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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 elaborated on this aspect using road construction
petroleum product used by human being as an history ofPerulOl1
adhesive and water proofing material by the
civilizations along the Euphrates river as early as Bitumen and Highways - Prehistoric
3800 B.CI. It is further believed that soft bitumen In order to form some idea of the reasons why a
'.vas used extensively in the preservation of bituminous material was ever used on a road it is
Egyptian mummies2 as well. Many theories have desirable to very briefly review highway
been advanced concerning origin and formation of conditions prevailing before and after the coming
petroleum and native bitumen3.4. Red Wood's of the automobile. The roads/highways of
suggested that bitumens are of inorganic origin. preautomobile period (around the turn of present
Lucas and Maberry2 however believed in an century) were mainly of stone or gravel, or of such
organic origin of bitumen as later confirmed by other materials as would compact and support the
Peckham4 who showed that bitumen was a product loads transported. Those were demanded by
of distillation. Modem theories are also in favour .farmers, the postal service, and the people living
of the organic origin. outside cities as improved means for travel. The
The use of bitumen for walls and pavement birth of automobile thereafter is considered more
surfaces in ancient days has been well responsible for the development of use of bitumen
authenticated by excavations and inscriptions on than any other agency12.
vases and tablets of different periodss,s. Bitumen base crude oils were plentiful in many
Considerable research has been carried out to southern sections of California, USA and its use
determine whether bitumen was used in any way soon spread to all parts of the west and, as its
on old roads so that one can bridge the enormous beneficial effect became known, to the eastern part
gap in time between its use in ancient days and the of the country. No specifications were then in
present. Little information has come to ~ight, existence. The cutback bitumen had not been
although one reference of considerable interest and developed, and the methods of application were
importance is worth recording. Abraham9 has indeed crude. Engineers therefore, experimented
r ,"*II,l '. ,I , ,.1, " ,

260 INDIAN 1. CHEM. TECHNOL., NOVEMBER 1997

with other types of construction using this performance required under the current and also
promising material. Many references to its under the projected traffic and environmental
successful use can be found in reports of State conditionsl6. The daily and seasonal variations in
Highway Departments13 of USA. In addition to the temperature and traffic loadings besides changes in
use of liquid bitumens for dust elimination, original properties during construction and
numerous experiments were conducted, in many inservice aging makes the task of designer more
states, using mixes of stone and heated bitumen as difficult to select an appropriate binding material.
binders. The processing and placing of road mixes The quality of bitumen is judged'7 by : (i) its
of sand, gravel, or stone were all done by flow properties at different temperatures, (ii)
manually, a method inefficient and costly (A chemical composition, (iii) resistance to change in
practice followed in our country even today). flow properties during inservice aging and climatic
Highway engineers felt need of mechanised system variations. The compositional changes during
to mix bitumen with aggregate, spread and aging and corresponding effect on flow can help
consolidate the mixture to the proper grade and explain serviceability of bituminous roads. Hence,
camber. quality of a bitumen to achieve performance levels
The introduction of cut back bitumen in the required by present and projected traffic loadings
early 1930' s was largely res}Jonsible for the and environmental exposures prevailing in
development of road machines to incorporate practically world over can be controlled by a set of
bitumen with the aggregates. The self operated specifications based on valid relationship between
spreading machine come into general use in the its properties, mix properties and field
early 1930's replacing all hand spreading on major performance 18. Hence, as a result of increased
projects. Further developments of hot mix plants traffic loading conditions, variations in nature of
are probably responsible for the excellent crudes and developed quality consciousness among
performance of sheet bitumen and bituminous highway engineers, recent trends all over the world
concrete pavements than any other mechanical are to move from a simple to performance base
device. The importance of the machinery required specifications'9. Since an approach allows field
and the proper handling of the mix therefore engineers to match materials to desired levels of
assumes great significance as the very success of a pavement serviceability and to tailor the choice of
pavement is largely dependent on the machinery bituminous binder and bitumen - aggregate
used. The percentage of bitumen in the mix as a mixtures to alleviate or minimize specific road
binder usually varies from 3 to 10% as compared distress associated with bitumen characteristics20.
to 90% and above of aggregate depending upon the Besides taking care of key performance factors, the
requirement of traffic and specifications. specifications should also enable the control of (i)
constructability and (ii) safety aspect involved in
'Ill
Bitumen Quality Aspects bituminous road construction.
In view of huge expenditure involved in the A performance based specification may be
construction of new roads and maintenance of the defined 17 as "the limi ts and requirements
existing road network, the quality considerations developed from an extensive data base related to
of bitumen have become a subject ofinterese4. The performance based tests by means of well
bitumen quality varies with the variation in crude established performance prediction models, which
oil source and refining process, which often cause have been validated by correlation within place
considerable' distress to road pavement. Bitumen field performance data". In the 4th Eurobitume
obtained from refineries, though meet the existing Conference held at Madrid, Spain, Shell Research
specifications'5 but do not give required inservice Laboratories Amsterdam presented Qualagon21
performance under the prevailing heavy traffic and concept for performance based specifications. This
environmental conditions thus indicating concept consist of 9 tests that includes 6 tests on
deficiencies in the specifications itself. It is bitumen and 3 tests on bituminous mixtures which
desirable that the specifications should enable the cover the following three key performance
engmeers to select a bitumen on the basis of elements:

