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Review
Advanced hydrodesulfurization catalysts: A review of design and synthesis
Abdulkadir Tanimu, and Khalid Alhooshani
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/[Link].9b00354 • Publication Date (Web): 22 Mar 2019
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3 Advanced hydrodesulfurization catalysts: A review of design and synthesis
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6 Abdulkadir Tanimu, Khalid Alhooshani*
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9 aDepartment of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran
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12 31261, Saudi Arabia.
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27 *Corresponding author
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30 Email: hooshani@[Link]
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33 Phone: +966 13 860 3065
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36 Fax: +966 13 860 4277
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3 Abstract
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6 Proliferating energy consumptions, particularly fossil fuels, has led to an increasing generation of
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9 pollutants; many of these harmful products have been of serious environmental concerns recently.
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11 While energy demand will continue to grow due to massive urbanization and industrialization, the
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13 ability to remove such pollutants has not yet been achieved. Therefore, policies are always being
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reviewed to accommodate the existing reality of minimizing the amount of pollutants released to
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18 the environment on daily basis. Sulfur dioxide, a major environmental pollutant gets to the
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20 environment through the combustion of sulfur-containing fuel in the engine of automobiles. Over
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the years, regulatory bodies such as European Emission Standard have set limits to the amount of
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25 sulfur in transportation fuel to safeguard the environment. Lately, the limit for clean fuel
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27 specification with respect to sulfur content is set to nearly zero ppm. This policy came at a time
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29 when the crude oil experienced a large decline in price, in addition to the increased sulfur content
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32 and crude density experienced day-in-day-out. Compliance with this tight regulation will mean
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34 that refineries are expected to either modify their hydrotreating unit, which is capital intensive, or
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36 adopt robust catalysts, through research, that can work in-tandem with the existing conventional
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hydrotreating catalysts to bring down the sulfur level to the required limit. This urgent demand has
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41 once more drawn the attention of the scientific community. Since there has been a great stock of
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43 research outcomes with respect to catalysts for hydrodesulfurization application in a recent time,
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our aim is to collect and review those recent articles on hydrodesulfurization catalysts design and
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48 development. The tutorial review is therefore intended to cover a basic hydrodesulfurization
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50 overview, followed by detailed discussions on the recent development in the choice of active
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52 phases, their supports, and the synthesis strategies. The work is expected to guide researchers,
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3 especially beginners that are interested in refinery hydrotreating, on the recent development in
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6 hydrodesulfurization catalyst design and development.
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53 Keywords: hydrodesulfurization; catalyst support; active metals; refractory sulfur compounds;
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catalyst poisoning
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3 Contents
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6 1. Introduction
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9 2. Active phases
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11 2.1. Monometallic and bimetallic catalyst
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13 2.2. Trimetallic and multi-metallic catalysts
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3. Active phase supports
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18 3.1. Alumina and modified alumina supports
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20 3.2. Mesoporous silica and other molecular sieve supports
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3.3. Carbon and carbon-based support
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25 4. Synthesis strategy
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27 4.1. Preparation methods
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29 4.2. Precursors
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32 4.3. Chelating agents
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34 4.4. Surfactants and swelling agents
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36 4.5. Catalysts activation methods
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4.5.1. Decomposition of thiosalts
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41 4.5.2. In situ generation of MoS2
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43 4.6. Non-MoS2 active phase HDS catalysts
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4.6.1. Metal silicides
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48 5. Conclusion
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50 Acknowledgement
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52 References
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3 1. Introduction
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6 There is currently an apparent increase in demand for fossil fuel energy in some countries, but the
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9 need for mitigating the effects of the use and acquisition of non-renewable energy sources on the
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environment has gained global attention 1–3. The increased demand for fossil fuels is a result of
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13 continuing increase in population, especially in the developing countries where the energy options
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are limited, and the global interest in offsetting and/or eliminating the effects of burning these
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18 fossil fuels highlights the severity in consequence of large scale industrial and automobile
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20 emissions. Such emissions are leading to climate change, more specifically global warming 4, but
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they also pose many risks on the environment and human health 5. For example, sulfur (iv) oxide,
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25 a major emission of combusted fuel, can cause severe respiratory and other several health problems
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27 when inhaled, and in the atmosphere, it forms the acid rain which can harm sensitive ecosystems
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29 5. In addition to being linked to health and environmental problems, sulfur in fuel is known to
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32 cause damage by deactivating the hydroprocessing catalysts and resulting in the corrosion of
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34 pipelines, pumps, and refinery equipment 6. Due to these undesirable consequences, environmental
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36 regulations have prompted restraining the level of sulfur in the fuel, and a recent regulation by the
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European Emission Standard (Euro VI) targeted zero sulfur in the transportation fuel 7. With so
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41 many countries gradually adopting this policy and transiting to zero sulfur transportation fuel (Fig.
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43 1a and b), the refineries are being forced to find ways to meet the newly increasing demand for
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ultra-low sulfur fuel, which ultimately requires that the refineries invest in research. Recently,
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48 Honeywell, an oil and gas technology inventor and manufacturer, developed an ULTIMet™
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50 catalyst that was designed to address the challenge of the refineries by having more active sites for
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52 chemical reaction, thus resulting in an increased hydrotreating performance 8. According to the
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55 company, the catalyst can as well work in-tandem with the conventional hydrotreating catalyst in
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3 the hydrotreating plant, thus saving refineries the cost of redesigning an additional hydrotreating
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6 unit for ultra-low sulfur fuel production. Though catalyst producers like Honeywell and
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8 ExxonMobil have achieved a great milestone in catalysts’ designs, their technology is mostly
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10 trademarked or patented, which make access to vital scientific information quite difficult. We do
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know that in the hydrotreating plants of most refineries, the technology of removing sulfur from
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15 the transportation fuel involves hydrodesulfurization (HDS) 9. However, other methods such as
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17 oxidative desulfurization, supercritical water desulfurization, and adsorptive desulfurization 10 are
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still used by a few refineries, albeit less frequently than HDS.
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23 Fig. 1. Worldwide on-road diesel sulfur limit, sourced from Stratas Advisors, (a) October, 2015
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25 and (b) February, 2018 11.
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28 Although HDS is the most commonly used chemical technology for removing organic sulfur from
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30 crude oil and transportation fuel such as gasoline, jet fuel, and diesel 12, it is often considered
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33 pricey. The HDS technology is known to be financially tasking in terms of its operational
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35 conditions, which require an active solid catalyst as well as high temperature and hydrogen gas
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37 pressure conditions. Though HDS technology has its financial drawbacks, its desulfurization
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performance is unmatched by other desulfurization technologies 13. Because of its high efficiency
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42 of removing sulfur, refractory sulfur compounds such as dibenzothiophene (DBT), 4-
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44 methyldibenzothiophene (4-MDBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT), and
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benzonaphthothiophene (BNT) (Fig. 2) which are mostly found in heavy gas oil and vacuum gas
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49 oil can be treated easily with a highly robust HDS catalyst. Since the crude oil reserve in many
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51 parts of the world is becoming heavy nowadays, the demand for highly robust HDS catalysts has
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53 dramatically increased. Additionally, the continuous emergence of alternative energy supply
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3 international market; therefore, cheaper but efficient HDS technologies are continuously being
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14 S S S
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19 Fig. 2. Some refractory sulfur compounds: (a) dibenzothiophene; (b) 4-methyldibenzothiophene;
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21 (c) 4,6-dimethyldibenzothiophene; (d) benzonaphthothiophene
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24 The predominant metals often used as the active species in the HDS catalyst design are
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27 Co(Ni)Mo(W). These active species have been used for more than a century as bulk catalyst and
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29 later as a supported catalyst due to their cost. Interestingly, the approach to HDS has somewhat
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31 drastically evolved through the years although the active species have not been able to be
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completely replaced. Perhaps this evolution is correlated with the advances in synthesis and
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36 characterization tools which has now made it much easier than ever before to fully comprehend
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mainly based on scientific guess through trial and error approach. In contrast to those days, we can
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43 now use more sophisticated instrumentation and quantum computational calculations to
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45 understand the active phase design and active-phase-support interaction and how these factors
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50 that active sites play in the reaction pathway and product selectivity. These advances have enabled
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3 cumbersome nature and the large energy consumption that are both associated with the synthesis
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9 2. Active phases
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12 The active phases are primarily the active metals that perform the catalysis job of HDS, although
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recently, HDS has been reported on a metal-free carbon materials 14. The active metals are
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16 employed both as unsupported catalysts (bulk) or as supported catalysts. For more than a century,
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the active metals utilized in HDS have been predominantly Mo(W) and Co(Ni) 15–19, and till today
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21 they have not been successfully replaced, although there has been quite a lot of improvement in
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23 their synthesis strategy. The actives phases used are monometallic, bimetallic, trimetallic, or even
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25 multi-metallic depending on the required catalyst performance; however, the bimetallic
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28 combination is still the generally accepted catalyst system.
