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A review of methods for the demetallization of residual fuel oils

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DOI: 10.1016/j.fuproc.2006.03.001

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 Fuel Processing Technology 87 (2006) 573 – 584
www.elsevier.com/locate/fuproc

Review
A review of methods for the demetallization of residual fuel oils
Mohammad Farhat Ali ⁎, Saeed Abbas
H.E.J. Research Institute of Chemistry, International Center for Chemical, Sciences, University of Karachi, Karachi 75270, Pakistan
Received 25 January 2006; received in revised form 6 March 2006; accepted 8 March 2006

Abstract

Crude oils typically contain trace amounts of metals with vanadium and nickel being the most common. Usually they are in an oil-soluble form
and in conventional refining processes they become concentrated in the residual fuel oil fractions. The deleterious effects of metals in petroleum
have been known for some time. The metals not only contaminate the products, the metal chelates also cause poisoning and fouling of catalyst and
corrode equipments. The metals also tend to form particulate emissions in the sub-micron range. This review presents discussion of methods for
the removal of metals from the heavy oils and residuum fractions. These methods include physical, chemical and catalytic treatment processes.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Demetallization; Petroleum residue; V, Ni porphyrin

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
2. Physical methods — distillation, solvent extraction and filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574
3. Chemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
4. Catalytic hydroprocessing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
5. Metal passivators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 582

1. Introduction
The amount of metals in crude oil usually varies from a few
parts per million to more than 1000 ppm. The metals found are
sodium, potassium, lithium, calcium, strontium, copper, silver,
vanadium, manganese, tin, lead, cobalt, titanium, gold,
chromium and nickel. The metals are usually in combination
with naphthenic acid as soaps and in the form of complex
organometallic compounds such as metalloporphyrins [1–3].
The occurrence of metals in petroleum has been discussed by
several researchers. In fact, these studies are so numerous as to
⁎ Corresponding author. Tel.: +92 3003737481; fax: +92 21 4819018.
E-mail address: mfali2k@yahoo.com (M.F. Ali).
0378-3820/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2006.03.001
be the subject matter of several books and review articles with
references to earlier work [4–15]. These will not be repeated
here, as it is the purpose of this paper to review methods that
have been developed for the demetallization of petroleum as
well as some methods that offer a different perspective to
composition studies.
Among these metals the most abundant and undesirable are
vanadium and nickel. Depending on the origin of crude oil, the
concentration of the vanadium varies from as low as 0.1 ppm to
as high as 1200 ppm, while that of nickel commonly varies from
trace to 150 ppm. Ali et al. [16] studied trace metals in four
market quality Arabian crude oils. The amount of vanadium and
nickel ranged from 2.2 to 57.9 and 0.55 to 16.7 ppm,
respectively. The sulfur contents of these crude oils varied
574 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
from 1.1 to 2.8 wt.%. In another study on the isolation and
characterization of nickel and vanadyl porphyrins in Arabian
Heavy crude residue [535 °C+], Ali et al. [17] reported 189 ppm
of vanadium and 62 ppm of nickel in the residue.
Vanadium and nickel are thought to occur in petroleum in two
forms; porphyrinic and nonporphyrinic. Little is known about the
nature of nonporphyrins. However, the porphyrins have been
extensively studied not only because of their deleterious effects
but also for their considerable role as geochemical markers [17].
Vanadium, nickel and iron are sometimes collectively known as
heavy metals. The heavy metals (Me) in crude oil residue are
agglomerated in asphaltenes in the form of porphyrin compounds
(Fig. 1). The molecular weight of this type of compound varies
between 420 and 520 i.e., from C27N4–C33N4 [18].
The metalloporphyrins were the first compounds claimed to be
of conclusive biological origins. Treibs discovered in the year
1934 that a wide variety of petroleum and bitumen contain
porphyrins [19]. The subject of metal porphyrins in petroleum
was reviewed extensively and published [20–22].
Crude oils containing large proportions of metals are
frequently treated for their removal, as these substances tend
to accumulate in the residuum during distillation and affect its
properties adversely. Some of the organometallic compounds
may also volatilize at refinery distillation temperatures in the
higher-boiling distillates. The presence of metal contaminants in
FCC feeds presents another and potentially more serious
problem because although sulfur can be converted to gaseous
forms which can be readily handled in an FCC unit, the non-
volatile metal contaminants tend to accumulate in the unit and
during the cracking process they are deposited on the catalyst
together with the coke. Because both nickel and vanadium
exhibit dehydrogenation activity, their presence on the catalyst
particles tends to promote dehydrogenation reactions during the
cracking sequence and this result in increased amounts of coke
and light gases at the expense of gasoline production. Vanadium
and nickel seriously affect cracking, when they accumulate on
the particles of the catalyst over time, causing alteration in the
catalyst structure [23]. Also, small amounts of nickel and
vanadium in the charge stocks poison clay and synthetic cata-
lysts. Metals in fuel oils produce ash, when the oil is burned. Ash
deposits in engines result in abrasion of the moving parts of the
engines, and the ash is injurious to the walls of the boilers and
furnaces. Residues are demetallized due to these and several
R'
R'' N R
N Me N and centrifuging the mixture. Thus, a residual oil containing
N 159 ppm V was heated [3°/min to 182–216 °C for 1 h], refluxed
R''
R''' R was not heated.
Fig. 1. Example of porphyrin complex.
more disadvantages of the large concentration of the metals in
the heavy petroleum residue.
The metals in crude oil are usually present in two
combinations [4]:
i. Zinc, titanium, calcium, and magnesium are usually present
in combination with naphthenic acid as soaps.
ii. Vanadium, copper, nickel, and part of the iron are present as
oil soluble porphyrin-type compounds.
Distillation concentrates the metallic compounds in the
residue. The majority of the metal compounds may be
precipitated along with the asphaltenes by hydrocarbon
solvents. Thus the removal of asphaltenes with n-alkane
reduces the metal content of the oil by up to 95%.
Since the most common metal contaminants are nickel and
vanadium, which are generally present in the form of porphyrins
or asphaltenes and are concentrated in residues, much work has
been devoted to the treatment of crude oil residues for their
removal. Both physical and chemical methods are used. The
physical method is essentially deasphalting. The chemical
method includes thermal processes such as visbreaking and
coking; and chemical treatment. In the deasphalting process, the
lighter oils are physically separated from heavier asphaltenes by
mixing the heavy oil/residue with a very low boiling solvent
such as propane, butane or isobutene. The thermal processes are
basically the reshuffling of the hydrogen distribution in the
residue to produce lighter products containing more hydrogen
while the asphaltenes and metals are removed in the form of
coke or visbreaking residue.
2. Physical methods — distillation, solvent extraction and
filtration
Distillation separates crude oils into fractions according to
boiling point, so that each of the processing units following will
have the feedstock that meet their particular specifications. The
metallic constituents concentrate in the residues.
