understanding of the compositional aspects of the
bitumens.
Fractionation using solvents-The fractionation
of bitumens by selective solvents dates back to
1916. This is based on the pioneering work of
Marcusson36 relating to the differentiation between
264 INDIAN 1. CHEM. TECHNOL., NOVEMBER 1997

native and petroleum bitumens. In the succeeding and dicylic hydrocarbon types over Alcoa grade 'F-
forty years a number of investigators have 20 alumina. Serguienko et al.50 fractionated three
followed methods reported by Abraham37. In 1944 Russian asphaltic oils by first precipitating
Hoiberg and Garris38 described a procedure for the asphaltene with n-pentane. The pentane solution
separation of bitumen into five fractions. Hexane was percolated through silica to remove the resins.
was used to precipitate asphaltenes. This method The mass was washed with petroleum ether to
was found applicable to bitumens varying in remove oils and resins displaced from the silica gel
consistency from road oils to highly air blown by carbon tetrachloride (fraction I), benzene
products. Chelton and Traxler9 fractionated (fraction II), and acetone (fraction III). The total
asphaltenes precipitated by n-pentane by treatment (unfractionated) resins were determined in a
witb increasing amounts of methanol in benzene. separate experiment.
Traxler and Schweyer40 developed a procedure Kleinschmidth51 fractionated air blown bitumens
which gave a three component analysis that proved by adsorbing the n-pentane soluble materials on
useful in classifying bitumens on the basis of their fuller's earth. White oils, dark oils, and asphaltic
colloidal, rheological and physical properties. resins were then removed by washing with n-
Hewett and Faid41 modified the procedure (as pentane, methylene chloride and methyl-ethyl
mentioned by Traxler and Schweyer) by first ketone, successively. Fuchs and Nettescheim52 and
precipitating the asphaltenes with n-pentane from Middleton53 separated different bitumens by
roofing bitumens' and then' fractionating the adsorption of silica gel followed by elution with
pentane soluble material with acetone at -23.3C solvents including benzene and aromatic ketones.
(1l.2F). It is noteworthy to mention here that The study based on 5 bitumens concludes that
throughout the history of studies related to "Efficient fractionation in. elution analysis is
petroleum composition, there has been assured if the composition of the eluent is changed
considerable attention paid to the asphaltic during the fractionation in a smooth, uniform
constituents, i.e., the asphaltenes and resins42 due manner towards a stronger eluent". The principles
to their being responsible for high yields of of forming such gradients have been discussed by
thermal coke and also for shortened catalyst life in Bock and Ling54. Chelton and Traxler9 analyzed
refinery operations43. Although the early studies44.45 three typical vacuum reduced residua and a 50
were primarily focussed on the compositional penetration air blown bitumen from each residuum
behaviour of bitumen, the techniques developed by first precipitating the asphaltenes with n-
for those investigations have provided an excellent pentane. The three residua represented the gel, sol-
means of studying heavy petroleum feed stocks. gel; and sol types bitumens respectively.
Corbett55 described a convenient method for
Adsorption chromatography-In 1932 Poll46 determining bitumen composition based on
developed a method for separation of bitumens fractionation into four generic components. This
into several fractions by first removing the method follow chromatographic separations
asphaltene with light petroleum naphtha then involving elution of each component from an
contacting the pentane solubles (maltenes) with absorbent with solvents of increasing polarity. The
fuller's earth. Hubbard and Stanfield47 used polar nature and adsorption tendency become the
adsorption on anhydrous alumina followed by separation criteria. Based on Corbett method
washing with n-pentane and a methanol-benzene Mullin et al.56 developed mathematical equations
solution to obtain oils and resins, respectively. relating generic components of bitumens obtained
Grader48 used carbon tetrachloride, benzene, and by the above procedure with essential properties.
trichloroethane as the agents for removing Fractionation methods based on electrical
materials from the adsorbents. O'Donne1l49, in his deposition and urea/thiourea adduction 57.58 of
elaborate study of the analysis of bitumen used asphaltics from crude oil are also reported for the
adsorption on silica-gel followed by elution with separation of long, straight chain hydrocarbons
iso-pentane and other solvents. The aromatics were from branched molecules.
dissolved in iso-pentane and separated into mono-

