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Review

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Nitrogen Removal from Oil: A Review


Glaucia H. C. Prado,* Yuan Rao, and Arno de Klerk
Department of Chemical and Materials Engineering, University of Alberta, 9211 116th Street, Edmonton, Alberta T6G 1H9, Canada

ABSTRACT: The selective removal of nitrogen-containing compounds from oil and oil fractions is of interest because of the
potential deleterious impact of such compounds on products and processes. Problems caused by nitrogen-containing compounds
include gum formation, acid catalyst inhibition and deactivation, acid−base pair-related corrosion, and metal complexation. A
brief overview of the classes of nitrogen compounds found in oil is provided. The review of processes to remove nitrogen from oil
emphasizes studies that investigated denitrogenation of industrial feedstocks, such as refinery fractions, heavy oils, and bitumens.
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The main topics covered are hydrotreating, liquid−liquid phase partitioning, solvent deasphalting, adsorption, chemical
conversion followed by separation, and microbial conversion. Chemical conversion processes include oxidative denitrogenation,
N-alkylation, complexation with metal salts, and conversion in high-temperature water. There are many processes for
denitrogenation by separation of the nitrogen-rich products from oil without removing the nitrogen group from the nitrogen-
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containing compounds. As a consequence, most of these processes are viable mainly for removal of nitrogen from low-nitrogen-
content oils, typically with <0.1 wt % N. At present, hydrodenitrogenation appears to be the only industrially viable process for
nitrogen removal from oils with high nitrogen content.

1. INTRODUCTION base strength, and the temperature. The reaction of


Nitrogen-containing compounds are often tolerated in oils and weaker acid−base pairs is easier to reverse by increasing
refined products because fuel specifications do not directly limit the reaction temperature. Catalysts containing acid sites
the nitrogen content of transportation fuels. The nitrogen that are operated at lower temperatures are poisoned by
content and the properties of nitrogen-containing compounds nitrogen bases, but catalysts operated at higher temper-
present in fuel are indirectly regulated through fuel atures, such as hydrocracking catalysts (>350 °C) and
specifications such as gum content, storage stability, and fluid catalytic cracking catalysts (>480 °C), are only
thermal stability. inhibited by nitrogen bases. At high temperatures, the
Nitrogen-containing compounds impose limitations on equilibrium constant of the acid−base reaction is smaller,
process operation, catalyst selection, and process development and a larger proportion of the acid sites are available to
for oil upgrading and refining. In some cases, the presence of perform acid catalysis. The reaction rate in the presence
nitrogen-containing compounds may require on-purpose of nitrogen bases is nevertheless lower than in the
pretreatment steps and even specialized process workarounds. absence of nitrogen bases. For example, about 100 °C
The deleterious effects of nitrogen-containing compounds on higher temperature was required to achieve the same
oil processing are varied, and the most important ones are the conversion over a hydrocracking catalyst operated at 6
following:
MPa H2 pressure with 6 kPa NH3 partial pressure
(a) The formation of “red tars” from pyrrolic compounds via compared to 0 kPa NH3.4
autoxidation has long been known,1 and the detrimental (c) Basic nitrogen-containing compounds can also react with
effect of pyrrolic compounds on storage stability has acids present in the oil, such as carboxylic acids, acids
been noted in the literature.2 Compounds that contain formed during processing, or acids added to the process.
nitrogen in a five-membered ring, such as pyrroles and The products from the acid−base reactions are heavier
2,3-dihydropyrroles, are particularly prone to free radical and may exhibit different phase behavior. Precipitation of
addition reactions.3 The same type of chemistry can take
organic salts formed by the acid−base reactions can
place at higher temperatures, as are found in aircraft
cause fouling of process equipment. At higher temper-
where the fuel is used as a heat exchange fluid as well as
atures, the acids can be liberated from the acid−base
in many refinery processes. This sensitivity to high
temperature causes poor thermal stability. Irrespective of pairs, and in the presence of water, this may lead to
the origin of free radical formation, whether it is oxidative localized corrosion. For example, severe localized
or thermal, nitrogen-containing compounds containing corrosion of the atmospheric distillation unit (ADU)
nitrogen in a five-membered ring are susceptible to free was reported following the processing of oil that
radical addition to form heavier products, or gums. contained amine chloride salts, which released hydro-
(b) Basic nitrogen-containing compounds, such as pyridines chloric acid during distillation.5
and amines, can react with acid catalysts to neutralize the
acid sites of the catalyst. The reaction equilibrium Received: October 24, 2016
governing the extent of these acid−base neutralization Revised: December 6, 2016
reactions depends on the acid site strength, the nitrogen Published: December 21, 2016

© 2016 American Chemical Society 14 DOI: 10.1021/acs.energyfuels.6b02779


Energy Fuels 2017, 31, 14−36
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(d) The metals most commonly reported in crude oil are Ni Table 1. Nitrogen Contents of Selected High-Nitrogen-
and V; some oils also contain meaningful (>10 μg·g−1) Content Oils
amounts of other metals, such as Fe.6 Although metals in
nitrogen content
oil are not exclusively found in metalloporphyrin oil location (wt %) ref
structures, nitrogen plays an important role in metal bitumen Canada, AB, Cold Lake 0.34 10
coordination. Fouling of process equipment and catalysts bitumen Canada, AB, Athabasca 0.40−0.56 10
occurs as a result of deposition of metals during bitumen Canada, AB, Peace River 0.51 10
processing, and in this respect nitrogen is indirectly bitumen Canada, AB, Athabasca 0.66 11
responsible for the processing problems attributed to heavy crude oil Republic of Tatarstan, 0.63 12
metals in oil. Ashal’cha
(e) In catalytic processes, nitrogen-containing compounds heavy oil (coal- China, Shengli 0.50 13
competitively adsorb with other compounds. Such derived)
heavy oil United States, OK, Sho- 0.37 14
competitive adsorption limits the access of other vel-tum
compounds to the catalyst surface, thereby reducing medium oil United States, CA, 0.41 14
the rate of conversion of such compounds. For example, Ventura
nitrogen-containing compounds compete with sulfur- heavy oil United States, CA, San 0.91 14
containing compounds for active sites during hydro- Ardo
treating, causing hydrodesulfurization to be less efficient heavy oil United States, CA, Gato 0.67 15
Ridge
when nitrogen-containing compounds are present in the heavy oil United States, CA, Oxnard 0.88 15
feed.7,8 bitumen United States, CA, Edna 1.23 15
In view of the inefficiencies and challenges caused by bitumen United States, UT, 0.96 15
nitrogen-containing compounds, it is desirable to remove Sunnyside
nitrogen-containing compounds from oil, and it is preferable to bitumen United States, UT, Vernal 1.18 15
do so before refining. While several studies can be found in the
literature dealing with sulfur removal, much less has been The most prominent nitrogen-containing classes in crude oil
reported on nitrogen removal from oil. These served as are pyridine derivatives and pyrrole derivatives, including
motivations for the present review of nitrogen removal. Studies porphyrins, which have a tetrapyrrole macrocycle (Figure 1).
involving model oils are included in the review, but because of
our specific interest in real industrial feedstocks, emphasis is
placed on denitrogenation of refinery fractions as well as
straight-run heavy oils and bitumens.

2. CLASSES OF NITROGEN-CONTAINING
COMPOUNDS IN OIL
The nitrogen content of crude oils is usually less than 1 wt % N.
In about 90% of crude oils the nitrogen content is <0.25 wt %,
and many have <0.1 wt % nitrogen. This led to the convenient
classification of crude oils into high-nitrogen oils with nitrogen
contents higher than 0.25 wt % and nitrogen-poor oils with
nitrogen contents lower than 0.25 wt %. High-nitrogen oils are
found mainly in South America, California (USA), and Alberta
(Canada).9,10 Nitrogen content of different high-nitrogen oils is
presented in Table 1.10−15 There is no relationship between the
sulfur content and nitrogen content of crude oils.16
In all crude oils, the concentration of nitrogen-containing
Figure 1. Examples of pyridinic and pyrrolic compounds.
compounds increases monotonically with increasing boiling
fraction. Most of the nitrogen-containing compounds are
therefore found in the residuum fraction. Generally reference is made to the presence of only
Nitrogen compounds in crude oils are conventionally heterocyclic nitrogen in crude oil, but there is evidence that
classified as basic (derivatives of pyridine) and nonbasic low concentrations of primary amines (R−NH2) might also be
(derivatives of pyrrole). This classification is a matter of present.18,19
analytical convenience because the basic nitrogen content can Nitrogen is not always present as single heteroatom, as
be determined using acid titration. illustrated by the porphyrin class of compounds, which have
It was reported that the ratio of basic nitrogen to nonbasic four nitrogen atoms in the tetrapyrrole macrocycle. Com-
nitrogen remained within the range 0.25−0.35 irrespective of pounds containing more than one nitrogen atom per molecule
the origin of the crude oil.9,17 However, it is worthwhile to keep as well as nitrogen in combination with oxygen have been
in mind that during refining, hydroprocessing can convert identified. Analysis of crude oil from the Liaohe oil field in the
nonbasic nitrogen compounds into strong bases (derivatives of Bohai Basin, China, by negative-ion electrospray ionization
cyclic amines) before the amine is eliminated as ammonia, Fourier transform ion cyclotron resonance mass spectrometry
which is also a base. From the perspective of acid−base (ESI-FT-ICR-MS) indicated that the relative abundance of
interactions in an oil refinery, all nitrogen-containing nitrogen-containing compounds was N1 ≫ N1O1 > N1O2 > N2
compounds are potential participants in acid−base interactions. > N2O1 ≈ N1O3 > N1O4.20
15 DOI: 10.1021/acs.energyfuels.6b02779
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In a study of Arabian crude oils, nitrogen-containing type of technology depends to a large extent on the boiling
compounds were identified using a combination of gas range and properties of the feed material.
chromatography coupled with mass spectrometry (GC−MS), To facilitate discussion, a process flow diagram of a generic
high-performance liquid chromatography (HPLC), infrared packed-bed hydrotreating process is shown in Figure 3. The
spectroscopy, and UV−vis spectroscopy.21 Some of the lower-
molecular-mass compounds with multiple heteroatoms that
were identified (Figure 2) were amides and hydroxyquinolines

Figure 3. Process flow diagram of a generic packed bed hydrotreating


process.