The short-path distillation of atmospheric residues from
California crude oil at 358 °C removed 98% of metallopetropor-
phyrins. The vapor phase contained metal complexes 92% of
which were metallopetroporphyrins. The hydrotreatment of this
distillate diluted with gas oil in a fixed bed of a low-activity
catalyst removed all the metallopetroporphyrins. The spectro-
scopic analysis of metallopetroporphyrins remaining in the
distillate-gas oil after very mild treatment suggested that they
were degraded to chlorins which were intermediates in either
thermal or catalytic residuum demetallization [24].
Yamada et al. [25] described a method of extraction by heating
the oils to 177–238 °C, refluxing the oils with an organic solvent,
with hexane, and then centrifuged to give a hexanesoluble portion
containing 0 ppm V, vs. 105 ppm when the hexane–oil mixture
The lowering of kinematic viscosity and concentrations of
metals in heavy oils by visbreaking was improved by adding
 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
aqueous ammonia solution to the oil. Thus, visbreaking Melones
crude at 232 °C and 6895 kPa for 260 s with equal weight of water
gave a product with viscosity 410 cP. The removal of Ni, V, and S
in this case was 12%, 13%, and 5%, respectively. When the water
contained also 0.7% ammonia (on crude wt.) the product viscosity
became 180 cP and the removal of Ni, V, and S was 26%, 20%,
and 14%, respectively. The use of ammoniacontaining water
instead of water only decreased coke deposition in the visbreaker
from 0.61% to 0.27% [26].
The extraction methods of deasphalting with liquid hydrocar-
bon or gasses such as propane, butane or isobutene are very
effective and used by refineries for removal of metals from
vacuum residues. In practice, a solvent deasphalting unit asso-
ciated with an oil refinery mixes residual oil produced by a
refinery with a light hydrocarbon solvent in which the asphaltenes
and most of the metals remain insoluble and are removed from the
product stream. Thus, removal of the asphaltenes with n-pentane
reduced the vanadium contents of the residual fuel oil by up to
95% with substantial reductions in the amount of iron and nickel
[27].
Observation of porphyrin–metal complexes in the propane
deasphalted raffinate of a mid-continent crude oil prompted an
intensive investigation of their identities and characteristics.
Chromatographic and solvent-extraction methods were combined
to isolate the complexes. The vanadium and nickel–porphyrin
complexes were identified by spectrophotometric analysis of the
extracts [28].
Ni- and V-containing metalloporphyrins in heavy petroleum
feedstocks were removed by solvent extraction with a solvent
chosen from g-butyrolactone, acetonitrile, phenol, furfural, 2-
pyrrolidone, dimethylformamide, pyridine–water mixtures,
ethylene carbonate, propylene carbonate, ethylene trithiocarbo-
nate, and dimethylsulfoxide: the solvent was regenerated by
contacting it with a highly aromatic oil stream. Solvent
extraction was carried out at 27–93 °C; regeneration was carried
out at b 52 °C lower than the extraction step, suitably with
vacuum gas oils, vacuum residues, and (preferably) catalytic
cracking residues. A heavy Arab vacuum residue [b. 510–
677 °C] was extracted 3 times with sequential portions of 1:2
(wt. ratio) 1-butyrolactone residue, resulting in 97% removal of
vanadium. The choice of solvent depends on a solubility
parameter characterized by certain values of dispersion forces,
dipole-coupled forces, and H-bonding forces. Preferred solvents
are ethylene carbonate, propylene carbonate, ethylene trithio-
carbonate, and dimethylsulfoxide [29].
A petroleum atmospheric residue was deasphalted–demetal-
lated by precipitation with individual n-C5-8 alkanes, petroleum
ether, EtOAc, or BuOAc. EtOAc gave the highest metal (V + Ni)
removal of 89.5 wt.% at a solvent–feed ratio of 8:1. The metals,
particularly V, were concentrated mainly in the asphaltene
precipitate [30].
Treatment of fractions derived from Boscan asphaltenes with
lithiumethylenediamine, with Raney nickel, and electrolysis in
lithium chloride–ethylene diamine effected reduction, desul-
furation, decrease in vanadium and metalloporphyrin contents,
and altered solubilities. Loss in vanadium correlated with loss in
metalloporphyrins [31].
575
In recent years, processes based on membrane technology
that reduce the viscosity, asphaltene content, and the sulfur and
metals content of both heavy oil and residues have been
described. Most of these methods use membranes for the
recovery of solvent from an initial extraction, phase separation,
or dilution step. Only a few reports are available on the direct
use of membranes for the removal of asphaltene, sulfur, and
metals from heavy oil.
Kutowy et al. [32] presented a method of filtration to remove
high molecular weight contaminants and inorganic substances
from aliphatic hydrocarbon liquids by passing through a
membrane system having an outer layer, on the high-pressure
side, of a microporous membrane of an aliphatic hydrocarbon-
swellable, polysulfone compound. The viscosity of the
hydrocarbon liquid was reduced by heating or by mixing with
a solvent to b 600 cP before being contacted with the membrane.
The method was found to be especially suitable for removal of
N, S, Al, Cr, Cu, Ni, V, and asphaltenes from spent diesel,
lubricating oil, crude oil, heavy oils or bitumen.
Arod et al. [33] of Energie Atomique, France, described the
ultrafiltration of a vacuum residue at high temperature [330 °C]
using a ceramic membrane with an average pore diameter of
10 nm. The membrane was operated at a cross-flow velocity of
5.6 m/s and a trans-membrane pressure of 500 kPa. The
asphaltene content of the heavy oil was reduced from 6.3 to
4.1 wt.%. The vanadium content was also reduced (from 195 to
90 ppm) and the permeate flux was reportedly at 667 L/m2 per
day. However the effect of time on-stream and membrane
fouling was not examined, and it is not clear if the permeate flux
was stable during the operation.
Osterhuber [34] of Exxon developed a method for upgrading
heavy oils by solvent dissolution and ultra-filtration at high
pressure. The process is especially suitable for removing trace
metals (mainly Ni and V) and lowering the Conradson Carbon
Residue (CCR) of the resulting oil. The process includes the
steps of diluting the heavy oil with a solvent (such as toluene)
and subjecting the resulting mixture to an ultra-filtration step
using selected membranes. Preferred membranes include those
of modified cellulose and polyvinylidine fluoride, such as
Nuclepore type F. In one of the examples, the author tested the
ultrafiltration of Arabian Heavy vacuum residue mixed with
toluene at a weight ratio of 1:1. The vanadium and nickel
contents of the feed were reduced from 180 and 43 to 25.8 and
7.1 ppm in the permeate fraction.
