Advanced hydrodesulfurization catalysts: A review of design and

Subscriber access provided by UNIV OF LOUISIANA

Review

Advanced hydrodesulfurization catalysts: A review of design and synthesis Abdulkadir Tanimu, and Khalid Alhooshani Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b00354 • Publication Date (Web): 22 Mar 2019 Downloaded from http://pubs.acs.org on March 22, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Advanced hydrodesulfurization catalysts: A review of design and synthesis Abdulkadir Tanimu, Khalid Alhooshani* aDepartment

of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia.

*Corresponding author Email: [email protected] Phone: +966 13 860 3065 Fax: +966 13 860 4277

1 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 100

Abstract Proliferating energy consumptions, particularly fossil fuels, has led to an increasing generation of pollutants; many of these harmful products have been of serious environmental concerns recently. While energy demand will continue to grow due to massive urbanization and industrialization, the ability to remove such pollutants has not yet been achieved. Therefore, policies are always being reviewed to accommodate the existing reality of minimizing the amount of pollutants released to the environment on daily basis. Sulfur dioxide, a major environmental pollutant gets to the environment through the combustion of sulfur-containing fuel in the engine of automobiles. Over the years, regulatory bodies such as European Emission Standard have set limits to the amount of sulfur in transportation fuel to safeguard the environment. Lately, the limit for clean fuel specification with respect to sulfur content is set to nearly zero ppm. This policy came at a time when the crude oil experienced a large decline in price, in addition to the increased sulfur content and crude density experienced day-in-day-out. Compliance with this tight regulation will mean that refineries are expected to either modify their hydrotreating unit, which is capital intensive, or adopt robust catalysts, through research, that can work in-tandem with the existing conventional hydrotreating catalysts to bring down the sulfur level to the required limit. This urgent demand has once more drawn the attention of the scientific community. Since there has been a great stock of research outcomes with respect to catalysts for hydrodesulfurization application in a recent time, our aim is to collect and review those recent articles on hydrodesulfurization catalysts design and development. The tutorial review is therefore intended to cover a basic hydrodesulfurization overview, followed by detailed discussions on the recent development in the choice of active phases, their supports, and the synthesis strategies. The work is expected to guide researchers,


Page 3 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

especially beginners that are interested in refinery hydrotreating, on the recent development in hydrodesulfurization catalyst design and development.

Keywords: hydrodesulfurization; catalyst support; active metals; refractory sulfur compounds; catalyst poisoning 3 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 100

Contents 1. Introduction 2. Active phases 2.1. Monometallic and bimetallic catalyst 2.2. Trimetallic and multi-metallic catalysts 3. Active phase supports 3.1. Alumina and modified alumina supports 3.2. Mesoporous silica and other molecular sieve supports 3.3. Carbon and carbon-based support 4. Synthesis strategy 4.1. Preparation methods 4.2. Precursors 4.3. Chelating agents 4.4. Surfactants and swelling agents 4.5. Catalysts activation methods 4.5.1. Decomposition of thiosalts 4.5.2. In situ generation of MoS2 4.6. Non-MoS2 active phase HDS catalysts 4.6.1. Metal silicides 5. Conclusion Acknowledgement References


Page 5 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

1. Introduction There is currently an apparent increase in demand for fossil fuel energy in some countries, but the need for mitigating the effects of the use and acquisition of non-renewable energy sources on the environment has gained global attention

1–3.

The increased demand for fossil fuels is a result of

continuing increase in population, especially in the developing countries where the energy options are limited, and the global interest in offsetting and/or eliminating the effects of burning these fossil fuels highlights the severity in consequence of large scale industrial and automobile emissions. Such emissions are leading to climate change, more specifically global warming 4, but they also pose many risks on the environment and human health 5. For example, sulfur (iv) oxide, a major emission of combusted fuel, can cause severe respiratory and other several health problems when inhaled, and in the atmosphere, it forms the acid rain which can harm sensitive ecosystems 5.

In addition to being linked to health and environmental problems, sulfur in fuel is known to

cause damage by deactivating the hydroprocessing catalysts and resulting in the corrosion of pipelines, pumps, and refinery equipment 6. Due to these undesirable consequences, environmental regulations have prompted restraining the level of sulfur in the fuel, and a recent regulation by the European Emission Standard (Euro VI) targeted zero sulfur in the transportation fuel 7. With so many countries gradually adopting this policy and transiting to zero sulfur transportation fuel (Fig. 1a and b), the refineries are being forced to find ways to meet the newly increasing demand for ultra-low sulfur fuel, which ultimately requires that the refineries invest in research. Recently, Honeywell, an oil and gas technology inventor and manufacturer, developed an ULTIMet™ catalyst that was designed to address the challenge of the refineries by having more active sites for chemical reaction, thus resulting in an increased hydrotreating performance 8. According to the company, the catalyst can as well work in-tandem with the conventional hydrotreating catalyst in 5 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 100