Figure 2. Examples of nitrogen-containing compounds with more than liquid feed and part of the hydrogen is combined and preheated
one heteroatom that were identified in crude oil samples.21 to the reactor inlet temperature. Hydrogen is always present in
excess. The packed reactor contains a hydrotreating catalyst,
and hydrotreating is accompanied by a temperature increase.
(N1O1), pyrrolecarboxylic acids (N1O2), imidazoles (N2), and Hydrogen quench, which is the injection of cold hydrogen, is
caffeines (N4O2). The N2 species may also include compounds employed for heat management and to replenish hydrogen that
with more than one pyridine ring according to a different was consumed by hydrotreating. The reactor product is cooled
study.22 and phase-separated to recover the hydrotreated liquid. The gas
Despite the diversity of compound classes, the literature is in contains mainly hydrogen but also gaseous products produced
agreement that species with a single nitrogen atom (N1) are the during hydrotreating, such as ammonia due to HDN and
most abundant in crude oil and that the dominant classes of hydrogen sulfide due to HDS. The gas is cleaned to remove the
nitrogen-containing compounds are pyrroles and pyridines. other gases from the hydrogen before it is recycled. Some of the
non-hydrogen compounds remain in the recycle gas, and to
3. HYDROTREATING avoid buildup of compounds that are not efficiently removed
Industrially, catalytic hydrodenitrogenation (HDN)23,24 is the during gas cleaning, some of the recycle is purged.
most commonly applied method for removal of nitrogen from In many industrial hydrotreating processes, multiple catalyst
oil. Hydrotreating is the “base case” technology against which beds and even multiple reactors in series might be employed.
all other methods of nitrogen removal are compared. Any The catalyst loading diagrams can be complex, and usually
alternative nitrogen removal technology must demonstrate a more than one type of hydrotreating catalyst is loaded.
clear advantage over HDN before it will be considered for The start-of-run inlet temperature (250−350 °C), pressure
industrial use. (1.5−15 MPa), space velocity (0.7−12 h−1), and hydrogen-to-
Hydrotreating is not a selective nitrogen removal process. liquid feed ratio (250−6000 normal m3·m−3) all depend on the
Hydrodemetalation (HDM), hydrodesulfurization (HDS), feed material and extent of hydrotreating required.26 These are
hydrodeoxygenation (HDO), hydrodearomatization (HDA), just typical ranges. For deep HDN of high-nitrogen-content
and olefin saturation all take place in parallel with HDN. Of the oils, such as coal-derived oils, more severe conditions might be
most abundant heteroatoms in oils (S, N, and O), nitrogen is required. For example, hydrotreating of creosote distillate to
actually the most difficult to remove by hydroprocessing.25 produce a distillate blending material for diesel fuel is
Pyridinic nitrogen removal is particularly challenging because it industrially performed at 280−380 °C and 18.5 MPa.27
requires 1 double bond and one single bond to be broken for Most aspects of the process shown in Figure 3 are common
denitrogenation to occur; in comparison only two bonds need to hydrotreating processes in general. However, when the feed
to be broken for desulfurization of thiophenic sulfur and material has higher nitrogen content and HDN is the primary
deoxygenation of furanic oxygen. objective, the following aspects of the hydrotreating process will
3.1. Hydrotreating Process Technology. There are likely be affected:
approximately 30 different hydrotreating processes than can (a) More severe operating conditions will be required.
be licensed.16 An overview of some of these process (b) Because of the reaction requirements of HDN (discussed
technologies can be found in the literature.26 Hydrotreating in section 3.2), it is likely that HDA will increase
processes operate on the same principles even though there are concomitantly with HDN. Both HDN and HDA are very
differences in catalysts, reactor technology, heat management, exothermic reactions. The adiabatic temperature increase
product workup, and gas loop design. The selection of a specific during hydrotreating would therefore be higher. The heat
16 DOI: 10.1021/acs.energyfuels.6b02779
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Figure 4. Heterocyclic ring-opening pathways during HDN in the presence of an acid−base pair as illustrated by the conversion of indole.

Figure 5. Substitution reaction leading to denitrogenation during HDN in the presence of H2S, as illustrated with the product shown in Figure 4, i.e.,
2-ethylaniline.

management of the process design must make provision to be sp3-hybridized, which in turn requires ring saturation by
for this. hydrogenation.
(c) The H2 consumption will increase as the nitrogen Heterocyclic ring opening by either nucleophilic substitution
content of the feed increases. Although this seems or Hofmann degradation is facilitated by the presence of an
obvious, the increase is not directly proportional to the acid−base pair, H+B− (Figure 4). An increase in the HDN rate
nitrogen content because the extents of all of the in the presence of H2S, which supplies H+ and HS− as acid−
base pair, has been noted in many studies.29 Irrespective of the
hydrotreating reactions are affected by the more severe
pathway, it leads to ring opening, yielding the same products
conditions required for HDN as well as the mechanism that contain amine and olefinic groups.
of hydrodenitrogenation (discussed in section 3.2). The steps involved in denitrogenation of alkylamines over
(d) The gas cleaning step in the gas loop for H2 recycle will sulfided base-metal catalysts were explored by Prins et al.,30
have to deal with an increased amount of NH3. who found that denitrogenation occurred through substitution
3.2. Hydrodenitrogenation Chemistry. The chemistries of the alkylamine by H2S to form the alkanethiol and NH3.
of nitrogen and sulfur removal during the hydrotreating process When an amine group is bonded to an sp3-hybridized carbon
differ from each other, even though similarities can be found. In and when H2S is present as an acid−base pair, the acid−base
both sulfur and nitrogen removal, alkyl substituents in pair that is eliminated is not H2S, but NH3. The elimination
heterocyclic compounds provide steric hindrance, which leaves the thiol group (B = SH) attached to the molecule from
decreases heteroatom removal from ring structures. Nitrogen which the nitrogen was removed as ammonia. This is illustrated
is more difficult to remove in hydrotreating than sulfur. This is in Figure 5.
the case because ring hydrogenation is not required for sulfur A detailed description of HDN chemistry focusing on
removal while ring saturation is an obligatory step for nitrogen homogeneous catalysis to explore single-site HDN catalysis can
removal.28 be found in the recent work by Bachrach et al.31
Many studies with nitrogen model compounds have been 3.3. Hydrodenitrogenation Catalysts. The catalysts
conducted to understand the reaction mechanism for hydro- commercially used for hydrotreating processes are tungsten
denitrogenation. In heterocyclic nitrogen-containing com- and molybdenum sulfides (active components) supported on
pounds, the C−N bonds cannot be cleaved directly through alumina, and their properties are modified by adding cobalt or
hydrogenolysis. Denitrogenation over hydrotreating catalysts nickel (hydrogenation promoters). Even though both catalysts
proceeds through heterocyclic ring opening as an intermediate can remove both nitrogen and sulfur, Co/Mo is more selective
step, either by nucleophilic substitution or Hofmann-type for sulfur removal while Ni/Mo is more selective for nitrogen
degradation.29 In both instances, scission of the C−N bond to removal. This is the case because Ni/Mo catalysts have higher
form the ring-opened intermediate requires the adjacent carbon hydrogenation activity than Co/Mo catalysts. Although Ni/W
17 DOI: 10.1021/acs.energyfuels.6b02779
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has a higher denitrogenation rate than Ni/Mo, Ni/W is more showed that nitrogen conversion was increased by increasing
expensive than Ni/Mo, so Ni/Mo is more often used in oil the temperature and decreasing the liquid hourly space velocity
refineries for nitrogen removal.16 Review papers on this topic (LHSV) for both boron- and phosphorus-containing cata-
are available.23,24 lysts.41−43
The nitrogen removal efficiency and kinetic parameters In comparison with alumina, other metal oxide supports
depend on the feed, and many studies can be found in the usually result in higher HDN activities but are more difficult to
literature.32−36 Nevertheless, an investigation with eight prepare with high surface areas. The main research activities
different kinds of heavy oils with different properties has consist in developing new preparation procedures with the
revealed that nitrogen removal using commercial catalysts is objective of increasing the surface area and structural stability.
inversely proportional to compounds containing three or more In a recent study, ZrO2 was prepared with and without the
aromatic rings. It is explained that these compounds inhibit chelating ligand ethylenediaminetetraacetic acid (EDTA), and
hydrodenitrogenation by competing with nitrogen compounds its hydrodenitrogenation activity was evaluated using heavy gas
for catalytic sites as well as hydrogen (since hydrogenation is a oil from Athabasca bitumen. It was found that the nitrogen
required step for hydrodenitrogenation).37 conversion was higher for Ni/Mo/Meso-Zr with EDTA than
Since the nitrogen content of heavy oils is high and its for Ni/Mo/Meso-Zr without EDTA. In addition, Ni/Mo/
removal is achieved with higher pressure and higher temper- Meso-Zr with EDTA presented equal nitrogen conversion as
ature, hydrotreating becomes an expensive process for heavy Ni/Mo/Al2O3 at 395 °C. It was explained that EDTA provides
crude oil, and more active catalysts have been studied with the an increase in active metal dispersion, a decrease in metal−
purpose of achieving high nitrogen removal with less energy support interactions, and an increase in nickel sulfidation
and hydrogen consumption. The majority of the research temperature.46
consists of the use modifiers of supports or new supports to Ni/W supported on citric-treated Y zeolite mixed with a
replace alumina. The main supports studied are silica−alumina, titania−silica composite catalyst was used to study the removal
zeolites, mesoporous silica, metal oxides, and mixed oxides,38 of basic and nonbasic nitrogen compounds from Liaohe
while the main alumina support modifiers studied are fluorine, Chinese coker gas oil.47 As for conventional hydrotreating
boron, and phosphorus, 39,40 even though boron and catalysts, total nitrogen removal was improved by increasing the
phosphorus were also used to modify Ni/Mo/Al2O3 itself.41−44 pressure and temperature and decreasing the LSHV. Unlike
The direction of these developments makes sense considering heavy gas oil treated with Ni/Mo or Co/Mo catalyst, higher
the heterocyclic ring-opening chemistry (Figure 4), which removal of basic nitrogen was achieved compared with
involves an acid−base pair. nonbasic nitrogen.45
Hydrodenitrogenation of heavy gas oil and coker kerosene Zeolites have been used as catalyst supports because they
distillates, both derived from Athabasca bitumen, has shown contain strongly acidic protons in their crystalline lattices,
that the use of hydrogenation promoters such as Ni and Co in resulting in high carbonium ion activity. Hydrotreatment of
MoO3 supported on alumina increased nitrogen removal from heavy gas oil from Athabasca bitumen using Ni/W, Ni/Mo, and
both feeds. For example, 36% of the nitrogen was removed Co/Mo catalysts supported on zeolitic silica−alumina and its
from coker kerosene when the unpromoted catalyst was used, hydrodenitrogenation was compared with that of the catalysts
while 50% of the nitrogen was removed over the promoted supported on commercial alumina. It was observed that the
catalyst. Furthermore, nonbasic nitrogen compounds had catalysts supported on zeolitic silica−alumina promoted 2-fold
higher removal rates than basic nitrogen compounds, and higher nitrogen removal than the commercial supports.48
nitrogen removal was increased by increasing the ratio of Metal chloride catalysts were studied as an alternative for
hydrogenation promoter to Mo up to a maximum of 0.6.45 hydrodenitrogenation of heavy California gas oil. It was found
Many explanations for the improvement in nitrogen removal that NiCl2 supported on silica−alumina presented higher
by addition of hydrogenation promoters have been proposed in denitrogenation activity than commercial Ni/W supported on
the literature, such as the monolayer theory, pseudointercala- silica−alumina and Co/Mo supported on alumina. It was
tion theory, and remote control theory.38 However, it is clear explained that addition of 5% methylene chloride to the system
from the heterocyclic ring-opening chemistry (Figure 4) that results in HCl formation, which allows the catalyst to remain in
hydrogenation is a prerequisite for ring opening, and increasing its chloride form rather than its sulfide form. HCl can then
the hydrogenation power of a catalyst would facilitate this. react with NiCl2 to form H+(NiCl3)−, which is a Friedel−Crafts
Fluorine, boron, and phosphorus have been added to the catalyst that possess hydrogenation and cracking activities. If
alumina support or the catalyst itself because they increase the water is present in the system, NiCl2 can react with water to
extremely strong acid sites of the catalyst. By substituting some form H+(NiCl2OH)−, which is another Friedel−Crafts catalyst.
Al by B3+, both Brønsted and Lewis acidic sites can be formed Because an insoluble solid was obtained for the reactions at low
in the presence of water, which increases nitrogen removal.39 temperatures, it is suggested that nitrogen compounds are
On the other hand, the higher nitrogen conversion obtained by removed in the form of NH4Cl through the formation of a
phosphorus addition is attributed to geometrical changes carbonium ion by the interaction between the HCl and the
caused by phosphorus. Phosphorus causes an increase in the catalyst.49
number of stacks of the active site (MoS2) that are more Generally the presence of CO and CO2 in the gas feed is
accessible to bulky molecules, consequently increasing nitrogen negative, resulting in lower HDN conversion. Some examples
removal. Addition of 1.7 wt % boron and 2.7 wt % phosphorus are given to illustrate the point. Hydrotreatment of gas oil in
to Ni/Mo/Al2O3 catalyst increased the nitrogen conversion the presence of CO2 using a Co/Mo/Al2O3 catalyst resulted in
during hydrotreating of heavy gas oil from Athabasca bitumen 64 wt % nitrogen removal, compared with 86 wt % when CO2
from 61.9 to 78.0 wt % and from 61.9 to 78.4 wt %, was not co-fed into the reactor.50 The presence of CO during
respectively.44 Optimized process conditions as well as kinetic hydrocracking of bitumen using Co/Mo/Al2O3, Mo/Al2O3, and
parameters were determined in a number of studies, which FeSO4/SiO2 catalysts also decreased nitrogen removal from
18 DOI: 10.1021/acs.energyfuels.6b02779
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Table 2. Denitrogenation of Real Industrial Feedstocks by Hydrotreating