, II !.. !I!!:tJlU, !:!"I~:" ,,,.,llJikl,(:I,,j,


KJjlJj'- .llj.
f '''''I'' I "1'111'1 "'I " ,;JL "
SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING PROCESSES 261

Cohesion - Low temperature ductility has evolved an elaborate approach/set .of


Adhesion - Retain Marshall stability specifications22 to be followed at refineries during
Durability - Rolling thin film oven test manufacturing of bitumen and later for
The background philosophy of quality polygon performance during application.
for performance emanates from the fact that by
proper choice of feedstock and processing Relationship between bitumen composition!
conditions, the bitumen may be produced with constitution and performance-Bitumens are
right balance in properties, i.e., visco-elastic materials and their behaviour varies
from purely viscous to elastic, depending upon
A balance in molecular weight distribution. time of loading and temperature. Viscosity of
A balance in chemical composition. paving bitumen therefore plays an important role
A balance in physical properties. during bituminous road construction and
subsequent performance 17. During mixing,
In case the properties of the bitUmenprepared from compaction of bituminous mixes at high service
any crude/feedstock does not fall within the temperatures their properties can be expressed
preferred limits of qualagon they are brought through a stiffuess modules. The field performance
within the area by altering the process conditions. of bitumen is further linked with their chemical
These liinits are however not used as pass/fail compositions in terms of concentration of
criteria. asphaltenes and wax present.
According to Strategic Highway Research Cerrone23 studied the influence of asphaltenes in
Programme IS (SHRP) concept of specifications, it controlling the properties of paving grade bitumen.
should be based on a set of validated relationship With increase in percentage of asphaltenes, there is
between, bitumen properties, mixture properties a substantial change in the bitumen's colloidal
and pavement performance factors that establish structure which tend to assume more and more the
acceptable response to changes during construction configuration of a "Gel" type. At the same time
and inservice aging. SHRP specifications are important properties of bitumen are altered in a
presented in Table 1. It is reported that moisture manner more favourable to their use. The altered
sensitivity and adhesion can be controlled by properties are thermal susceptibility and
specifying limits of strength of the bitumen rheological characteristics in general and the
aggregate bond in blister test. Fatigue cracking can mechanical and elastic properties in particular.
be controlled by specifying limits in repeated Asphaltenes theref6re constitute an important
bending beam test. Details of both the tests are element in estimating the commercial value of
given under SHRP specifications IS. bitumen. It is possible that a bitumen of specified
Summary of specifications representing origin containing small quantity of asphaltene may
American view point is as follows : posses a structure and characteristics which are
Average 7 days maximum pavement more favourable than those of bitumen of another
temperature. type containing a higher percentage of asphaltene
Minimum pavement design temperature. constituents24 Asphalt Institute25, USA opined that
Flash point. chemically asphaltenes are most complex fraction
Maximum viscosity at 135C. of bitumen, they contain largest tendency to
Dynamic shear (G* Sin 8) interact and associate. Indonesian specification25
Physical hardening index. stipulate a range of 15-25% asphaltenes a:;..more
Rolling thin film oven test residue appropriate.
Mass loss In petroleum industry paraffins (wax) is the
Dynamic shear (G*Sin 8). collective name given to a crystalline material with
melting point above 45C that is present in oil
A tripartite group of lIP, IOC R&D Centre and products including bitumen. The melting point of
CRRI has also worked into the prevailing BIS the paraffin increases with the increase in carbon
bitumen specifications1s in our country. The group number of the paraffin chain and decreases when
N
0'\
N

-- Z
-.J G'sin 0, Mitr, 1.0;;:0 - r-
n0 to 0 s:
::c
;;
<
Z
~
tTl 0
t'I1
n
Z
~
\D
tTl
-failure
725
34
0-16
28
-18
22
16
-46
-6
-19
-18
31
-10
22
2810
28
6-16
-28
-24
-34
13
40
-22
-40
-12
-30
25
-16
-36
10
-28
4616
-6
10 .Temp,
-28V Aging
Dynamic
G'sin
PA 0,DC
Performance
Min, kPa
100SHRP
shear,
Grade
2.2
Temp, kPa
....., Test
70
PG-64
64
DC<70
<64
100
PG-7002552
<
-10
52
B-003
Test PG-58 <
Temp
100/(100)
Report 5858 PG-52
90 Table 1- SHRP Binder
Z
1.0
135
230
Specifications22 - 1992 s:
::I::