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31 2.1. Monometallic and bimetallic catalyts
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34 Monometallic catalyst systems frequently contain an active metal such as Mo or W, but the use of
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36 such a monometallic catalyst in HDS is slowly declining due to the discovery of the advantages of
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38 using some base metals such as Co and Ni as promoters, except for the noble metals 20. The
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bimetallic catalyst is like the monometallic system, but in addition to Mo or W, it also contains a
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43 base metal as a promoter, which is usually Co or Ni. Many metals have been explored as
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due to the cost of the metals or due to electronic effects that lead to low activity. Although the
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50 noble metal catalysts can work even at low operating temperature and can maintain high
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3 predisposition to sulfur poisoning has deterred their practical application in the catalyst industries
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6 It is anticipated that the excellent HDS activity that can be achieved with the noble metal-
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selecting better supports and/or adopting more practical synthesis, which includes better choice in
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metal size tuning, higher dispersion on support 29,30, and unsurprisingly the use of very minimal
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17 amount of the metals 31–34. For instance, Wenya et al. reported the role of low-temperature
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hydrogen plasma in the synthesis of graphene-supported palladium nanoparticles catalysts for
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22 hydrodesulfurization application 35. This new one-step synthesis approach (Fig. 3) formed well-
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26 hydrodesulfurization ability above the conventional activated carbon or graphene-supported
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44 Fig. 3. Preparation of Pd/GS composites. Reprinted with permission from 35.
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3 positive site was linked to the mesoporous electronegative HZSM-5 zeolite surface, thus resulting
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42 Fig. 4. Demonstration of the dispersion principle for Pd nanoparticles over DBD-Pd/MHZ-5.
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47 Shen and Semagina reported the effect of palladium nanoparticle size on the hydrodesulfurization
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of 4,6-DMDBT by using 4, 8, 13, and 87 nm sizes nanoparticles 37. Because the 4 nm Pd has a low
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3 pathway contribution. The 87 nm nanoparticles presented the lowest HDS activity due to the low
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49 subscripts XL, L, M and S represent 87 nm, 13 nm, 8 nm and 4 nm respectively. Reprinted with
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54 The DDS selectivity of Pd nanoparticles in HDS was also enhanced by the addition of efficient
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3 DDS selectivity in Pd nanoparticles supported on alumina 38,39. Iridium promoted the DDS
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6 pathway up to 26% against the 5% of the bare Pd nanoparticle catalyst while yttrium increased the
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38 Generally, bimetallic M-Pd (M = noble metal) catalysts have been observed to resist higher sulfur
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40 poisoning than monometallic Pd or Pt catalysts especially when the bimetallic catalyst is supported
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43 on strong BrØnsted acidity supports Gold, Au, though expensive, has been adopted as co-
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45 promoter of the HDS activity of Pd catalysts. In the early 20th century, Venezia et al. first described
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47 the structure-modifier role of Au on Pd catalyst for HDS application 41,42, and more recently,
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50 Herzing et al. and Suo et al. reported the effect of heat treatment and atmosphere on the
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54 resistance-to-sulfur poisoning AuxPdy/SiO2 alloy phase formed bimetallic catalyst that inhibit the
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3 formation of less active Pd4S phase which enhanced its HDS activity. The dispersion and stability
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6 of Au-Pd on HMS silica support was also enhanced by grafting mercaptopropyl groups on the
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8 support framework 45. The apparent favorable interactions between M (Au or Pd) and S are a result
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13 The vast applications of Pd-based bimetallic catalysts in catalysis science including
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hydrodesulfurization was recently reviewed by Fenglin et al. Other noble metals such as
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18 ruthenium 47–50 and rhodium 51–53 have also been explored for the hydrodesulfurization application;
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25 of predominantly alumina-supported NiMo and CoMo catalysts. Metals such as Zn and Fe have
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29 57. Dating back to the 1980’s, Pecoraro and Chianelli first reported that metals in the 1st, 2nd and
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32 3rd row of transition metals could be good catalysts for HDS, although the 1st row metals
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34 demonstrated lower activity 54,55. Sulfur poisoning that results from the strong interaction between
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HDS application of these metals Research areas have become focused on improving the
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41 activity of these metals and/or understanding the synergetic effect of these metals combined with
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43 the promoter effect associated with the low activity metal on the HDS. For instance, it has been
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established that incorporation of carbon into the lattice of early transition metals increased their d-
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electron density 59–61. Inspired by this, Pinto et al. prepared a vanadium carbide (a mixture of
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50 vanadium nanoparticles and activated carbon in THF solvent) and studied the HDS activity of the
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52 vanadium carbide catalyst after activation under the flow of H2/H2S 62. They observed that
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55 vanadium carbide activity was greater than that of the alumina supported NiMo catalyst. The
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3 structural and electronic state of alumina-supported CoMo catalyst was also modified after
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6 incorporation of vanadia to the alumina support structure by co-precipitation. The presence of
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8 vanadia shifted the reaction toward the HYD pathway, and the HDS activity of sterically hindered
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10 4,6-DMDBT was significantly enhanced 63. Li et al. described the conversion of inefficient iron
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sulfide HDS catalyst to a highly efficient catalyst by the promoter effect of Zn at a Zn:Fe ratio of
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15 nearly 1:1 64. The remarkable performance of the bimetallic FeZnS catalyst was explained, based
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inactive sulfur vacancies, which promote the adsorption of sulfur-containing molecules as depicted
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43 Fig. 7. FeZnS catalyst. Reprinted with permission from 64.
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46 Niobium is another easily accessible and cheap metal that has demonstrated great potential for
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51 is clearly explained from the perspective of its thermodynamics parameters 69 and the combination
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3 effect of copper (Cu:Nb = 0.3) has been reported by Mansouri and Semagina 71. The choice of Cu
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6 as promoter was purely based on thermodynamic calculations of the energy parameters of severally
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8 cheap and available metals when in combination with Nb metal (Fig. 8). Both Cu and Cd satisfied
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10 the thermodynamic criteria; however, due to safety considerations, Cu was considered as the
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potential promoter of the niobium oxide sulfidation. The promoter effect of V, Fe, Co and Ni on
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15 the stability of Mo-NbS2 catalyst was also studied extensively using the DFT and first principle
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17 surface thermodynamics calculations at HDS conditions 72. All the studied metal promoters
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showed a positive effect on the Mo-NbS2 stability and HDS activity except Fe metal as shown in
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22 Fig. 9. Conversely, Nb has been utilized as modifier of the support surface acidity and metal-
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33 Non-metals such as phosphorus, fluorine and boron have also been incorporated as promoters to
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the bimetallic catalytic system to minimize catalyst poisoning, enhance catalytic performance,
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improve catalyst stability, and product selectivity 75–81. Recently, fluorine influence on the
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40 hydroprocessing properties of NiW/Al2O3-SiO2 catalyst was studied using a low-temperature coal
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42 tar feed 82. In addition to improving both acidity and active phase properties of the catalyst, fluorine
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45 addition (≤ 1.0 wt.%) also enhanced clean fuel properties like dynamic viscosity, density,
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47 distillation range and hydrocarbon content. Similarly, 1 wt.% phosphorus addition to CoMo/γ-
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49 Al2O3 catalyst yield the highest HDS performance, especially for 4,6-DMDBT 75. Generally, the
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presence of quinoline in fuel inhibits the HDS performance of the hydrotreating catalysts because
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54 of the competition of the HYD active sites by both compounds. Interestingly, the competitive HDS
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56 and HDN of 4,6-DMDBT and quinoline respectively showed that with a 1 wt.% loading of
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3 phosphorus, there was an increased HDS activity for a quinoline concentration below 90 ppmw N
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6 (Fig. 10). This increased activity is due to the increased dispersion of NiMoS active sites and
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8 BrØnsted acidity. However, at higher phosphorus loading, the NiMoS active sites dispersion
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10 decreased while the BrØnsted acidity increased significantly, which leads to decreased HDS
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activity and increased HDN activity, respectively.
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35 Fig. 10. Relationship between NiMoS actives sites and products distribution on the competitive
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37 HDS and HDN reactions at different quinoline concentrations: (a) HYD/DDS ratio and (b) HDN
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(%) (275 °C, 51 bar, 4 h–1). Reprinted with permission from 83.
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2.2. Trimetallic and multi-metallic catalysts
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45 The potential application of trimetallic and multi-metallic catalysts used as HDS catalysts has also
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48 been recently explored. These special types of catalysts have the advantage of having mixed
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50 phases, and their catalytic properties can be better tailored than in bimetallic or monometallic
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52 catalysts 84,85. Typically, the trimetallic system comprises of Ni or Co promoter combined with the
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55 two prominent active metals, Mo and W, and the synergetic behavior among these metals are
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3 continuously being studied 86–90. Van Haandel et al. studied the synergetic effect of Mo and W in
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6 MoxW(1-x)/γ-Al2O3 catalysts’ sulfidation and activity, and they also observed that although there
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8 was no significant improvement in the catalysts’ degree of sulfidation, the NiMo0.75W0.25/γ-Al2O3
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10 performed more efficiently than the corresponding bimetallic catalysts in the HDS of gas oil 91.