I " t
 SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING
Spectral methods-The successful use of
infrared and ultra violet spectrometry in the study
of chemical compounds and mixtures such as
lubricating oils suggests their applicability to
bitumens and fractions thereof. The ACS
Symposium of April 195959on "Spectroscopy in
the Petroleum Industry" at Ohio presented an
excellent picture of the status and future
possibilities of the various spectroscopic fields.
Most of the investigations considering the
vanadium and nickel porphyrins found in oils and
bitumens have used infrared spectroscopy for
analysis. Knotnerus60used infrared analysis in his
excellent studies of the oxygen containing
functional groups in air blown bitumens. By this
technique he obtained evidence that the
saponifiable matter in the bitumen consists mainly
of ester groups and that acid anhydrides and
ketones were almost entirely absent. Beitchman61
reported "infraredspectra of a number of bitumens
in films 1.5 to 2.0 mm thick. He inferred that, in
general, the less durable bitumens exhibited
stronger hydroxyl absorption than the more
durable ones. Stewart62, after fractionating
weathered and unweathered roofing bitumens by
selective adsorption obtained infrared absorption
spectra of the fractions. His data indicated
differences in the chemical composition of the
bitumen from various sources as well changes in
concentration produced by weathering.
Ultraviolet absorption has been used49to follow
the separation of aromatic compounds found in
bitumen. An exploratory study of the absorption of
the ultraviolet and infrared energy of several
bitumens was made by Schweyer63. He also
investigated the applicability of Beer-Lambert Law
to bitumens dissolved in a mixture of iso octane
and butanol for ultraviolet absorption, and in
carbon tetrachloride as thin films for infrared
absorption. Infrared absorption data were obtained
on 10 fractions separated by thermal diffusion64
from the petrolenes (maltenes) of a paving
bitumen. From these and other values it was
possible to make deductions' concerning
hypothetical structures of different bitumen
fractions. Fischer and Schram65 used infrared
absorption in conjunction with mild hydrogenation
to obtain evidence concerning the structure and'
PROCESSES 265
composition of asphaltenes, resins and oils
separated from bitumens.
Developments in mass spectrometry66-68have
also led to the application of this technique to the
study of molecular structure of oils and heavier
hydrocarbons obtained from Bitumen by various
procedures. Various ;mthors from their studies
concluded that the structural composition of such
molecules are simpler than have been suggested by
most authors. Swaminathan and Swami69used a
photoelectric absorbtiometer to analyze road
building bitumens. On the assumption that
extinction coefficient is constant for a given
wavelength, the authors .found that absorption
characteristics bear no relationship to the usual
physical properties of the bitumen and these can
only be related to the chemical composition of the
constituents of the bitumen. The changes in the
structure of the bitumen as a result of weathering,
over heating, etc., thus can be predicted by this
approach.
Shanxiang70.72 based on the assumption of equal
degree of substitution or equal number of
substituents on an aromatic ring estimated the
aromatic ring distribution of bitumen by. proton
NMR spectroscopy. He also estimated aromatic
carbons in bitumens and developed an improved
method for characterizing saturated carbons,
including naphthenic internal carbons, methyl and
alkyl substituted naphthenic carbons etc. Strausz73
detected new classes of compounds appearing as
homologous series in bitumen using combination
of instrumental and chemical methods like NMR,
IR and potentiometric titration. Sadeghf4
characterized fractions of bitumen based on
polarity by using elemental analysis and FTIR and
IH NMR spectroscopy by the modified Brown-
Ladner equations as well as the 5-regions method.
Phillip75 also characterized corbett fractions of
bitumens by FTIR and NMR spectroscopic
methods. Very recently Shanxiang76established a
complete system for estimating concentrations of
structural groups and parameters of bitumen from
NMR spectra and paraffinic chain distribution
obtained by selective oxidation of the protonated
carbons in aromatics. Zho et al.77 analyzed
paraffinic wax fraction in bitumen by Differential
Scanning Calorimetry (DSC) methods. Qian and
Hsu78,79studied the use of on-line LC/MS
 266 INDIAN 1. CHEM. TECHNOL., NOVEMBER
combined with low voltage electron impact
ionization (LV-En medium resolution mass
spectrometry (MR-MS) and advanced analytical
data handling system to provide in depth molecular
level characterization of high boiling petroleum
and synthetic fuel fractions: This approach is
expected to be very useful in understanding the
chemistry of bitumen in the coming years.
Smith and Patterson80 used gas chromatography
to determine the Henry's Law constants and
infinite dilution activity coefficients for
hydrocarbons and other vapour phase solutes in
two bitumens. They discussed its use for
components with widely varying molar masses and
of parameters (measuring solvent/solute
interaction energies) as is used in polymer systems.
Mitera81 reported a quantitative mas~ spectrometric
determination of petroleum asphaltenes and lactum
oliogomers. Equations for calculating the average
molecular weight of the compounds studied were
presented. Sebor et al.82 characterized metal-
loporphyrins in bitumen and asphaltene fractions
of a Russian crude oil by mass spectrometry.
Brule83 determined the molecular size of bitumens,
asphaltenes and maltenes using Gel permeation
chromatography. He found that there was usually a
linear relationship between the molecular size
distribution coefficient and maximum molecular
size. Selueky et al.84 used gel permeation and other
chromatographic means to separate asphaltenes
and resins from Athabasca bitumen. Kozlova et
al.85 reported an absorption
spectroscopic method
for the rapid quantitative determination of
petroleum bitumen group compounds in solution.
The method is based on individual luminescence
characteristics of light, middle, and heavy aromatic
hydrocarbons, resins, and asphaltenes. Paukku and
coworkers86 reported polar components of
asphaltenes-resinous substances of petroleum with
metals (Fe, Ti or V) of variable valence.
Khu1be et al.87.88 employed ESR (Electron Spin
Resonance) to determine free radical concentration
and their formation in Athabasca bitumens. Studies
on the effect of solvents (C02, polar and non-polar
solvents) and heating rates provided information
on free radical formation. Interactions of bitumen
with CO2 are important in petroleum reservoir
engineering. ESR was also used to study the
possible mechanism of bitumen oxidation with
,,:1 I. H I
1997
oxygen or ppotoexcited oxygen89 Charge-transfer
complexes were presented as the reaction pathway
for the oxidation of bitumens. The method
elucidates the oxidative reaction chemistry of