the hydrotreating plant, thus saving refineries the cost of redesigning an additional hydrotreating unit for ultra-low sulfur fuel production. Though catalyst producers like Honeywell and ExxonMobil have achieved a great milestone in catalysts’ designs, their technology is mostly trademarked or patented, which make access to vital scientific information quite difficult. We do know that in the hydrotreating plants of most refineries, the technology of removing sulfur from the transportation fuel involves hydrodesulfurization (HDS) 9. However, other methods such as oxidative desulfurization, supercritical water desulfurization, and adsorptive desulfurization 10 are still used by a few refineries, albeit less frequently than HDS.

(a)


Page 7 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(b)

Fig. 1. Worldwide on-road diesel sulfur limit, sourced from Stratas Advisors, (a) October, 2015 and (b) February, 2018 11. Although HDS is the most commonly used chemical technology for removing organic sulfur from crude oil and transportation fuel such as gasoline, jet fuel, and diesel

12,

it is often considered

pricey. The HDS technology is known to be financially tasking in terms of its operational conditions, which require an active solid catalyst as well as high temperature and hydrogen gas pressure conditions. Though HDS technology has its financial drawbacks, its desulfurization performance is unmatched by other desulfurization technologies 13. Because of its high efficiency of removing sulfur, refractory sulfur compounds such as dibenzothiophene (DBT), 4methyldibenzothiophene

(4-MDBT),

4,6-dimethyldibenzothiophene

(4,6-DMDBT),

and

benzonaphthothiophene (BNT) (Fig. 2) which are mostly found in heavy gas oil and vacuum gas oil can be treated easily with a highly robust HDS catalyst. Since the crude oil reserve in many parts of the world is becoming heavy nowadays, the demand for highly robust HDS catalysts has dramatically increased. Additionally, the continuous emergence of alternative energy supply sources (e.g. biofuel and solar energy) has contributed to the drop in the value of crude oil in the 7 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 100

international market; therefore, cheaper but efficient HDS technologies are continuously being sought.

(a)

(b)

(c)

S

S

S

S

(d)

Fig. 2. Some refractory sulfur compounds: (a) dibenzothiophene; (b) 4-methyldibenzothiophene; (c) 4,6-dimethyldibenzothiophene; (d) benzonaphthothiophene The predominant metals often used as the active species in the HDS catalyst design are Co(Ni)Mo(W). These active species have been used for more than a century as bulk catalyst and later as a supported catalyst due to their cost. Interestingly, the approach to HDS has somewhat drastically evolved through the years although the active species have not been able to be completely replaced. Perhaps this evolution is correlated with the advances in synthesis and characterization tools which has now made it much easier than ever before to fully comprehend the HDS process, much unlike previous research conditions when catalyst development was mainly based on scientific guess through trial and error approach. In contrast to those days, we can now use more sophisticated instrumentation and quantum computational calculations to understand the active phase design and active-phase-support interaction and how these factors affect catalyst performance and deactivation. Moreover, we now have a better grasp on the role that active sites play in the reaction pathway and product selectivity. These advances have enabled development of interesting synthesis strategies that yielded unique supports and minimized the


Page 9 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

cumbersome nature and the large energy consumption that are both associated with the synthesis steps. 2. Active phases The active phases are primarily the active metals that perform the catalysis job of HDS, although recently, HDS has been reported on a metal-free carbon materials

14.

The active metals are

employed both as unsupported catalysts (bulk) or as supported catalysts. For more than a century, the active metals utilized in HDS have been predominantly Mo(W) and Co(Ni) 15–19, and till today they have not been successfully replaced, although there has been quite a lot of improvement in their synthesis strategy. The actives phases used are monometallic, bimetallic, trimetallic, or even multi-metallic depending on the required catalyst performance; however, the bimetallic combination is still the generally accepted catalyst system. 2.1. Monometallic and bimetallic catalyts Monometallic catalyst systems frequently contain an active metal such as Mo or W, but the use of such a monometallic catalyst in HDS is slowly declining due to the discovery of the advantages of using some base metals such as Co and Ni as promoters, except for the noble metals

20.