process nitrogen conversion/removal
feed catalyst conditions co-feed (%) ref
gas oil from bitumen NiMo/Al2O3 + 2.7 wt % P 9.4 MPa − 97.0 wt % N converted 41
LSHV: 0.5 h−1
400 °C
gas oil from bitumen NiMo/Al2O3 + 1.7 wt % B 9.4 MPa − 94.0 wt % N converted 41
LSHV: 0.5 h−1
400 °C
heavy gas oil from Athabasca bitumen NiMo/Al2O3 + 1.7 wt % B 8.79 MPa − 78.0 wt % N converted 44
LSHV: 1 h−1
385 °C
heavy gas oil from Athabasca bitumen NiMo/Al2O3 + 2.7 wt % P 8.79 MPa − 78.4 wt % N converted 44
LSHV: 1 h−1
385 °C
coker kerosene from Athabasca bitumen Mo/Al2O3 13.9 MPa − 36% N removed 45
LSHV: 2 h−1
320 °C
coker kerosene from Athabasca bitumen NiMo/Al2O3 and CoMo/Al2O3 13.9 MPa − 50% N removed 45
LSHV: 2 h−1
320 °C
heavy gas oil from Athabasca bitumen NiMo/Meso-Zr 8.8 MPa − ∼40% N converted 46
LSHV: 1 h−1
395 °C
heavy gas oil from Athabasca bitumen NiMo/Meso-Zr (EDTA) 8.8 MPa − ∼50% N converted 46
LSHV: 1 h−1
395 °C
heavy gas oil from Athabasca bitumen NiMo/Al2O3 8.8 MPa − ∼50% N converted 46
LSHV: 1 h−1
395 °C
heavy gas oil from Athabasca bitumen NiMo/SBA-15 8.8 MPa − ∼20% N converted 46
LSHV: 1 h−1
395 °C
Liaohe Chinese coker gas oil NiW/CYCTS 6.0 MPa − 80% N converted 47
LSHV: 1 h−1
420 °C
heavy gas oil from Athabasca bitumen NiMo/zeolite−alumina−silica 6.89 MPa − 89% N removed 48
LSHV: 1 h−1
422 °C
heavy California gas oil NiCl2/alumina silica 6.89 MPa 5 vol % methylene ∼95% N removed 49
LSHV: 0.5 h−1 chloride
427 °C
heavy California gas oil NiW/silica−alumina 6.89 MPa − ∼85% N removed 49
LSHV: 0.5 h−1
427 °C
heavy California gas oil CoMo/alumina 6.89 MPa − ∼75% N removed 49
LSHV: 0.5 h−1
427 °C
straight-run gas oil CoMo/Al2O3 6.2 MPa − 86 wt % N removed 50
LSHV: 2 h−1
360 °C
straight-run gas oil CoMo/Al2O3 6.2 MPa 906.14 mLCO2/h 64 wt % N removed 50
LSHV: 2 h−1
360 °C
straight-run gas oil CoMo/Al2O3 5.0 MPa − ∼92% N removed 52
LSHV: 1 h−1
330 °C
straight-run gas oil CoMo/Al2O3 5.0 MPa 3.13 wt % ethyl decanoate ∼79% N removed 52
LSHV: 1 h−1
330 °C
straight-run gas oil CoMo/Al2O3 5.0 MPa 1.16 wt % propanoic acid ∼83% N removed 52
LSHV: 1 h−1
330 °C

19 DOI: 10.1021/acs.energyfuels.6b02779
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bitumen.51 Although these observations were explained in Table 3. Solubility Parameters of Selected Nitrogen-
terms of the water gas shift reaction, the decrease in H2 partial Containing Compounds55
pressure and competitive adsorption appear to be more
compound δ (MPa1/2)
plausible explanations.
The presence of different oxygenated compounds during piperidine 20.2
hydrotreating of straight-run gas oil using a CoMo/Al2O3 pyridine 21.8
catalyst was also investigated.52 The impact of oxygenates on quinoline 21.4
HDN depended on the oxygen-containing functional group. It acridine 22.6
was found that 2-propanol, cyclopentanone, anisole, and pyrrolidine 20.4
guaiacol did not inhibit nitrogen removal, as the nitrogen pyrrole 21.6
removal was similar to when no oxygenate was added to the gas indole 22.1
oil. However, ethyl decanoate and propanoic acid inhibited carbazole 23.5
nitrogen removal from gas oil. Analogous observations were aniline 22.5
reported by Leckel,53 and the results could be explained by the
preferential adsorption of oxygenates on either the metal sites two liquid phases is not governed by just the difference in the
or the support material. Carboxylic acids, and the acids derived solubility parameters. Compounds that form an irregular
from esters, preferentially adsorb on metal sites, suppressing the solution may be soluble in each other despite large differences
hydrogenation activity, which would explain the decrease in in their solubility parameters.
HDN activity in the presence of such oxygenates. Alcohols and 4.1. Liquid−Liquid Extraction Technology. A process
carbonyls preferentially adsorb on the support material, which flow diagram for a generic multistage liquid−liquid extraction
would explain their lack of impact on HDN. process is shown in Figure 6. The steps involved in the process
Some examples of hydrodenitrogenation of real feedstocks
with different catalysts and conditions can be found in Table 2.

4. LIQUID−LIQUID PHASE PARTITIONING


Phase partitioning of nitrogen-containing compounds between
oil and a second immiscible liquid phase forms the basis for
many processes based on liquid−liquid extraction. Liquid−
liquid extraction exploits the differences in the Hildebrand
solubility parameters (δ) of the bulk oil, nitrogen-containing
compounds, and immiscible liquid used as second liquid phase
for extraction. Processes based on “pure” liquid−liquid
extraction, which does not rely on a chemical interaction
between the nitrogen-containing compounds and the molecules
in the extracting liquid, can be described using regular solution
theory, as the term was originally defined.54 The liquid-phase Figure 6. Process flow diagram of a generic multistage liquid−liquid
extraction process.
preference for a nitrogen-containing compound with solubility
parameter δN would then depend on its difference with respect
to the solubility parameters of the two phases. For selective are mixing of the two liquid phases to facilitate liquid−liquid
extraction of the nitrogen-containing compounds, the solubility extraction, phase separation of the two liquid phases, and
parameter of the extracting liquid, δext, compared to the oil, δoil, recovery and recycling of the solvent that was used for
must be such that eq 1 preferably holds true: extraction.
|δ N − δext| < |δ N − δoil| < |δext − δoil| The number of equilibrium stages and the method of
(1)
contacting depend on the liquid-phase partitioning, extraction
Equation 1 is a mathematical expression of the phrase “like requirements, mass transport rate, and physical properties of
dissolves like”. Most organic compounds have solubility the liquid phases. Various types of liquid−liquid extractors are
parameters in the range 14−29 MPa1/2. Exceptions are lower- available.56 Operating parameters such as mixing intensity,
density apolar molecules, such as propane, which have lower mixing time, and temperature can be manipulated to improve
values, and high-density polar molecules, such as methanol, the mass transport.
which have higher values. Nitrogen-containing compounds The choice of solvent is critical, and it is affected by a number
tend to have solubility parameters that are more typical of polar of considerations. First, and the most obvious, is the nature of
compounds (Table 3).55 To put these values into perspective, the nitrogen-containing compounds to be extracted, which
the Hildebrand solubility parameter of Athabasca bitumen is would determine whether extraction is performed on the basis
18.25 MPa1/2.28 of polarity, acid−base character, or some other chemical
Mixed solvents can in principle be used to obtain a solvent property of the solvent.57 Second, but by no means secondary,
system with different solubility parameter and characteristics is the recoverability of the solvent. The efficiency of solvent
than those of the pure solvents. However, this would recovery affects the operating cost of the process. Solvent can
complicate subsequent solvent recovery and recycling (section be lost through solubility in the oil, incomplete liquid−liquid
4.1). separation, and incomplete recovery from the extracted
Liquid−liquid extraction can also exploit chemical inter- nitrogen-containing compounds. Other properties of the
actions to solvate the nitrogen-containing compounds in the solvent, such as volatility, oil miscibility and density difference
extracting liquid. In such cases the extraction solution would be with respect to the oil, might be critical in solvent selection.
termed an “irregular” solution, and the partitioning between the Third is the purpose of the nitrogen removal. The degree of
20 DOI: 10.1021/acs.energyfuels.6b02779
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Energy & Fuels Review

Table 4. Denitrogenation of Real Industrial Feedstocks by Solvent Extraction


process
feed solvent type of solvent conditions nitrogen conversion/removal ref
distillates from Battle River methanol + water organic + water 30 °C ∼50% N extracted 58
coal liquid 10 min
distillates from Wandoan methanol + water organic + water 30 °C ∼34% N extracted 58
coal liquid 10 min
straight-run diesel methanol + water + acetic acid + complexing agent organic + water 30 °C 90.8% basic N removed 59
+ acid 3 min
Fushun shale oil phosphoric and sulfuric acids acid 60 °C 97.43% basic N removed, 38.2% 60
acid:oil = 1:1 total N removed
20 min
Fushun shale oil phosphoric and acetic acids acid 60 °C 90.71% basic N removed, 30.5% 60
acid:oil = 1:1 total N removed
20 min
catalytically cracked diesel acetic acid acid 20 °C ∼78% basic N removed 61
oil 80% acetic acid
10 min
vacuum gas oil acetic acid acid room 63% basic N removed 62
temperature
90% acetic acid
15 min
gasoline HCl (1 mol L−1) acid room 94.26% basic N removed 63
temperature
20 min
straight-run gas oil triethylmethylammonium acetate and ionic liquids 30% N removed 70
triethylmethylammonium butyrate