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This is in line with previous studies using DFT calculations by Thomazeau et al. which reported
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15 nearly 30% HDS activity enhancement in the trimetallic NiMoW/γ-Al2O3 in the HDS of gas oil
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17 feed (Fig. 11) 92. However, the observed result is not generally conclusive since the HDS activity
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of NiMo/γ-Al2O3 bimetallic catalysts using thiophene and DBT model fuels were observed to be
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22 way better than the NiMoW/γ-Al2O3 trimetallic catalysts. The observed behavior can be explained
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24 by EXAFS and was related to the available metal at the edge sites of the catalysts (Fig. 12), in
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26 which the Ni-Mo-S edge sites are more active in thiophene and DBT HDS than the Ni-W-S edge
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29 sites. Conversely, the DFT calculations and experimental results of the work of Cervantes-Gaxiola
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31 et al. on the comparative study of HDS of DBT on Al-Ti-Mg mixed oxide-supported NiMoW
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33 showed that the NiMoW catalyst performed best in comparison to NiMo and NiW. This result was
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correlated with the high metal dispersion observed in the catalyst on Al-Ti-Mg mixed oxide
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38 support 93. The conflicting behavior of the trimetallic catalysts explained above further reiterated
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40 that there are indeed many factors that influence the activity of catalysts in addition to the active
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metals. Among these factors is the catalysts support.
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17 Fig. 11. Diagram showing the relative positions of the Co(Ni)MoWS systems on the volcano curve
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19 and explanation of the new synergy effects for NiMoWS systems. Reprinted with permission from
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21 92.
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40 Fig. 12. Possible structures of the active phase in Ni-promoted MoxW(1–x) catalysts (x ≤ 1): (left)
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43 separate MS2 particles (M = Mo, W); (middle) randomly mixed MS2 particles; and (right) mixed
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45 MS2 particles with a two-dimensional core–shell structure. S atoms are represented by yellow
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47 balls, Mo atoms are blue, and W atoms are pink. For the sake of clarity, Ni has been omitted from
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50 the drawings. Reprinted with permission from 91.
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The use of noble metal combined with Ni(Co) and Mo(W) metals to form trimetallic catalysts
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55 systems have also been explored recently 94–96. This is one of the adopted strategies of minimizing
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3 the usage of large amount of highly expensive noble metals for the construction of HDS catalysts
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6 while still retaining their catalytic properties. These properties consist of high activity and
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8 directing the reaction towards the HYD pathway which is required in the HDS of sterically
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10 hindered sulfur compounds. Aguirre-Gutiérrez et al. reported a 30% increase in reaction rate for
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the HDS of 4,6-DMDBT when Pd was incorporated to the alumina-titania supported NiMo catalyst
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94. This promoter effect of Pd was correlated to the synergetic effect of Pd and Ni on the Mo, which
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17 enhanced both the HYD and DDS reaction rate. A similar promotion effect was observed when
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Ru and Pd were added to commercial Ni(Co)Mo/γ–Al2O3 catalysts 95. Niobium promotion effects
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22 on the HDS of 4,6-DMDBT activity of NiMo/Al2O3 catalysts was studied both theoretically and
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24 experimentally. The Nb promotion effects was investigated using the DFT calculation by
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26 substituting some Ni and Mo atoms on the edge of the Ni-Mo-S (Fig. 13) nanocluster by Nb atoms
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28 96.
29 The substitution was performed in pairs (two Nb atoms replaced a Mo and a Ni atom or two Ni
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31 atoms) since Nb has an odd atomic number whereas both Ni and Mo have even atomic number.
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33 The DFT results presented both S-edge and Mo-edge stabilization due to Nb substitution and
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enhanced the C-S bond cleavage at partial Nb substitution. Strong Nb and C atoms interaction was
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38 reported at full Nb substitution, and this hinders the C-S bond cleavage. Interestingly, these
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40 theoretical findings were further confirmed by the experimental results. An extensive review on
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the synthesis approaches and different applications of trimetallic nanocomposites was recently
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45 reported 97.
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18 Fig. 13: Configuration of the model Ni-Mo-S nanocluster (a) schematic of the nanocluster (b)
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20 side view of the Ni-Mo-edge and (c) side view of Ni-S-edge. Reprinted with permission from 96.
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24 Another emerging catalyst system based on four of above metals combined (multi-metallic) is
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26 being explored as a possible strategy for enhancing the HDS catalytic activity. Motivated by the
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28 combined effect of trimetallic catalysts in HDS activity, Wang et al. synthesized a multi-metallic
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30 NiAlMoW catalyst with layered structure (Fig. 14) using NiAl-LDH as structure-directing
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32 template and studied their efficiency in HDS of 4,6-DMDBT 98. The multi-metallic catalyst with
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34 even lower active metal loading than the corresponding trimetallic NiMoW catalyst performed
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36 twice as effective as the commercial catalyst in the HDS of 4,6-DMDBT. Similar studies were
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38 carried out by the same research group using Zn in place of Al to form the NiZnMoW catalyst 99.
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30 Fig. 14. Diagram showing the formation of sulfide NiAlMoW catalyst with LDH structure.
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32 Reprinted with permission from 98.
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34 Again, intrigued by the success of the two four-metal catalyst systems, the same group advanced
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36 their research by studying the effect of combining all the five metals in a one catalyst system. The
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38 NixZnyAlzMoW catalyst with different Zn/Al molar ratio were prepared using a NiZnAl-layered
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40 hydroxide precursor 100. The use of multi-metallic catalyst system is still a new area open for
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42 further exploration, and it is anticipated that more research outcomes will emerge from this area
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44 in the next few years.
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47 3. Active phase support
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50 One of the bold steps taken when specializing catalysts is to minimize the cost of catalyst
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53 production and increase catalyst activity by using exceptionally cheap yet highly mesoporous
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active metals supports, such as alumina and silica 101–105. The supports must have properties
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3 suitable for catalytic application, such as 1) mechanical strength to minimize catalyst attrition 106–
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6 2) a large surface area to enhance fast interaction of active phases with the organo-sulfur
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8 reactants 110,111, 3) an availability of acidic sites to improve the dispersion of active metals 112–114,
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10 and 4) moderate metal-support interaction for easy reduction and sulfidation of the active phases
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12 115,116.
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3.1. Alumina and modified alumina supports
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The principal role of a catalytic support is to maximize and stabilize the concentration of active
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21 surface. However, secondary properties of support do exist depending on the catalyst desired
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23 application. Based on the required support properties of HDS catalysis, catalyst producers have
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25 since aligned their interest more on alumina support. Even though it deactivates quickly due to the
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28 strong metal-support interaction, it has not been easily replaced because of its unique mechanical
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30 strength and textural properties 117–119. The main disadvantage of alumina support is the strong
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32 metal-support interaction that exist between Mo oxides and alumina, which results in the formation
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35 of strong tetrahedral molybdenum oxide that coordinate tetrahedrally mainly with other Mo oxides
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37 monolayers 120. Unlike the octahedral molybdenum oxide that is easily reduced and sulfided, the
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39 strongly bounded tetrahedral molybdenum oxides tend to resist reduction and sulfidation 121.
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Therefore, research findings for modifying the alumina metal-support interaction through the
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44 incorporation of heteroatoms are continuously being reported. A prominent heteroatom that has
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46 recently been used to modify the metal-support interaction of alumina is gallium 122–126. Like other
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48 trivalent heteroatoms, gallium has a strong affinity for the tetrahedral sites of alumina, and it can
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51 successfully relocate the Co(Ni) promoter from the tetrahedral sites to the octahedral sites of
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53 alumina support 126. Consequently, the MoS2 slabs decoration get enhanced and furthermore, the
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55 strong metal-support interaction between Mo and alumina became moderate, which result to
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3 increased MoS2 slabs stacking. Overall, the HDS activity of the alumina-supported catalysts gets
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6 increased upon modification with gallium. The HYD activity of the NiMo/γ-Al2O3 catalyst was
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8 also reported to be enhanced after support modification with gallium 123. Also, the presence of
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10 gallium on the surface of aluminum has played a significant role on the formation and dispersion
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of WOx species in the synthesis of the alumina-supported W catalyst for the HDS of DBT 125. The
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15 gallium-modified alumina-support was also used to support NiW catalysts, and the HDS of both
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17 DBT and 4,6-DMDBT were greatly enhanced at 2.4 wt.% loading of gallium as shown in Fig. 15
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19 124.
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42 Fig. 15. Catalytic activity of NiW/Ga(x)-γ-Al2O3 catalysts on the HDS of DBT. Reaction in a batch
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44 reactor at 593 K and 800 psi. Catalysts were sulfided at 673 K. Reprinted with permission from 124.
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47 In a more recent study, the role that gallium incorporation into alumina support plays on the
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product selectivity was exhaustively addressed 122. The γ-Al2O3–α-Ga2O3 support synthesized in a
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52 one-step precipitation method was loaded with a NiW catalyst, and higher dispersion of the catalyst
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3 in the HDS of 3-methyl-thiophene (3MT) and DBT. It was reported that the GaAl2O4 spinels and
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6 α-Ga2O3 observed in the catalyst greatly influenced the HYD capacity of the catalyst and therefore
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8 directs the reaction towards the HYD pathway as shown in the HDS of 3MT in Fig. 16.