The

bimetallic catalyst is like the monometallic system, but in addition to Mo or W, it also contains a base metal as a promoter, which is usually Co or Ni. Many metals have been explored as alternatives to the predominantly Mo(W) and Co(Ni), but little success has been achieved either due to the cost of the metals or due to electronic effects that lead to low activity. Although the noble metal catalysts can work even at low operating temperature and can maintain high hydrogenation activity especially platinum and palladium 21–23, which are of special interest in the HDS of highly refractive (sterically hindered) sulfur compounds24, their expensiveness and


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 100

predisposition to sulfur poisoning has deterred their practical application in the catalyst industries 25–28.

It is anticipated that the excellent HDS activity that can be achieved with the noble metal-

based catalysts can counteract their expensiveness, and as a result, there are earnest efforts being made to improve HDS performance. For example, there has been considerable attention given to selecting better supports and/or adopting more practical synthesis, which includes better choice in metal size tuning, higher dispersion on support amount of the metals

31–34.

29,30,

and unsurprisingly the use of very minimal

For instance, Wenya et al. reported the role of low-temperature

hydrogen plasma in the synthesis of graphene-supported palladium nanoparticles catalysts for hydrodesulfurization application 35. This new one-step synthesis approach (Fig. 3) formed welldispersed 2 nm particle size palladium nanoparticles on the graphene sheets which enhanced its hydrodesulfurization ability above the conventional activated carbon or graphene-supported palladium nanoparticles.

Fig. 3. Preparation of Pd/GS composites. Reprinted with permission from 35. The Pd nanoparticle size modulation and dispersion on mesoporous HZSM-5 support has also been achieved by decamethonium bromide assisted approach 36. As presented in Fig. 4, one of the two positive sites of decamethonium ion was linked to PdCl42- via electrostatic attraction, and the other


Page 11 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

positive site was linked to the mesoporous electronegative HZSM-5 zeolite surface, thus resulting in high dispersion of the Pd nanoparticles.

Fig. 4. Demonstration of the dispersion principle for Pd nanoparticles over DBD-Pd/MHZ-5. Reprinted with permission from 36. Shen and Semagina reported the effect of palladium nanoparticle size on the hydrodesulfurization of 4,6-DMDBT by using 4, 8, 13, and 87 nm sizes nanoparticles 37. Because the 4 nm Pd has a low edge/terrace atom ratio, the HDS reaction is directed more towards the direct desulfurization (DDS) pathway, which has low HDS activity courtesy of the reduced hydrogenation (HYD)


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 100

pathway contribution. The 87 nm nanoparticles presented the lowest HDS activity due to the low availability of edge atoms required for perpendicular sulfur atom sigma-mode adsorption. Therefore, optimum Pd nanoparticles size was observed at 8 nm as depicted in Fig. 5 below.

Fig. 5. Catalyst performance in HDS of 4,6‐DMDBT at 300 °C, 50 bar H2: (a) 4,6‐DMDBT consumption rate per total mass of Pd; (b) the consumption rates per mole of surface Pd. The subscripts XL, L, M and S represent 87 nm, 13 nm, 8 nm and 4 nm respectively. Reprinted with permission from 37. The DDS selectivity of Pd nanoparticles in HDS was also enhanced by the addition of efficient hydrogenolysis co-metal. Iridium and yttrium have been independently reported as promoters of 12 ACS Paragon Plus Environment

Page 13 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

DDS selectivity in Pd nanoparticles supported on alumina

38,39.

Iridium promoted the DDS

pathway up to 26% against the 5% of the bare Pd nanoparticle catalyst while yttrium increased the % DDS pathway from 71 to 84 (Fig. 6). In addition, both heteroatoms increased the thermal stability of the Pd nanoparticles against metal sintering which leads to better metal dispersion and increased HDS activity.

Fig. 6. Role of yttrium heteroatom on the selectivity and HDS activity of Pd nanoparticles supported on alumina. Reprinted with permission from 39. Generally, bimetallic M-Pd (M = noble metal) catalysts have been observed to resist higher sulfur poisoning than monometallic Pd or Pt catalysts especially when the bimetallic catalyst is supported on strong BrØnsted acidity supports

40.

Gold, Au, though expensive, has been adopted as co-

promoter of the HDS activity of Pd catalysts. In the early 20th century, Venezia et al. first described the structure-modifier role of Au on Pd catalyst for HDS application Herzing et al.

43

and Suo et al.

44

41,42,

and more recently,

reported the effect of heat treatment and atmosphere on the

distribution of Au and Pd on alumina and silica supported Au-Pd catalysts respectively. The high resistance-to-sulfur poisoning AuxPdy/SiO2 alloy phase formed bimetallic catalyst that inhibit the


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 100

formation of less active Pd4S phase which enhanced its HDS activity. The dispersion and stability of Au-Pd on HMS silica support was also enhanced by grafting mercaptopropyl groups on the support framework 45. The apparent favorable interactions between M (Au or Pd) and S are a result of the high dispersion of the Au-Pd on the thiol functionalized HMS support. The vast applications of Pd-based bimetallic catalysts in catalysis science including hydrodesulfurization was recently reviewed by Fenglin et al.