nitrogen removal and/or the recovery of the nitrogen- Table 5. Solubilities of Nitrogen-Containing Compounds
containing compounds might also affect the solvent choice. Listed in Table 2 in Ethanol and Water at 20−25 °Ca
The main solvents used for nitrogen removal from crude oil
solubility in polar solvents
are organic solvents,58,59 acidic solvents,60−63 and ionic
liquids.64−70 Examples of denitrogenation of oils, excluding compound ethanol water ref
model oils, by liquid−liquid extraction using different types of quinoline − 6191 mg/L 74
solvents can be found in Table 4. pyrrole − 55.685 g/L 75
A special class of solvents that have been investigated only indole 35.85 g/100 g of ethanol − 76
with model oils are deep eutectic solvents.71,72 Deep eutectic aniline − 3.65 g/100 g of water 77
a
solvents are a new class of ionic liquids. What differentiate these Based on a solubility data search using the Reaxys database.
solvents from ionic liquids are their chemical properties, since
they have similar physical properties. A deep eutectic solvent is
on the toxicity of nitrogen-containing heterocyclic compounds,
a eutectic mixture of a Lewis or Brønsted acid or base
which was developed as part of the synthetic fuels programs in
containing a variety of anions and cations, while an ionic liquid the United States in the 1970s and 1980s.78 Process
is composed of one type of discrete anion and cation.73 information from the Char-Oil-Energy-Development (COED)
4.2. Solvents Used for Liquid−Liquid Extraction. coal liquefaction process indicates that the aqueous product
4.2.1. Polar Solvents. A mixture of methanol and water was from the first stage of coal pyrolysis contained 0.05 wt % N and
used to extract nitrogen compounds from middle distillates of had a pH of 3.6 and that the aqueous product from the second
Battle River and Wandoan coal liquids. Nitrogen extraction stage of coal pyrolysis contained 0.93 wt % N and had a pH of
increased with increasing amount of methanol in the mixture. 8.8.79 Although ammonia is often a significant contributor to
The percentage of nitrogen extracted from Battle River coal the nitrogen content of such process water streams, not all of
liquids was ∼50% and from Wandoan coal liquids was ∼34%. the nitrogen was due to ammonia.
Because of the polarity of the solvents, phenolic compounds There is consequently a clear gap in the basic data for
were also extracted, which lowered the selectivity of nitrogen liquid−liquid extraction using the most common of solvents,
compounds extracted.58 water. Considering the impact that partitioning of nitrogen-
Metallic ions were added as complexing agents in a containing compounds between the organic and aqueous phase
methanol/water/acetic acid mixture for the removal of basic can have on water toxicity, it is surprising that so little
nitrogen compounds in straight-run diesel. It was found that fundamental work has been reported.
the highest basic nitrogen removal (90.8%) was achieved using 4.2.2. Acidic Solvents. The use of acidic solvents has the
undisclosed metallic ions as complexing agents at room objective of removing primarily basic nitrogen compounds from
temperature and 3 min reaction time.59 crude oil by an acid−base reaction that precedes extraction. As
It was surprising to find that there were very few solubility basic nitrogen compounds possess a lone pair of electrons, they
data available for aromatic nitrogen-containing compounds in are Lewis bases. Acid−base reactions with Lewis acids result in
common polar solvents such as water and ethanol (Table the formation of complexes. Acid−base reactions with Brønsted
5).74−77 This is the case despite a significant body of literature acids result in the protonation of the nitrogen to form salts of
21 DOI: 10.1021/acs.energyfuels.6b02779
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Energy & Fuels Review

the pyridinium ion. Salts of the pyridinium ion are usually liquids.67 On the other hand, ionic liquids containing
water-soluble and readily extracted into an aqueous phase. bistriflimide and chloride salts of copper and iron selectively
An acid will be a good solvent for nitrogen removal if it has removed nitrogen compounds in the presence of sulfur
high acid strength and low volatility, is water-soluble for easier compounds in a model oil. The selectivity was improved by
recovery, and can form reversible bonds with nitrogen using such ionic liquids supported on monolithic silica.68
compounds. Even though formic acid is a stronger acid than The validation of such processes with real feeds is of extreme
acetic acid, it is not commonly used because it is very importance, as petroleum-derived oils are complex mixtures
unstable.61 The use of acetic acid for removal of basic nitrogen and the presence of other compounds and differences in
compounds has been reported for shale oil,60 catalytically physical properties compared with model oils may affect
cracked diesel oil,61 and vacuum gas oil.62 Process parameters nitrogen removal. For example, in a study with several ionic
for denitrogenation of catalytically cracked diesel oil and liquids containing imidazole or quaternary ammonium groups,
vacuum gas oil by acetic acid were determined, and the highest denitrogenation was successfully achieved by removal of
basic nitrogen removal was ∼78% for catalytically cracked quinoline, indole, and carbazole from a model oil. However,
diesel oil61 and 63% for vacuum gas oil.62 Even though acetic when some of the ionic liquids were evaluated for nitrogen
acid in combination with phosphoric acid and formic acid could removal from straight-run gas oil, some of them failed to
remove 90.71% and 88.65% of basic nitrogen compounds, remove nitrogen-containing compounds. The highest nitrogen
respectively, from shale oil, the highest removal (97.43%) was removal was 30% using triethylmethylammonium butyrate and
achieved with phosphoric acid and sulfuric acid in a ratio equal triethylmethylammonium acetate ionic liquids.70
to 17:3.60 The main limitations regarding the use of ionic liquids
It is interesting to note that nonbasic nitrogen compounds include limited reuse, high energy consumption, loss of
were also extracted along with basic nitrogen compounds by hydrocarbons, and the need for several extraction cycles to
aqueous acetic acid in the study by Qi et al.61 The explanation achieve reasonable denitrogenation. It was recommended that
given by the authors was that weak bases such as nonbasic research should focus on methods to overcome such problems
nitrogen compounds reacted with strong acids, which resulted before ionic liquids can be considered for nitrogen removal by
in their extraction by the acid. Following on these observations, industry.69 Another limitation not cited would be the physical
it was suggested to employ strong acids, such as hydrochloric state of the ionic liquid when it is used for the real feed
acid, for removal of nonbasic nitrogen compounds.61 extraction. For example, the ionic liquid could turn into a solid
In the study by Feng,63 aniline and quinoline were the main or dissolve in a real feed.
compounds extracted from gasoline with hydrochloric acid at 4.2.4. Deep Eutectic Solvents. The use of deep eutectic
concentrations less than 1 mol·L−1, while indole was the main solvents for crude oil nitrogen removal has recently been
compound extracted when the hydrochloric acid concentration investigated. They are an alternative to ionic liquids as they
was 6 mol·L−1. The author did not provide any explanation for have the same basic properties, such as low volatility and
the removal of nonbasic nitrogen compounds with hydrochloric existence in the liquid phase over a wide range of temperature,
acid. but with lower cost, lower toxicity, and simpler synthesis. They
It was claimed that the removal of pyrrolic compounds from are composed of a salt combined with a hydrogen-bond donor
shale oil was achieved by acidification with strong acids, such as or a complexing agent. Like ionic liquids, deep eutectic solvents
sulfuric acid, because of polymerization.80 Addition reactions of may have their properties changed by manipulation of the salt
pyrrolic compounds take place under acidic conditions,1,81 and and hydrogen-bond donor/complexing agent combination.71
acid-catalyzed addition, rather than extraction, could potentially In the first study reported,72 choline chloride and phenyl-
also explain the removal of neutral nitrogen-containing acetic acid deep eutectic solvents presented the highest
compounds in the work of Qi et al.61 and Feng.63 Whatever extraction from model oil: 99.2% of pyridine and 98.2% of
the correct explanation is, it is important to understand the carbazole were removed. It was explained that the denitroge-
mechanism involved in nitrogen removal, since polymerization nation performance is dependent on the acidity of the
taking place in a liquid−liquid extraction process will affect its hydrogen-bond donor component, as high acidity causes low
design and operation. affinity with basic nitrogen compounds and excessive acidity
4.2.3. Ionic Liquids. Ionic liquids are composed of leads to chemical reactions instead of physical separation.
heterocyclic organic cations and organic or inorganic anions.
They have low vapor pressure, are nonflammable, and exist in 5. SOLVENT DEASPHALTING
the liquid phase over a wide range of temperatures. Different Solvent deasphalting is a commonly employed process in oil
cation/anion combinations provide unique properties of ionic refining for processing of heavy oil fractions, and it operates on
liquids, which can be tailored to facilitate the extraction of the principle of liquid−solid phase partitioning. In a solvent
nitrogen-containing compounds.64 The majority of denitroge- deasphalting process, a light paraffinic solvent is mixed with the
nation studies involving ionic liquids have been reported for oil to change the solubility parameter and solubility character-
model oils in order to investigate the chemistry and selectivity. istics of the bulk liquid phase. Molecules in the oil that exceed
For example, dicyanamide-based ionic liquids were effective in the solubility threshold or that become immiscible because the
removing carbazole and pyridine from a model oil,65 while zinc- Gibbs free energy of mixing becomes positive, will form a
containing ionic liquids were effective in removing quinoline, separate phase. In solvent deasphalting, the second solid phase
acridine, and indole from a model oil.66 Model oils containing that is formed is called the asphaltenes fraction.
not only nitrogen compounds but also sulfur compounds were The nature of the solvent and method used to induce liquid−
also investigated. Acidic ionic liquids were able to remove solid phase partitioning affects the yield and composition of the
93.8% of carbazole and 97.8% of pyridine in a model oil that asphalthenes fraction that is precipitated from the oil. Using a
also contained sulfur compounds. In this study, 93.8% of the light paraffinic solvent to create the driving force for
sulfur compounds were also removed by the acidic ionic precipitation causes the asphaltenes fraction to contain
22 DOI: 10.1021/acs.energyfuels.6b02779
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Energy & Fuels Review