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10 Interestingly, the DBT of HDS was still maintained via the DDS pathway even after the support
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was modified with α-Ga2O3.
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Fig. 16. Diagram showing the catalytic systems and main yield. The atoms are not to scale, and
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41 the sizes only are illustrative. Reprinted with permission from 122.
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44 The isomerization and cracking capacity of CoMo and NiMo/γ-Al2O3 catalysts were also enhanced
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46 when the alumina support acidity was modified with boron 127. A boria over-layer, stabilized
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through the Al-O-B bridges in a B2O5-Al2O3 support system was used as a support for CoMo
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catalyst in the HDS of DBT and 4,6-DMDBT 128. This support system inhibits the formation of
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53 undesirable bulk α-CoMoO4 due to the strong interaction between Co and B of the Al-O-B bridge
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3 Higher mechanical strength, enhanced degree of metal sulfidation, increased catalytic activity and
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6 selectivity, and resistance to coke formation were achieved when γ-Al2O3 was modified with CaO
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8 to form Ni and NiMo/γ-Al2O3-CaO catalysts 129. Alumina support has also been modified with
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10 carbon to enhance its HDS performance 130–132. Typically, the deposition of carbon on the
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hydrotreater catalysts has been identified as a good method for suppressing sediment formation on
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the catalyst and its subsequent deactivation 133. Additionally, pore size and pore volume of the
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17 alumina support was successfully tailored by mixing the alumina paste with carbon mesh, and the
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dried extrudate was then calcined under different conditions 130. This is particularly important for
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22 the HDS of sterically hindered sulfur compounds that are likely to have diffusion limitation which
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24 results in an inaccessibility of active sites and poor HDS activity. By tailoring the pore size and
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26 pore volume, larger pore diameters (macropores) can be formed, and this creates a bimodal catalyst
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29 structure that is likely to have both mesopore and macropore. Alumina modification with carbon
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31 has also resulted in moderate metal support interaction, thus enhancing metal dispersion and
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33 sulfidation 131. The slab length and stacking number of the MoS2 slab in a carbon modified γ-Al2O3
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supported CoMo catalyst that has been prepared by using different monocarboxylic acids as carbon
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38 sources were reported as being relatively low compared to the unmodified alumina. This property of the
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40 catalyst directs the adsorption of 4,6-DMDBT on the edges sites of the MoS2 stack, which favors the
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DDS mechanism 132,134. Alumina modification with P has also been shown to have many advantages.
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45 For example, it has enhanced the support textural properties and metal dispersion (due to decreased
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47 metal-support interaction); inhibited the formation of inactive species, such as NiAl2O4 and MoO4;
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49 increased the strength and distribution of acid sites; and improved the support thermal stability 135–137.
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52 The slab length and stacking degree of NiWS2 slabs have been successfully modulated by exploring the
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54 supports’ intrinsic effects of Al2O3, TiO2, ZrO2, and Al2O3- TiO2 and ZrO2-TiO2 mixed oxides 138. Each
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3 support affects the electronic and structural arrangements of the WS2 active phase in a different way,
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6 which creates unique WS2 phase characteristics as shown in Fig. 17. The WS2 unique phases were
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8 determined from the average slab length (obtained from HRTEM) and the W-W bond distance that was
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10 obtained from the EXAFS 139 using the Kastelan geometric model 140. The Wt and We in the Fig. 17
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represent the total number of W forming at each slab and the amount of W at the edge of slab,
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15 respectively. The We is presumably the catalytically active phase, and as depicted in the Fig. 17, the
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17 We/Wt of Al2O3-TiO2 and ZrO2-TiO2 mixed oxides supported NiWS2 are higher, which results in their
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better HDS activity than the catalysts. DFT calculations was further used to deduce that each of the
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22 supports confers entirely different activity, dispersion, promotion, total acidity, and specific surface
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24 bonding to the NiWS2 catalyst 141. In the study, an optimized model of the supports and well-defined
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26 cluster W12S24 (C1) or Ni3W12S24 (C2) (Fig. 18) were prepared, and the interaction between the
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29 supports and clusters presented in Fig. 19 were discussed. It was reported that the C1-ZrO2-TiO2
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31 interaction is strongest among all the studied interactions. In fact, the Me-S (Me = Al, Ti, Zr) in the C1-
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33 ZrO2-TiO2 interaction had reached a peak of 18 bonds which then lead to the cluster deformation so that
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35 141.
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some of the sulfur in C1 cluster were already being pulled towards the support The cluster is
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38 therefore forced to bend due to charge redistribution, which leads to the reconfiguration of the cluster
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40 and loss of some crystallinity.
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43 Mixed oxides of alumina, for example, Al2O3-TiO2 and Al2O3-TiO2-SiO2 have also been used to support
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noble metal catalysts 142. In the work of Wan et al., the sulfur tolerant and highly stable Al2O3-TiO2-
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48 SiO2 supported Pt-Pd bimetallic catalyst performed better in hydrodearomatization and HDS of diesel
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50 fuel than the Al2O3-TiO2 supported Pt-Pd counterpart 143.
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19 sulfide phase over the different supports. Blue: tungsten, Yellow: sulfur. Reprinted with permission
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41 Fig. 18. Two different orientations for a) C1=W12S24 (WS) and b) C2=Ni3W12S24 (NiWS) cluster
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with optimized configurations. Reprinted with permission from 141.
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33 Oxides of magnesium, titanium, iron, zinc and niobium have also been used as support for metal
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catalysts in the HDS reaction 144–147. Nickel is a metal catalyst that has an interesting catalyzing ability
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38 for the cleavage of cyclic sulfur compounds. However, the Ni activity is typically in the initial HDS
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40 reaction, and after few hours, quick deactivation occurs due to sulfidation of the Ni active sites to NiS,
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42 which renders the catalyst inactive. One of the adopted strategies used to extend the lifetime of Ni
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45 catalyst is to support it on ZnO 144. The ZnO support prevents complete deactivation of Ni sites through
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47 an activation reaction of NiS to regenerate Ni metal as depicted in equation 1 and Fig. 20. This approach
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49 extends the lifetime of Ni active sites until nearly all the ZnO support have been converted to ZnS.
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Fig. 20. A schematic illustration of reactive adsorption of thiophenic compounds on Ni decorated
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23 ZnO NW. ZnO NW support keeps Ni sites free of sulfur and thereby active for hydrogenolysis.
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25 Reprinted with permission from 144.
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28 It is also considered that the tungsten oxysulfide interaction with Ni sulfide particles in NiW/TiO2
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30 nanotubes catalyst was enhanced due to the TiO2 nanotubes support properties 146. Studies of the
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33 combined effect of MgO and TiO2 as support for NiW active metals determined that undesirable
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35 NiO and NiWO4 phases were not formed in any of the NiW/MgO-TiO2 catalysts formed when
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37 varying the ratio of MgO to TiO2 147.
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40 3.2. Mesoporous silica and other molecular sieve supports
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43 In general, silica and silica-based materials have drawn attention as catalysts support for heterogeneous
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catalysis 148–150 but also for HDS in particular 151–153. These silica-based materials are desirable because
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48 of their highly ordered pore size and volume and their large surface area, but it is important to note that
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50 these materials have also demonstrated a weak metal-support interaction. Because of this low metal-
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52 support interaction in silica, it became essential to be able to modify the support to increase the
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3 interaction and active phase dispersion of silica-based supported HDS catalysts. The use of heteroatoms
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6 such as alumina, titania and zirconia to modify the mesoporous silica properties have been extensively
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8 studied 154–158. The work of Jiang et al. studied the effect of Si/Al ratio on the NiMo/Al-SBA-15 catalytic
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10 properties 159. It was observed that the total acidity of the NiMo/Al-SBA-15 catalysts and the metal-
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support interaction increase with Si/Al ratio; however, the BrØnsted acidity was highest when Si/Al
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15 ratio is 10. Furthermore, the average stacking number of NiMoS slab decreased with Si/Al ratio while
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17 the layer length was shortened at Si/Al ratio of 10. The acid-base property of ceria was also utilized to
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increase the SBA-15 support properties, and at 2.5 wt.% ceria, an optimum metal-support interaction,
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support acidity and active phase formation and dispersion was reported 160. A curved fullerene-like
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24 morphology due to 1) the excellent dispersion of MoS2 active phase on the Al- or Ti-modified SBA-15
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26 support and 2) the stabilization of the Co-promoted MoS2. The latter effect is reported to impact on the
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29 HDS activity of the Al- or Ti-modified SBA-15 CoMo catalyst 161. Zirconia modification of SBA-15
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31 was found to increase the promoter dispersion due to the Co-support interaction, and this enhanced the
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33 promotion effect of the Co on MoS2 active phase. Additionally, the inactive β-CoMoO4 phase, which
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is often detected in CoMo/SBA-15 catalyst, was not observed after support modification with ZrO2 162.
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38 Further studies on how to increase the dispersion of active phase through the Ti-Zr bi-heteroatom
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40 modification of SBA-15 support demonstrated that the electronegativity difference between the Ti and
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Zr further stabilized the inactive and undesirable MoO42- phase, which leads to low sulfidation 163.