46.

Other noble metals such as

ruthenium 47–50 and rhodium 51–53 have also been explored for the hydrodesulfurization application; however, like Pt and Pd, they have not been widely accepted for practical application in refineries. On the other hand, cheaper metals are also continuously being explored for possible replacement of predominantly alumina-supported NiMo and CoMo catalysts. Metals such as Zn and Fe have found application in HDS catalysis either as a single metal or in combination with other metals 54– 57.

Dating back to the 1980’s, Pecoraro and Chianelli first reported that metals in the 1st, 2nd and

3rd row of transition metals could be good catalysts for HDS, although the 1st row metals demonstrated lower activity 54,55. Sulfur poisoning that results from the strong interaction between these metals and the sulfur of sulfur-containing compounds is considered the major setback for the HDS application of these metals

27,58.

Research areas have become focused on improving the

activity of these metals and/or understanding the synergetic effect of these metals combined with the promoter effect associated with the low activity metal on the HDS. For instance, it has been established that incorporation of carbon into the lattice of early transition metals increased their delectron density

59–61.

Inspired by this, Pinto et al. prepared a vanadium carbide (a mixture of

vanadium nanoparticles and activated carbon in THF solvent) and studied the HDS activity of the vanadium carbide catalyst after activation under the flow of H2/H2S

62.

They observed that

vanadium carbide activity was greater than that of the alumina supported NiMo catalyst. The 14 ACS Paragon Plus Environment

Page 15 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

structural and electronic state of alumina-supported CoMo catalyst was also modified after incorporation of vanadia to the alumina support structure by co-precipitation. The presence of vanadia shifted the reaction toward the HYD pathway, and the HDS activity of sterically hindered 4,6-DMDBT was significantly enhanced 63. Li et al. described the conversion of inefficient iron sulfide HDS catalyst to a highly efficient catalyst by the promoter effect of Zn at a Zn:Fe ratio of nearly 1:1 64. The remarkable performance of the bimetallic FeZnS catalyst was explained, based on experimental and theoretical calculations results, as probably being due to the formation of inactive sulfur vacancies, which promote the adsorption of sulfur-containing molecules as depicted in Fig. 7.

Fig. 7. FeZnS catalyst. Reprinted with permission from 64. Niobium is another easily accessible and cheap metal that has demonstrated great potential for HDS application 65–68. However, the formation of NbS2 from the highly stable Nb oxide is rare and is clearly explained from the perspective of its thermodynamics parameters 69 and the combination of the elemental components (Nb and sulfur) at very high temperature (700 – 800 oC) resulting in metal sintering 66,70. Recent advancement in the sulfidation of niobium oxide through the promoter 15 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 100

effect of copper (Cu:Nb = 0.3) has been reported by Mansouri and Semagina 71. The choice of Cu as promoter was purely based on thermodynamic calculations of the energy parameters of severally cheap and available metals when in combination with Nb metal (Fig. 8). Both Cu and Cd satisfied the thermodynamic criteria; however, due to safety considerations, Cu was considered as the potential promoter of the niobium oxide sulfidation. The promoter effect of V, Fe, Co and Ni on the stability of Mo-NbS2 catalyst was also studied extensively using the DFT and first principle surface thermodynamics calculations at HDS conditions

72.

All the studied metal promoters

showed a positive effect on the Mo-NbS2 stability and HDS activity except Fe metal as shown in Fig. 9. Conversely, Nb has been utilized as modifier of the support surface acidity and metalsupport interaction of the HDS supported catalysts 73,74.

Fig. 8. Role of Cu in the sulfidation of Nb oxide to the sulfide. Reprinted with permission from 71.


Page 17 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 9. Effect of promotion on the NbS2 surface stability. Reprinted with permission from 72. Non-metals such as phosphorus, fluorine and boron have also been incorporated as promoters to the bimetallic catalytic system to minimize catalyst poisoning, enhance catalytic performance, improve catalyst stability, and product selectivity

75–81.