Duong et al. [35] of the University of British Columbia,
described an ultra-filtration study on Cold Lake heavy oil
using ceramic membranes with average pore diameter of less
than 0.1 μm. The ultra-filtration experiments were carried out
under relatively mild conditions [600 kPa and 110 °C]. The
results showed a significant reduction in density, viscosity, and
Ni and V contents. However, the permeate flux data showed a
strong effect of fouling that significantly reduced the permeate
flux but increased asphaltene retention. Experimental data
showing the effects of membrane pore diameter and cross flow
velocity were interpreted in terms of membrane fouling,
initially by the porerestriction mechanism and later with gel
layer formation.
576 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
3. Chemical methods
The basic chemical concept of demetallization is to
selectively remove the metal from the organic moiety with
minimal conversion of the remaining petroleum. The deme-
tallization of metalloporphyrins by acid is a reversible reaction
and can be represented by the following equation:
PM þ HX±PH þ MX
Treatment of petroleum fractions with sulfuric acid (H2SO4)
has been used commercially for many years. The objective of
this treatment was to remove sulfur, nitrogen, metals and
various hydrocarbon types to improve the quality of products. It
was first employed for refining animal and vegetable oils, and
since the beginning of the petroleum industry, about one
hundred and fifty years ago, sulfuric acid was successfully used
in various purification steps of petroleum products. A number of
patents for the use of sulfuric acid were issued at the very
beginning of the petroleum industry [36–38]. An early
reference to the use of sulfuric acid was made by Marcusson
and Eickmann in 1908, who first precipitated the asphaltenes
from asphaltic materials by treatment of the sample with low
boiling naphtha, followed by fractionation of the naphtha-
soluble material with concentrated sulfuric acid [15].
In the treatment of petroleum residues with sulfuric acid,
some of the acid is almost always reduced to sulfur dioxide.
This sulfur dioxide may also react with some of the unsaturated
hydrocarbons, forming various addition products and thus
complicating still further the nature of the basic reactions. The
basic reactions of sulfuric acid with olefins and substituted
aromatics have been discussed extensively and it is a general
knowledge that the reaction products may be of the type of
sulfones, polysulfones, aromatic sulfonic acids and/or hetero-
polymeric gums. The fact that sulfuric acid reacts with and
promotes reactions of hydrocarbons is a drawback to its use as
an agent for removing metals, sulfur and nitrogen from oil. The
hydrocarbon reactions increase the quantity of acid required and
decrease the yield of fuel products.
Hydrofluoric acid has been found to be the most effective
acid as a demetallization reagent. Metals can be removed (90%)
with a high yield of the liquid fraction (85–90 wt.%).
Hydrochloric, sulfuric, sulfonic, polyphosphoric, hydrobromic,
and other acids also have some activity, particularly in the
presence of hydrocarbon solvents. Unfortunately, acids have a
number of disadvantages, including extensive side reactions and
product contamination [39].
Demetallization of petroleum feedstocks was carried out by
mixing and demulsification of hydrocarbon oils with aqueous
HCl or HNO3 solutions containing a demulsifying agent at 20–
14 °C, which transferred the metal to the aqueous phase.
Demetallization was carried out at pH 2–7, which was
controlled by addition of ammonia water, at a 3–50:100 vol.
ratio of water to hydrocarbon oils, and a 0.3–5:1 molar ratio of
HCl or HNO3 [40].
Kukes and Battiste [41] of Phillips Petroleum used
phosphorus acid (H3PO3) to remove Ni and V from heavy
oils. It is believed that H3PO3 reacts with the metals contained
in the hydrocarbons to form oil insoluble compounds that can be
removed either by filtration, centrifugation, or settling/decan-
tation. The demetallization of Venezuelan Monagas oil (V
content 335 ppm and Ni content 98 ppm) was studied in a stirred
autoclave using variable amounts of phosphorus compounds at
atmospheric pressure and various temperatures for a period of
one hour. After cooling the mixture in the autoclave, it was
passed through a glass filter and analyzed for Ni and V by
atomic absorption spectrometry and plasma emission spectrom-
etry. H3PO3 was more effective in removing Ni and V,
particularly V from heavy oil, than a known demetallizing
agent, phosphoric acid (H3PO4). In the range of 2–4 wt.% acid,
H3PO3 was far superior to H3PO4 in removing Ni and V.
Eidem [42] demonstrated a method for reducing the metals
contents of petroleum feed stock by H3PO4. 250 g sample of
vacuum residue [b. N 538 °C] was stirred and heated under a
nitrogen gas blanket to 150 °C, 1 wt.% aq. H3PO4 was added,
the mixture was blended under nitrogen, and the temperature
gradually raised to ∼ 260 °C; the sample, after 44 min was
separated into maltenes fraction and asphaltenes fraction. The
total contents of Fe, Ni, and V in the maltenes and asphaltenes
fractions of H3PO4 treated residue were b 0.06, 14.5, and 9.70
(vs. 64, 101, and 63.3, respectively in the original residue).
Heavy hydrocarbon feedstocks were demetallized by contact
at 375–450 °C with active carbon that has previously been
treated with a highly acidic oxidizing fluid. Thus, a commercial
active carbon (C) was contacted at 20–25 °C with a solution of
3.3 wt. parts conc. H2SO4 and 1 wt. part conc. HNO3 in a ratio
of 4 cm3 solution/g active C. The temperature rose to ∼130 °C,
and after ∼ 20 min the C was washed free of acid and dried at
140–150 °C. The residual oils from both the atmospheric
distillation and the vacuum flashing of a Gulf Coast crude oil
were combined to give a feedstock containing 33 ppm Ni and
99 ppm V. The feedstock (10 wt. parts) was combined with 1 wt.
part treated active C, and the mixture was heated 5 h at 400 °C.
Upon cooling the product yielded two phases separable by
decantation: a thick dense lower phase (∼ 20 vol.%) and a more
volatile, less-dense, less-viscous upper phase (∼ 80 vol.%). The
upper phase contained ∼ 5 ppm Ni and ∼ 4–5 ppm V. When the
procedure was repeated in the absence of the treated active C,
the upper low-metal-containing phase was reduced in volume to
∼30 vol.% [43].
The concentration of metal contaminants (e.g., Ni and V) in
high-boiling petroleum distillates was reduced by treating an
atmospheric residue in a contacting zone with SO2 or SO2
precursors (e.g., H2SO3) at 93–232 °C for 0.01–5 h. The
treated residue was vacuum distilled and separated into a
distillate [b.p. = 271 °C] having relatively low metals content
and a residue having a relatively high metal content. Thus, an
atmospheric residue was treated with SO2 at 173 °C for 2 h.
After heat soaking, the product vacuum distillate [b. b 312 °C]
had a V content of 1.36 wt. ppm, vs. 1.70 wt. ppm for the
distillate prepared without SO2 treatment [44].