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45 Indeed, the poor performance of Ti-Zr bi-heteroatom modified SBA-15 supported CoMo catalyst has
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47 deterred further studies into the use of bi-heteroatom to modify the SBA-15 properties even though
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49 different heteroatom combination could likely result in different electronic and structural re-
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52 arrangement. Gutiérrez et al. reported the effect of four different supports: γ-Al2O3, SBA-15, Zr-SBA-
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54 15 and Ti-SBA-15 for the simultaneous HDS of DBT and hydrodenitrogenation (HDN) of o-
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3 propylaniline (OPA). The Zr and Ti modification of the SBA-15 considerably decreased the SBA-15
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6 surface area; however, more active sites were observed (due to increased Lewis acid sites) in the Ni
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8 promoted Zr- and Ti-SBA-15-Mo catalysts than in the unmodified SBA-15-Mo catalyst 164,165. Dinh et
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10 al. optimized the loading of TiO2 on calcined SBA-15 support for CoMo catalyst 152. Within the range
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of 10-40 wt.% nanocrystallites TiO2 loading, an excellent dispersion of the active phase was observed
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15 at 20 wt.%. At lower TiO2 loading (below 20 wt.%), the inactive CoMoO4 phase was observed, and at
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17 higher loading, large aggregates of TiO2 were noticed. Both are detrimental to the HDS activity of the
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CoMo catalyst. The effect of Ti-SBA-15 and γ-Al2O3 hybrid as a support for NiMo catalysts was also
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22 compared with that of the Ti-SBA-15 and γ-Al2O3 counterparts in the HDS of DBT and 4,6-DMDBT,
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24 and it was reported that the incorporation of Ti-SBA-15 to alumina inhibits the formation of the inactive
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26 MoO4 phase 166. In addition, the hybrid supported NiMo catalysts performs 40% more than NiMo/γ-
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29 Al2O3 in the HDS of 4,6-DMDBT even though nearly the same conversion was recorded for the HDS
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31 of DBT. Trimetallic catalysts have also been supported on SBA-15 to form highly active HDS
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33 catalysts. The work of Mendoza-Nieto et al. compared the efficiency of NiMoW/SBA-15 catalysts over
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the bimetallic NiMo/SBA-15 and NiW/SBA-15 catalysts and discovered that the Mo(W)S2 active
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phases were better dispersed on the support than in the bimetallic systems 167. More so, the highest
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40 number of active phases are located on the edge sites of the catalyst, which afforded the catalysts highest
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DDS and HDS activity (Fig. 21).
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Fig. 21. Comparison of the catalytic activity of NiMo, NiMoW and NiW catalysts supported on
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28 SBA-15 in HDS of DBT (◊) and 4,6-DMDBT (□). Open triangles correspond to the results
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30 obtained with trimetallic NiMo-NiW/SBA-15 catalyst prepared by mechanical mixing of
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corresponding bimetallic counterparts. Reprinted with permission from 167.
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Mechanically mixed SBA-15 and SBA-16 support for CoMoW catalyst has also proved to be
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38 better support than the individual SBA-15 or SBA-16. The mixed support contains mixed porosity,
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40 which may be the reason for the better diffusion of active phase precursor solution through the
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42 support medium (thus inhibit external mass transfer limitation) 168.
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45 KIT-6 and KIT-5 silica are another class of mesoporous molecular sieves that have shown great
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48 potential as HDS support catalyst 169–172. The three dimensional (3D) mesoporosity of KIT-6/KIT-
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50 5 afford it an extra advantage of better catalyst dispersion, higher reducibility of the Mo oxides,
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52 and faster diffusion of reactants and products over other 2D molecular sieves (e.g., SBA-15) 173.
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Similar to SBA-15, modification of the KIT-6/KIT-5 properties by incorporating heteroatoms such
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3 as Al, the metal-support interaction and surface acidity have been enhanced, which in turn has
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5 174,175.
6 increased the HDS performance of catalysts Zeolites are a class of materials with unique
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8 pore architectures that can be made to fit almost any chemical conversion, and these materials have
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10 easily accessible active sites 176. As such, zeolites have also found application as support in HDS
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reaction 177,178. However, the small pore size of many zeolites hinders the diffusion of large sulfur
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15 molecules. For example, the molecular size of 4,6-DMDBT (0.78 × 1.13 nm by DFT calculations)
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17 was larger than the pores of BETA (0.65–0.68 nm) and ZSM-5 (0.55 nm) mesoporous zeolites 179.
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Furthermore, most zeolites are characterized with excessive acidity, which causes cracking more
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22 than the HDS activity 180. Therefore, the zeolites are mostly used as HDS support after their pores
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24 have been expanded and their acidity has been reduced. Tang et al. have developed parallel
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26 mesopore channels in the nanofiber of microporous mordenite and have efficiently dispersed the
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29 CoMo in both the micropores and mesopores of the mordenite support 181. The active phase in the
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31 micropores significantly affect the overall HDS activity of the mordenite supported CoMo catalyst
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33 by producing a large amount of spillover hydrogen that later diffuse onto a nearby CoMo active
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phase in the mesopores, consequently boosting the HYD pathway of the catalyst. An in-depth
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38 study into the HDS mechanism of thiophene over a zeolite L-supported CoMo catalyst using
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40 computational calculations revealed that the zeolite L acted as an electron donor and that its pore
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framework decreased the HYD energy barrier, which made the HYD pathway more favorable 182.
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45 The work of Quan Huo et al. demonstrated the modification of zeolite L by slowly adding the
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47 zeolite to a solution of CTAB in water and later adjusting the pH to 9.6 183. The solution was heated
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49 at 100 oC for 2 days in a Teflon-lined autoclave to yield the micro-meso molecular sieve composite
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52 with increased textural properties and moderate acidity, which resulted in better metal dispersion
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54 and HDS activity. Y-zeolite porosity and surface acidity was easily modulated by direct
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3 incorporation of Ga in the Si-O-Al framework. Thus, some of the strong acid sites (Si–O(H)Al) in
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6 the Y-zeolite got substituted by weak acid sites (Si–O(H)Ga). Moreover, the Ga species promoted
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8 the sulfidation of both Ni and Mo species and changed the morphology of the active phases 184.
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10 With small amounts of Ga species, more Ni atoms were easily doped into MoS2 crystals to form
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more NiMoS active phase. Composite materials made up of mixed supports of highly acidic
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15 microporous zeolites and weakly acidic mesoporous molecular sieves have been characterized
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17 with combined oxides properties such as presence of micro and meso porosity, moderate acidity,
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and hydrothermal stability. The combined effect of ZSM-5 and KIT-6 as mixed support lead to the
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22 formation of hierarchical porous structures that allows efficient diffusion of reactants and products
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24 171. Furthermore, the BrØnsted surface acidity of the NiMo/ZSM-5-KIT-6 catalyst was found
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26 suitable for the efficient HDS of 4,6-DMDBT, especially via the isomerization pathway (Fig. 22).
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29 Similarly, improved textural properties, acidic strength and edge-cornered MoS2 sites were
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31 achieved when a mixed support of zeolite L and KIT-6 was used to support CoMo active metals
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33 170.
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Fig. 22. Comparison of GC peaks of the products in the HDS of 4,6-DMDBT over NiMo/Al2O3,
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27 NiMo/ZK-W, and NiMo/ZSM-5 at LHSV = 120 h−1. Reprinted with permission from 171.
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30 Series of composite supports (ZS) consisting of ZSM-15 and SBA-16 in specific ratios have been
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32 adopted as support for NiMo metals, and the support’s morphological properties as depicted in
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34 Fig. 23 were considered as a major determinant of the catalysts HDS activity 185. The uniform
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37 spherical aggregates morphology of ZS-3 consisted of uniform hexagonal-prismatic ZSM-5
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39 monocrystals enabled the transfer of spillover hydrogen that had formed in the micropores of
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41 ZSM-5 onto nearby MoS2 active phases in the mesopores of SBA-16. Moreover, the enhanced
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reactants and products diffusion and active phase accessibility by reactants have been attributed to
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46 the ZS-3 uniform morphology. Further incorporation of cation additives (K+, Mg2+, Mn2+, Zn2+,
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48 and Cu2+) to the ZS series using inorganic salts of the cations changed the textural properties,
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50 acidity, metal-support interaction, and morphology of the supports 186. The NiMo/ZS-Mg catalyst
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53 presents exceptionally higher HDS activity than the other series of cation-modified ZS supported
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55 NiMo catalysts due to its desired catalytic properties, which include the distribution of pores,
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3 acidity, and metal-support interaction. Similarly, a ZSM-5/KIT-6 composite mesoporous sieve had
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6 been developed with interesting support properties and more interestingly, the pore structure was
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8 successfully tuned by varying the mole ratio of support precursors 187.
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47 Fig. 23. SEM images of the series ZS and pure SBA-16 supports: (a) ZSM-5; (b) SBA-16; (c)
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49 ZS-1; (d) ZS-2; (e) ZS-3; (f) ZS-4; (g) ZS-5; (h) ZS-Mechanical. Reprinted with permission from
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51 185.