molecules that on average have a higher heteroatom content, The types of adsorbents that have been reported in the
are more polar in nature, and have a higher molecular mass literature for nitrogen compound removal are silica gel,8,63,83−85
than the bulk oil. As a consequence, nitrogen-containing activated alumina,63,86,87 activated carbon,87−92 metal−organic
compounds partition between the liquid and solid phases in frameworks,93,94 ion-exchange resins and modified poly-
such a way that the solid phase (asphaltenes fraction) is mers,97−106 and zeolites107−109,114,110,111 as well as a number
enriched in nitrogen-containing compounds (Figure 7).82 The of diverse materials such as solid acids and modified silica−
oil that remains in the liquid phase, after solvent recovery, has a aluminas.115,116 A summary of the nitrogen removal from real
lower nitrogen content than the oil feed from the solvent petroleum-derived feed materials with each of the adsorbents is
deasphalting process. presented in Table 6.
6.1. Adsorption Technology. Adsorption technology
processes usually consist of at least two vessels containing
adsorbents in parallel to enable continuous operation (Figure
8). This is necessary because adsorption technologies have two
modes of operation: adsorption and regeneration.
During the adsorption mode of operation, the oil feed is
passed over the adsorbent, and the nitrogen-containing
compounds are removed by adsorption onto the adsorbent.
The nitrogen content of the oil at the outlet of the adsorption
vessel is lower than that in the feed and remains constant until
breakthrough occurs. Breakthrough occurs when the adsorption
capacity is sufficiently consumed that the remaining capacity is
insufficient to achieve the same extent of nitrogen removal. Not
all of the adsorbent capacity is used when breakthrough occurs
because adsorption is not instantaneous and part of the
Figure 7. Partitioning of nitrogen-containing compounds during adsorbent is only partially loaded. The adsorption kinetics
solvent deasphalting.82 determines how much of the adsorption capacity remains at
breakthrough, with faster adsorption kinetics causing less
unused capacity to remain at breakthrough. Once breakthrough
From Figure 7, it should be clear that solvent deasphalting is is reached, the adsorbent must be regenerated.
not capable of deep nitrogen removal from oil. For example, if During the regeneration mode, the nitrogen-containing
heavy oil containing 1 wt % N is solvent-deasphalted so that the compounds on the adsorbent are desorbed. The method of
asphaltenes yield is 20 wt %, the deasphalted oil will still have desorption depends on the nature and strength of the
around 0.7 wt % N. adsorption as well as the nature of the adsorbent. The most
common methods of regeneration are by temperature and
6. ADSORPTION chemical reaction. Physisorption can be reversed by increasing
Adsorption processes employed for the removal of nitrogen- the temperature. When the temperature is increased, the
containing compounds from oil use a solid material, the physisorbed nitrogen-containing compounds are desorbed and
adsorbent, to retain the nitrogen-containing compounds as the can then be removed by washing the adsorbent with a stripping
oil flows over the adsorbent. The adsorbent material is selected liquid. Chemisorption usually requires a chemical reaction to
so that the nitrogen-containing compounds would be attracted remove the chemisorbed compounds. The reaction can either
and retained by interactions with the surface of the adsorbent. displace the adsorbed materials, such as regeneration of acidic
Compounds can be adsorbed on the surface by chemical or support materials with a stronger acid, or involve destruction of
physical interactions. When there is a chemical interaction the adsorbed material, such as complete oxidation of the
(chemisorption), a chemical bond is formed between the compound by reaction with hot air. The ease of regeneration
adsorbent and the compound, and the electronic configuration affects both the amount of time required for regeneration and
of the compound is changed. When the compound is retained the cost of regeneration.
on the surface by a physical interaction (physisorption), such as In the simplest configuration, shown in Figure 8, the first
through van der Waals or electrostatic forces, the compound vessel is used for adsorption while the adsorbent in the second
maintains its identity and no new bonds are formed. The type vessel is being regenerated.
of interaction affects the strength of retention and the Irrespective of the adsorption technology selected and the
selectivity. Chemisorption is generally more selective because adsorbent used, adsorption processes are better suited for
it makes use of the chemical identity of the nitrogen-containing removing nitrogen-containing compounds from oils with low
compounds, and the compounds are retained more strongly. nitrogen content than for bulk nitrogen removal for oils with
Although this is advantageous during adsorption, it also makes high nitrogen content. For example, to remove the nitrogen-
it more difficult to remove the adsorbed compounds after containing compounds from oil containing 1 wt % N using an
adsorption, when the adsorbent is regenerated for reuse. The adsorbent with a capacity of 2.4 molN·kg−1 and very fast
main parameters relevant to adsorption studies are adsorption adsorption kinetics, at least 0.3 kg of adsorbent/kg of oil is
kinetics, adsorbent capacity, selectivity, adsorbent regener- required. In a continuous process, the amount of adsorbent that
ability, adsorbent lifetime, and cost. is required is determined by both the nitrogen content of the
Different types of adsorbents for denitrogenation of oil have oil and the time it takes to regenerate the adsorbent. Using the
been reported and were recently reviewed by Laredo et al.7 The same example as before, if it takes 4 h to regenerate the
maximum adsorption capacity reported for any of the materials adsorbent, the amount of adsorbent required in each vessel is at
tested was in the range 2−3 mol of N/kg of adsorbent. least 1.2 kg per kg·h−1 of oil flow rate.
23 DOI: 10.1021/acs.energyfuels.6b02779
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Table 6. Denitrogenation of Real Industrial Feedstocks by Adsorption


type of adsorbent feed adsorbent process conditions nitrogen conversion/removal ref
silica gel light cycle oil room temperature 97.5% N removed 8
gasoline room temperature 98.22% basic N removed 63
diesel (tar sands, Canada) room temperature 99.6% N extracted 83
30 min
Diesel (Rota, Spain) room temperature 99.7% N extracted 83
30 min
SK SRGO room temperature 82% N removed 84
1000 bbl/day
Coker gas oil room temperature 86% N removed 84
1000 bbl/day
activated carbon Japanese SRGO MAXSORB-II 0.14 MPa 77% N removed 88
30 °C
Japanese SRGO MGC-B 0.14 MPa 41% N removed 88
30 °C
Japanese SRGO OG-20A 0.14 MPa 43% N removed 88
30 °C
metal−organic frameworks SRGO and LCO MIL-101(Cr) 403 K for 12 h 90% N removed 94
remaining time at 298 K
LSHV: 0.8 h−1
ion-exchange resins Arabian straight-run fuel oil HPQ 313 K 41% N removed 98
15 min
polymers Iranian SRGO PGMA-TENF room temperature 50% N removed 100
gas oil:polymer = 8:1
bitumen-derived HGO PGMA-TENF room temperature 6.7% N removed 101
1h
15 wt % polymer
bitumen-derived LGO PS-NN-DNF 22 °C 9.4% N removed 102
400 rpm
24 h
oil:polymer = 4:1
bitumen-derived LGO PGMA-NN-TriNF 22 °C 400 rpm 14.4% N removed 102
24 h
oil:polymer = 4:1
bitumen-derived LGO PGMA-NN-TENF 22 °C 11.2% N removed 102
400 rpm
24 h
oil:polymer = 4:1
bitumen-derived LGO PGMA-NN-TENF 20 °C 11.4% N removed 103
200 rpm
48 h
oil:polymer = 1:5
bitumen-derived LGO PS-NN-TENF 20 °C 0.8% N removed 103
200 rpm
48 h
oil:polymer = 1:5
bitumen-derived HGO PGMA-NN-TENF 50 °C 5.3% N removed 103
200 rpm
48 h
oil:polymer = 1:5
bitumen-derived LGO PGMA-DAP3-TENF 22 °C 19% N removed 105
400 rpm
48 h
oil:polymer = 4:1
bitumen-derived LGO P3-ON-TENF 22 °C 14.6% N removed 106
200 rpm
24 h
oil:polymer = 4:1
alumina gasoline room temperature 99.29% basic N removed 63
zeolites commercial diesel oil CrY ambient pressure 56.58% N removed 107
room temperature
commercial diesel oil CuY ambient pressure 60.16% N removed 107

24 DOI: 10.1021/acs.energyfuels.6b02779
Energy Fuels 2017, 31, 14−36
Energy & Fuels Review

Table 6. continued
type of adsorbent feed adsorbent process conditions nitrogen conversion/removal ref
room temperature
commercial diesel oil ZnY ambient pressure 37.41% N removed 107
room temperature
commercial diesel oil NaY ambient pressure 23.72% N removed 107
room temperature
commercial diesel oil CuY ambient pressure 99.8% N removed 108
room temperature
Anqing naphtha 13X impregnated with H3PO4 20 °C 84.5% N removed 109
feed velocity 6 h−1
Cold Lake bitumen Chabazite clay 400 °C 74% N removed 110
1h
50% zeolite
FCC diesel oil Co-MCM-41 ambient pressure 33.46% N removed 113
room temperature
30 min
commercial diesel oil Ti-HMS ambient pressure >90% N removed 114
room temperature
methyl viologen aluminosilicate commercial light oil 298 K 86% N removed 115
24 h
straight-run light gas oil 298 K 65% N removed 115
24 h
light cycle oil 298 K 72% N removed 115
24 h
other solid acids lubricant base oil solid acid 110 °C 87% basic nitrogen removed 116
1 wt % solid acid
30 min