sulfur and nitrogen species. Also, the effect of the
addition of charge-transfer deactivating chemicals
was related to bitumen's physical properties.
Smiljanic et al.90 reported aging studies on pave
roads by characterization of asphalts, extracted
from the wearing coarse of the Belgrade highway.
Stefanova et al.91 predicted paving grade bitumen
performance by a triangular diagram. They
concluded that it is possible to judge the
characteristics for producing paving grade bitumen
of a given quality.
Manufacture of Bitumen
Bitumen production - early attempts
Production of bitumen from petroleum
developed slowly during the years immediately
preceding and following the advent of the
twentieth century. In the beginning, heavy residues
from the distillation of almost any crude oil were
used to soften the relatively hard native bitumens92
It soon became evident that residues from the
paraffin oils were not suitable. Thus, when
available, the heavy viscous bottoms from the
distillation of asphaltic and semi-asphaltic oils
were used. The refiners begin to distill asphaltic
oils to harder residues, some times obtaining good
bitumens, some time inferior ones. Applications
other than road building were found for the hard
bitumens. Roofing and water proofing developed
as outlets and demanded radical alterations in
manufacturing procedures. Air blowing and
compounding procedures were developed.
Assessment of crude oil for bitumen manufacture
The chemical nature of the crude source has a
profound effect on the composition of bitumen.
Usually bitumens are of two types, i.e., sol and gel
type. In the presence of sufficient quantities of
resins and aromatics of adequate solvating power
the asphaltenes are fully peptised, and the resulting
micelles have good mobility within the bitumen.
These are known as 'sol' types bitumen93 If the
aromatic/resin fraction is not present in sufficient
quantity to peptise the micelles, or has insufficient
solvating power, the asphaltenes can associate
'"'' I" I
 SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING
further together. This can lead to an irregular open
packed structure of linked micelles, in which the
internal voids are filled with an intermiceller fluid
of mixed constitution. These bitumens are known
as 'gel' type bitumens. Some crude oils yield
bitumen having essentially sol characteristics.
Other may give bitumens with such pronounced
gel properties that they are unsuitable for road
building purposes, though useful for other
applications94. When evaluating any new asphaltic
or semi asphaltic crude it is necessary to determine
the amount of bitumen that can be obtained on a
volume and weight basis. A laboratory run usually
is made to determine the amount present of
bitumen of an established consistency, e.g., 100
penetration at 25C. If a reasonable amount of
quality bitumen (around 10%) is available further
work is carried out to establish the commercial
feasibility including the use of other light products.
In fact Institut of Francais Du Petrole (IFP) has
proposed a procedure how to select crude for
asphalt (bitumen) making - based on various
physico-chemical characteristics9s. Stanfield96 has
presented in detail a procedure for evaluating an
asphaltic crude oil in the laboratory. Operating
procedures for atmospheric and vacuum
distillation, standard tests, and results on 12
different crudes are given in detail.
Indian Institute of Petroleum (IIP)97-IOO has also
done considerable work on this subject as
technological support to industry. Over 30
imported and indigenous crudes have been
evaluated for their bitumen yields and quality.
The refinery helps to manufacture bitumen from
the particular crude. If a few grades of road
building bitumen best fit the manufacturing and
marketing facilities of the refinery, the problem is
fairly simple. The required grades of bitumen are
selected from the evaluation run and the properties
are compared with the specifications established
by the purchaser or qualifying organisations. If the
manufacturing and sales departments are interested
in the handling of roofing bitumens and wide range
of speciality product, the evaluation becomes quite
involved and expensive. For full scale evaluation,
it may be necessary to start with one or two barrels
of crude oil in order to that adequate residua of
different viscosities may be obtained for use as
blending and air blowing stocks. It is therefore,
PROCESSES 267
evident that the complete evaluation of crude oil as
a suitable source for a wide variety of asphaltic
material is a tedious and expensive procedure1ol. It
also require skill and experience for proper
interpretation of the results obtained. Even, afler a
favourable evaluation is completed, an
experimental plant run is sometimes advisable
since difficulties not apparent in the small scale
laboratory or pilot plant operations may appear in
commercial manufacture.
Bitumen manufacturing practices
Bitumen from vacuum distillation-Various
types of equipments have been used to fractionate
asphaltic-base petroleums, but the vertical stilI is
universally used today. The modem unit is a
precise tool made up of integrated units plus their
auxiliary service facilities. The crude oil is
pumped, preferably after desalting (to control
bituminous electrical properties and water
absorbing tendency), through a furnace in wltich
the oil is heated to about 315C (600Df) and then
injected into the atmospheric section of the still to
flash off the lower boiling point products. The
heavy oil at the bottom of the atmospheric tower
goes to the vacuum section of the still, at a
temperature of about 357-400C (675-750Df),
where a vacuum of 10 to 150 mm of mercury is
maintained, depending on the type of crude being
processed. Low pressure makes it possible to
vapourize the heavier oils without over heating the
residuumlo2-104.The consistency of the asphaltic
residuum at the bottom of the vacuum tower
depends upon (a) the nature of the oil (b) rate at
which it enters the distillation unit, (c) temperature
at which it enters and progresses through the still,
(d) pressure in the vacuum section, and (e) rate at
which the residuum leaves the unit. GaglelO4 has
supplied a succinct review of the design and
operation of an asphaltlbitumen plant. He gave
flow sketches for atmospheric and vacuum
distillation, high vacuum distillation, and propane
deasphalting units. A modernized bitumen plant
was described by PruesslOS.
Air blowing operation (non-catalytic blowing)-
Some heavy crudes give vacuum residues which
can be used directly in the manufacture of paving
bitumen. In many refinery situations, however, this
268 INDIAN J. CHEM. TECHNOL., NOVEMBER
is not an acceptable route as the use of such crudes
could have an adverse effect on mainline refinery
products. For instance, many of these crudes are
waxy, or have high sulphur contents, or do not
yield the required amounts of main refinery
products using the existing refinery process plants.
Other. crudes, which are better su'ited for the
production of main refinery products, give vacuum