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3.3. Carbon and carbon-based support
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3 The use of carbon supports in the preparation of hydrotreating catalysts for the upgrading of heavy
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5 188–195.
6 oils has shown some fascinating results in recent years The advantages of using carbon
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8 supports include its low cost, easy recovery of deposited metals from the catalyst, very high
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10 thermal and acid stability, and reasonably easily controlled pore structure 196,197. However, with
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the large amount of coke generated in the refineries, the use of carbon or carbon-based support
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15 may not be of special interest for practical industrial applications. Single-walled carbon nanotubes
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17 (SWCNTs) has recently been used as support for Ni and Yttrium metals, which were deposited via
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arc discharge method. Higher HDS activity was specifically observed when the Ni-Y/SWCNTs
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22 are oxidized by heat treatment at 200 oC 198. Single-layered nanocatalysts of CoMo supported on
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24 carbon nanotubes were also reported to have high HDS activity with the support properties
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26 inhibiting the formation of undesirable CoS2 phases 190. Similarly, Ning et al. reported the
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29 incorporation of MoS2 on graphene sheets (GS) (obtained after annealing of graphene oxide) via
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31 the microwave irradiation of functionalized GS (FGS) and ammonium tetrathiomolybdate (Fig.
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33 24) for efficient HDS application 195.
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3 Fig. 24. Schematic representation of the preparation of M-MoS2/GS catalyst. Reprinted with
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6 permission from 195.
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9 The effect of nitrogen on mesoporous carbon support for HDS application was further studied by
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11 Hu et al. 193. The N-doped mesoporous carbon (NMC), prepared using urea and glucose as nitrogen
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13 and carbon precursors respectively, was used as MoS2 support with tunable pore structure
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(adjusted using various silica template) and nitrogen content (Fig. 25). The work of Nath and
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18 Verma discovered the use of activated carbon fiber as NiMo catalyst support for a tubular flow
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20 reactor 191. The small pore diffusion resistance and low pressure drop properties of the carbon fiber
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in addition to the general properties of carbon support was instrumental in the high HDS
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25 performance.
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3 A nanohybrid of 3D graphene supported NiS-MoS2 catalyst was synthesized for HDS application.
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6 The 3D graphene layers inhibit the aggregation of NiS nanoparticles and MoS2 layers.
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8 Consequently, uniform distribution of NiS on the few layers of 3D MoS2/graphene hybrid was
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10 achieved as reported by Lonkar et al. 199. The promoter role of NiS served the MoS2 active sites
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with hydrogen via the hydrogen spillover mechanism presented in Fig. 26.
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35 Fig. 26. Proposed hydrogen spillover mechanism during the HDS of DBT using 3D NiS-
36 MoS2/graphene nanohybrid catalysts. Reprinted with permission from 199.
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41 Carbon-based materials have also been used in conjunction with other supports to improve the
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43 support properties. The modification of TiO2 support with graphene to enhance the HDS activity
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45 200.
of NiMo/TiO2 catalysts was due to the hydrophobic property of graphene Li et al. observed
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48 that the graphene-modified TiO2 supported NiMo catalyst has high hydrophobicity, which
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50 weakens the adsorption of polar molecules (e.g., H2S) and ultimately minimizes the catalyst
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52 deactivation 201. The H2S gas quickly desorp from the catalyst’s surface as shown in Fig. 27.
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55 Similarly, the HDS activity of MoCo/Alumina catalyst was enhanced after support modification
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3 with carbon nanofiber. It was reported that the carbon nanofiber modification improves the
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6 support’s textural properties and the metal-support interaction, which result in better catalyst
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8 dispersion and HDS activity 202.
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31 Fig. 27. Proposed mechanism for the HDS of NiMo/TGC-0.5 and H2S desorption rate (inset)
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detected by rapid gas detector tube. Reprinted with permission from 201.
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Based on the different supports discussed, it is quite clear that the choice of support plays a
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39 significant role in both the HDS activity and selectivity of the catalysts. With this background
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41 knowledge, the question that would come to our mind is, “Could there be new supports in the
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nearest future?” There still exist quite interesting mesoporous supports with excellent textural
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46 properties that have not yet found use in HDS. Large pore zeolites such as ITQ-44 and ITQ-33 are
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48 potential HDS catalyst supports, especially for sterically large refractory sulfur compounds 203–205.
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50 MOFs are another class of high surface area molecular sieve material that are increasingly gaining
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53 attention in all field of practical applications. Recently, there has been a huge success in developing
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55 highly stable MOFs that can withstand high thermal, chemical, and mechanical stabilities 206,207.
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3 The use of MOFs as catalyst or catalyst support for HDS application is therefore an area worthy
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6 of in-depth study.
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9 4. Synthesis strategy
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12 The type of synthesis used for a catalyst has a significant impact on its physico-chemical properties
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14 and HDS activity. The synthesis approach covers a wide range of the step-by-step procedures that
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16 are followed to achieve the desired catalyst material. In this section, we intend to cover the major
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factors that can typically be expected to impact the physico-chemical properties of the catalysts
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21 during their synthesis.
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24 4.1. Preparation method
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27 The most common method for preparing unsupported catalysts is the hydrothermal synthesis of
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29 the precursor solutions at high temperature 208,209. However, the nature of catalyst’s precursor can
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31 warrant the decomposition approach under the flow of H2 or Ar gas 210,211. For supported catalysts,
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34 the impregnation approach is the most common, but it is still probable that support synthesis may
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be via hydrothermal approach 212. In the impregnation approach, the precursor solution of the
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38 active metals is introduced into the support and later dried and calcined. When the precursor
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solution volume is exactly equal to the support pore volume (incipient wetness impregnation),
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43 better dispersion of active phase occurs under optimum mass transfer conditions within the support
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45 pores. However, the incipient wetness impregnation may limit the active metal loading due to the
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precursor’s solubility in the solution. In that case, the wet impregnation approach (using excess
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precursor solution) is a viable option 213. For bi-, tri- and multi-metallic catalysts, the metal
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52 precursors solution can be introduced to the support in a sequential or two-step impregnation
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3 co-impregnation approach (all the metals precursor solutions added at once) 82. Recently, a single-
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6 pot approach, that involves hydrothermal synthesis of combined support and active metal
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8 precursors have been developed 157,214, and effects of hydrothermal synthesis conditions and
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10 molybdenum metal loadings have been studied extensively 158. Fig. 28 below shows the summary
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of procedure for (a) Co-impregnation approach and (b) single-pot hydrothermal synthesis
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47 Fig. 28. (a) Co-impregnation loading of active metals on Al2O3–SiO2 support 82.(b) Single-Pot
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50 (SP) synthesis of NiMo Supported on Metal-Modified SBA-15 Catalysts. Reprinted with
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3 In the sequential impregnation approach, it is worth mentioning that the sequence in which metal
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6 species are deposited on the catalyst support has a significant impact on both the catalyst activity
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8 and selectivity. In a typical example, addition of Ir to Pd/Al2O3 catalyst increases both HDS
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10 activity and C-S hydrogenolysis selectivity, but the addition of Pd to Ir/Al2O3 leads to a decrease
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in activity 38. A similar scenario was observed when Yttrium was used to enhance the HDS activity
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15 of palladium supported on alumina 39 and when P2O5 was used to modify the catalytic properties
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17 of NiMo/Al2O3 137. A colloidal chemistry approach has also been employed in the synthesis of HDS
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catalysts. Recently, nanosized islands of Pd were deposited on 12 nm colloidal iron oxide
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22 nanoparticles supported on alumina via the galvanic exchange reaction of Pd2+ to Pd0 by Fe0 and/or
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24 Fe2+ on preformed iron oxide seed 20. This approach greatly improved the dispersion of palladium
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26 islands on the support and ultimately resulted in a better (4-fold) activity than Pd/Al2O3 and
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29 Pd/Fe2O3 (commercial) catalysts. An ultrasound irradiation followed by non-thermal (glow discharge)
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31 plasma treatments of functionalized multiwalled carbon nanotubes supported NiMoW catalyst via co-
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33 impregnation were reported to enhance the phase structure, textural properties, and especially the
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dispersion of the active phases on the support 215. An anion-assisted approach, using CTAB has also
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38 been used to synthesize a dendritic mesoporous silica nanospheres (DMSNs) support with a large
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40 average pore diameter (26.4 nm) 216. The center-radial pore channels in the dendrimer-like silica
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support causes the large pore diameter, which is exceptionally good for sterically large sulfur
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45 compounds since they will have easy diffusion and access to and from the active sites. After Al
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47 modification of the DMSNs and further impregnation of Ni and Mo active phase, the average pore
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49 diameter is still more than 20 nm (Fig. 29). The interesting textural properties of the support result
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3 HDS activity. The type of metal and support precursor used in the catalyst preparation will also
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Fig. 29. An illustration of NiMo/DMSNs and NiMo/Al-DMSNs catalysts’ synthesis. Reprinted
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33 with permission from 216.