Michlmayr [45] of Chevron Research Co. studied the
upgrading of metal-contaminated oils containing vanadium
and nickel. The oil contained 80 ppm of vanadium, 25 ppm of
 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
nickel, and 4 ppm of iron. The oil stream was subjected to an
extraction with an aqueous solution of ferric or stannic salts
such as ferric or stannic chloride soluble in acidified water. The
aqueous solution was maintained at a pH at least sufficiently
acidic to inhibit precipitation of the agent as hydroxide or basic
salt. The experiments demonstrated the effectiveness of ferric
slats as agents for removing vanadium and nickel. Ferric nitrate
in nitric acid was very effective in the demetallization; however
it caused some increase in the viscosity of the oil, presumably
by promoting the oxidation and/or polymerization of the
unsaturated components of the oil.
Garwood [46] presented a process for the removal of sulfur
by treatment with H2SO4 and the removal of vanadium by
treatment with MgSO4. Residual oil from a storage tank in an
electric generating plant was contacted with 90 wt.% sulfuric
acid at a ratio of 0.005 gallon acid/gallon of oil. The oil feed rate
was 0.5 gallon/min, and the rotational speed of the contact ro-
tor was 7500 rev./min. Total sulfur was reduced from 2.6 to
0.02 wt.%. The desulfurized oil was then treated with 20 wt.%
aqueous solution of magnesium sulfate to remove the sodium
and vanadium compounds. The ratio of solution used was about
one volume of solution per 10 volumes of oil. Vanadium was
reduced from 395 to 24 ppm, and sodium was reduced from 21
to 2 ppm.
Metal salts were removed from crude petroleum and
petroleum fractions by extraction into an aqueous solution
using a demetallization agent and a demulsifying agent. The
feedstock was emulsified at 30–140 °C for 0.5 s to 10 min in
order to transfer the metal to the aqueous phase. The
demetallization agent is a C1-4-fatty acid-containing byproduct
prepared by air oxidation of paraffin waxes. Solvent extraction
was carried out at a 3–50:100 vol. ratio of the water phase
(containing 10–40 wt.% fatty acids) to the hydrocarbon phase,
at a 0.5–10:1 molar ratio of demetallization agent to total Ca2+.
Demulsifying agent was present at a ratio of 1–100 ppm to the
hydrocarbon phase [47].
Greaney and Polini [48] reported a process for demetalliza-
tion of a petroleum stream by contacting a metal-containing
petroleum feed in the presence of an aqueous base selected from
Group IA and IIA hydroxides and carbonates and NH4OH and/
or (NH4)2CO3, an oxygen containing gas, and a phase-transfer
agent at 180 °C for a time sufficient to produce a treated
petroleum feed having a decreased metal content. The method
enhances the value of petroleum feeds that traditionally have
limited use in refineries due to their metals, e.g., Ni and V
contents.
Hurter [49] studied the removal of trace metals and ash
contaminants from vacuum residue or used lubricating oil. The
hydrocarbon stream was treated with an aqueous solution of an
anion capable of reacting with the metal to form water-soluble
salts such as aqueous solutions of ammonium chloride or nitric
acid and NaCl. The reaction between the anion solution and the
contaminated oil was conducted at an elevated temperature,
preferably at or just below the boiling point of water. The ratio
of solution to oil was about 1:9. The ash phase formed was
separated by a centrifuge filter to remove particulate matter with
a specific gravity such that it floated in the oil. A centrifuge
577
filter to remove particulate matter with a specific gravity such
that it floated in the oil separated the ash phase formed. Fe, Ca,
Na, and Al showed maximum reduction for a mixture of
lubricating oil, fuel oil, and lubricating oil sludge.
The use of boron trifluoride ether as a precipitant for as-
phaltenes was studied experimentally [50]. When 2.5% to 4% of
this reagent was mixed with Kuwait crude oil, the reagent
settled with about 8% of the asphaltenes and aromatic
hydrocarbons. The tar layer was then distilled to recover
boron compound. The metal contents of the crude oil was
reduced by about half and the percentage of carbon residue by
about 30%.
Gould [51] described oxidative demetallization of petro-
leum asphaltenes and residua. Cold Lake asphaltenes,
Arabian Heavy asphaltenes and Cold Lake vacuum residuum
were treated with a variety of oxidizing agents. Of these,
reagents such as air at 100 °C and NaOH/air were found to
have no appreciable demetallization activity while oxidants
such as sodium hypochlorite and peroxyacetic acid exhibited
high demetallization activity coupled with the ability to
remove or destroy petroporphyrins. The sodium hypochlorite,
however, was found to suffer from the disadvantage of
causing chlorine incorporation into the feed. This oxidative
demetallization appears to be rather unselective reaction with
both metals and porphyrin removal being proportional to the
amount of oxidant used. Various peroxy acids were found to
be effective.
The demetallization was done by adding 0.5–3 wt.% cumene
hydroperoxide at 80–250 °C to petroleum fractions b. N 250 °C,
which resulted in increased amounts of asphaltenes, containing
93–96% of the initial amount of heavy metals and thus the
remainder of the petroleum fractions for cracking was purified
from catalytic poisons. The increased amounts of asphaltenes
were due to polymerization, polycondensation, and oxidation
caused by cumene hydroperoxide [52].
Ni and V were removed from heavy petroleum oil by
pyrolysis at 182–288 °C in the presence of a hydrogenating
compound containing N rings, and removal of a residue from
the pyrolysis product. Thus, a 20:60 (g) mixture of a vacuum-
distillation residue (288 ppm V) and 1,2,3,4-tetrahydroquino-
line was autoclaved [5 ml/min to 216 °C for 60 min], cooled,
and filtered, 83% of the V was removed [53].
Ni and V were removed from hydrocarbon feedstocks, par-
ticularly heavy residues destined to be hydrocracked, by
blending them with ZnCl2 and TiCl4 [2.0–4.5 lb/bbl (2.0–
4.5 ppb) oil] and treating the resulting mixtures with hydrogen
at approx. 288–482 °C. 70% of the Ni and V contaminants were
converted to oil-insoluble forms with coke formation being
b3 wt.%. Thus, a heavy Iranian residue [b. 262–558 °C; 9 wt.%
C residue; 41 ppm Ni and 126 ppm V] was hydrogenated at
343 °C, 1034–2500 kPa, 2 h residence time, and 7000 rpm
stirring rate in the presence of ZnCl2 [4.2 ppb]. The resulting
products were an oil [b. = 260 °C; yield 96.9 vol.%; containing
11 ppm Ni and 20 ppm V] and a coke product (0.8 wt.%).
Experiments showed that ZnCl2 and TiCl4 were superior to
FeCl3 and AlCl3 as catalysts in demetallating the heavy
residuum [54].
578 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
Strong chlorinating compounds such as Cl2, SOCl2, or inor-
ganic salts like FeCl2, SnCl2, ZnCl2, TiCl4, RuCl3, CrCl3,
COCl2, or their aqueous solutions have been employed for
nickel and vanadium removal from heavy oils. Up to 70% of the
metals are reported to be removed at temperatures ranging from
40 to 300 °C. The metals were converted to insoluble
constituents and removed by filtration. The use of these
reagents, however, results in chlorine and metal incorporation
into the production and, therefore, degrades rather than improves
the quality of the oil (U.S. Patent nos: 4148717, 4043900,
4039432, 3996130, 3483117).