residues which are unsuitable for direct use in
bitumen manufacture. For example, the viscosity
of the vacuum residue could be too low for
bitumen production. Air blowing of such feed
stocks enables acceptable bitumens to be made
from these crudes provided that care is taken to
select the correct residue length (cut point). In
some cases it is also possible to include surplus
refinery components (fluxes) in the feed stock
intended for air blowing as this can provide a
valuable method of disposing off such stocks.
Industrial grade bitumen, which have high
softening points, can also be made using the
bitumen blowing process. By selecting the
appropriate feed stock for blowing it is possible to
prepare a wide variety of industrial grade
bitumens, with differing penetration values for a
given softening point, to meet specific industrial
useslO6.
References to early experimental work on
oxidation (air blowing) of asphaltic oils are well
documented by Abraham107.The continuous type
of converter come into use during mid 30'SI08.It
usually comprises a series of two or more vertical
vessels. Hot residuum enters and finished bitumen
leaves the system at the same rate. The rate of flow
regulates the time of contact between the air and
hot oil. Longer type of contact and an increased air
flow rate yields a bitumen possessing higher
consistency. Continuous converters are flexible
and economical in operation and require a
minimum of time to reduce a ton of residuum to
bitumen of the desired consistency.
Mechanical agitation of liquid air mixture
reduces the time required to air blow a bitumen to
a particular consistency. Laboratory studies on
mechanical mixing were reported by Rescorla et
al.I09 Pilot plant experiments have been conducted
by others, and it appears that a high power input
per barrel of bitumen is required to increase
materially the rate of oxidation 110.The air blowing
i NI I
I I II "I II 'I" II 11'1 11'1
1997
is exothermic in nature. lbe amount of heat
liberated varies with the chemical nature source of t
the stock, extent of the oxidation, and temperature r
at which the oxidation is conducted. Crammer II1
proposed injecting water into the vapour sPllce
above the bitumen to control the temperature. The
effects of temperature, air rate, pressure, and liquid
level in the converter on the rate of reaction and
properties of the air blown bitumen were
determined in pilot plant studies by Chelton,
Traxler and Rombergll2.
A typical106flow diagram of a conventional
bitumen manufacturing process involving air
blowing step is shown in Fig. 1. In the bitumen
blowing process aromatic compounds present in
the feed stock are oxidised with air under
controlled conditions to produce hydrocarbons of
higher molecular weight (of which those soluble in
toluene and insoluble in n-heptane are called
asphaltenes), with the simultaneous formation of
water vapour. The main effect of this reaction is
that it increases the viscosity of the blown product.
For a given viscosity increase, however, the
asphaltene content increases much more rapidly
during air blowing than would be the case if the
feed stock were vacuum distilled, hence the air
blown product has different rheological properties.
An air blown product is characterised by having a
higher softening point than a bitumen of similar
penetration value obtained from the same crude
source by vacuum reduction. The air blowing thus
correct the deficiency of certain crudes which have
low asphaltene contents and can produce paving
bitumens suitable for use on the road and or in
industrial applications.
Lockwood1\3 and Patwardhan 114have published
studies on kinetics of air blowing. They concluded
that a first-order kinetic analysis describes the air
blowing reaction except at high temperatures and
low air rate. They mentioned that such an analysis
"gives a middle-of-the-road basis for pilot plant
design and control of operations". Many
patentsI15.116have been taken dealing with the
oxidation kinetics of bitumens.
Catalytic air blowing-The aim of air blowing
process is to generate asphaltenes. This phenomena
is characterized by three basic reactions namely :
reactions leading to the size increase of the
molecules through the process of oxygen linkage,
I~
I ""11 I" I
 SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING
Blowing Knock out druml
tower cyclone sepGrOtor
Steam -,
Steam
Water
Air
Product
pump
Fig. 1- Conventional bitumen manufacturing process - typical flow diagram
formation of cyclic hydrocarbons by means of
dehydrogenation and reactions during which the
size of the molecules decrease due to dealkylation
of side chains. The net effect of all the above
reactions is change in colloid-chemical
constitution and rheological properties of the
bitumen. In early 50's attempts were reportedl17
involving addition of external agents (catalysts) in
air blowing step of bitumen making. This was done
with a view to accelerate the blowing reactions
(reduction in time cycle), produce bitumen of
greater flexibility at low service temperature and to
increase resistance to flow at high temperatures.
Chlorine has also been investigated118.119 as an
agent for the dehydrogenation and hardening of
bitumen, but the process has not been used
commercially. Bencowitz and Boe120developed a
procedure for incorporating finely powdered
sulphur into bitumen without the generation of
much hydrogen sulphide. Properties of the
resulting mixtures were studied.
Catalytic air blowing process of bitumens most
widely used today is the one patented and
described by Hoiberg121.122 P20S and FeCl3 were
tried as catalysts for accelerating the rate of
oxidation. Later, Shearon and Hoiberg117described
in detail the use of P20S as a modifier in the air
PROCESSES 269
,.
tlc:inerator
S. to incinerator
or fuel
- - - -- _. OependinQon circumstances
Product
cool.
Product to storage
blowing process. Illman and Sommer123patented
the use of mono-, di-, or hexafluoro phosphoric
acid as an aid in producing air blown bitumens
possessing higher penetration indices. Fink et al.124
proposed heating of 80-98 parts asphaltic residuum
with 2-20 parts petrolatum followed by air blowing
in the presence of 0.2 to 2.0% by weight ferric
chloride.
Modern Methods of Making Paving Bitumens
The conventional "blowing operation" however,
has certain limitations with respect to efficient
oxygen utilization, temperature control
management, likely coking, leading to process
interruption and processing of wide variety of
current refinery feed stocks to yield quality
bitumens. All this has resulted in the development
of new generation processes with specified
internals in reactor/convertor and catalytic route to
make quality paving and industrial grade bitumens.
The two most notable developments of the
immediate past are the Biturox Process :
Compositionally controlled chemical processing of
bitumen making by PORNER12S126 and premium
asphalt making process of Petro Canada.
The reactor is key component of Biturox process
as it provides the reaction control to achieve the
 " I