~
S, Max,stiffness,
Direct
pavement
Creep 300,000
Tension,
strain, Min
design kPa,
SHRP m-value,
1.0%,B-006,
Test C
temperature,
B-002 Original Binder
-

..
.. .. A 1
,.
SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING PROCESSES 263

structural variations are presehe6 The structure It has also been shown1718 that the rheological
(crystallinity and hardness) of paraffin wax, its properties of biturilel) depend strongly on the
molecular weight, and its concentration all affect asphaltene content. At constant temperature the
bitumen performance in two ways : At low road viscosity of the bitumen increases as the
temperature (below 15C)paraffin crystallizes and concentration of the asphaltenes blended into the
bitumen surfacings show sign of distress in the parent malthenes is increased. The increase in
form of fine hair cracks. At high road temperature viscosity, however, is substantially high~r than.
(above 60C) paraffin melts, act as a flux and the would be expected if the asphaltenes. were
bituminous surfacings start bleeding. The presence spherical, non-solvated entities. This' suggests that
of high paraffin content reduces the net bitumen the asphaltenes can interact with each other and/or
content in the surfacings and thus affects its the solvating medium. Even in a dilute toluene
durability. Also presence of high paraffin content solution the viscosity increase observed when
in bitumen posses adhesive problems and affects increasing the asphaltene content corresponds to a
setting characteristics. Wax decreases the concentration of non-solvated sphere, some five
penetration viscosity number (PVN) making times higher than the amount of asphaltene used34
bitumen more susceptible to temperature changes. Bitumen asphaltenes are believed to be stacks of
The bitumen produced from indigenous crudes plate - like sheets formed of aromatic/naphthenic
particularly for special application in Assam region ring structures. The viscosity of a solution, in
at Digboi Refinerl7 contain paraffin wax as high particular a dilute solution, depends on the shape
as ~ 8% while bitumen deri~d fromimported of the asphaltene particles. Size is important only
crude the quantity of paraffin is below 4.5% at par if shape changes significantly as size increases. At
with the international standards.. high temperatures the hydrogen bonds holding the
The relationship between constitution and sheets/stacks together are broken, resulting in a
rheology-Rheology is the science of deformation change in both the size and shape of the
and flow of matter. A body is said to be deformed asphaltenes. Dissociation of the asphaltene entities
when application of appropriate loading system continues until the limiting moiety, the unit sheet
alters its shape and size. Considerable evidence2829 of condensed aromatic and naphthenic rings, is
exists that the stress versus strain characteristics of reached3s Consequently, viscosity falls as
the material comprising the structural section of temperature increases. However, as a hot bitumen
road pavements are stress dependent. Bitumen as cools, associations between asphaltene occur to
an integral constituent of road pavements, based on produce extended sheets. These, in turn, interact
its composition determines the resistance to flow with other chemical types present (aromatics and
under various conditions of loading. Systematic resins) as well as stacking together to form discrete
studies involving blending of saturates, aromatics, asphaltene particles. Thus property relationship of
resins and asphaltene fractions separated from late has become extremely important with the
bitumen have demonstrated the dependence of introduction of multigrade concept in paving
rheology on constituents30-33 By holding bitumen as well.
asphaltene content constant, and varying the
concentration of other three fractions, it has been Physico-chemical Methods for the Separation of
demonstrated that (i)increasing aromatic content at Bitumens
a constant saturate to resin ratio has little effect on Developments in the past two decades in the
rheology, other than a marginal reduction in shear field of separation science and advances in
susceptibility, (ii) maintaining a constant ratio of analytical techniques have provided better
resins to aromatics and increasing saturate contents understanding of the compositional aspects of the
softens the bitumen and (iii) addition of resins bitumens.
hardens the bitumen, reduces the penetration index Fractionation using solvents-The fractionation
(PI) and shear susceptibility but increases the of bitumens by selective solvents dates back to
viscosity. 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 PROCESSES 265

Spectral methods-The successful use of composition of asphaltenes, resins and oils