Baird and Bearden [55] used sodamide to desulfurize and
demetallize heavy hydrocarbons at elevated temperatures in the
presence of H2. The salt produced after the reaction was
separated from the desulfurized feedstock by filteration.
Safaniya atmospheric resid was treated with 9.9% sodamide
at 3447.5 kPa and 370 °C, resulting in 68% desulfurization and
77% demetallization. A detailed method for sodamide regen-
eration by electrolysis from the sodium sulfur salt was also
presented. Additionally, recycling for reaction with additional
feed was described. The methods include salt conversion to
sodium polysulfide, nitrate, or chloride and electrolysis thereof.
Another improved process for residual oil treatment with
molten sodium under H2 pressure between 1013 and 2026 kPa
and above 400 °C was studied by Bearden [56]. Sodium
treatment of Safaniya resid reduced sulfur to 0.2% and Ni + V to
less than 1 ppm compared to 3.91 wt.% and 97 ppm in the feed,
respectively.
Myers et al. [57] reported an improved sodium desulfurization
and demetallization process that was developed by a consortium
of three companies comprising Imperial Oil Resources (Esso),
Exxon R&E Company, and AEA Technology. The technology
was used for the treatment of high-sulfur bitumen.
Greaney et al. [58] of Exxon demonstrated a method for
decreasing the metal contents of petroleum streams by forming
a mixture of the petroleum fraction containing these metals and
an essentially aqueous electrolysis medium and passing an
electric current through the mixture at a voltage, pH, and time
sufficient to remove metals such as Fe, Ni, and V from the
stream. The electrochemical cell used in this study was a
commercially available coulometry cell consisting of a mercury
pool cathode, a platinum wire anode, a standard calomel
reference electrode, and a glass stirring paddle. One of the
examples in the patent discusses the electro-demetallization of
Arabian Light atmospheric residue having an API of 14 degrees.
A sample weighing 1.7 g of this residue was mixed with 10 ml
toluene and added to an aqueous solution of 40 wt.% tetra-butyl
ammonium hydroxide (20 ml) placed in the electrochemical
cell. The solution was purged under nitrogen [1 atm
(101.33 kPa)]. The applied potential was set at ∼ 2.5 V and
the solution was stirred. After 18 h, the stirring was stopped and
the aqueous/residue mixture was allowed to separate. The
toluene was evaporated and the treated residue was analyzed for
vanadium, nickel, and iron, which showed removal of 53%,
50%, and 65%, respectively.
V and Ni were removed from heavy oils and other
hydrocarbon feeds by treatment with red phosphorus (P).
Thus, red P (0.5–5.0 wt.%) added to the feed in the presence of
air or hydrogen for 1 h reacted with Ni and V in the feed at
∼204 °C and 6894.8 kPa to form oil-insoluble compounds that
were removed by physical separation methods. Ni and V were
0–72% and 60–100% removed respectively and the product
contained 100–9000 ppm P [59].
Phosphorus compounds, both organic and inorganic, were
found to be effective for vanadium removal from heavy oils and
residues at temperature in excess of 370 °C. The rate of
demetallization with the phosphorus compounds was found to
depend on the asphaltene. The solubility of the phosphorus
compounds and particularly the steric effects of the group
attached to the phosphorus are very important parameters. The
effectiveness of the additives declined in the following order:
ðROÞ3 PNAr2 PðOÞHNAr3 PNAr3 PONðNH4 Þ2 HPO4
where R = alkyl and Ar = phenyl groups.
The phosphorus compounds were found to be very active
and selective towards vanadium removal from heavy oils either
at elevated temperatures [390–420 °C] or at lower temperatures
[260–370 °C] if most of the asphaltenes were removed. Partial
dissociation of the vanadium compounds from the asphaltenes
was thought to be a limiting step in the chemical demetallization
reactions at elevated temperatures [60]. It was also interesting to
note that whereas the phosphorus compounds are effective at
vanadium removal, the nickel compounds remained almost
unaffected.
Organophosphate esters and light solvents were used to
remove metals from heavy petroleum refining residues. Thus,
99.0% V and 89.8% Ni removal was accomplished from a
Primrose crude residue (b. N 343 °C, containing 116 ppm Ni,
375 ppm V, and 13.9% Ramsbottom C) by hot extraction
[∼ 210 °C, 6205.5 kPa] with n-pentane containing di-methyl
phosphite (0.057:1 agent–oil ratio) [61].
Demetallization tests were carried out with more than 200
chemicals (chelating, methylating, halogen-containing, inor-
ganic oxides, redox, and P-containing) agents for heavy
petroleum crudes oils. P-containing compounds reacted with
V components of asphaltenes forming insoluble products which
can be removed. Thus, treating Monagas pipeline oil with 3%
P4S3 at 400 °C removed 90% V and 18% Ni. The most active
demetallation agents such as inorganic oxides, unfortunately,
produced also a variety of side reactions (e.g., cracking,
polymerization, element incorporation) [60].
Heavy hydrocarbon oils were demetallized by contacting the
feed oils with an aqueous solution containing chelating agent
such as EDTA, N-(hydroxyethyl)ethylenediamido triacetic acid,
N-[2-{bis(carboxymethyl)amino}-ethyl]-N-(2-hydroxyethyl)
glycine, diethylenetriamine pentaacetic acid or its salts. The
aqueous solution was preferably adjusted to a pH of = 2. thus a
vacuum distillation residual oil was treated with a 27% EDTA
aqueous solution (pH 4.5), resulting in the removal of Ca 99%,
Fe 35%, Ni 4% and V 3% [62].
A demetallization method for raw hydrocarbons (e.g., crude
oils) comprised (1) dosing the feed with aqueous solution of a
chelating agent containing phosphate salts, an emulsion breaker,
 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
and solid wetting agents, and (2) applying an electric field for
liquid–liquid separation to effectively remove Na, Ca, Mg, Fe,
etc. metals. Preferred phosphate salt was (NH4)3PO4; emulsion
breakers were AP 221 and BP 2040 [63].
Vanadium (80–92%) was removed from petroleum crude
(0.03 wt.% vanadium) by complexing with 0.001–0.09 mol%
TiCl4, FeCl3, ZnCl2, CuCl2, CuBr2, CuSO4, or AlCl3 at 30–
90 °C for 5–60 min. There was a correlation between the redox
potentials of the ligands and their reactivities [64].
Petroleum residual oil was treated with molten Sn or Sn
alloys [450–600 °C]. The molten Sn or Sn alloys adsorb heavy
metals in the residual oil. Thus, 650 g Sn was melted [500 °C] in
a reactor and into this was sprayed [at 1.6 ml oil/min, with
106 ml min/Ar(g) for 30 min] a residual oil containing V 110,
Ni 33, and S 5 ppm through nozzles at the bottom of the molten
Sn. The product was gas 8.7%, coke 14.8%, oily material
76.5%. The oily material contained V 7 and Ni 3 ppm and the
by-product coke contained V 177 ppm. When Pb was used, the
product was gas 8.4%, oily material 78.4%, and coke 12.9%.