silica gel before hydrotreating was able to reduce the nitrogen


content from 635 to 16 ppm while the sulfur and aromatic
contents remained unchanged.8
Pretreatment of middle distillates by silica gel was
commercially implemented by SK Corporation of Korea in
2002 to produce ultralow-sulfur diesel. The plant can process
1000 barrels/day, and 70−86% nitrogen removal can be
achieved depending on the feed (Table 6). Pretreatment with
silica gel to remove nitrogen-containing compounds resulted in
deeper desulfurization. The pretreated product after hydro-
treating contained 9−60 ppm sulfur, whereas the hydrotreated
Figure 8. Simple adsorption process with two vessels. One vessel is in
product without feed pretreatment contained 53−360 ppm
adsorption mode, and one vessel is being regenerated. sulfur.84 Improved hydrodesulfurization subsequent to nitrogen
removal was also reported by others.7,8
6.2. Adsorbents for Denitrogenation. 6.2.1. Silica Gel. 6.2.2. Activated Alumina. The use of activated alumina for
Silica gel removes nitrogen-containing compounds by phys- nitrogen adsorption has been mainly studied with model diesel
isorption. Since silica gel does not contain strong adsorptive oils containing sulfur, nitrogen, and aromatic compounds. It has
sites, the attraction between the adsorbent and polar nitrogen been demonstrated that activated alumina has more adsorption
compounds is by hydrogen bonding, which facilitates silica capacity for nitrogen than other compounds present in the
regeneration.85 Silica gel has therefore also been employed to model fuel oil. The mechanisms responsible for the higher
preconcentrate nitrogen-containing compounds for analysis, selectivity toward nitrogen compounds involve electrostatic
where denitrogenation of the oil is not the only objective. interactions and acid−base interactions.86,87 Basic nitrogen
Mushrush et al.83 used silica gel to remove nitrogen from 22 compounds present higher adsorption with acidic activated
finished diesel fuels from different parts of the world, and 97.8− alumina, while more acidic nitrogen compounds present higher
99.7% organic nitrogen extraction was achieved. Nitrogen adsorption with lower-acidity activated alumina.87 Alumina was
compounds were subsequently desorbed and analyzed by gas able to remove 99.29% of basic nitrogen from gasoline.63
chromatography−mass spectrometry (GC−MS). The most 6.2.3. Activated Carbon. The denitrogenation efficiency of
abundant compounds in the diesel fuels were pyridines (60%), adsorption using activated carbon depends on its surface area as
quinolines and tetrahydroquinolines (26%), and indoles and well as its surface chemical composition. Nitrogen removal
carbazoles (10%). from straight-run gas oil (SRGO) using three different types of
Silica gel appeared to be quite selective for nitrogen- activated carbon has shown that nitrogen removal is higher
containing compounds, despite the fact that it only physisorbed when the oxygen content of the activated carbon is increased
these compounds. Pretreatment of light cycle oil (LCO) by (Table 6).88 In a later study, it was found that nitrogen
25 DOI: 10.1021/acs.energyfuels.6b02779
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adsorption is higher when the activated carbon contains basic nitrogen-containing compounds through the acid−base
oxygenated compounds that release CO during temperature- reaction between the basic nitrogen compounds and the acidic
programmed desorption, while CO2-liberating groups inhibit groups. For example, it was reported that a high-acidity resin
nitrogen adsorption by activated carbon. Addition of CO- was able to remove only basic nitrogen compounds from
liberating groups can be achieved by manipulating the oxidation hydrotreated jet fuel, diesel fuel, and vacuum gas oil fractions
process of the activated carbon.89 derived from shale oil.97
The adsorption of nitrogen compounds from LCO was also The use of ion-exchange resins for removal of neutral
higher when wood-based activated carbon oxidized by nitrogen-containing compounds has been reported for Arabian
(NH4)2S2O8 was used, compared with the nonoxidized straight-run fuel oil.98 Around 41% of the neutral nitrogen
activated carbon. When the oxidant concentration increased compounds could be extracted from straight-run fuel oil by
from 0 to 15%, the nitrogen adsorption capacity increased by using an ion-exchange resin containing a pyridinium chloride
18%. A study with model fuel oil revealed that quinoline functionality. The resin was regenerated by washing with
adsorption was favored by carboxylic acid groups and lactone pentane and methanol. A total of 78% of the nitrogen-
groups present in the activated carbon, while indole and containing compounds could be extracted in a three-step
carbazole adsorption were favored by carboxylic anhydride extraction process (i.e., the extraction was repeated three
groups and phenolic groups.90 times).
A commercial activated carbon (Maxsorb I) oxidized by The success in removing neutral nitrogen compounds was
ammonium persulfate was also used to understand the explained in terms of hydrogen bonding between the chloride
mechanism of oxygenate compounds in activated carbon. The ion and the neutral nitrogen-containing compounds, such as
results showed that the surface of activated carbon containing carbazole, which acted as proton donors.98 However, it should
high oxygen content would interact with the nitrogen be noted that pyridinium halide perhalide in pyridine was
compounds by acid−base and hydrogen-bonding interactions, reported to be a good halogenation agent for indole,81,117 and
while the surface containing low oxygen content would interact the removal by the pyridinium chloride-containing resin might
by π−π interactions, which are weaker.91 also have involved halogenation.
The use of natural materials to prepare activated carbons for Modification of polymers with π-acceptor molecules in
nitrogen removal has also been investigated.92 Chemical principle enables adsorption of pyrrolic nitrogen-containing
activation of palm oil shell, coconut shell, olive stone, apricot compounds through complex formation as well as pyridinic
stone, and almond shell produced adsorbents with high surface nitrogen-containing compounds through Lewis acid−base
area, high density, high carbon content, and low ash content. interactions.99 Employing this approach enabled 50% nitrogen
6.2.4. Metal−Organic Frameworks. Metal−organic frame-
removal (and 5% sulfur removal) from an Iranian straight-run
works (MOFs) are composed of inorganic and organic
gas oil using 2,4,5,7-tetrafluorenone (TENF) as the π acceptor
materials and contain two components. The first component
and poly(glycidyl methacrylate) (PGMA) as the polymer
is a metal ion or a cluster of metal ions, while the second
support.100 When the same material was employed for nitrogen
component is an organic linker. The organic linker can be
removal from bitumen-derived heavy gas oil, only 6.7% of the
selected to enable nitrogen removal by acid−base interactions,
coordination bond formation, π complexation, hydrogen total nitrogen was removed; the majority of the nitrogen
bonding, and van der Waals forces. The main merits when compounds adsorbed were pyrrolic.101 Somewhat better
using MOFs as adsorbent materials are their high porosity and nitrogen removal was achieved when 2,4,7-trinitro-9-fluorenone
tunable chemical properties, while the main demerits are their (TriNF) was employed as the π acceptor instead of TENF.102
instability at high temperature and in basic media. The use of An investigation into the impact of the polymer support on
MOFs for adsorption and removal of nitrogen-containing nitrogen removal by TENF concluded that hydrophilic
compounds was recently reviewed by Ahmed and Jhung.93 polymers with higher surface area, such as TENF-modified
Only a few studies have reported the use of MOFs with real PGMA, are more selective and efficient for nitrogen removal
industrial feed materials. For example, straight-run gas oil and when sulfur and aromatic compounds are present in real
its mixtures with light cycle oil have been denitrogenated with feeds.103 In a different study,104 hydrophilic polymers achieved
MOF MIL-101(Cr), and the nitrogen removal was around higher nitrogen removal from diesel fuel compared with
90%. Regeneration studies showed that the adsorbent could be hydrophobic polymers, which led to the same conclusion.
used for at least 280 cycles while keeping almost the same The linker length was also investigated as a parameter that may
nitrogen removal capacity.94 affect nitrogen removal, and it was found that the linker length
It was reported that a functionalized MOF was able to had little effect on nitrogen adsorption apart from steric
remove both indole and quinoline from model oils.95,96 The hindrance.105 Polymers with high internal phase emulsion
success in removing nonbasic indole is attributed to hydrogen achieved 14.6% nitrogen removal from bitumen-derived gas
bonding between the neutral nitrogen and sulfonic or oil.106
carboxylic groups on the MOF. Since MOF preparation is 6.2.6. Zeolites. Different types of zeolites were studied for
time-consuming and high consistency is difficult to achieve, adsorptive denitrogenation of fuels/oils. Adsorptive denitroge-
other compounds containing sulfonic groups could possibly be nation of diesel oil using modified NaY zeolite achieved 23.72−
used for the removal of nonbasic nitrogen compounds in real 60.16% basic nitrogen removal (Table 6). The highest
industrial feed materials, as discussed in the next subsection. denitrogenation was achieved with higher-valence metal
6.2.5. Ion-Exchange Resins and Modified Polymers. The ions.107 CuY zeolite could reduce the nitrogen content of
types of nitrogen-containing compounds that will be adsorbed commercial diesel oil from 83 to 0.1 ppm by π-complex
by ion-exchange resins and modified polymeric materials formation between nitrogen compounds and the zeolite.108 13X
depend on the nature of the functional groups on the organic zeolite impregnated with phosphoric acid was able to remove
substrate. The use of acidic groups is efficient for the removal of 84.5% of nitrogen from naphtha.109
26 DOI: 10.1021/acs.energyfuels.6b02779
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Zeolites are also used in catalytic cracking of oils, and not eliminate the nitrogen group from the compound. When
denitrogenation can be achieved by adsorption of nitrogen the nitrogen content in the oil product is low, the derivatized
compounds in the zeolite catalyst under cracking conditions. product can be treated as a waste product after separation from
Modified natural chabazite was able to remove 74% of the the oil. This approach is viable because there is a small loss of
nitrogen from catalytic cracking of bitumen.110 In a later study material. In any process that employs derivatization to facilitate
with model compounds it was suggested that under cracking separation, the bulk of the material that is removed from the oil
conditions nonbasic nitrogen is converted into basic nitrogen, is not nitrogen but rather carbon and hydrogen that form part
which is then adsorbed on the acidic chabazite zeolite.111 of the nitrogen-containing compound. In cases where the
Heteroatom-containing mesoporous molecular sieves have nitrogen content is high, it is important also to have a strategy
been studied for denitrogenation of oils. In a first study it was to liberate nitrogen from the hydrocarbon matter so that the
observed that Co-MCM-41 molecular sieve was more effective hydrocarbon matter can be returned to the oil. Three steps are
in removing basic nitrogen from model oil compared with required (Figure 9): step 1 is the derivatization reaction; step 2
MCM-41. However, when they were used in commercial diesel
oil, MCM-41 mesoporous molecular sieve presented higher
removal of basic nitrogen (68.22%) than Co-MCM-41
(65.91%).112 In a later study, it was found that the content of
Co influences the absorption capacity of the mesoporous
molecular sieves. For example, the absorption capacity of basic
nitrogen from fluidized catalytic cracking (FCC) diesel oil was
9.11 mg of nitrogen/g for Co-MCM-41 and 7.36 mg of
nitrogen/g for MCM-41. Nevertheless, the absorption capacity
of Co-MCM-41 decreases with increasing Co content. It was Figure 9. Block flow diagram for nitrogen removal from oils with high
explained that Co enhances nitrogen absorption due to physical nitrogen content.
absorption and π complexation but that a high Co content
promotes the formation of Co3O4 on the channel surface, is the separation, which becomes more efficient as a result of
which blocks active sites and consequently decreases nitrogen the derivatization; and step 3 is the extrusion of the nitrogen
absorption. The total nitrogen removal from FCC diesel oil from the nitrogen-containing compounds so that the hydro-
achieved was 33.46%.113 Ti-HMS mesoporous molecular sieve carbon fraction can be recovered as denitrogenated oil. If step 3
could remove more than 90% of the nitrogen from diesel, is not performed, the loss of material can become excessive, and
where the adsorption process was spontaneous and exothermic. the method is not useful for high-nitrogen-content oils. To
In addition, adsorption occurs in the pores of the zeolite.114 illustrate the point, if the average molecular formula of the
6.2.7. Other Materials. Amorphous silica−alumina modified nitrogen-containing compounds in oil is C12H9N (carbazole),
with methyl viologen dichloride (C12H14N2+Cl2−) was inves- when 1 wt % N is removed, 12 wt % of the oil is removed.
tigated for denitrogenation and desulfurization of model oils as 7.1. Oxidation. Separation of nitrogen compounds from oil
well as light oils.115 While both sulfur and nitrogen could be by oxidation relies on the principle that oxidized nitrogen
removed from model oils, only denitrogenation was achieved compounds can be more efficiently extracted with polar
for the real feedstocks. It was explained that the presence of solvents that are immiscible with oil than the unoxidized
aromatic hydrocarbons in the light oils suppressed sulfur nitrogen-containing compounds. The main challenge in this
adsorption by the methyl viologen aluminosilicate, while process is to selectively oxidize nitrogen compounds, since
nitrogen adsorption was achieved as a result of the lower oxidation of other compounds present in the oil may result in
ionization potential of nitrogen compounds, which easily the formation of heavier products that are undesirable.
formed a charge-transfer complex with the adsorbent. The Two common modifications of simple oxidative denitroge-
adsorbent could be regenerated by toluene washing.115 nation (ODN) using oxidants such as air, hydrogen peroxide,
A nonspecified solid acid selectively removed nitrogen and organic peroxides are found. The first modification involves
compounds from lubricating base oil. Nitrogen compounds the use of a catalyst, either to assist with the decomposition of
are known to be detrimental to the oxidation stability of base peroxides (R−O−OH) into free radicals (R−O· + ·OH) or to
oils, while sulfur has the opposite effect. The solid acid was able lower the activation energy of the transition state during
to remove 87% of the basic nitrogen compounds and only 13% oxidation. The second modification is the use of UV light to
of the sulfur compounds.116 increase the oxidation rate by free radical formation.
Only a few studies of oxidation of industrial oils for nitrogen
7. CHEMICAL CONVERSION FOLLOWED BY removal have been reported, and in those instances oxidative
SEPARATION desulfurization and oxidative denitrogenation are performed in
The chemical conversion of nitrogen-containing compounds tandem. For example, the oxidation process described by Guth
has one of two objectives: either to derivatize the nitrogen- and Diaz118 uses a gaseous mixture of oxides of nitrogen to
containing compounds to improve subsequent removal or to oxidize sulfur and nitrogen in fuel oils, which are then extracted
eliminate the nitrogen functional group to produce a nitrogen- with methanol. The selectivity of the process is improved by
containing product that can easily be removed, such as by pretreating the oil to remove other compounds that can also be
forming NH3 or NOx. Hydrogenation, which was discussed as a oxidized and form coke.118
separate topic (section 3), belongs to the latter group of In the study by Conceiçaõ et al.119 nitrogen compounds in a
chemical conversions. gas oil were selectively oxidized by a mixture of ethanoic acid
Derivatization of nitrogen-containing compounds usually and hydrogen peroxide, and the oxidized compounds were
employs a reagent that is capable of addition or substitution removed in the aqueous phase. When hydrogen peroxide is
reactions to produce a chemically modified product but does mixed with an organic acid, it generates the corresponding
27 DOI: 10.1021/acs.energyfuels.6b02779
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Table 7. Denitrogenation of Real Industrial Feedstocks by Oxidation


nitrogen conversion/
feed oxidant separation process oxidation conditions removal ref
hydrotreated VGO peracetic acid acetic acid extraction 60 °C 90% N removed 121
30 min
Japanese LGO t-BuOOH + 16 wt % adsorption by silica gel atmospheric 94.1% N removed 122
MoO3/Al2O3 pressure
WHSV: 30 h−1
straight-run LGO H2O2 + AcOH acetonitrile−water azeotropic mixture 70 °C 43.7% N removed 123
extraction atmospheric
pressure
3h
commercial light oil H2O2 + AcOH acetonitrile−water azeotropic mixture 70 °C 58.2% N removed 123
extraction atmospheric
pressure
3h
light cycle oil H2O2 + AcOH acetonitrile−water azeotropic mixture 70 °C 62.1% N removed 123
extraction atmospheric
pressure
3h