infrared and ultra violet spectrometry in the study separated from bitumens.
of chemical compounds and mixtures such as Developments in mass spectrometry66-68have
lubricating oils suggests their applicability to also led to the application of this technique to the
bitumens and fractions thereof. The ACS study of molecular structure of oils and heavier
Symposium of April 195959on "Spectroscopy in hydrocarbons obtained from Bitumen by various
the Petroleum Industry" at Ohio presented an procedures. Various ;mthors from their studies
excellent picture of the status and future concluded that the structural composition of such
possibilities of the various spectroscopic fields. molecules are simpler than have been suggested by
Most of the investigations considering the most authors. Swaminathan and Swami69used a
vanadium and nickel porphyrins found in oils and photoelectric absorbtiometer to analyze road
bitumens have used infrared spectroscopy for building bitumens. On the assumption that
analysis. Knotnerus60used infrared analysis in his extinction coefficient is constant for a given
excellent studies of the oxygen containing wavelength, the authors .found that absorption
functional groups in air blown bitumens. By this characteristics bear no relationship to the usual
technique he obtained evidence that the physical properties of the bitumen and these can
saponifiable matter in the bitumen consists mainly only be related to the chemical composition of the
of ester groups and that acid anhydrides and constituents of the bitumen. The changes in the
ketones were almost entirely absent. Beitchman61 structure of the bitumen as a result of weathering,
reported "infraredspectra of a number of bitumens over heating, etc., thus can be predicted by this
in films 1.5 to 2.0 mm thick. He inferred that, in approach.
general, the less durable bitumens exhibited Shanxiang70.72 based on the assumption of equal
stronger hydroxyl absorption than the more degree of substitution or equal number of
durable ones. Stewart62, after fractionating substituents on an aromatic ring estimated the
weathered and unweathered roofing bitumens by aromatic ring distribution of bitumen by. proton
selective adsorption obtained infrared absorption NMR spectroscopy. He also estimated aromatic
spectra of the fractions. His data indicated carbons in bitumens and developed an improved
differences in the chemical composition of the method for characterizing saturated carbons,
bitumen from various sources as well changes in including naphthenic internal carbons, methyl and
concentration produced by weathering. alkyl substituted naphthenic carbons etc. Strausz73
Ultraviolet absorption has been used49to follow detected new classes of compounds appearing as
the separation of aromatic compounds found in homologous series in bitumen using combination
bitumen. An exploratory study of the absorption of of instrumental and chemical methods like NMR,
the ultraviolet and infrared energy of several IR and potentiometric titration. Sadeghf4
bitumens was made by Schweyer63. He also characterized fractions of bitumen based on
investigated the applicability of Beer-Lambert Law polarity by using elemental analysis and FTIR and
to bitumens dissolved in a mixture of iso octane IH NMR spectroscopy by the modified Brown-
and butanol for ultraviolet absorption, and in Ladner equations as well as the 5-regions method.
carbon tetrachloride as thin films for infrared Phillip75 also characterized corbett fractions of
absorption. Infrared absorption data were obtained bitumens by FTIR and NMR spectroscopic
on 10 fractions separated by thermal diffusion64 methods. Very recently Shanxiang76established a
from the petrolenes (maltenes) of a paving complete system for estimating concentrations of
bitumen. From these and other values it was structural groups and parameters of bitumen from
possible to make deductions' concerning NMR spectra and paraffinic chain distribution
hypothetical structures of different bitumen obtained by selective oxidation of the protonated
fractions. Fischer and Schram65 used infrared carbons in aromatics. Zho et al.77 analyzed
absorption in conjunction with mild hydrogenation paraffinic wax fraction in bitumen by Differential
to obtain evidence concerning the structure and' Scanning Calorimetry (DSC) methods. Qian and
Hsu78,79studied the use of on-line LC/MS
266 INDIAN 1. CHEM. TECHNOL., NOVEMBER 1997

combined with low voltage electron impact oxygen or ppotoexcited oxygen89 Charge-transfer
ionization (LV-En medium resolution mass complexes were presented as the reaction pathway
spectrometry (MR-MS) and advanced analytical for the oxidation of bitumens. The method
data handling system to provide in depth molecular elucidates the oxidative reaction chemistry of
level characterization of high boiling petroleum sulfur and nitrogen species. Also, the effect of the
and synthetic fuel fractions: This approach is addition of charge-transfer deactivating chemicals
expected to be very useful in understanding the was related to bitumen's physical properties.
chemistry of bitumen in the coming years. Smiljanic et al.90 reported aging studies on pave
Smith and Patterson80 used gas chromatography roads by characterization of asphalts, extracted
to determine the Henry's Law constants and from the wearing coarse of the Belgrade highway.
infinite dilution activity coefficients for Stefanova et al.91 predicted paving grade bitumen
hydrocarbons and other vapour phase solutes in performance by a triangular diagram. They
two bitumens. They discussed its use for concluded that it is possible to judge the
components with widely varying molar masses and characteristics for producing paving grade bitumen
of parameters (measuring solvent/solute of a given quality.
interaction energies) as is used in polymer systems.
Mitera81 reported a quantitative mas~ spectrometric Manufacture of Bitumen
determination of petroleum asphaltenes and lactum
Bitumen production - early attempts
oliogomers. Equations for calculating the average
molecular weight of the compounds studied were Production of bitumen from petroleum
presented. Sebor et al.82 characterized metal- developed slowly during the years immediately
loporphyrins in bitumen and asphaltene fractions preceding and following the advent of the
twentieth century. In the beginning, heavy residues
of a Russian crude oil by mass spectrometry.
Brule83 determined the molecular size of bitumens, from the distillation of almost any crude oil were
used to soften the relatively hard native bitumens92
asphaltenes and maltenes using Gel permeation
It soon became evident that residues from the
chromatography. He found that there was usually a
linear relationship between the molecular size paraffin oils were not suitable. Thus, when
distribution coefficient and maximum molecular available, the heavy viscous bottoms from the
size. Selueky et al.84 used gel permeation and other distillation of asphaltic and semi-asphaltic oils
chromatographic means to separate asphaltenes were used. The refiners begin to distill asphaltic
and resins from Athabasca bitumen. Kozlova et oils to harder residues, some times obtaining good
al.85 reported an absorption
spectroscopic method bitumens, some time inferior ones. Applications
other than road building were found for the hard
for the rapid quantitative determination of
petroleum bitumen group compounds in solution. bitumens. Roofing and water proofing developed
The method is based on individual luminescence as outlets and demanded radical alterations in
characteristics of light, middle, and heavy aromatic manufacturing procedures. Air blowing and
hydrocarbons, resins, and asphaltenes. Paukku and compounding procedures were developed.
coworkers86 reported polar components of Assessment of crude oil for bitumen manufacture
asphaltenes-resinous substances of petroleum with The chemical nature of the crude source has a
metals (Fe, Ti or V) of variable valence.
profound effect on the composition of bitumen.
Khu1be et al.87.88 employed ESR (Electron Spin
Usually bitumens are of two types, i.e., sol and gel
Resonance) to determine free radical concentration
and their formation in Athabasca bitumens. Studies type. In the presence of sufficient quantities of
resins and aromatics of adequate solvating power
on the effect of solvents (C02, polar and non-polar
the asphaltenes are fully peptised, and the resulting
solvents) and heating rates provided information
on free radical formation. Interactions of bitumen micelles have good mobility within the bitumen.
These are known as 'sol' types bitumen93 If the
with CO2 are important in petroleum reservoir
aromatic/resin fraction is not present in sufficient
engineering. ESR was also used to study the
quantity to peptise the micelles, or has insufficient
possible mechanism of bitumen oxidation with
solvating power, the asphaltenes can associate