Recently, fluorine influence on the

hydroprocessing properties of NiW/Al2O3-SiO2 catalyst was studied using a low-temperature coal tar feed 82. In addition to improving both acidity and active phase properties of the catalyst, fluorine addition (≤ 1.0 wt.%) also enhanced clean fuel properties like dynamic viscosity, density, distillation range and hydrocarbon content. Similarly, 1 wt.% phosphorus addition to CoMo/γAl2O3 catalyst yield the highest HDS performance, especially for 4,6-DMDBT 75. Generally, the presence of quinoline in fuel inhibits the HDS performance of the hydrotreating catalysts because of the competition of the HYD active sites by both compounds. Interestingly, the competitive HDS and HDN of 4,6-DMDBT and quinoline respectively showed that with a 1 wt.% loading of 17 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 100

phosphorus, there was an increased HDS activity for a quinoline concentration below 90 ppmw N (Fig. 10). This increased activity is due to the increased dispersion of NiMoS active sites and BrØnsted acidity. However, at higher phosphorus loading, the NiMoS active sites dispersion decreased while the BrØnsted acidity increased significantly, which leads to decreased HDS activity and increased HDN activity, respectively.

Fig. 10. Relationship between NiMoS actives sites and products distribution on the competitive HDS and HDN reactions at different quinoline concentrations: (a) HYD/DDS ratio and (b) HDN (%) (275 °C, 51 bar, 4 h–1). Reprinted with permission from 83. 2.2. Trimetallic and multi-metallic catalysts The potential application of trimetallic and multi-metallic catalysts used as HDS catalysts has also been recently explored. These special types of catalysts have the advantage of having mixed phases, and their catalytic properties can be better tailored than in bimetallic or monometallic catalysts 84,85. Typically, the trimetallic system comprises of Ni or Co promoter combined with the two prominent active metals, Mo and W, and the synergetic behavior among these metals are 18 ACS Paragon Plus Environment

Page 19 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

continuously being studied 86–90. Van Haandel et al. studied the synergetic effect of Mo and W in MoxW(1-x)/γ-Al2O3 catalysts’ sulfidation and activity, and they also observed that although there was no significant improvement in the catalysts’ degree of sulfidation, the NiMo0.75W0.25/γ-Al2O3 performed more efficiently than the corresponding bimetallic catalysts in the HDS of gas oil 91. This is in line with previous studies using DFT calculations by Thomazeau et al. which reported nearly 30% HDS activity enhancement in the trimetallic NiMoW/γ-Al2O3 in the HDS of gas oil feed (Fig. 11) 92. However, the observed result is not generally conclusive since the HDS activity of NiMo/γ-Al2O3 bimetallic catalysts using thiophene and DBT model fuels were observed to be way better than the NiMoW/γ-Al2O3 trimetallic catalysts. The observed behavior can be explained by EXAFS and was related to the available metal at the edge sites of the catalysts (Fig. 12), in which the Ni-Mo-S edge sites are more active in thiophene and DBT HDS than the Ni-W-S edge sites. Conversely, the DFT calculations and experimental results of the work of Cervantes-Gaxiola et al. on the comparative study of HDS of DBT on Al-Ti-Mg mixed oxide-supported NiMoW showed that the NiMoW catalyst performed best in comparison to NiMo and NiW. This result was correlated with the high metal dispersion observed in the catalyst on Al-Ti-Mg mixed oxide support 93. The conflicting behavior of the trimetallic catalysts explained above further reiterated that there are indeed many factors that influence the activity of catalysts in addition to the active metals. Among these factors is the catalysts support.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 100

Fig. 11. Diagram showing the relative positions of the Co(Ni)MoWS systems on the volcano curve and explanation of the new synergy effects for NiMoWS systems. Reprinted with permission from 92.

Fig. 12. Possible structures of the active phase in Ni-promoted MoxW(1–x) catalysts (x ≤ 1): (left) separate MS2 particles (M = Mo, W); (middle) randomly mixed MS2 particles; and (right) mixed MS2 particles with a two-dimensional core–shell structure. S atoms are represented by yellow balls, Mo atoms are blue, and W atoms are pink. For the sake of clarity, Ni has been omitted from the drawings. Reprinted with permission from 91. The use of noble metal combined with Ni(Co) and Mo(W) metals to form trimetallic catalysts systems have also been explored recently 94–96. This is one of the adopted strategies of minimizing 20 ACS Paragon Plus Environment

Page 21 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

the usage of large amount of highly expensive noble metals for the construction of HDS catalysts while still retaining their catalytic properties. These properties consist of high activity and directing the reaction towards the HYD pathway which is required in the HDS of sterically hindered sulfur compounds. Aguirre-Gutiérrez et al. reported a 30% increase in reaction rate for the HDS of 4,6-DMDBT when Pd was incorporated to the alumina-titania supported NiMo catalyst 94.

