HEAVY OIL UPGRADING BY

SUPERCRITICAL WATER
TREATMENT

By
Deeksha Pandey
M.Tech (Chemical) 1st year
2017CL06
Heavy Oil

 Heavy oil is the highly viscous oil, having density or specific

gravity more than other oil.
 The oil with specific gravity less than 22.3°API is considered as
heavy oil. Besides, they also have higher molecular weight, large
proportion of asphaltenes, large content of heteroatoms such as
sulfur, nitrogen and oxygen compounds and heavy metals including
vanadium, nickel, chromium, iron, etc., but low atomic hydrogen to
carbon ratio.
 The heavy crude oil as well as vacuum residue is considered as
heavy oil.
Heavy Oil Upgrading

 It is the process of improving the quality of oil by

reducing asphaltenes, metals, sulfur, etc. and being able
to get lighter products by conversion of heavier products.
 Different heavy oil upgrading processes are:
 Thermal Cracking
 Catalytic Cracking
 Hydrotreating and Desulfurization
 Hydrocracking
 Delayed coking
Supercritical Fluid

 A supercritical fluid is
any substance at a
temperature and
pressure above it’s
critical point, where
distinct liquid and gas
phase don’t exist. It can
effuse through solid like
a gas and dissolve
materials like a liquid.
Introduction
 ELSEVIER publication in “The Journal Of
Supercritical fluids” from page no 14-24 published in
february 2017.
 Vacuum residue upgrading is been successfully done by
the cracking process under supercritical water conditions
in presence of various metal oxide nanocatalysts, namely
NiO, CuO, ZnO, Co2O3 and Cr2O3 synthesized at
supercritical water.
 The various heavy oil upgrading processes mentioned
before face a major issue named coke formation.
Nevertheless, it is found that the presence of H2 during
hydro-thermal cracking can obviate the coke formation to
some extent.
Introduction

 We use supercritical water because:

 It’s excellence feature to dissolve the organic
components easily and to cause better miscibility
between water and heavy oil.
 The dispersion effect in which heavy organic
molecules can be repeled from each other during the
treatment process in supercritical water.
 It is capable of producing in-situ hydrogen through
hydrocarbons reforming, and/or partial oxidation of
hydrocarbons led from water gas shift reactions
 Experiment

 Materials
 Highly pure zinc (II) nitrate hexahydrate, copper (II)
nitrate trihydrate, nickel (II) nitrate hexahydrate,
chromium (III) nitrate nonahydrate, and cobalt (II)
nitrate hexahydrate used as precursors for catalyst
synthesis in supercritical water.
 N-hexane 99%, toluene, and chloroform used as solvents
after cracking reaction for speciation of maltene,
asphaltene and coke.
 A stock of vacuum residue provided from the bottom of
the vacuum distillation column.
Instruments
 X-ray diffraction (XRD) analysis was conducted by a Philips
X’pert powder with Cu-Kα to study the crystal structure and
composition of the samples.
 Fourier transform infrared spectroscopy (FTIR) of the metal
oxide nanoparticles was recorded using standard KBR disc
technique by a Bruker FTIR model-Vector22.
 Temperature programmed hydrogen reduction was employed
to study catalyst reducibility.
 Gas chromatography – mass spectroscopy was used to study
the maltene content in vacuum residue.
 The NMR spectroscopy of samples were carried out using a
Bruker AVANCE 500 MHz NMR spectrometer.
 Elemental compositions were also determined by using a
CHNS analyzer
Method
 Synthesis of metal oxide nanaoparticles in SCW
 A rigid cylindrical batch reactor was used for nanoparticle
synthesis. As a safety hint, the reactor was merely loaded to
one third of its capacity and was set in a preheated furnace,
which was heated to the desired temperature, i.e. 500 ◦C.
 Elapsing 3 h reaction time, the reactor was then removed
from the furnace and was quickly quenched in cold water.
 The formed nanoparticles inside the reactor were repeatedly
rinsed with distilled water and then all the nanoparticles
were separated from the remnant aqueous solution using a
high speed centrifuge at 14000 rpm for 15 min. Subsequently,
the nanoparticles were washed three times with distilled
water and were then dried at the room temperature.
Method
 Vacuum residue cracking experiment
 By dissolving in the chloroform and then centrifuging at
5000 rpm, all impurities in feedstock (i.e. vacuum residue)
such as coke, ash, etc. whose presence might cause
significant error in experiment result were removed.
 All catalytic and non-catalytic cracking experiments were
carried out in a stainless steel batch reactor with an inner
volume of about 12 ml. All runs were triggered using 500
mg VR and 4 ml distilled water and 100 mg catalyst.
 After purging the remnant air in the reactor by injection
of nitrogen gas into the reactor, the reactor was tightly
capped. An electric furnace, which heated virtually in no
time to high temperatures, was used in the study course
and set to 450 ◦C.
Method
 Vacuum residue cracking experiment
 After spanning reaction time, 60 min, the reaction was
suppressed by disjunction of the reactor from the furnace
and submerging the reactor in a cold-water bath.
 After cracking, the yielded component should be treated
via three steps using three solvents: chloroform, n-hexane
and toluene.
Method
 Vacuum residue cracking experiment
 Asphaltene (coke) = weight of asphaltene (coke) (g)
yield weight of loaded VR (g)
 maltene yield (wt%)=100–(asphaltene yield + coke
yield(wt%))
 H NMR and C NMR analyses give useful information
about the distribution of various carbons, hydrogen,
aromatic rings, and naphthene structures.
Results and discussion
 Catalyst Characteristics
 Using XRD pattern, the average size of sample’s
crystals are measured by the Debye Scherrer formula
as follows: d = 0.089λ
βCosθ
Results and discussion

 Catalyst Characteristics
 Based on our interpretation, the synthesized metal
oxide nanoparticles have good reducibility feature
and can be used in the oxidative reactions in which
catalysts’ lattice oxygen is shared through the
reaction.
Results and discussion
 Vacuum residue cracking
Results and discussion
 Vacuum residue cracking
Results and discussion
 Vacuum residue cracking
Results and discussion
 Vacuum residue cracking
Conclusion

 The effect of the nanocatalysts presence was clear from

the improvement of VR upgrading result and prevention
of coke formation to some extent. The catalytic
performance based on overall effectiveness of
nanocatalysts was found to be ranged in the order of
NiO > Cr2O3 > Co3O4 > ZnO >CuO. The result of GC–
MS, NMR, TGA, and CHNS analyses confirmed that
heavy hydrocarbons converted to the lighter ones in the
final products of non-catalytic and catalytic reactions.
 we came to the conclusion that only NiO could maintain
it’s appropriate performance during SCW cracking
condition.
Thank You