,,:1 I. H I
'"'' I" I
SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING PROCESSES 267

further together. This can lead to an irregular open evident that the complete evaluation of crude oil as
packed structure of linked micelles, in which the a suitable source for a wide variety of asphaltic
internal voids are filled with an intermiceller fluid material is a tedious and expensive procedure1ol. It
of mixed constitution. These bitumens are known also require skill and experience for proper
as 'gel' type bitumens. Some crude oils yield interpretation of the results obtained. Even, afler a
bitumen having essentially sol characteristics. favourable evaluation is completed, an
Other may give bitumens with such pronounced experimental plant run is sometimes advisable
gel properties that they are unsuitable for road since difficulties not apparent in the small scale
building purposes, though useful for other laboratory or pilot plant operations may appear in
applications94. When evaluating any new asphaltic commercial manufacture.
or semi asphaltic crude it is necessary to determine
the amount of bitumen that can be obtained on a Bitumen manufacturing practices
volume and weight basis. A laboratory run usually Bitumen from vacuum distillation-Various
is made to determine the amount present of types of equipments have been used to fractionate
bitumen of an established consistency, e.g., 100 asphaltic-base petroleums, but the vertical stilI is
penetration at 25C. If a reasonable amount of universally used today. The modem unit is a
quality bitumen (around 10%) is available further precise tool made up of integrated units plus their
work is carried out to establish the commercial auxiliary service facilities. The crude oil is
feasibility including the use of other light products. pumped, preferably after desalting (to control
In fact Institut of Francais Du Petrole (IFP) has bituminous electrical properties and water
proposed a procedure how to select crude for absorbing tendency), through a furnace in wltich
asphalt (bitumen) making - based on various the oil is heated to about 315C (600Df) and then
physico-chemical characteristics9s. Stanfield96 has injected into the atmospheric section of the still to
presented in detail a procedure for evaluating an flash off the lower boiling point products. The
asphaltic crude oil in the laboratory. Operating heavy oil at the bottom of the atmospheric tower
procedures for atmospheric and vacuum goes to the vacuum section of the still, at a
distillation, standard tests, and results on 12 temperature of about 357-400C (675-750Df),
different crudes are given in detail. where a vacuum of 10 to 150 mm of mercury is
Indian Institute of Petroleum (IIP)97-IOO has also maintained, depending on the type of crude being
done considerable work on this subject as processed. Low pressure makes it possible to
technological support to industry. Over 30 vapourize the heavier oils without over heating the
imported and indigenous crudes have been residuumlo2-104.The consistency of the asphaltic
evaluated for their bitumen yields and quality. residuum at the bottom of the vacuum tower
The refinery helps to manufacture bitumen from depends upon (a) the nature of the oil (b) rate at
the particular crude. If a few grades of road which it enters the distillation unit, (c) temperature
building bitumen best fit the manufacturing and at which it enters and progresses through the still,
marketing facilities of the refinery, the problem is (d) pressure in the vacuum section, and (e) rate at
fairly simple. The required grades of bitumen are which the residuum leaves the unit. GaglelO4 has
selected from the evaluation run and the properties supplied a succinct review of the design and
are compared with the specifications established operation of an asphaltlbitumen plant. He gave
by the purchaser or qualifying organisations. If the flow sketches for atmospheric and vacuum
manufacturing and sales departments are interested distillation, high vacuum distillation, and propane
in the handling of roofing bitumens and wide range deasphalting units. A modernized bitumen plant
of speciality product, the evaluation becomes quite was described by PruesslOS.
involved and expensive. For full scale evaluation,
it may be necessary to start with one or two barrels Air blowing operation (non-catalytic blowing)-
of crude oil in order to that adequate residua of Some heavy crudes give vacuum residues which
different viscosities may be obtained for use as can be used directly in the manufacture of paving
blending and air blowing stocks. It is therefore, bitumen. In many refinery situations, however, this
268 INDIAN J. CHEM. TECHNOL., NOVEMBER 1997