The oily material contained V 27 and Ni 10 ppm and the coke
contained V 600 ppm [65].
Recently, Reynolds [66] suggested various methods for the
pretreatment of heavy oils to remove metals before subjecting
the oils through the high costs processes of hydrogen addition.
Surrogate metal solutions containing the metal bound as
petroporphyrin, or petroporphyrin fractions isolated from
heavy crude oils were treated with a variety of chemical agents,
and then washed with aqueous solutions to remove the metal.
The most effective reagents were found to be maleic acid in
dimethylformamide, montmorillonite in 1-metyl naphthalene
(1-MN), CF3SO3H in 1-MN and FSO3H in 1-MN. A more
detailed examination and effectiveness of low concentrations of
superacids, fluorosulfonic acid, and trifluoromethane sulfonic
acid, as demetallation agents for nickel and vanadium porphyrin
compounds was conducted.
4. Catalytic hydroprocessing
Catalytic hydroprocessing is a hydrogenation process used to
remove compounds containing nitrogen, sulfur, oxygen and/or
metals from liquid petroleum fractions. These compounds
adversely influence equipment and catalysts in the refinery. A
reduction in the amount of metals in the oil is accomplished by
the process of hydrodemetallization (HDM), where the
molecules that contain metals lose these atoms by reactions of
hydrogenation. The products of HDM reactions can accumulate
in the catalyst pores, causing the formation of deposits which
end up obstructing those pores irreversibly, blocking access to
the catalyst sites and leading to a progressive loss of catalytic
activity [67]. Therefore, hydroprocessing units are installed
prior to units for processes such as catalytic reforming and
catalytic cracking so that the expensive catalyst is not
contaminated by untreated feedstock. One of the most practical
and effective methods of feedstock demetallization (especially
for vanadium and nickel) is the use of HDM catalysts. It has
been shown that the most active HDM catalysts are those
prepared from synthetic aluminium oxide or natural aluminium
579
silicate enriched with the oxides of molybdenum, cobalt and
nickel. The natural aluminosilicate activated with sulfuric acid
was found to be best at removing vanadium and nickel [68].
Further, HDM catalysts with very small amounts of oxides of
active metals belonging to sixth and seventh subgroups of the
periodic table of the elements were found to be several times
more effective than the usual hydrodesulfurization catalysts.
The use of model compounds in reaction kinetic studies has
provided valuable insight into the fundamental processes
occurring in resid HDM. The reaction of Ni and V porphyrins
under commercial HDM conditions involves a sequential
mechanism on two distinct types of catalytic sites. The
porphyrins are initially hydrogenated, forming precursor
species which subsequently undergo ring cleavage reactions,
depositing the metal on the catalyst surface:
M  P±M  PH2 Y deposit þ hydrocarbon
where P represents the starting porphyrin. Metal deposition
occurs from the dehydrogenated metalloporphyrin intermediate
(M-PH2). The resulting metal deposition ultimately deactivates
the catalyst through fouling and pore blockage.
Investigation of nonporphyrin metallic compounds has not
been very extensive, and their behavior during HDM are not
known. It is expected that these compounds will behave roughly
the same as porphyrin compounds. There are indications that the
nonporphyrin metallic compounds may cause more severe
problems than the porphyrins.
Catalytic method reported by Wieckowska et al. [69] for the
demetallation of petroleum, petroleum products, and petroleum
refining residues comprised contacting the feed with a SiO2 and/
or Al2O3, or silica gel-adsorbent (pore size 100–1000 Å) activated
with a mineral acid (esp. H2SO4) followed by contacting the feed
with an Fe catalyst at 249–397 °C with simultaneous introduction
of H2 at a flow rate equal to that of the feed. Absorbent-catalyst
was prepared by treating silica gel 100 g with H2SO4 30 g, drying
of the activated silica gel, and combining 1 / 3 of the activated
adsorbent with 2 / 3 volume parts of a catalyst containing Fe2O3.
The activated adsorbent and catalyst were placed in a reactor
followed by feeding heavy petroleum distillate 100 kg containing
V, Ni, and Fe totally 80 ppm. Hydrogen 300 m3 was fed to the
reactor and the temperature was kept at 397 °C. The contact time
was 1.8 × 103 s. The product contained V, Ni, and Fe, 8 ppm in
total amount.
Bowes et al. [70] of Mobil oil described a method to
demetallize and desulfurize residual oils by adding to the oil an
aromatic solvent and contacting the mixture in the presence of
hydrogen with an alumina having an average pore size greater
than about 220 Å. Two samples of Arabian Heavy and Light
resids were mixed with ortho-xylene in ratios of 1:8 and 1:4.
The samples were demetallized and desulfurized by pressuriz-
ing them in an autoclave for one hour at 350 °C and 6890.1 kPa.
Aldridge et al. [71] of Exxon achieved the removal of
metallic contaminants from heavy hydrocarbons using vanadi-
um oxide supported on activated carbon. A schematic of the
process and the effects of process variables were provided in
this patent. Several examples cited in the patent showed
580 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
removal of vanadium and nickel from heavy hydrocarbons such
as a 20–30% cut of Arabian Heavy vacuum resid at 5268 kPa
and 290 °C. The reaction was highly selective with minimal
occurrence of other reactions. Hydrogen consumption was only
50 to 150 scf/bbl (1.416–4.248 m3/bbl). The results showed that
the activity of vanadium removal can be increased by increasing
the percentage of vanadium on the activated carbon support.
Rankel [72] of Mobil oil used activated carbon catalysts to
treat heavy oils in the presence of hydrogen. The main objective
was to reduce the content of nickel and vanadium in the feed-
stock and achieve conversion of the carbon residue for pro-
ducing a lighter oil. An atmospheric resid containing 4.2 wt.%
sulfur, 104 ppm vanadium, and 32 ppm nickel was treated in a
trickle bed micro unit reactor. The trickle bed was charged with
different types of commercially activated carbon catalysts and
operated at 400 °C under hydrogen pressure. The hydrotreating
process typically achieved at least about a 23% reduction of the
original metal content (i.e., Ni and V content) together with
significant reductions in the sulfur content and Conradson Car-
bon Residue.
A process for the hydrotreating of heavy hydrocarbons in
supercritical fluids was demonstrated by Piskorz et al. [73] of
Natural Resources Canada. This single-step process uses
supercritical fluids and activated carbon as a catalyst. Examples
cited include the treatment of Athabasca bitumen (sulfur content
5.44 wt.%, Ni + V 300 ppm) with n-dodecane as a solvent in a
hydrogen atmosphere. Sulfur content was reduced to 1.16%
with complete demetallization. Three runs were performed at
different pressures, all with a 1:1 by mass mixture of bitumen
and n-dodecane as feed; the hydrogen feed ratio was 1220 m3
hydrogen (STP) per m3 of liquid feed. The same weight of
catalyst was used in all tests.