270 INDIAN 1. CHEM. TECHNOL., NOVEMBER 1997

c'hemica1 modification 127. The process IS from the same crude source. The hard asphalt is
economical and represents a significant advance produced in a catalytic asphalt modifier and is
over simply increasing penetration index by blended to specification grade product utilizing the
processes which employ air rectification of short soft asphalt as the cutter stock127 The blending step
residues or fluxed feed stocks. Table 2 reports is accomplished using a programmable in line
comparison of performance properties of blender yielding product to a shipping tank or
conventional bitumen with that of multigrade routed directly to the loading rack (truck, rail, etc.).
product - Mobil bitumen128 The premium asphalt technology has the potential
The catalyst based production technology of to upgrade the residue derived from marginal
Petro Canada for making premium asphalt is still a crudes to the point where minimum asphalt
closely guarded secret. Basically it involves the specifications can often be met. This value-added
following steps: potential has attracted keen attention from refiners
looking for enhanced profitability from residuum.
Premium asphalt is produced by blending.
Table 3 reports comparison of performance
A catalytic polymerization/air oxidation
properties of conventional bitumen with that of
process is used.
premium asphalt.
Hydrocarbon emissions are controlled by
incineration. With the discovery of Bombay High crude in
1976 and earlier availability of Assam crude mix
The blended premium asphalt product is produced for the processing in Indian refineries, there has
from a hard and soft asphalts, usually originating always been an attempt to establish the feasibility

Table 2-Mobil australia - compositionally controlled (multigrade) bitumen

Properties
3-0.6
250
160
6.7
297
MA
CA 00
--1.2
9.0
-0.5
50/70
6.0
7.5
CA**
8.0
600
635
35/45
5.5
8.5
4.0
520
C600
3.0
+0.2
255
195
334
-1.4
C320
450
80/100
250
283 9.5
C170
170
-0.7
200
13.1 Asphalt
>700
** CA: Conventional ~.

Table-3-Petro canada-premium asphalt (comparison of properties)

Properties Conventional Premium
36
3572
+0.5
150
100
3092
38
29
+0.1
53
0.0
1034
13124
20
-0.9 Rutting Resistance
2999
1453 Vis. at 60C, Poise
-05
27
TFOT, Vis. at 60C, Poise

Low Temp. Flexibility

PEN 4C, 200 g, 60 S

TFOT PEN 4C, 200g, 60 S

Temperature Susceptibility
TFOTPVN

TFOTPI

I II I
 SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING
of using these crudes in bitumen making in
locations like AOD (laC) refinery at Digboi and
other coastal refineries receiving BH crudel29 The
R&D efforts in this direction met with limited
success due to techno-economic reasons, that
required to eliminate or reduce waxes in feed stock
and upgrade the asphaltene constituents \30. This
situation still needs more R&D efforts to find a
suitable solution. Similar examples also exist in
USA as well, where procedures based on solvent
deasphalting were found to over come such
problems. The most recent advance reported in this
effort is the development of Paratox Process for
making bitumen from waxy crudel3l.
High Performance Bitumens
With the continuing increase in traffic, both in
terms of vehicle numbers, axle weight (upto 22
tonnes in the case of heavy goods vehicles) and
tyre pressures, there is a growing concern within
the r<?adindustry regarding resistance to rutting
(permanent deformation or mechanical stability) of
asphalt mixes and the consequential cost of
building and maintaining the road system132
Due to viscso-elastic behaviour of bitumen in
asphalt mixes permanent deformation (Fig. 2)
develops typically under heavy axle load and at
high pavement service temperatures 133. In short the
above features calls for pavement to be constructed
with high stability of asphalts mixes in order to
preve~t excessive rutting. With the standard and
convention materials the mix design options are
limited : An increase of mechanical stability may
lead to a trade off between the low temperature
mix properties (resistance to cracking and fretting)
or the mix durability- (resistance to aging). For
conventional asphalt mixes in most cases, an
optimum choice has been made in terms of, for
example, bitumen hardness and bitumen content,
giving an adequate balance between pavement
RUTTING( PERMANENT DEFORMATION 1
~-~=-.,
A- RUT DEPTH
'\ SURFACE
RUTTED PAVEMENT
PROFILE
Fig. 2-Rutting in asphalt concrete pavements
PROCESSES 271
rutting and pavement cracking under normal
loading conditions134 With the move towards more
closely specified performance from bituminous
binders, conventional paving grade bitumen may
be upgraded using bitumens obtained from
modified/improved processes.
As stated earlier bitumen is a complex mixture
of chemical compounds (hydrocarbons) in a
complex equilibria, hence the proportion of each
chemical species is critical to performance. This is
shown in Fig. 3. Performance of bitumens (both
paving and industrial) is related to their chemical
composition. This in turn is determined by the
crude source used and the processing scheme used.
Mobil, Shell, Petro-Canada and other US
companies have developed processes by which the
chemical composition and rheology of bitumen
may be controlled leading to development of high
performance bitumen commonly designated as
multigrade/premium asphalt/super pave
products 127.135. The controlled chemical balance
also ensure that properties such as durability and
adhesion are optimized as well.
Basically the high performance bitumens are
based on Penetration Index (PI), i.e., the higher the
PI, lower is the dependence of rheology on
temperature. These materials have therefore
characteristics of a softer grade at low temperature
and of harder grade at high temperature. They have
a higher penetration at lower temperature and a
higher viscosity at higher temperature than those
of conventional bitumens 132, \36.
Multigrade/premium and super pave bitumens
are all proprietary engineered oil-based bitumen
which exhibits superior rutting and low
temperature cracking resistance, temperature
susceptibility and fatigue resistance as compared to
,I
,I ~ -
I Sol_I
\ phaM
\ '-
'
/
\
/I
Y
,II
Fig. 3-Chemistry - physical property performance relationships
272 INDIAN 1. CHEM. TECHNOL., NOVEMBER 1997