is not an acceptable route as the use of such crudes is exothermic in nature. lbe amount of heat
could have an adverse effect on mainline refinery liberated varies with the chemical nature source of t
products. For instance, many of these crudes are the stock, extent of the oxidation, and temperature r
waxy, or have high sulphur contents, or do not at which the oxidation is conducted. Crammer II1
yield the required amounts of main refinery proposed injecting water into the vapour sPllce
products using the existing refinery process plants. above the bitumen to control the temperature. The
Other. crudes, which are better su'ited for the effects of temperature, air rate, pressure, and liquid
production of main refinery products, give vacuum level in the converter on the rate of reaction and
residues which are unsuitable for direct use in properties of the air blown bitumen were
bitumen manufacture. For example, the viscosity determined in pilot plant studies by Chelton,
of the vacuum residue could be too low for Traxler and Rombergll2.
bitumen production. Air blowing of such feed A typical106flow diagram of a conventional
stocks enables acceptable bitumens to be made bitumen manufacturing process involving air
from these crudes provided that care is taken to blowing step is shown in Fig. 1. In the bitumen
select the correct residue length (cut point). In blowing process aromatic compounds present in
some cases it is also possible to include surplus the feed stock are oxidised with air under
refinery components (fluxes) in the feed stock controlled conditions to produce hydrocarbons of
intended for air blowing as this can provide a higher molecular weight (of which those soluble in
valuable method of disposing off such stocks. toluene and insoluble in n-heptane are called
Industrial grade bitumen, which have high asphaltenes), with the simultaneous formation of
softening points, can also be made using the water vapour. The main effect of this reaction is
bitumen blowing process. By selecting the that it increases the viscosity of the blown product.
appropriate feed stock for blowing it is possible to For a given viscosity increase, however, the
prepare a wide variety of industrial grade asphaltene content increases much more rapidly
bitumens, with differing penetration values for a during air blowing than would be the case if the
given softening point, to meet specific industrial feed stock were vacuum distilled, hence the air
useslO6. blown product has different rheological properties.
References to early experimental work on An air blown product is characterised by having a
oxidation (air blowing) of asphaltic oils are well higher softening point than a bitumen of similar
documented by Abraham107.The continuous type penetration value obtained from the same crude
of converter come into use during mid 30'SI08.It source by vacuum reduction. The air blowing thus
usually comprises a series of two or more vertical correct the deficiency of certain crudes which have
vessels. Hot residuum enters and finished bitumen low asphaltene contents and can produce paving
leaves the system at the same rate. The rate of flow bitumens suitable for use on the road and or in
regulates the time of contact between the air and industrial applications.
hot oil. Longer type of contact and an increased air Lockwood1\3 and Patwardhan 114have published
flow rate yields a bitumen possessing higher studies on kinetics of air blowing. They concluded
consistency. Continuous converters are flexible that a first-order kinetic analysis describes the air
and economical in operation and require a blowing reaction except at high temperatures and
minimum of time to reduce a ton of residuum to low air rate. They mentioned that such an analysis
bitumen of the desired consistency. "gives a middle-of-the-road basis for pilot plant
Mechanical agitation of liquid air mixture design and control of operations". Many
reduces the time required to air blow a bitumen to patentsI15.116have been taken dealing with the
a particular consistency. Laboratory studies on oxidation kinetics of bitumens.
mechanical mixing were reported by Rescorla et Catalytic air blowing-The aim of air blowing
al.I09 Pilot plant experiments have been conducted process is to generate asphaltenes. This phenomena
by others, and it appears that a high power input is characterized by three basic reactions namely :
per barrel of bitumen is required to increase reactions leading to the size increase of the
materially the rate of oxidation 110.The air blowing molecules through the process of oxygen linkage,

i NI I
I I II "I II 'I" II 11'1 11'1 I~
I ""11 I" I
SINGH & JAIN: BITUMEN QUALITY AND MANUFACTURING PROCESSES 269
,.