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36 4.2. Precursors
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39 The type of active metals and support precursors used to prepare catalysts can significantly impact
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41 the dispersion of the active phases, catalyst textural properties, reducibility of the oxides metals,
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43 and the HDS performance of the catalyst 217–219. Basically, the active metal precursors are sourced
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either from different salts each having a single representative active metal such as ammonium
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molybdate and copper nitrate 218 or from a single salt of all the active metals such as Keggin
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50 polyoxometalate 220. In the former case, inconsequential counter ions are generated after
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dissolution of the precursor salt, which might affect the catalyst properties, and it requires multi-
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3 impregnation of active metals on support. The latter case has the advantage of only having single
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6 preparation of the active metal solution since all the active phase are in one compound (heteropoly
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8 compound or polyoxometalates). Moreover, better dispersion of the active phase due to intimate
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10 interaction from the all-metals-precursor solution is usually observed. Some precursors such as
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alkyltrimethylammonium-thiomolybdate-thiotungstate-cobaltate (II) comprised of trimetallic
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15 system plus the sulfur component required for metal sulfidation 221. It is important to consider the
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17 recent progress in the use of precursors for HDS reaction. The combined effect of pH and precursor
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19 222.
on the morphology of (Co)MoS2 catalysts has been studied recently by Zhang et al. The pH
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22 modulates the MoS2 nucleation rate, and precursors influence the slab length of the MoS2 catalyst
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24 (thus affect HDS of thiophene selectivity). At lower pH, fast nucleation was reported, which leads
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26 to the formation of large specific area small MoS2 crystallites with more active sites (Fig. 30).
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29 When the MoO3 and Na2S·9H2O precursor combination was used, shorter slab length occurred
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31 than in the case of (NH4)6Mo7O24·4H2O and CS(NH2)2 combination.
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33 Fig. 30. An illustration of the synthesis procedure of MoS2 catalysts with different crystallite size
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36 and MoS2 catalysts with similar stacking number but different slab length. Reprinted with
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38 permission from 222.
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41 The work of Liang et al. reported the application of well-defined Strandberg polyoxometalates
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43 (Ni(NH4)2[(HPO3)2Mo5O15] and Ni[(HPO3)2Mo5O15]) as active phase precursors, which were
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supported on γ-Al2O3 via incipient wetness impregnation. The use of these well-defined crystal
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48 and molecular structured precursors significantly affect the nature of active phase dispersion,
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50 number of accessible sites, and ultimately HDS activity for the NiMoS- γ-Al2O3 catalyst 223.
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52 Afterward, the same group adopted a ligand-induced self-assembly synthesis strategy using 4,4’-
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3 synthesize a new set of single crystals of Ni2(4,4’-bipy)Mo4(4,4’-bipy)2 and Ni(4,4’-
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6 bipy)(H2O)3].2(4,4’-Hbipy).3H2O polyoxometalates and subsequently impregnated them on the γ-
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8 Al2O3 support (Fig. 31) 224. The framework, promotion, and ligand effect significantly impacted
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3 Fig. 31. From small Ni–Mo–O clusters in solution to solid-state coordination frameworks of Mo2Ni and
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6 PMo11Ni via a ligand-induced self-assembly strategy. Reprinted with permission from 224.
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9 Nickel metal organic framework, [Ni2(dhtp)] (H4dhtp = 2,5-dihydroxyterephthalic acid), with
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11 well-defined crystallinity and molecular structure has also been used as a Ni precursor in the
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13 preparation of bulk NiMoS catalyst, while Mo was introduced into the pore structure of the
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[Ni2(dhtp)] via sublimation of Mo(CO)6 to form the [Ni2(dhtp)Mo(CO)3] MOF complex as shown
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18 in Fig. 32. The MOF complex was later decomposed under the flow of H2/H2S at 350 oC to form
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20 highly active HDS catalyst 225.
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3 4.3. Chelating agent
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6 Chelating agents are usually some organic ligands that can easily bind with the active metals
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9 (mostly the promoter) to form a stable complex. The formation of the stable co-promoter complex
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11 is particularly important in the gas-solid activation approach of the metal oxide catalysts. The
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13 sulfidation of Mo or W begin at a temperature around 150 oC while the sulfidation temperature for
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Ni or Co promoter is mostly within 50 oC. Obviously, it means the promoter gets sulfided prior to
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18 the formation of MoS2 active phase. Consequently, the amount of promoter on the MoS2 slabs will
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20 be significantly less, which leads to less active sites on the catalyst. However, by capping the
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promoter with a complexing agent, its sulfidation is typically delayed. This enables the formation
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25 of MoS2 slabs prior to the decomposition of the promoter complex, which later decomposes to
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27 release the promoter ion at the edges of the MoS2 slabs. Hence, there are increased active phases
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29 and HDS performance of catalyst 121. Furthermore, the chelating agents have been identified as
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31 226.
32 facilitators of formation of octahedral polymolybdates, which are generally easier to sulfide
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34 The report of Santolalla-Vargas et al. presented that chelating agents also prevent strong metal-
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36 support interaction between active metals and support 227. The method of introducing the chelating
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39
agent during catalyst preparation arguably impacts the catalyst performance. While Chen et al.
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41 considered co-impregnation of chelating agent as being the best performing method 228, the work
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43 of Li et al. considered the sequential impregnation of the chelating agent followed by active metal
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45 229.
impregnation to be the most appropriate Several chelating ligands such as ethylene diamine
46
47
48 tetraacetic acid, citric acid, glycol, nitriloacetic acid, 1,2-cyclohexanediamine-tetraaceticacid,
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50 citric acid, and ethylenediamine have been tested 121. More recently, trimesic acid 230 and
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52 thioglycolic acid 231 have also been used as chelating agents in the preparation of HDS catalysts.
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55 4.4. Surfactants and swelling agents
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3 Advances in the synthesis of highly ordered, large porous material are typically based on the use
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6 of large molecular structure directing agent known as surfactant and/or utilization of suitable
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8 swelling agent 232. While the surfactants primarily direct the material structure through its
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10 templating property, the swelling agents typically tailor the pore diameter over a wide range by
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swelling the surfactants 233. Some of the prominent surfactants that are widely used in the synthesis
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15 of highly ordered support or catalyst materials for HDS applications include CTAB 183, P123 233
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17 and P127 234. The role of surfactant has also been extended to acting as an active metal linker and
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disperser. In the work of Xu et al., polymolybdate anion from ammonium heptamolybdate
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22 tetrahydrate was stabilized using a gemini surfactant ((C16H33-N(CH3)2-C6H12-N(CH3)2-
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24 C16H33)Br2) 235. The gemini surfactant-linked polymolybdate was used as a precursor in the
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26 preparation of the NiMo/SiO2-Al2O3 catalyst. The gemini surfactant modification of Mo species
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29 resulted in highly dispersed MoS2 phases with improved stacking. There are also large numbers of
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31 swelling agents that have been used in the literature to modulate the pore size of catalytic materials
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33 which include classes of both aliphatic 236,237, alicyclic233,238, and aromatics compounds 233,239. The
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use of 1,3,5-trimethylbenzene as a swelling agent for CTAB surfactant has been recently reported
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38 in the pore size controlled synthesis of meso-microporous zeolite Y, which was used to support
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40 NiMo active species for HDS of sterically hindered 4,6-DMDBT 240. In addition to enabling the
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42
diffusion of 4,6-DMDBT, it was further discovered that the larger pore size observed due to the
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45 swelling agent inhibited the polarization effect of Al3+ and decreases metal-support interaction,
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47 which enhances the degree of sulfidation of Ni and Mo species, increases stacking level, and
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49 decreases MoS2 slab length.
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52 4.5. Catalyst activation methods
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3 The active sites in HDS catalyst is mainly due to the MoS2 slabs, which may be surrounded by co-
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6 promoter (such as Ni or Co) at the edges/corners or rims of the slabs. Generally, the prepared
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8 catalysts contain the metals in their oxide forms and will consequently require an activation step
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10 (sulfidation) to form the MoS2 prior to HDS application. The commonly adopted strategy for the
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oxide sulfidation of catalysts is the gas-solid phase approach that involves using H2 gas to reduce
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15 the metal oxides and then subsequent flowing H2S gas to do the sulfidation. This approach is
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17 performed at high temperature (usually above 350 oC) for over 5 h and can therefore be considered
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as harsh treatment of the catalysts oxides to form the sulfide form. It may also be connected with
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22 some health issues due to the risk of working in an environment with H2S. However, at the
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24 industrial scale, this approach has remained the best viable option due to the availability of excess
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26 H2S and the design of the hydrotreater plants. Interestingly, new approaches have been adopted to
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29 sulfide the catalysts without necessarily using direct H2S gas such as:
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32 4.5.1. Decomposition of thiosalts
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35 Though slight modification of the direct flow of H2S, this particular approach involves thermal
36
decomposition of the thiosalt to give a desired active catalysts 211,241. Series of thiosalts such as
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39 ammonium tetrathiotungstates, tetraalkylammonium thiotunstate 210, alkyldiammonium
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41 242 221
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thiomolybdate and alkyltrimethylammonium-thiomolybdate-thiotungstate-cobaltate (II)
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44 have been synthesized and decomposed to form the active MoS2 catalysts.