conventional bitumen. All the products are 100%
recyclable and no special handling and mixing
operations are required for during pavement lay-
down, compared to conventional bitumen.
Multigrade bitumens are produced by a technique
of physical and chemical modification that alters
the chemistry and balance of the bituminous
components to a desired optimum. The process
creates those components which have right
chemical balance leading to acceptable road
performance, from those available in the feed
stocks being processed. Premium bitumen process
technology involves the catalytic polymerization
of straight run bitumen using liquid catalysts
supplemented by air-blowing and special in-line
blending techniques137-139.
Polymer modified materials-The literature140,141extreme climatic conditions.
is full with suggestion for using small amount of
non-petroleum compounds for improving the
properties of bitumens. Materials to increase the rubber and bitumen under the trade name "Surfa-
adhesion of bitumen to solid surfaces (stone and
aggregates) have received greatest attention. Next
often mentioned are additives for improving concluded from their field evaluations that the
rheological properties and, especially low
Attempts at improvement of bitumens through
blending with small amount of polymers
particularly rubbers, have been the subject matter
of attention and imagination of great many
workers in both the bitumens and rubber/polymer
fields. The main objective has been to obtain
bituminous binder of improved service
performance level (capable of meeting the
developing needs). Beyond those when
manufactured according to conventional
processing step145,i.e., vacuum distillation, air
blowing or solvent deasphalting. Bahl et al.146
reviewed the bitumen properties modification
using organic polymers. They concluded that
addition of certain organic polymers to bitumen in
small concentration improve their performance,
enhances service life and ability to withstand
Naugautuck Chemical 147,a division of United
States Rubber Company, is marketing a blend of
Sealz". They have made extensive investigations
of the rheological properties of the blends. They
mixture prevent rutting and shoving, and stripping ..

temperature characteristics. Finally, a number of from the aggregate by water, and give increased
materials have been proposed for adjusting the resistance to skidding. The presence of the
colloidal characteristics in order to reduce
polymer in the bitumen also increases the elasticity
syneresis and incompatibility. of the pavement, reduces temperature
Lewis and Welbom142investigated the use of susceptibility and decreases the rate of age
different kinds of powdered rubber (natural and hardening148.Aromatic oils, resins, and pitches
synthetic) in different kinds of bitumen. They have been proposed149as a":ditive for improving
concluded that the properties of the blend depend the physical and rheological properties of
on the kind and quality of rubber used, the nature bitumens. Usually several per cent of such
of bitumen, and the manner in which the blend is materials are required to effect a useful change in
processed. Addition of rubber was found to colloidal properties oftb.e hitllmen.
increase the viscosity and decrease temperature Recent studies '. characterisation of
susceptibility and tendency to flow. Gregg and bitumens-Whiting et al.150 employed use of
Alcoke143studied the effect of rubber in road elemental and functional group analysis for
building bitumens. A flexure-fatigue test was used monitoring compositional changes occurring on air
to evaluate the merits of the various blends. The blowing of a natural asphfilts. The heteroatom
influence of rubber on the brittleness and viscosity content, degree of unsaturarion and functional
of bituminous material was studied by Mason et group composition were found to be related to
al.I44 The blends were subjected to an imposed asphalt durability. Subramanian et al.l5l studied
tensile strain at -17.SoC; stress and strain were compositional studies of bitl:men and bitumen
measured throughout the test. The deformation derived product by gas chromatography. Borrego
characteristics of the bitumens, blends, and et al.152 reported NMR and FTIR spectroscopic
mixtures with sand were measured in a concrete studies of bitumen and shale oil from selected
cylinder viscometer. Spanish oil shales. Results related to composition