This promoter effect of Pd was correlated to the synergetic effect of Pd and Ni on the Mo, which

enhanced both the HYD and DDS reaction rate. A similar promotion effect was observed when Ru and Pd were added to commercial Ni(Co)Mo/γ–Al2O3 catalysts 95. Niobium promotion effects on the HDS of 4,6-DMDBT activity of NiMo/Al2O3 catalysts was studied both theoretically and experimentally. The Nb promotion effects was investigated using the DFT calculation by substituting some Ni and Mo atoms on the edge of the Ni-Mo-S (Fig. 13) nanocluster by Nb atoms 96.

The substitution was performed in pairs (two Nb atoms replaced a Mo and a Ni atom or two Ni

atoms) since Nb has an odd atomic number whereas both Ni and Mo have even atomic number. The DFT results presented both S-edge and Mo-edge stabilization due to Nb substitution and enhanced the C-S bond cleavage at partial Nb substitution. Strong Nb and C atoms interaction was reported at full Nb substitution, and this hinders the C-S bond cleavage. Interestingly, these theoretical findings were further confirmed by the experimental results. An extensive review on the synthesis approaches and different applications of trimetallic nanocomposites was recently reported 97.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 100

Fig. 13: Configuration of the model Ni-Mo-S nanocluster (a) schematic of the nanocluster (b) side view of the Ni-Mo-edge and (c) side view of Ni-S-edge. Reprinted with permission from 96.

Another emerging catalyst system based on four of above metals combined (multi-metallic) is being explored as a possible strategy for enhancing the HDS catalytic activity. Motivated by the combined effect of trimetallic catalysts in HDS activity, Wang et al. synthesized a multi-metallic NiAlMoW catalyst with layered structure (Fig. 14) using NiAl-LDH as structure-directing template and studied their efficiency in HDS of 4,6-DMDBT 98. The multi-metallic catalyst with even lower active metal loading than the corresponding trimetallic NiMoW catalyst performed twice as effective as the commercial catalyst in the HDS of 4,6-DMDBT. Similar studies were carried out by the same research group using Zn in place of Al to form the NiZnMoW catalyst 99.


Page 23 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 14. Diagram showing the formation of sulfide NiAlMoW catalyst with LDH structure. Reprinted with permission from 98. Again, intrigued by the success of the two four-metal catalyst systems, the same group advanced their research by studying the effect of combining all the five metals in a one catalyst system. The NixZnyAlzMoW catalyst with different Zn/Al molar ratio were prepared using a NiZnAl-layered hydroxide precursor

100.

The use of multi-metallic catalyst system is still a new area open for

further exploration, and it is anticipated that more research outcomes will emerge from this area in the next few years. 3. Active phase support One of the bold steps taken when specializing catalysts is to minimize the cost of catalyst production and increase catalyst activity by using exceptionally cheap yet highly mesoporous active metals supports, such as alumina and silica

101–105.

The supports must have properties 23

ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 100

suitable for catalytic application, such as 1) mechanical strength to minimize catalyst attrition 106– 109,

2) a large surface area to enhance fast interaction of active phases with the organo-sulfur

reactants 110,111, 3) an availability of acidic sites to improve the dispersion of active metals 112–114, and 4) moderate metal-support interaction for easy reduction and sulfidation of the active phases 115,116.

3.1. Alumina and modified alumina supports The principal role of a catalytic support is to maximize and stabilize the concentration of active surface. However, secondary properties of support do exist depending on the catalyst desired application. Based on the required support properties of HDS catalysis, catalyst producers have since aligned their interest more on alumina support. Even though it deactivates quickly due to the strong metal-support interaction, it has not been easily replaced because of its unique mechanical strength and textural properties

117–119.

The main disadvantage of alumina support is the strong

metal-support interaction that exist between Mo oxides and alumina, which results in the formation of strong tetrahedral molybdenum oxide that coordinate tetrahedrally mainly with other Mo oxides monolayers 120. Unlike the octahedral molybdenum oxide that is easily reduced and sulfided, the strongly bounded tetrahedral molybdenum oxides tend to resist reduction and sulfidation

121.

Therefore, research findings for modifying the alumina metal-support interaction through the incorporation of heteroatoms are continuously being reported. A prominent heteroatom that has recently been used to modify the metal-support interaction of alumina is gallium 122–126. Like other trivalent heteroatoms, gallium has a strong affinity for the tetrahedral sites of alumina, and it can successfully relocate the Co(Ni) promoter from the tetrahedral sites to the octahedral sites of alumina support 126. Consequently, the MoS2 slabs decoration get enhanced and furthermore, the strong metal-support interaction between Mo and alumina became moderate, which result to 24 ACS Paragon Plus Environment

Page 25 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

increased MoS2 slabs stacking. Overall, the HDS activity of the alumina-supported catalysts gets increased upon modification with gallium. The HYD activity of the NiMo/γ-Al2O3 catalyst was also reported to be enhanced after support modification with gallium

123.