Heavy oil is hydrodesulfurized and demetallized by
treatment in a first stage with hydrogen in the presence of a
catalyst with fine pores, and in a second stage in the presence of
a catalyst with larger pores and a specified pore size dis-
tribution. Thus, second stage treatment of heavy oil containing
53.4 ppm Vover a catalyst containing CoO 4.5%, MoO3 16.0%,
and Al2O3 79.5% with pore vol. 0.525 mL/g and average pore
radius 84 Å removed approximate 60% V, compared with
approximate 40% for a catalyst with pore volume 0.47 mL/g
and average pore radius 35 Å [74].
A Co–Mo catalyst for hydrodesulfurization–hydrodemetal-
lization of petroleum distillation residues is supported on
γ Al2O3 which has been calcined at 871–1093 °C for 0.25–
10 h, to induce the formation of high-temp. δ- or θ-phase Al2O3.
The catalyst has total pore vol. 0.4–0.65 cm3/g and has 10% of
its pore volume in pores with diameter 150–300 Å. Examples of
the preparation of the catalyst from α and γ Al2O3 are given in
[75].
Mobil Oil Corp., USA developed a catalyst for demetallizing
and desulfurizing hydrocarbons. The catalyst contained 1–10
wt.% of an Fe-group metal (Co or Ni) and 5–25 wt.% of a
Group VIB metal as the oxides or sulfides on a calcined [373–
497 °C] support containing 85% Al2O3 (boehmite) and 0.5–7.0
wt.% of a rare earth. At least 60% of the pore volume of the
catalyst was comprised of 80–200 Å pores. The demetallized
hydrocarbons then underwent catalytic cracking, hydrocrack-
ing, or coking. Thus, a catalyst contained 3.5 wt.% CoO, 10 wt.%
MoO3, and 1.5, 3, or 6 wt.% rare earth. A Lago atmospheric
residuum containing 235 ppm V and 2.12 wt.% S was treated
over the catalyst after it had been calcined at various
temperatures [281–466 °C ] V removal was 56.6–71.1 wt.%
and S removal 48.7–55.9 wt.% [76].
Residfining, an Exxon catalytic desulfurization-demetalliza-
tion process for heavy petroleum fractions, was extended by a
series of catalyst improvements and engineering to include
hydroconversion of distillation residues [b. N 566 °C] [77].
The heavy petroleum oils, containing heavy metals (e.g., Ni)
and S compounds, were catalytically hydrodesulfurized [300–
450 °C, 50–250 kg/cm2, 0.1–4.0 h/1 liquid space velocity,
200–1500:1 H-oil vol. ratio] and then demetallized in a mag-
netic field. Thus, a vacuum distillation residue was hydrode-
sulfurized [400 °C, 150 kg/cm2, 0.5 h/1 liquid space velocity,
1000:1 H-oil vol. ratio) in a fluidized bed of zeolite catalyst and
then demetallized in a magnetic field. About 80% of the S
compounds and 45% of the Ni were removed [78].
Heavy and sour petroleum fractions were hydrodemetallized
in a bed of sulfurized Al2O3 catalyst. Thus, a catalyst was
prepared by passing (CH3)2S2 [250 °C, 1 h/1 space velocity)
through a bed of Al2O3 granules (surface area 188 m2/g, pore
vol. 0.77 cm3/g). The catalyst was then used to hydrodeme-
tallize a refining residue (d. 1.025, Conradson carbon 18%, S
5%, V 120 ppm, Ni 55 ppm). At 410 °C the removal of S, V, and
Ni reached 15%, 85%, and 68%, respectively [79].
Chen and Massoth [80] performed hydrodemetallization of
vanadium and nickel porphyrin model compounds over sulfided
cobalt–molybdenum/alumina catalyst in a batch stirred auto-
clave at several temperatures with changing hydrogen (H)
pressure and initial porphyrin concentration. A hydrogenated
intermediate leading to deposited metal was found for both
reactants. The time course of the reaction followed pseudo first
order in reactant concentrations at N350 °C but followed lower
order at lower temperatures. Runs at different initial concentra-
tions showed that reaction was inhibited by adsorption of
reactant and products. HDM rates increased with temperature
and H pressure and were very low without catalyst or H present.
An apparent activation energy of 24 kcal/mol for the overall
disappearance was obtained for both reactants. Kinetic analysis
of HDM of Ni porphyrin (NiP) showed, in addition to a pathway
through the hydrogenated intermediate, an apparent direct
pathway to hydrocarbon products. The latter was interpreted in
terms of a direct conversion of adsorbed NiP to products in a
single adsorption step, without desorption of hydrogenated
intermediate. Evidence was obtained to show that the reaction
order in porphyrin was less than unity at a lower temperature,
increasing to first order above about N350 °C.
Crude oils that could not be easily or economically
transported or processed using conventional facilities, with
microcarbon residue content (ASTM D 4530) N 0.1 wt.%, total
acid no. (TAN) N 0.1, and with N 10 wt.% material boiling in the
vacuum gas oil range (ASTM D 5307), were hydrotreated and
hydrodemetalated in the presence of a supported Group VIB
metal catalyst, esp. Mo and W on Al2O3, with median pore
 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
diameter N 180 Å. Additional elements of the catalysts were
derived from Groups VIB, Group VIII and Group VA elements.
The crude oil product had a microcarbon residue content of
b 90% of the initial microcarbon residue content, b 10% of the
initial TAN, and 70–130% of the initial vacuum gas oil content
[81].
A cracking unit for cracking of petroleum refining residues
included a riser reactor and a stripper/separator with adjustable
outlets in flow communication with separate regeneration units
for regeneration of cracking catalysts and adsorbents. The
adsorbents, which were used for removal of Conradson carbon
precursors, high-molecular weight nitrogen compounds, and
impurity metals (esp. Ni and V) in the residues were injected
into the riser reactor such that they came into contact with fresh
residue feedstock prior to coming into contact with fresh and/or
regenerated cracking catalyst. Suitable adsorbents were selected
from microspheres derived from calcined clay, calcined and
crushed coke, magnesium oxide, silica-alumina, and a residue
cracking additive for removal of Conradson carbon precursors
and metals [82].
The kinetics of hydrodemetallization (HDM) of vanadyl
etioporphyrin (VO-EP) was studied in a batch autoclave at
543 K and 5 MPa of total pressure, with white oil as solvent and
presulfiding CoMo/A1203 (TK 710) as catalyst. The most
widely accepted kinetic model comprised of only dihydroge-
nated intermediate (VOEPH2) did not fit the experimental data.