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47 4.5.2. In situ generation of MoS2
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49
50 The synthesis of MoS2 active phase have also been performed via traditional wet chemistry approaches.
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52 For example, new synthesis strategy (Fig. 33) was developed recently based on the use of oleylamine
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54 as solvent, reducing agent, and surfactant in a one-pot containing Ni(acac)2/Co(acac)3 and Mo(CO)6 as
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3 Ni/Co and Mo precursors respectively, and sulfur at 300 oC. This approach yielded a highly disordered
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6 monolayer of MoS2 with ultra-small lateral size (4.2 - 4.6 nm) and high density of active sites 243.
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35 Fig. 33. An illustration of the one-step synthesis procedure to prepare MoS2, MoNiS and MoCoS
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38 catalysts. Reprinted with permission from 243.
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41 Another simple HDS catalyst synthesis strategy involves in situ generation of the NiS
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43 nanoparticles and MoS2 layers supported on graphene aerogel, and this approach is based on the
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45 hydrothermal synthesis of the metal thiosalts solutions and graphene support (Fig. 34) 199. The 3D
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NiS-MoS2/graphene assembly shows a promising interfacial interaction between the 3D highly
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50 porous graphene and the NiS and MoS2, which result in high dispersion of the actives phases.
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27 Fig. 34. Schematic representation for preparation of 3D NiS-MoS2/Graphene. Reprinted with
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permission from 199.
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32
Unsupported hierarchical porous NiMoS nanoflowers have also been synthesized via a simple
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35 hydrothermal approach that involves direct mixing of the elemental sulfur with as-prepared dried
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37 powder of Ni, Mo and Si mixture in various silica ratio 244. Silica that had been used to tune the
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39 NiMoS porosity was then removed by dissolving the formed silica supported NiMoS in HF.
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42 Typical ligand-directed colloidal synthesis strategy has recently been adopted to selectively grow
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dimensionally and shape-controlled NbS2 nanostructures 245. In section 2.1, we highlighted the
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46 challenge of niobium sulfidation using H2S. Interestingly, this reported approach has provided yet
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another viable option to not just sulfide Nb but also to modulate the shape and dimension of NbS2
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51 by changing the reaction conditions such as molar ratio of reactants, capping ligand, and
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53 oleylamine solvent as depicted in Fig. 35 below.
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Fig. 35. Schematic illustration of the colloidal synthesis protocol of NbS2 nanostructures.
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30 Reprinted with permission from 245.
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33 4.6. Non MoS2 active phase HDS catalysts
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36 There is good amount of highly active and relatively stable non-MoS2 catalysts for HDS
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38 application that are more-or-less safe to deal with than the sulfides. The metal phosphides and
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40 silicides have shown some promising results 246,247. However, metal borides, carbides, and nitrides
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43
were found to first decompose and then form the respective metal sulfides under the harsh HDS
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reaction conditions 248. The synthesis and HDS application of metal phosphides especially the
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47 nickel phosphide (both bulk249,250 and supported251–254) have been extensively studied and recently
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reviewed 246,255.
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4.6.1. Metal silicides
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3 The metallic silicides have a long history of being widely used as catalyst256–260 and have recently gained
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6 relevance in the field of HDS due to their great resistance to sulfur poisoning and easy regeneration
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8 procedure 261–264. The resilience to sulfur poisoning by the Ni silicide was first investigated using
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10 the first-principle theoretical calculations where the nature of the ordered phases in the silicide was
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12 265.
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studied DFT computational calculations revealed an overlap in the density of states of Si-sp
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15 states and Ni states which leads to downshift of the d-band center in the Ni states. The resultant
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17 effect is difference in behavior between the Ni and the NiSi2, as explained in the d band theory of
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Norskov (Fig. 36a).
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37 Fig. 36. (a) DOS of surface atoms of Ni (111) and NiSi2 (111); b) energy diagram for the H2S adsorption
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and dissociation on Ni (111) and NiSi2 (111) surfaces. Reprinted with permission from 266.
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Chen et al. reported that the adsorption energies of H2S, HS, and H on the NiSi2 phase was much
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45 lower than that of the Ni phase as presented in Fig. 36b and further reiterated that by using the
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47 Evans-Polanyi relationship, the decreased H2S adsorption can be explained by a higher energy
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49
barrier 266. This was further supported by experimental findings that showed an exceedingly higher
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52 turnover frequency for HDS of DBT by using NiSi2 as depicted in Fig. 37. The HDS activity of
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54 NiSi2 was further improved by the incorporation of additional metal to the NiSi2 structure.
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15 Fig. 37. a) TOFs of DBT during HDS over the Ni–Si IMCs in comparison with metallic Ni catalysts at
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17 different reaction temperature. b) HDS TOFs of DBT as a function of time on the Ni–Si IMCs in
18
19
comparison with Ni. Reprinted with permission from 266.
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22 The direct silicification of nickel cobalt oxide with SiH4 was created in order to synthesize Ni-Co silicide
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25 (Ni1-xCoxSi2). By optimization of Ni to Co molar ratio, the fluorite structured ferromagnetic
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27 Ni0.75Co0.25Si2 catalyst was formed, which also demonstrated higher HDS activity than the NiSi2 or
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29 CoSi2 catalysts. This approach also directed the reaction to the hydrogenation pathway by almost 32%
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31 267.
32 Another modification of the NiSi2 catalyst with Fe to form Ni1-xFexSi2 catalysts was also reported
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247. The favorable binding of Fe with Ni to form Ni-Fe alloy and its further silicification to give Ni1-
34
35
36 xFexSi2 catalyst with high electron density at the metal sites was achieved at Ni:Fe molar ratio of
37
38
39
0.75:0.25 (Ni0.75Fe0.25Si2). These results are shown from the 57Fe Mossbauer spectroscopy and XPS
40
41 analysis results. Because of the geometrical and electronic structure modification of the NiSi2 catalyst
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43 due to Fe substitution, the HDS activity was enhanced significantly (Fig. 38).
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Fig. 38. Fe-substituted Ni-Si intermetallic catalysts (Ni1-xFeSi2). Reprinted with permission from
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247.
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33 Pd supported on carbon nanotubes (Pd/CNT) was also silicidized by addition of
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35 dichlorodimethylsilane solution to the Pd/CNT catalyst in a furnace at 500 oC via the chemical
36
37 vapor deposition approach. The formed Pd2Si/CNT demonstrated strong resistance to sulfur
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40 poisoning, and the Pd modification with Si redirected the reaction pathway to DDS 268. The high
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42 sulfur tolerance is likely attributed to the formation of electron deficient Pd, due to the donation of
43
44 electron to silicon (Pd-Si interaction) as depicted in Fig. 39 268.
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50 Fig. 39. XPS of (a) the Pd3d region of the 3 wt% Pd/CNTs and the 3 wt% Pd2Si/CNTs. (b) XPS
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53 of the Si2p region, (c) the calculated electron localization function map, and (d) the calculated total
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55 electronic DOS of Pd2Si. Reprinted with permission from 268.
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3 5. Conclusion
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6 The advancement of catalyst design and synthesis for HDS application is largely driven by its
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9 increasing demand for use as well as the quest for improved efficiency of catalysts. Over the last
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11 decade, there has been great advances in the design and synthesis of catalysts including (but not
12
13 limited to) the choice of active metal, the support, and the preparation methods. Computational
14
15
16
calculations have been a key player in the recent successes of improved catalysts. In this review,
17
18 the discovery of new, cheaper base metals such as Zn, Fe and Cu as HDS catalysts has been
19
20 discussed alongside the traditional Co(Ni) and Mo(W) species. Indeed, the ZnFe binary catalyst
21
22
has shown high potential for HDS of DBT. Advancement in the use of expensive noble metals
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24
25 including the support effect studies, nanoparticles size modulation, co-promoter effect and so on,
26
27 and how these impacted on the activity of the HDS per weight of catalyst have been elaborated.
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29 Non-metal (such as phosphorus, fluorine and boron) promoting effect and the use of multi-metallic
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31
32 catalysts have been explored. Advancement in the use of catalyst supports and the use of new
33
34 supports, mixed supports, and support modifications have also been well-discussed. Indeed,
35
36 catalyst support properties have a direct impact on the acidity, active phase dispersion, and HDS
37
38
39
activity of the catalyst. The preparation approaches including the traditional co-impregnation and
40
41 sequential impregnation and the single-pot approach for catalyst preparation have been carefully
42
43 analyzed. The roles of other preparation parameters such as precursors, chelating agent,
44
45
surfactants, and swelling agents on the textural properties, ease of reduction and sulfidation of
46
47
48 metal oxides, and dispersion of active phases have been highlighted. The various catalyst
49
50 activation approaches which typically involves the formation of active MoS2 phases have been
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52 discussed and the review was concluded with non-MoS2 active phase that have shown good
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55 potential as HDS catalysts such as the phosphides and silicides.
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3 Acknowledgement
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6 Financial support from KFUPM through a project No. DSRNUS15105 is gratefully
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9 acknowledged.
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