Table 8. Denitrogenation of Real Industrial Feedstocks by Oxidative Photoirradiation


feed polar solvent process conditions nitrogen conversion/removal ref
commercial light oil H2O 50 °C 70% N removed 124
36 h
straight-run light gas oil H2O 50 °C 48% N removed 124
36 h
light cycle oil H2O 50 °C 23% N removed 124
36 h
commercial light oil H2O + 30% H2O2 50 °C 93% denitrogenation yield 124
36 h
straight-run light gas oil H2O + 30% H2O2 50 °C 92% denitrogenation yield 124
36 h
light cycle oil H2O + 30% H2O2 50 °C 80% denitrogenation yield 124
36 h
vacuum gas oil acetonitrile 50 °C >90% denitrogenation yield 125
10 h

peroxy acids of the carboxylic acids, which can convert pyridinic that polymeric materials formed during the reaction contained
nitrogen to N-oxides.120 Other compounds such as hydro- nitrogen and oxygen.122
carbons, olefins, ketones, and phenols remained constant after Oxidation of nitrogen and sulfur compounds present in three
oxidation and separation of Brazilian petroleum gas oil. different light oils were successfully achieved by hydrogen
Another process to achieve the same utilized nonaqueous peroxide and acetic acid followed by extraction with an
organic peroxide as the oxidant will generate acetic acid as a acetonitrile−water azeotropic mixture.123 When tert-butyl
byproduct, in which oxidized nitrogen compounds would be hydroperoxide was employed as the oxidant, the most difficult
soluble without the need for further polar solvent extraction.121 nitrogen compound to denitrogenate was carbazole.
By this method, the nitrogen and sulfur contents of In a variation on the standard autoxidation process,
hydrotreated vacuum gas oil (VGO) were reduced by 90% photoirradiation was employed as means to increase the
and 73%, respectively. The results of this process and other efficiency. The light oil was mixed with acetonitrile or water,
and sulfur and nitrogen compounds present in the oil were
processes for oxidative denitrogenation are given in Table
transferred to the polar phase and then photoirradiated with
7.121−123
UV light to form highly polarized compounds that were not
During oxidative desulfurization of light gas oil, it was also
miscible with the low-polarity oil. The oxidized nitrogen-
observed that nitrogen compounds were oxidized and removed containing compounds were removed in the form of an NO3−
from the oil.122 The oxidant employed was tert- butyl ion that was soluble in the polar phase. This process was
hydroperoxide (t-BuOOH) in the presence of 16 wt % investigated with model compounds (aniline, indole, and
MoO3/Al2O3 catalyst. Oxidized compounds were further carbazole)124 and industrial oil feedstocks.124,125 Carbazole
removed from the oil by adsorption on silica gel. The nitrogen was the nitrogen compound that was the most difficult to
content was reduced from 13.5 to 0.8 ppm. A study with model denitrogenate by photoirradiation. It was explained that the
compounds revealed that indole was the most reactive photodecomposition of carbazole is “suppressed by triplet-
compound, followed by quinoline, acridine, and carbazole. energy transfer from photo-excited carbazole to ground-state
Even though it was not possible to identify which types of double-ring aromatic hydrocarbons.” However, denitrogenation
compounds were extracted from the oil, the results suggested of light oils is increased by adding hydrogen peroxide into the
28 DOI: 10.1021/acs.energyfuels.6b02779
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oil/water mixture to increase the oxidant power. Nevertheless, Table 9. Denitrogenation of Real Industrial Feedstocks by
autoxidation with photoirradiation in acetonitrile presented N-Alkylation
higher denitrogenation than in water/hydrogen peroxide
nitrogen
solvent.124 Shiraishi et al.125 presented how photoirradiation alkylating alkylation conversion/
could be incorporated into the conventional refining process, as feed agent conditions removal ref
this process could also remove both nitrogen and sulfur commercial CH3I/AgBF4 30 °C 83 wt % N 131
compounds from oils. Denitrogenation yields of some industrial light oil 11 h removed
oils are presented in Table 8. N2
Other kinds of oxidants and catalysts have been investigated atmosphere
for oxidation of nitrogen model compounds. For example, light gas oil CH3/AgBF4 30 °C 96 wt % N 131
removed
oxidation of pyridine and its derivatives by H2O2 catalyzed by a 11 h
polyoxometalate intercalated into a layered double hydroxide N2
atmosphere
modified with tris(hydroxymethyl)aminomethane (tris-
light cycle oil CH3/AgBF4 30 °C 94 wt % N 131
LDHLa(PW11)2) was successfully achieved at room temper- removed
11 h
ature. Further denitrogenation of model oil containing
N2
quinolines was achieved within 40 min at 75 °C.126 Natural atmosphere
and reduced limonite were also used as catalysts for the vacuum gas CH3/AgBF4 30 °C 93 wt % N 132
oxidation of quinoline by H2O2 and formic acid. Reduced oil 11 h removed
limonite provided higher oxidation (90% conversion after 360 N2
min) because Fe2+ could react with H2O2/formic acid via atmosphere
Fenton-like mechanism.127
The effect of nitrogen compounds on oxidative desulfuriza- pyridine derivatives with bromoacetic acid using ethyl acetate as
tion for different catalysts has also been reported in the a solvent. The polar bromide salts were used as substrates for
literature. For example, the presence of pyridine and pyrrole the production of indolizines. Salt formation resulted from
decreased the removal rate of thiophene during oxidation with alkylation at the nitrogen atom instead of the acid−base
H2O2 over Ti-containing molecular sieves.128 In contrast, reaction with the carboxylic acid group (Figure 10). Since the
quinoline and indole did not affect oxidative desulfurization. In
the case of benzothiophene and 4,6-dimethyldibenzothiophene,
the presence of carbazole decreased their removal rate. By
applying an excess of oxidant, the authors concluded that the
decrease in the removal rate is not due to the competition for
H2O2 but rather the adsorption of nitrogen compounds on the
catalyst active sites.128
The same explanation was forwarded for a decrease in Figure 10. Reaction between pyridine and bromoacetic acid.
oxidative desulfurization of model compounds by V2O5/Al2O3
and V2O5/TiO2 catalysts performed in the presence of polar bromide salts were insoluble in ethyl acetate, basic
quinoline, indole, and carbazole.129 The presence of indole nitrogen compounds in oil could be removed by reacting them
and quinoline also decreased the reaction rate of oxidation of with bromoacetic acid to form insoluble salts. The salts could
sulfides by H2O2 catalyzed by H3+nPMo12−nVnO40 supported on then be separated from the oil by filtration or liquid−liquid
silica-encapsulated γ-Fe2O3 nanoparticles.130 extraction.
7.2. N-Alkylation. Alkylation as a reaction has been Mehranpour et al.134 also obtained insoluble salts by reacting
investigated for denitrogenation of light oils131 and vacuum quinoline derivatives with bromoacetic acid, even though the
gas oil.132 The nitrogen compounds are methylated and then reaction conditions were slightly modified. Quinoline and
removed by precipitation. The alkylating agents used were pyridine derivatives could be recovered later by hydrolyzing the
CH3I and AgBF4. Nitrogen compounds are then precipitated as salts in a basic environment. As presented in the work of
N-methylated tetrafluoroborates. Denitrogenation of light oils Bogardus and Higuchi,135 the carbon−nitrogen bond of N-(4-
and vacuum gas oil was successfully achieved by this method hydroxy-3,5-dimethylbenzyl)pyridinium bromide was cleaved
(Table 9), and it was accompanied by alkylation of sulfur and during its hydrolysis under basic conditions to generate
aromatics.131,132 Studies with model compounds revealed that pyridine and 4-hydroxymethyl-2,6-dimethylphenol, and the
aniline, pyridine, quinoline, and carbazole were removed as rate of the hydrolysis was increased by decreasing the pH of
precipitates of their corresponding methylated products, while the solution.
indole and pyrrole were removed as insoluble polymerized The procedure described above is suitable for basic nitrogen
materials. In addition, denitrogenation of basic nitrogen compounds only, since it is a nucleophilic substitution
compounds and compounds containing alkyl substituents was alkylation reaction and nonbasic nitrogen compounds are not
more effective than that of nonbasic nitrogen compounds. This good nucleophiles. Nevertheless, nonbasic nitrogen compounds
is because denitrogenation by this method depends on the can react with bromoacetic acid if basic conditions are provided.
electron density on the nitrogen atom, which is increased by Pyrrole and carbazole were successfully converted into 1-
alkyl substituents.131 pyrroleacetate sodium salt and N-carbazolylacetate sodium salt,
Bromoacetic acid (CH2BrCOOH) was also explored as a respectively, when reacted with bromoacetic acid under basic
reagent for N-alkylation. Basic nitrogen compounds could be conditions.136,137 Since oils contain basic and nonbasic nitrogen
removed from crude oil by an alkylation denitrogenation compounds and hydrolysis of quaternary ammonium deriva-
method with bromoacetic acid. In the work of Zhang et al.,133 tives of tertiary amines is achieved under basic conditions,135
polar pyridinium bromide salts were obtained by reacting the removal of nonbasic nitrogen compounds by this procedure
29 DOI: 10.1021/acs.energyfuels.6b02779
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would require two steps: (i) the removal of basic nitrogen nitrogen could be removed by this method, suggesting that
compounds by selective alkylation with bromoacetic acid and other factors are involved in nitrogen removal by CuCl2 rather
(ii) the removal of nonbasic nitrogen compounds by alkylation than a Lewis acid−base reaction. Following this approach, 95%
with bromoacetic acid under basic conditions. of the CuCl2 could be recovered and regenerated.
7.3. Complexation with Metallic Salts. Basic nitrogen A study with model compounds also revealed that nitrogen
compounds can be removed from oil by complexation with removal was selective, i.e. the sulfur and hydrocarbon contents
metallic salts. This is because the metal ions are Lewis acids remained constant after the complexation process with
(electron-pair acceptors) and basic nitrogen compounds are CuCl2.139
Lewis bases (electron-pair donors). The Lewis acid−base It was found that the nitrogen removal efficiency with CuCl2
reaction results in the formation of an organometallic complex. could be increased by the addition of some water during the
Examples of denitrogenation by complexation using metal salts process.140 The denitrogenation of heavy coker gas oil derived
can be found in Table 10.63,138−141 from Athabasca bitumen was increased from ∼20% to 60% by
increasing the water content from ∼3.5% to 9%. It was
Table 10. Denitrogenation of Real Industrial Feedstocks by explained that copper chloride dissolves in water, which
Metal Complexation improves the contact between the salt and components at the
oil−water interface. The method was selective for nitrogen
nitrogen
process conversion/ removal, as the sulfur content of the oil was not meaningfully
feed metal salt conditions removal ref affected.
gasoline 20 wt % FeCl3 room 98.89% 63 Metallic ion/complexing extraction was also studied for
temperature basic N straight-run diesel. The authors did not specify what kinds of
20 min removed
salt were used for the study; nevertheless, 90.8% of the total
gasoline 20 wt % SnCl2 room 95.72% 63 nitrogen could be removed from straight-run diesel.141
temperature basic N
20 min removed Hydrated iron(III) chloride adsorbed on attapulgus clay was
shale oil CuCl2 65 °C ∼85% N 138
suggested by Rayner-Canham and Dickerhoof142 to deni-
45 min removed trogenate petroleum distillates by complexation. Amines were
LGO from shale CuCl2 65 °C 88% N 139 successfully complexed by iron chloride−clay suspended in
oil 2h removed toluene, while quinoline and pyrazole complexed with iron
LGO from coal CuCl2 65 °C 87.3% N 139 chloride were retained on the surface of the clay only when
liquid 2h removed pentane was used as a solvent for the complexation process.142
pyrolysis product CuCl2 65 °C 63.4% N 139 7.4. Conversion in High-Temperature Water. Two