A new model with two reversible hydrogenation steps and a
lumped irreversible hydrogenolysis step was proposed, and
followed the concentration trace of reactants (VO–EP and VO–
EPH2) very well for most reaction times [83].
A feasibility study of the decomposition and demetallation
of metalloporphyrins by ultrasonic irradiation is presented in
a paper by Tu and Yen [84]. Two representative model
compounds, NiTPP and VOTPP, were investigated in this
ultrasonic process on the laboratory scale. The extent of the
decomposition was detected by UV–vis. The metals were
measured by ICP/MS. In the initial investigation, the
decomposition of metalloporphyrins, which were dissolved
in different solvent–water mixtures, was performed under the
ultrasonication process. Among these solvents, the chlorinat-
ed-type solvents (e.g., chloroform and dichloromethane)
achieved a higher efficiency because they generated more
oxidizing species under sonication at 20 kHz frequency. Other
additives such as surfactant and hydrogen peroxide, which
affect the decomposition efficiency, were also investigated.
Under optimal condition, the decomposition efficiency
reached about 90% in 1 h for both model compounds. An
oxidative intermediate existed for both metalloporphyrins
under ultrasonication. The decomposition reaction rates of
these two compounds followed pseudo-first-order in reactant
concentration and were inhibited by initial feed concentration.
The dependence of the rate constants on the different initial
concentrations could be determined by the Langmuir Hinshel-
wood equation.
The influence of the hydrodynamic effects on the plug flow
model deviation in the hydrodesulfuration (HDS) and hydro-
demetallation (HDM) reactions of a petroleum residue was
581
evaluated by Callejas and Martinez [85]. The removal of sulfur,
vanadium, and nickel from a heavy residual oil was examined,
using a commercial catalyst. The possibility of incorporating
chemical and hydrodynamic complexity in the kinetics analysis
of hydrotreating reactions in a pilot trickle bed reactor were
discussed. The study was done in a small pilot scale trickle bed
reactor in continuos operation at 375 °C and 10 MPa of partial
hydrogen pressure with a commercial NiMo/alumina catalyst.
The nickel removal reaction, a firstorder liquid-limited reaction,
was used to test the predictions of several models, which
incorporate the influence of the hydrodynamics on the catalyst
utilization. For this task, additional experiments in a stirred tank
reactor at the same conditions were done in order to determine
the value of the effectiveness factor for denickelation reactions.
Comparison of model predictions and experimental data
indicated that the use of a hydrodynamic parameter in the
models improved the data fit.
5. Metal passivators
Although most of the metallic constituents of crude oil are
concentrated in the residues, some of the organometallic com-
pounds are actually volatilized at refinery distillation tempera-
tures and appear in the feed to the FCC cracking units. Metal
contaminants in the feedstock tend to deposit on the matrix of
FCC catalysts wherein they catalyze the combustion of carbon
monoxide (CO). Generally, only a portion of the total (25–
30%) deposited metal is active. Nickel in FCC feed and iron
scale are predominant sources of such contaminants. Iron scale
in the flue gas lines, cyclones, and dilute phase of the
regenerator can be a cause of after burning problems. Other
metal contaminants such as lead, sodium, and vanadium will
act as poisons to the active precious metal contained in CO
oxidation promoters. Significant increases in contaminant
levels will increase the severity and usage rates for CO
promoters. Because the compounds of these metals cannot, in
general, be removed from the cracking unit as volatile
compounds the usual approach has been to passivate them or
render them innocuous under the conditions that are
encountered during the cracking process. One passivation
method has been to incorporate additives into the cracking
catalyst or separate particles that combine with the metals and
therefore act as “traps” or “sinks” so that the active zeolite
component is protected. The metal contaminants are removed
together with the catalyst withdrawn from the system during its
normal operation and fresh metal trap is added together with
makeup catalyst so as to affect a continuous withdrawal of the
deleterious metal contaminants during operation. Depending
upon the level of the harmful metals in the feed to the unit, the
amount of additive may be varied relative to the makeup
catalyst in order to achieve the desired degree of metals
passivation.
Antimony and tin are used to passivate the activity of
vanadium and nickel on FCC catalyst. Their purpose is to
reduce gas make caused by metals catalyzed dehydrogenation.
Their effect on CO promotion catalysts is to reduce their activity
as well. Thus, the increased use of passivators will increase the
582 M.F. Ali, S. Abbas / Fuel Processing Technology 87 (2006) 573–584
severity of the promotion application and the possibility of
afterburn problems [86].
The existing metal passivator are classified into two
categories in terms of function, i.e., the single-function metal
passivator which is nickel passivator or vanadium passivator
composed of single effective metal like Sb, Sn or Bi; and
difunction metal passivator composed of composite metals like
Sb–Sn, Sb–Bi, Sb–Re, etc which can simultaneously passivate
nickel and vanadium. There are two ways for the addition of
metal passivators: one is to add it to the reactor with the catalytic
cracking feedstock and this method is usually applied for the
liquid metal passivator. The other is to add it to the reactor with
the catalyst and this method is usually applied for solid metal
passivator such as vanadium trapping agent. Additives
proposed for this purpose include the alkaline earth metals
and rare earths such as lanthanum and cerium compounds as
described in U.S. Patents Nos. 4,465,779; 4,519,897;
4,485,184; 4,549,958; 4,515,683; 4,469,588; 4,432,896; and
4,520,120. These materials which are typically in the oxide
form at the temperatures encountered in the regenerator
presumably exhibit a high reaction rate with vanadium to
yield a stable, complex vanadate species which effectively binds
the vanadium and prevents degradation of the active cracking
component in the catalyst.
6. Conclusions
The metal-containing compounds in petroleum are very
detrimental to petroleum processing. They cause rapid catalyst
poisoning and other problems in refining. The metals are
typically removed in petroleum refineries by a solvent
deasphalting process. This process also removes a large amount
of convertible material along with the metal-containing species.
The literature search revealed that various research organiza-
tions, oil companies, and individual researchers are exploring
non-conventional options for metal removal from residual oil.
These options include chemical treatment with acids and alkali,
selective oxidation/solvent extraction, the photocatalytic meth-
od, electrochemical treatment, and novel thermal and catalytic
methods. In general, these efforts are at the laboratory to small
pilot plant stages, and no dates have been set for commercial-
ization. The only processes which have been proven capable of
effecting substantial removal of metals are hydrotreating and
gasification. Hydrotreating may not be economical or practical
for heavy, high metal contents resids. If metals could be removed
in a pretreatment step by one of the above reviewed methods,
then heavy resids could be more economically upgraded by
traditional methods of catalytic cracking. Ability to remove
metals prior to hydrotreatment increases the amount and the
types of fuels that might be processed.
Acknowledgement
The authors would like to thank the Higher Education
Commission, Govt. of Pakistan for financial support. The facility
support provided by H. E. J. Research Institute of Chemistry,
University of Karachi is gratefully acknowledged.
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