Blowing Knock out druml tlc:inerator


tower cyclone sepGrOtor

Steam -,

Steam
Water S. to incinerator
or fuel

- - - -- _. OependinQon circumstances
Air

Product Product
pump cool.
Product to storage

Fig. 1- Conventional bitumen manufacturing process - typical flow diagram

formation of cyclic hydrocarbons by means of blowing process. Illman and Sommer123patented


dehydrogenation and reactions during which the the use of mono-, di-, or hexafluoro phosphoric
size of the molecules decrease due to dealkylation acid as an aid in producing air blown bitumens
of side chains. The net effect of all the above possessing higher penetration indices. Fink et al.124
reactions is change in colloid-chemical proposed heating of 80-98 parts asphaltic residuum
constitution and rheological properties of the with 2-20 parts petrolatum followed by air blowing
bitumen. In early 50's attempts were reportedl17 in the presence of 0.2 to 2.0% by weight ferric
involving addition of external agents (catalysts) in chloride.
air blowing step of bitumen making. This was done
with a view to accelerate the blowing reactions Modern Methods of Making Paving Bitumens
(reduction in time cycle), produce bitumen of The conventional "blowing operation" however,
greater flexibility at low service temperature and to has certain limitations with respect to efficient
increase resistance to flow at high temperatures. oxygen utilization, temperature control
Chlorine has also been investigated118.119 as an management, likely coking, leading to process
agent for the dehydrogenation and hardening of interruption and processing of wide variety of
bitumen, but the process has not been used current refinery feed stocks to yield quality
commercially. Bencowitz and Boe120developed a bitumens. All this has resulted in the development
procedure for incorporating finely powdered of new generation processes with specified
sulphur into bitumen without the generation of internals in reactor/convertor and catalytic route to
much hydrogen sulphide. Properties of the make quality paving and industrial grade bitumens.
resulting mixtures were studied. The two most notable developments of the
Catalytic air blowing process of bitumens most immediate past are the Biturox Process :
widely used today is the one patented and Compositionally controlled chemical processing of
described by Hoiberg121.122 P20S and FeCl3 were bitumen making by PORNER12S126 and premium
tried as catalysts for accelerating the rate of asphalt making process of Petro Canada.
oxidation. Later, Shearon and Hoiberg117described The reactor is key component of Biturox process
in detail the use of P20S as a modifier in the air 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 PROCESSES 271

of using these crudes in bitumen making in rutting and pavement cracking under normal
locations like AOD (laC) refinery at Digboi and loading conditions134 With the move towards more
other coastal refineries receiving BH crudel29 The closely specified performance from bituminous
R&D efforts in this direction met with limited binders, conventional paving grade bitumen may
success due to techno-economic reasons, that be upgraded using bitumens obtained from
required to eliminate or reduce waxes in feed stock modified/improved processes.
and upgrade the asphaltene constituents \30. This As stated earlier bitumen is a complex mixture
situation still needs more R&D efforts to find a of chemical compounds (hydrocarbons) in a
suitable solution. Similar examples also exist in complex equilibria, hence the proportion of each
USA as well, where procedures based on solvent chemical species is critical to performance. This is
deasphalting were found to over come such shown in Fig. 3. Performance of bitumens (both
problems. The most recent advance reported in this paving and industrial) is related to their chemical
effort is the development of Paratox Process for composition. This in turn is determined by the
making bitumen from waxy crudel3l. crude source used and the processing scheme used.
Mobil, Shell, Petro-Canada and other US
High Performance Bitumens companies have developed processes by which the
With the continuing increase in traffic, both in chemical composition and rheology of bitumen
terms of vehicle numbers, axle weight (upto 22 may be controlled leading to development of high
tonnes in the case of heavy goods vehicles) and performance bitumen commonly designated as
tyre pressures, there is a growing concern within multigrade/premium asphalt/super pave
the r<?adindustry regarding resistance to rutting products 127.135. The controlled chemical balance
(permanent deformation or mechanical stability) of also ensure that properties such as durability and
asphalt mixes and the consequential cost of adhesion are optimized as well.
building and maintaining the road system132 Basically the high performance bitumens are
Due to viscso-elastic behaviour of bitumen in based on Penetration Index (PI), i.e., the higher the
asphalt mixes permanent deformation (Fig. 2) PI, lower is the dependence of rheology on
develops typically under heavy axle load and at temperature. These materials have therefore
high pavement service temperatures 133. In short the characteristics of a softer grade at low temperature
above features calls for pavement to be constructed and of harder grade at high temperature. They have
with high stability of asphalts mixes in order to a higher penetration at lower temperature and a
preve~t excessive rutting. With the standard and higher viscosity at higher temperature than those
convention materials the mix design options are of conventional bitumens 132, \36.
limited : An increase of mechanical stability may Multigrade/premium and super pave bitumens
lead to a trade off between the low temperature are all proprietary engineered oil-based bitumen
mix properties (resistance to cracking and fretting) which exhibits superior rutting and low
or the mix durability- (resistance to aging). For temperature cracking resistance, temperature
conventional asphalt mixes in most cases, an susceptibility and fatigue resistance as compared to
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