from Athabasca 2h removed important reviews have discussed the use of water as a reagent
bitumen at high temperature. The first review, in two parts,143,144
Athabasca HGO CuCl2 + 65 °C 60.0% N 140
8.6 wt % H2O removed
considered the role of water in reactions that are relevant to the
2h
transformation of organic material under geological conditions
salt:oil = 0.2
to ultimately produce fossil fuels. Akiya and Savage145 provided
straight-run diesel not specified salt:oil = 1.0 90.8% N 141
removed a systematic study of the different roles of water in conversion
3 min
chemistry. These reviews covered the chemistry of water over a
20−30 °C
wide temperature range, which included supercritical con-
ditions. The critical point of water is at 374 °C and 22 MPa.
Aqueous solutions of SnCl2 and FeCl3 were mixed with
7.4.1. Subcritical Water. The dissociation constant of water
gasoline, and basic nitrogen compounds were successfully
removed (98.89% for FeCl3 and 95.72% for SnCl2) by increases with temperature, reaching a maximum at around
complexation with the metal halides.63 250−275 °C, which makes this an interesting temperature
The use of metal salts for nitrogen removal from shale oil by range for subcritical water chemistry. In a series of
complexation was investigated.138 Different solids (transition papers,146−148 the conversion of pyridine and its derivatives
metal halides, sulfates, acetates, nitrates, phosphates, and was investigated by keeping the pyridines and water at reaction
fluoroborates) were screened for their removal of pyridine conditions of 250 °C and high pressure for several days.
and its derivatives. Copper chloride (CuCl2) demonstrated high Although some conversions were observed, the nitrogen group
affinity for all pyridine compounds, including 2,6-dimethylpyr- was not eliminated from the pyridines. Most pyrroles and
idine, where the nitrogen is sterically crowded. In addition, it indoles were not denitrogenated by water when kept at 250 °C
was found that the Lewis acidity of the metal is not the only for 5 days, the exception being 2,5-dimethylpyrrole.149 About
factor affecting nitrogen complexation. The crystal structure of half of the products from the reaction of 2,5-dimethylpyrrole
the formed solid affects the nitrogen complexation, since and water were denitrogenated ketones. Arylamines were not
pyridine has to permeate into the solid crystal, which affects the denitrogenated by water at 250 °C, but in the presence of
capacity. More than 85% of the nitrogen content was removed phosphoric acid, significant conversion to phenols was
by treating shale oil with CuCl2 at 65 °C for 45 min. CuCl2 found.150 It was further found that hydroxydeamination (the
could be regenerated by water washing followed by Bucherer reaction) did not take place in the presence of
evaporation. NaHSO3 and water, despite the severe reaction conditions.150
Synthetic crude oils from various sources, shale oil, coal At a reaction temperature of 350 °C, which is sufficiently
liquid, and oilsands bitumen, were also reacted with CuCl2 with high for thermal cracking to become significant, the conversion
the purpose of removing nitrogen compounds.139 The results of nitrogen-containing compounds in the presence of water was
revealed that not only the total nitrogen content decreased but higher. Denitrogenation of various nitrogen heterocycles was
also 80.6−91.2% basic nitrogen and 29.8−68.3% nonbasic found at 350 °C but was not observed at 250 °C.151
30 DOI: 10.1021/acs.energyfuels.6b02779
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7.4.2. Supercritical Water. The high diffusivity of super- Table 11. Denitrogenation of Real Industrial Feedstocks by
critical fluids has been explored for heavy oil upgrading, and Supercritical Water
studies using supercritical water for removal of nitrogen from
process nitrogen conversion/
oil are available in the literature. The reason cited for the use of feed process conditions removal ref
water specifically is that water’s dielectric constant can be
heavy oil batch 400 °C 62.5% N removed 161
changed with temperature and pressure, which increases the
30 min
miscibility with organic compounds and thereby the rate of
20 vol %
reaction.152 Data on the change in properties of water can be diluent
found in the review by Akiya and Savage.145 crude oil continuous 400 °C 57.3% N removed 161
The challenge with interpreting any of the literature on 23.4 MPa
supercritical water conversion is that the temperature is already crude oil continuous 400 °C 43.75% N removed 161
in a range where thermal cracking takes place. Distinguishing 23.4 MPa
between thermal cracking reactions and those caused by water
is difficult, noting that water also plays a moderate role by
suppressing reactions such as free radical recombination. microorganisms occurs aerobically. First, oxygenases insert
Denitrogenation studies with supercritical water were oxygen into the substrate to yield hydroxylated intermediates,
initiated using model compounds with the objective of after which ring cleavage occurs. Quinoline, indole, and pyrrole
understanding the chemical reaction mechanism. Various are readily degraded by microbial attack, while carbazole is the
pyridines, pyrroles, N-oxides, and oxime derivatives were most difficult one to degrade. It is believed that the difficulty in
studied.153−157 The model compounds were reacted with degrading carbazole arises from the fact that its degradation
supercritical water with or without catalysts (ZnCl2 and starts with angular deoxygenation, which is difficult to
FeO3).153,154 The reaction mechanism differs for each model achieve.162 Because biodenitrogenation results in ring destruc-
compound and process parameter. Briefly, the main denitroge- tion, the main disadvantage of this method is that it promotes
nation reactions for isoquinoline and quinoline involve carbon the loss of the fuels energetic value, and a current focus of this
oxidation, decarboxylation,153 and C−N hydrolysis preceded by area involves genetic modification of microorganisms to obtain
hydrogenation and hydrocracking of heterocycles.154 In ones that can selectively remove nitrogen without degrading
addition, ZnCl2 increases the reactivity of less reactive the carbon skeleton.162,163
species.153 In the absence of other reagents, water alone was In the study of Sugaya et al.,164 quinoline was added to
not efficient at converting pyridine and pyrrole derivatives, and Arabian light crude oil, and it was degraded by Comamonas sp.
very small amounts of denitrogenated compounds were found TKV3-2-1. Quinoline was completely converted into water-
after reaction.155,156 The N-oxide and oxime derivatives were soluble 2-hydroquinoline in 30 min. In addition, the strain
more reactive.157 maintained its denitrogenation activity for 7 days, and more
Yuan et al.158 studied catalytic denitrogenation of quinoline than 99% of the cells could be recovered by centrifugation.
in supercritical water with oxygen. Oxygen was supplied into Biodenitrogenation studies with real feedstocks have rarely
the system while hydrogen was generated in situ by been reported, and a summary is presented in Table 12. One
supercritical water. The catalyst was the sulfide NiMo catalyst. example is the use of the HY9 strain to remove nitrogen from
By varying the operational conditions, they achieved an 85% diesel oil. It was found that addition of the surfactant Tween80
reduction in nitrogen, and the denitrogenation pathway increased the removal of nitrogen from 12.9% to 19.3%. It was
involved three reactions: oxidation of hydrocarbons, the water explained that the surfactant improves the solubility of diesel oil
gas shift reaction, and hydrodenitrogenation, where the water in nutrients.165 Heavy gas oil derived from Brazilian petroleum
gas shift reaction and hydrodenitrogenation were catalyzed by was submitted to biodenitrogenation with Rhodococcus
the NiMo catalyst.158 erythropolis ATCC 4277. The oil was mixed with water at
The patents U.S. Patent 4,594,141159 and EP 0671454 different concentrations, and the nitrogen reductions were
(A2)160 describe the use of supercritical water for nitrogen 43.2%, 40.2%, and 31.2% for the systems containing 40%, 20%,
removal by using it in conjunction with olefin/halide and 60% heavy gas oil, respectively. On the other hand, there
compounds and high-pressure carbon monoxide, respectively. was no nitrogen removal for the system containing only heavy
The olefins were used in conjunction with supercritical water gas oil. High dispersion of cells in the reaction medium
because they increase the cracking rate of organic saturated containing 40% heavy gas oil and aggregated cells in the
materials, while CO facilitates the transfer of hydride ions for medium containing only oil were observed, which explains the
hydrogenation. The claim of both patents was proved with higher denitrogenation achieved when the oil concentration
model compounds. On the other hand, patent WO was 40%.166
2009085436161 used crude oils with different properties to
prove denitrogenation with supercritical water in the absence of 9. CONCLUDING REMARKS
any other additive. The results are presented in Table 11. The A considerable diversity of processes have been proposed as
reactions that take place when the oils are reacted with denitrogenation strategies for the removal of nitrogen-
supercritical water are thermal cracking, steam reforming, water containing compounds from oil. The processes can be divided
gas shift, demetalization, and desulfurization. into two broad categories:
(a) Conversion processes that extract nitrogen from the
8. MICROBIAL CONVERSION nitrogen-containing compounds to form products that
Different strains of microorganisms have been studied for can readily be separated from the denitrogenated oil. In
denitrogenation of oil. Even though denitrogenation pathways these processes, most or all of the hydrocarbon matter
differ for each compound and for different strains, there are that was associated with the nitrogen remain in the oil.
some similarities. The degradation for the majority of The most widely applied industrial process in this
31 DOI: 10.1021/acs.energyfuels.6b02779
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Table 12. Denitrogenation of Real Feedstocks by and return the hydrocarbon matter to the oil (Figure 9)
Biodenitrogenation become important considerations before industrial
application can be considered. There appears to be little
nitrogen
process conversion/ literature on the elimination of nitrogen from the
feed strain conditions removal ref nitrogen-rich products obtained from denitrogenation
diesel oil HY9 35 °C 12.9% N removed 165 of oil.
125 rpm Judging by the current state of the literature on the topic,
4 days removal of nitrogen from real industrial feedstocks with high
0 g Tween 80 nitrogen contents appears to be viable only by hydrotreating.
diesel oil HY9 35 °C 19.3% N removed 165 Most of the alternative processes for denitrogenation rely on
125 rpm the removal of nitrogen-containing compounds without
4 days eliminating the nitrogen from these compounds. When
0.175 g nitrogen is not eliminated from the molecule and the
Tween 80
hydrocarbon matter is rejected with the nitrogen, the loss of
heavy gas R. erythropolis 28 °C 43.2% N removed 166
oil ATCC 4277 material from the oil increases as the nitrogen content of the oil
200 rpm
increases. The loss of material from an oil containing 1 wt % N
18 h
can easily be of the order 10−20 wt % of the oil, even for a
40% HGO in
water process with high selectivity for removing nitrogen-containing
heavy gas R. erythropolis 28 °C 40.2% N removed 166 compounds from the oil. There is a gap in the literature with
oil ATCC 4277 200 rpm respect to processes for eliminating the nitrogen from nitrogen-
rich products obtained by denitrogenation of oil.


18 h
20% HGO in
water AUTHOR INFORMATION
heavy gas R. erythropolis 28 °C 31.2% N removed 166 Corresponding Author
oil ATCC 4277 200 rpm *Tel: +1 780-655-3437. Fax: +1 780-492-2881. E-mail:
18 h glaucia@ualberta.ca.
60% HGO in
water ORCID
heavy gas R. erythropolis 28 °C 0% N removed 166 Arno de Klerk: 0000-0002-8146-9024
oil ATCC 4277 200 rpm Notes
18 h The authors declare no competing financial interest.
100% HGO

category is hydrotreating (section 3), which eliminates


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36 DOI: 10.1021/acs.energyfuels.6b02779
Energy Fuels 2017, 31, 14−36