ill; H 'II I
 SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING PROCESSES
of bitumen and shale oil suggest that with increase
in maturity the similarity of bitumens and Shale
oils increase. Mojelsky et al.153reported structural
features of Alberta oil sand bitumen and heavy oil
asphaltenes. Rafenomanantsoa et al.154 reported
structural analysis by NMR and FIMS of the tar-
sand of Bemolanga. Huang et al.m reported photo-
oxidation of corbett fractions of asphalt by FTIR
spectroscopy. Bukka et al.156.157 reported the
influence of carboxylic acid content on bitumen
viscosity by FTIR characterization, fractionation
and characterization of Utah tar-sand bitumens by
NMR and IR spectroscopy. The results suggest
that a discrete group of compounds present in polar
fraction of bitumen may have a significant
influence on viscosity and may be of equal, if not
greater importance than the asphaltene content
itself. Quddus et al.158 studied the chemical
composition of catalytic air blown asphalts. They
reported chemical changes during air blowing of
asphalts, in the presence of transition metal salt by
adsorption-desorption chromatography. They
proposed general transformation mechanism.
Recently Huang and Bertholf59 stUdied the
molecular weight distribution of bitumen fractions
obtained by corbett method using Gel permeation
chromatography. Laurent et al.l60 studied
qualitative and quantitative functional
determination in bitumen acidic fractions by 29Si
NMR spectroscopy.
Conclusions
Based on th~ review presented current state of
technology of feed stocks for making quality
bitumen, process technology involved and
relationship between compositional parameters and
performance properties can be summarized as
follows:
1 Bitumen making which was considered to be
a "Black Art" till early 70's has now attained the
status of an important refining process converting
variety of feed stocks to quality paving and
industrial grade bitumens.
2 Advances in 'separation science' and
'instrumental' techniques have enabled improved
understanding of chemical/structural parameters of
bitumen feed stocks, products, and their inter-
relationship with performance properties.
273
3 Although majority of quality paving bitumen
continues to be made from bitumen bearing curdes
but slowly non-bitumen bearing. crudes (having
high wax and low in asphaltenes) are also being
increasingly aC'1eptedas feed stock for bitumen
making through new technological schemes and
processes.
4 There has been deep understanding of science
and chemical engineering principles involved in
the air blowing process of bitumen making. This
has led to the development of: (a) New generation
reactor intemals enabling more efficient utilization
of oxygen and reduction in time duration and (b)
Reaction kinetics involved in air blowing operation
thus linking the feed stock! fluxing component
compositions with operating parameters to obtain
an acceptable balance of hydrocarbon type
combinations, leading to required performance
features.
The studies reported in the subsequent chapters
makes an attempt to confirm some of the reported
findings and presents new' correlations for making
use of non-bearing bitumen crudes as feed stock
for paving bitumens and equations relating
compositional parameter with performance
properties.
Acknowledgements
Authors are thankful to Dr T.S.R. Prasada Rao,
Director, Indian Institute of Petroleum for
encouragements. Our thanks are also due to Shri
Suresh Kothari for typing the manuscript.
References
1 Spielmen, P E, Bituminous Substances (Ernest Benn Ltd,
London), 1925,5.
2 Lucas, L, & Mabbery M, Egypt Arch, 10 (1924) 132.
3 Redwood, B, A Treatise on Petroleum, Charles Griffin
and Co Ltd London, 1922,259.
4 Peckham, S F, Solid Bitumens. Their Physical and
Chemical Properties and Chemical Analysis, (Myron C.
Clark Publishing Co, New York), 1909,312 ..
5 Louis, M, Eisma, E, Hanson, W E, Jackson, A: F &
Schultze, G R, Proc. Fifth World Petroleum Congress,
Sect I, (1959), 1037.
6 Tresanguet, M, Highway Construction 5th ed (Wiley,
New York), 1907,286.
7 Devereux, Roy & Macadam, R, The Clussus of Roads,
(New York University Press, New York), .1936, 89.
8 Telford Thomas, American Highways,XXVI/(1945) 161.
9 Abraham Herbert, Asphalt and Allied Substances, 6th Ed
(Van Nostrand Co, Princeton), 1960, 140..
 274 INDIAN 1. CHEM. TECHNOL., NOVEMBER 1997

10 Prescott W L, History of the Conquest of Peru (Harper, 34 Reerink H, Ind Eng Chem Prod Res Dev, 12(1), (1973)
New York), 1947,92. 123.
II Von Hagen, Victor, Highway of the Sun (Duell, Sloan, 35 Grriffin R L & Miles, T K, J Chem Eng Data, 6 (1961)
and Pearce, New York), 1955, 199. III.
-.,.

12 Page Logan WalJer, Effect of Motor and Horsedrawn 36 Marcusson J Z, A ngew Chem, 29 (1916) 21.
Vehicles on Roads Eng Record, (1910), 251. 37 Abraham H, Asphalt and Allied Substances, 5th Ed (D
13 State of New York, Report of State Commission of Van Nostrand Company, Inc), 2 (1945) 1847.
Highways, (1910), II. 38 Hoiberg A J & Garris, WE, Ind Chem, Am Ed, 16 (1944)
14 Tyagi, B R, Gwasikoti, N P, Srivastava, S P & 294.
Bhatnagar, A.K, Seminar on Bitumenous Roads Design 39 Chelton H M & Traxler R N, Proc Fifth World
and Construction Aspects, IRC, New Delhi, August 25- Petroleum Congress, V (1959) 247.
26 (1994), 1-25. 40 Traxler R N & Schwyer, Chem Rev, 19 (1936) 119.
15 IS:73-1992, Specifications for Paving Bitumen. 41 Hewett C M & Faid R W, I29th Meeting Am Soc Symp
16 Button, J W Little, D N & Gallaway, B.M, Influence of on Bituminous Materials, DalJas, Texas, April (1956).
Asphalt Temperature Susceptibility on Pavement 42 Tissot B P, Ed, Characterization of Heavy Crude Oils
Construction and Performance, National Cooperative and Petroleum Residues, Technip, Paris, (1984) 68.
Highway Research Programme, Report No. 268 and its 43 Speight J G, Ed, In Characterization of Heavy Crude
suppl, 1983. Oils and Petroleum Residues, Technip, Paris, (1984) 32.
17 Sisko, A W & Brunstrum, L C, AAPT, 37 (1968) 448- 44 Koats J A & Speight J G, Fuel, 54 (1975) 179.
475. 45 Speight J G, Ed, The Desulphurisation of Heavy Oils and
18 Kennedy, T W & Harrigan, E T, Performance Based Residua (Marcel Dekker, New York) 1981 84.
Asphalt Specification, the Product of SHRP, Highway 46 Poll H, Petroleum (Berlin), 28-36 (1932) 511.
Research : S~aring the Benefits, Ed J Porter, Proc US 47 Hubbard R L & Stanfield K E, Anal Chem, 20 (1948)
SHRP, Instt of Civil Eng, London (1991). 460.
19 Asphalt Properties and Relationship to Pavement 48 Grader R, Oel u Kohle, 38 (1942) S67.
Performance - Literature Review, SHRP Report No 49 O'Donnell G, Anal Chem, 23 (1951) 894.
A IIR-90-0 15 (1990). 50 Serguienko S R, Davydov B E, Delone I 0
& Teterina,
20 Gloven C J, Davison R R, Button J A & Donaldson, G R, M P, Proc Fourth World Petroleum Congress, 5 (1955)
Transp Res Record, 1170 (1988) 71. 449.
21 Van Gooswi11igen G, de Bats, F Th, & Harrison, T, 51 Kleinschmidth L R, J Res Nat Bur Standards, 54(3)
Quality of Paving Grade Bitumen - A Practical (1955) 163.
Approach in Terms of Functional Tests, Proc of the 4th 52 Fuchs W & Nettescheim, G, Erdol Kohle, 10(1) (1957)
Euro Bitume Symp, Madrid, Oct, (1989) 290. 15.
22 Arya I R, Jain P K, Tyagi B R & Singh, Himmat, 53 Middleton W R, I33rd Meeting Am Chem Soc,
Seminar on Bitumenous Roads Design and Petroleum Division Symposium, San Francisco,
Construction Aspects, IRC, New Delhi, Aug 25-26, California, April (1958).
(1994) I. 54 Bock R M & Ling N, Anal Chem, 26 (1954) 1943.
23 Cerrone R, Proc 15th ARRB Conf, Part 2, (1990) 120. 55 Corbett, L W, Anal Chem, 4I(4} (1969) 576.
24 Sheu E Y, & MulJins 0 C, Asphaltenes Fundamentals 56 Mullin T E & Shortland M D, Hydrocarbon Processing,
and Applications (Plenum Press, New York), 1995, 155. 68(1) (1989) 374.
25 Shukla R S, Proc 2nd Int Conf on Roads and Roads 57 Preckshott G W, Dellisle N G, Cotteh C E & Katz, D L,
Transport, New Delhi, 1 (1995) 503. Trans Am Inst Mining Met Eng Pet Dev Technol, 151
26 Deo J C, & Horta, S, Transp Research Board, 1291, 1, (1943) 188.
National Research Council, Washington, D C, (1991) 58 Csanyi L H & Bassi, B S, Proc Assoc Asphalt Paving
127. Technol, 27 (1958) 52.
27 Jain, P K & Verrnani, N D, Highway Res Bull, 47 (1992) 59 Beerbower A & Nixon, J, Symp Spectroscopy in the
1. Petroleum Industry, Div Pet Chem, ACS, Ohio, April
28 Bahl J S, Singh H & Gulati I B, Feasibility Studies on (1959). '
Production of Quality Bitumens from Assam Crude Mix 60 Knotnerus K J, Ind Eng Chem, 38 (1951) 182.
for Digboi Refinery Expansion Modification, lIP 61 Beitchman B D, J Res Nat Bur Standards, 63A (1959)
Technical Report No 6, 456, June (1993). 189.
29 Shukla R S, Proc 2nd International Conference on 62 Stewart J E, J Res Nat Bur Standards, 58 (1957) 265.
Roads and Roads Transport, New Delhi, I (1995) 562- 63 Schweyer HE, Anal Chem, 30 (1958) 205.
568. 64 Gardner R A, Hardman H F, Jone, A L & Willians, R B,
30 Griffin R L & Miles, T K, J Chem Eng Data, 4 (1959) J Chem Eng Data, 4 (1959) 155.
61. 65 Fischer K A & Schram, A, Proc Fifth World Petroleum
31 ASTM Special Publication : The Influence of Asphalt Congress, V (1959) 259.
Composition on Rheology, (1960) 294. 66 0' Neal M, Hood A, Clerc R J, Andre M L & Hines C K,
32 Yoder E J, Highw Res Board Proc, 36 (1977) 388. Proc Fourth World Petroleum Congress, 5 (1955) 307.
33 Root W H, Highw Res Board Proc, 13 (1933) 339. 67 Levy E J, Appl Spectrosc, 12 (J::l5R) 20.