Also, the presence of

gallium on the surface of aluminum has played a significant role on the formation and dispersion of WOx species in the synthesis of the alumina-supported W catalyst for the HDS of DBT 125. The gallium-modified alumina-support was also used to support NiW catalysts, and the HDS of both DBT and 4,6-DMDBT were greatly enhanced at 2.4 wt.% loading of gallium as shown in Fig. 15 124.

Fig. 15. Catalytic activity of NiW/Ga(x)-γ-Al2O3 catalysts on the HDS of DBT. Reaction in a batch reactor at 593 K and 800 psi. Catalysts were sulfided at 673 K. Reprinted with permission from 124. In a more recent study, the role that gallium incorporation into alumina support plays on the product selectivity was exhaustively addressed 122. The γ-Al2O3–α-Ga2O3 support synthesized in a one-step precipitation method was loaded with a NiW catalyst, and higher dispersion of the catalyst was achieved, particularly at low Ga2O3 dosage. The formed catalyst showed remarkable activity


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 100

in the HDS of 3-methyl-thiophene (3MT) and DBT. It was reported that the GaAl2O4 spinels and α-Ga2O3 observed in the catalyst greatly influenced the HYD capacity of the catalyst and therefore directs the reaction towards the HYD pathway as shown in the HDS of 3MT in Fig. 16. Interestingly, the DBT of HDS was still maintained via the DDS pathway even after the support was modified with α-Ga2O3.

Fig. 16. Diagram showing the catalytic systems and main yield. The atoms are not to scale, and the sizes only are illustrative. Reprinted with permission from 122. The isomerization and cracking capacity of CoMo and NiMo/γ-Al2O3 catalysts were also enhanced when the alumina support acidity was modified with boron

127.

A boria over-layer, stabilized

through the Al-O-B bridges in a B2O5-Al2O3 support system was used as a support for CoMo catalyst in the HDS of DBT and 4,6-DMDBT

128.

This support system inhibits the formation of

undesirable bulk α-CoMoO4 due to the strong interaction between Co and B of the Al-O-B bridge layer. 26 ACS Paragon Plus Environment

Page 27 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Higher mechanical strength, enhanced degree of metal sulfidation, increased catalytic activity and selectivity, and resistance to coke formation were achieved when γ-Al2O3 was modified with CaO to form Ni and NiMo/γ-Al2O3-CaO catalysts carbon to enhance its HDS performance

129.

Alumina support has also been modified with

130–132.

Typically, the deposition of carbon on the

hydrotreater catalysts has been identified as a good method for suppressing sediment formation on the catalyst and its subsequent deactivation

133.

Additionally, pore size and pore volume of the

alumina support was successfully tailored by mixing the alumina paste with carbon mesh, and the dried extrudate was then calcined under different conditions 130. This is particularly important for the HDS of sterically hindered sulfur compounds that are likely to have diffusion limitation which results in an inaccessibility of active sites and poor HDS activity. By tailoring the pore size and pore volume, larger pore diameters (macropores) can be formed, and this creates a bimodal catalyst structure that is likely to have both mesopore and macropore. Alumina modification with carbon has also resulted in moderate metal support interaction, thus enhancing metal dispersion and sulfidation 131. The slab length and stacking number of the MoS2 slab in a carbon modified γ-Al2O3 supported CoMo catalyst that has been prepared by using different monocarboxylic acids as carbon sources were reported as being relatively low compared to the unmodified alumina. This property of the catalyst directs the adsorption of 4,6-DMDBT on the edges sites of the MoS2 stack, which favors the DDS mechanism 132,134. Alumina modification with P has also been shown to have many advantages. For example, it has enhanced the support textural properties and metal dispersion (due to decreased metal-support interaction); inhibited the formation of inactive species, such as NiAl2O4 and MoO4; increased the strength and distribution of acid sites; and improved the support thermal stability 135–137. The slab length and stacking degree of NiWS2 slabs have been successfully modulated by exploring the supports’ intrinsic effects of Al2O3, TiO2, ZrO2, and Al2O3- TiO2 and ZrO2-TiO2 mixed oxides 138. Each