,I
~-~=-.,
A- RUT DEPTH
'\ SURFACE
RUTTED PAVEMENT

PROFILE
,I ~ -
I Sol_I
\ phaM
\ '-
'

/
\

/I
Y
,II

Fig. 2-Rutting in asphalt concrete pavements Fig. 3-Chemistry - physical property performance relationships
272 INDIAN 1. CHEM. TECHNOL., NOVEMBER 1997

conventional bitumen. All the products are 100% Attempts at improvement of bitumens through
recyclable and no special handling and mixing blending with small amount of polymers
operations are required for during pavement lay- particularly rubbers, have been the subject matter
down, compared to conventional bitumen. of attention and imagination of great many
Multigrade bitumens are produced by a technique workers in both the bitumens and rubber/polymer
of physical and chemical modification that alters fields. The main objective has been to obtain
the chemistry and balance of the bituminous bituminous binder of improved service
components to a desired optimum. The process performance level (capable of meeting the
creates those components which have right developing needs). Beyond those when
chemical balance leading to acceptable road manufactured according to conventional
performance, from those available in the feed processing step145,i.e., vacuum distillation, air
stocks being processed. Premium bitumen process blowing or solvent deasphalting. Bahl et al.146
technology involves the catalytic polymerization reviewed the bitumen properties modification
of straight run bitumen using liquid catalysts using organic polymers. They concluded that
supplemented by air-blowing and special in-line addition of certain organic polymers to bitumen in
blending techniques137-139. small concentration improve their performance,
enhances service life and ability to withstand
Polymer modified materials-The literature140,141extreme climatic conditions.
is full with suggestion for using small amount of
Naugautuck Chemical 147,a division of United
non-petroleum compounds for improving the
States Rubber Company, is marketing a blend of
properties of bitumens. Materials to increase the rubber and bitumen under the trade name "Surfa-
adhesion of bitumen to solid surfaces (stone and
Sealz". They have made extensive investigations
aggregates) have received greatest attention. Next
of the rheological properties of the blends. They
often mentioned are additives for improving concluded from their field evaluations that the
rheological properties and, especially low
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 273

of bitumen and shale oil suggest that with increase 3 Although majority of quality paving bitumen
in maturity the similarity of bitumens and Shale continues to be made from bitumen bearing curdes
oils increase. Mojelsky et al.153reported structural but slowly non-bitumen bearing. crudes (having
features of Alberta oil sand bitumen and heavy oil high wax and low in asphaltenes) are also being
asphaltenes. Rafenomanantsoa et al.154 reported increasingly aC'1eptedas feed stock for bitumen
structural analysis by NMR and FIMS of the tar- making through new technological schemes and
sand of Bemolanga. Huang et al.m reported photo- processes.
oxidation of corbett fractions of asphalt by FTIR 4 There has been deep understanding of science
spectroscopy. Bukka et al.156.157 reported the and chemical engineering principles involved in
influence of carboxylic acid content on bitumen the air blowing process of bitumen making. This
viscosity by FTIR characterization, fractionation has led to the development of: (a) New generation
and characterization of Utah tar-sand bitumens by reactor intemals enabling more efficient utilization
NMR and IR spectroscopy. The results suggest of oxygen and reduction in time duration and (b)
that a discrete group of compounds present in polar Reaction kinetics involved in air blowing operation
fraction of bitumen may have a significant thus linking the feed stock! fluxing component
influence on viscosity and may be of equal, if not compositions with operating parameters to obtain
greater importance than the asphaltene content an acceptable balance of hydrocarbon type
itself. Quddus et al.158 studied the chemical combinations, leading to required performance
composition of catalytic air blown asphalts. They features.
reported chemical changes during air blowing of The studies reported in the subsequent chapters
asphalts, in the presence of transition metal salt by makes an attempt to confirm some of the reported
adsorption-desorption chromatography. They findings and presents new' correlations for making
proposed general transformation mechanism. use of non-bearing bitumen crudes as feed stock
Recently Huang and Bertholf59 stUdied the for paving bitumens and equations relating
molecular weight distribution of bitumen fractions compositional parameter with performance
obtained by corbett method using Gel permeation properties.
chromatography. Laurent et al.l60 studied
qualitative and quantitative functional Acknowledgements
determination in bitumen acidic fractions by 29Si Authors are thankful to Dr T.S.R. Prasada Rao,
NMR spectroscopy. Director, Indian Institute of Petroleum for
encouragements. Our thanks are also due to Shri
Conclusions
Suresh Kothari for typing the manuscript.
Based on th~ review presented current state of
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'I 1_ II I

11f! I ~ 1 'I I
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