'I 1_ II I

11f! I ~ 1 'I I
 SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING PROCESSES 275

68 Hood A, Clerc R J & 0' Neal M J, J Inst Pet, 45 (1959) 98 Bah] J S, Gupta U C Singh l-!" & Krishna, R, Feasibility
168. of Making Paving Grade Bitumens from Santhol Crude,
69 Swaminathan C G & Swami S A, J Indian Road Cong, IIP Technical Report (1986) 6492.
'22 (1957) 109. 99 Bahl J S, Gupta U C & Singh H, Rev Inst Fr Pet, 48(2)
70 Shanxiang Lu, Gray M R, Huadong Ligong Daxue (1993) 141.
Xuebao, 20(4) (1994) 501. 100 Bahl J S, Gupta U C & Singh, H, Feasibility of Making
71 Shanxiang Lu & Gray M R, Haudong Ligong Eaxue Bitumens from PD Asphaltics in Combination with
Xuebao, 20(4) (1994) 507-13. Suitable Fluxes, lIP Technical Report (1994) II.
72 Shanxiang Lu & Gray M R, Haudong Ligong Daxue 101 Lowy L, Pet Eng, 29 (1957) 50.
Xuebao, 20(40) (1994) 514-21. 102 Nelson W L, Oil GasJ, 46, 25 25 (1947) 99.
73 Strausz, Otto P, Lown Elizabeth M, Fuel Sci TechnolInt, 103 Khropatyi F R, Neftyanik, 4(12)(1959) 14.
9(3) (1991) 269. 104 Gagle D W, Refining Eng, 30 (3) (1958) C-15.
74 Sadeghi Kazem M, Sadeghi Mohammed Ali & Wu 105 Pruess D B, Refining Eng, 30(11) (1958) C-6.
Wenhui, Fuel, 68(6) (1989)782. 106 Williams I H, BP Bitumen Manufacturing Process, BP
75 Phillip C V, Bullia J A, Glover C J & Davison R R, Prep Ventures (Pvt,Comm ), Britainnic House, Moor Lane,
Div Pet Chem, ACS, 34(2) (1989) 311. London (1986).
76 Shanxiang Lu, Gray M R, Xuobao Shiyou, Jiagong, ]07 AbrahamH, Asphalts and Allied Substances, 5th Ed, D
12(1) (1996) 95. Van Nostrand Company, Inc, New York (1945) 209.
77 Zho Ming, Shen Benzian, Liu Fuying & Fengminke, 108 Holland C J, Pet Eng, 6(8) (1935) 7.
Proc Int Symp Heavy Oil Residue Vpgrading Vtil (1992) 109 RescorIa A R, Forney W E, Blakey A R & Frino M J, Ind
63. Eng Chem, 48(3) (1956) 378.
78 Qian K, Hsu C S, Anal Chem, 64(20) (1992) 2327-33. 110 Dowlen T H, V SPat I, 8, 896 (1932) 380.
79 Hsu C, Quian K, Energy Fuels, 7(2) (1993) 268-72. III Crarnner J M, V SPat, 2, 762 (1956) 758.
80 Smith J & Patterson D, Can J Chem Eng, 70(4) (1992) 112 Chelton H M, Traxler R N & Romberg J W, Ind Eng
818-21. Chem, 51 (1959) 1353.
81 Miter~, J Sb VysSk Chem Technol Praze, Technol Pa/iv, 113 Lockwood D C, Pet Ref, 38 (1959) 197.
D 42 (1980) 149. 114 Patwardhan S R & Khade S B, Ind Eng Chem Process
82 Sebor G, Kubelka V & Weisser 0, Sb Vys Sk Chem Des Dev, 21 (1982) 154.
Technol Prase Technol Pa/iv, D 42 (1980) 213-36. 115 Stratford R K, Can Pat, 343 ~1934)216.
83 Brule B, Bull Liaison Lab Ponts Chausse's (1977) 89- 116 Allen, H L, V S Pat, I (1935) 466.
100. 117 Shearon W H & Hoiberg, A J, Ind Eng Chem, 45 (1953)
84 Se]ueky M L, Kim S S, Skinner F & Strauz, 0 P, Adv 2122.
Chem Ser No, 195 (1981) 83. 118 Sanderson F C, Highw Res Board Bull (1956) 118.
85 Kozlova G G, Shkredova N A & Bolvineva AM, Khim, I 19 Kastens M L, Ind Eng Chem, 40 (1948) 548.
Technol (1985) 85. 120 Bencowitz I & Boe, E S, Proc ASTM, II, 38 (1938) 539.
86 Paukku A, Posadov I A & Lazarev S Y, Wefiekhimiya, 121 HoibergLA J,U Sfatent 2450 (1948) 756.
21(5) (1981) 762. 122 Hoiberg A !' Proc AssocAsphalt Paving Technol, 19
87 Khulbe K C, Mann R S, Lamarche G & Macphee J A, (1950) 225.
Fuel Process Technol, 31(2) (1992) k9 I. 123 IlIman J C & Sommer, H J, V SPat, 2640 (1953) 803.
88 Khulbe K C, Mann R S & Lu B C Y, Fuel, 72(6) (1993) 124 Fink D F, Greger R A & Alsberg, F R, V SPat 2627
898. (1953) 498.
89 Wang I H, Boucher J L, Romine R A & Lei G D, Fuel 125 Presentation of the Biturox Process, Biturox Seminar,
Sci Techno/Int, 11(1) (1993) I. Pomer Engineering Company, Austria, New Delhi
90 Smiljanic Miloran, Stefanovic Jovan & Jovanovic Jovan, (1994).
Erdol Kohle - Erdgas petro chem, 46 (1993) 238. 126 Composition-Controlled Chemical Processing of
9] Stefanova M, Marinov S P & Nikolova K, Erdol und Bitumen, Potner Engineering Co, Austria, AI5W007B
Koh/e-Erdgas petro chem, 48 (1995) 179. Doc (1996) 507.
92 Day A J, Proc Assoc Asphalt Paving Technol, 19 (1950) 127 Wilkinson R, Petroleum Gazette, Australian Institute of
348. Petroleum Ltd, 31 (1996) 4-10.
93 Girdler R B, Constitution of Asphaltenes and Related 128 Holleran G, Presentation for Bitumen Technology
Studies, Proc of AAPT, 34 (1965)A5. Seminar, Compositionally Controlled Bitumen, New
94 Brown Stephen, The Shell Bitumen Hand Book, Shell Delhi, March (1994).
Bitumen, VK, July (1990) 91. 129 Ditrnan J G, Oil GasJ, 72 (1974) 84.
95 Picard P, Tentative de Classification des Petroles bruts, 130 Ditrnan J G, Oil GasJ, 72(2)(1974) 46.
BEICIP Report No 30,538, Paris, Dec (1972) 94. 131 The Biturox-Paratox Application, Pomer Engineering
96 Stanfiled K E, Bureau of Mines, Report of Investigations, Co, Austria, AI4APAA Doc (1996).
(1941) 3568. 132 Jain P K, Gupta, U C & Singh H, Proc 2nd ICORT, New
97 Bahl J S, Gupta U C Singh H & Krishna, R, Feasibility Delhi, I (1995) 545-553.
of Making Paving Grade Bitumens from North Kadi 133 Brown E R, Preprint, New Mexico Paving Conference,
Crudes, IIP Technical Report No 6, Sept (1986) 501. New Mexico (1988) 27.
276 INDIAN 1. CHEM. TECHNOL., NOVEMBER
134 Vander Werff J C, Beverwijk J H & Harrison T, 5th
Eurobitume Congress, Stockhalm, Sweden, June 16-18
(1993) 58.
135 Koole R C, Valkering C P & Lancon D J L, AAPA
Asphalt Conference, Sydney (1991) 39.
136 Singh D V, Indian Highw, May (1995) 37.
137 Faure M & Berthaux J M, 5th Eurobitume Congress,
Stockhalm, Sweden, June (1993) 32.
138 Robertus C, 5th Eurrobitume Congress, Stockhalm,
Sweden, June (1993) 72.
139 Nicholls J C, Assessment of Multiphalte, The Shell
Multigrade Bitumen, Highways Resources Centre,
Transport Research Laboratory, Crowthorne, RGI16AU,
Berkshire (1994) 3-4.
140 Welborn J Y & Babashok J F, Proc Am Chem Soc (Civil
Eng), 84 (1958) 1651.
141 Enders H A, Coleman R J, Pierson R M & Sinclair E A,
Ind Eng Chem, 43 (1951) 334.
142 Lewis R H & Welborn, J Y, Public Roads, 28 (1954) 64.
143 Gregg L E & Alcoke W H, Proc Assoc Asphalt Paving
Technol, 23 (1954)28.
144 Mason P, Thrower E N & Smith L M, J Appl Chem, 7
(1957) 451.
145 Bahl J S & Singh H, Rev L 'Institute Francais du Petrole,
38(3) (1983)413.
146 Bahl J S, Atheya N & Singh H, Erdol und Kohle -
Erdgas Petrochemie, 46 (1993) 22.
j '" ", I' "Il""'I'I II"~
1997
147 Rogge D F, Terrel R L & George A J, Polymer Modified
Hot Mix Asphalt-Oregon Experience, ASTM STP 1108
(1992) 151-157.
148 Nijveld HAW, Dedecker H C & Geesink H A 0 W,
Proc Fourth World Petroleum Congress, VI (1955) I.
149 Garwin L, US Pat, 28222 (1958) 282.
150 Whiting R & Smith C, Analyst, 118 (1993) 947..
151 Subramanian, M, Deo M D & Hanson F V, J Chrom Sci,
34 (1996) 20..
152 Borrego A G, Prado J G & Gullen M D, Energy Fuels,
10 (1996) 77.
153 Mojelsky T W, Ignasiak T M & Strausz 0 P, Energy
Fuels, 6 (1992)83:
154 Rafenomanantsoa A, Nocale D & Lauer J C, Energy
Fuels, 8 (1994) 618.
155 Huang J, Yuro R & RomeoG A, Fuel Sci Technol Int,
13(9) (1995) 1121.
156 Bukka K, Miler J D & Obland A G, Fuel, 73(2) (1994)
257-268.
157 Bukka K, Miller J D & Oblad A G, Energy Fuels, 5
(1991) 333.
158 Quddus M A, Sarwar S N & Khan Fasihullah, Fuel,
74(5) (1995) 684.
159 Huang J & Bertholf D, Fuel Sci Technol Int, 14(8)
(1996) 1037.
160 Laurent M, Hanguet, 0 & Didier M, Energy Fuels, 10(5)
(1996) 1142.
"I
'HI I~ \ 'I I