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 100

support affects the electronic and structural arrangements of the WS2 active phase in a different way, which creates unique WS2 phase characteristics as shown in Fig. 17. The WS2 unique phases were determined from the average slab length (obtained from HRTEM) and the W-W bond distance that was obtained from the EXAFS 139 using the Kastelan geometric model 140. The Wt and We in the Fig. 17 represent the total number of W forming at each slab and the amount of W at the edge of slab, respectively. The We is presumably the catalytically active phase, and as depicted in the Fig. 17, the We/Wt of Al2O3-TiO2 and ZrO2-TiO2 mixed oxides supported NiWS2 are higher, which results in their better HDS activity than the catalysts. DFT calculations was further used to deduce that each of the supports confers entirely different activity, dispersion, promotion, total acidity, and specific surface bonding to the NiWS2 catalyst 141. In the study, an optimized model of the supports and well-defined cluster W12S24 (C1) or Ni3W12S24 (C2) (Fig. 18) were prepared, and the interaction between the supports and clusters presented in Fig. 19 were discussed. It was reported that the C1-ZrO2-TiO2 interaction is strongest among all the studied interactions. In fact, the Me-S (Me = Al, Ti, Zr) in the C1ZrO2-TiO2 interaction had reached a peak of 18 bonds which then lead to the cluster deformation so that some of the sulfur in C1 cluster were already being pulled towards the support

141.

The cluster is

therefore forced to bend due to charge redistribution, which leads to the reconfiguration of the cluster and loss of some crystallinity. Mixed oxides of alumina, for example, Al2O3-TiO2 and Al2O3-TiO2-SiO2 have also been used to support noble metal catalysts 142. In the work of Wan et al., the sulfur tolerant and highly stable Al2O3-TiO2SiO2 supported Pt-Pd bimetallic catalyst performed better in hydrodearomatization and HDS of diesel fuel than the Al2O3-TiO2 supported Pt-Pd counterpart 143.


Page 29 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 17. Schematic representation of the average slab length and morphology data for the WS2 sulfide phase over the different supports. Blue: tungsten, Yellow: sulfur. Reprinted with permission from 138.

Fig. 18. Two different orientations for a) C1=W12S24 (WS) and b) C2=Ni3W12S24 (NiWS) cluster with optimized configurations. Reprinted with permission from 141.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 100

Fig. 19. Optimized configurations for the W12S24 cluster deposited on a) A, b) T, c) ATII and d) ZTIII. Reprinted with permission from 141. Oxides of magnesium, titanium, iron, zinc and niobium have also been used as support for metal catalysts in the HDS reaction 144–147. Nickel is a metal catalyst that has an interesting catalyzing ability for the cleavage of cyclic sulfur compounds. However, the Ni activity is typically in the initial HDS reaction, and after few hours, quick deactivation occurs due to sulfidation of the Ni active sites to NiS, which renders the catalyst inactive. One of the adopted strategies used to extend the lifetime of Ni catalyst is to support it on ZnO 144. The ZnO support prevents complete deactivation of Ni sites through an activation reaction of NiS to regenerate Ni metal as depicted in equation 1 and Fig. 20. This approach extends the lifetime of Ni active sites until nearly all the ZnO support have been converted to ZnS. NiS + ZnO +H2 → Ni + ZnS + H2O --- (1)


Page 31 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 20. A schematic illustration of reactive adsorption of thiophenic compounds on Ni decorated ZnO NW. ZnO NW support keeps Ni sites free of sulfur and thereby active for hydrogenolysis. Reprinted with permission from 144. It is also considered that the tungsten oxysulfide interaction with Ni sulfide particles in NiW/TiO2 nanotubes catalyst was enhanced due to the TiO2 nanotubes support properties 146. Studies of the combined effect of MgO and TiO2 as support for NiW active metals determined that undesirable NiO and NiWO4 phases were not formed in any of the NiW/MgO-TiO2 catalysts formed when varying the ratio of MgO to TiO2 147. 3.2. Mesoporous silica and other molecular sieve supports In general, silica and silica-based materials have drawn attention as catalysts support for heterogeneous catalysis 148–150 but also for HDS in particular 151–153. These silica-based materials are desirable because of their highly ordered pore size and volume and their large surface area, but it is important to note that these materials have also demonstrated a weak metal-support interaction. Because of this low metalsupport interaction in silica, it became essential to be able to modify the support to increase the metal-support interaction. Recently, there has been a lot of effort to improve the metal-support 31 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 100

interaction and active phase dispersion of silica-based supported HDS catalysts. The use of heteroatoms such as alumina, titania and zirconia to modify the mesoporous silica properties have been extensively studied 154–158. The work of Jiang et al. studied the effect of Si/Al ratio on the NiMo/Al-SBA-15 catalytic properties 159. It was observed that the total acidity of the NiMo/Al-SBA-15 catalysts and the metalsupport interaction increase with Si/Al ratio; however, the BrØnsted acidity was highest when Si/Al ratio is 10. Furthermore, the average stacking number of NiMoS slab decreased with Si/Al ratio while the layer length was shortened at Si/Al ratio of 10. The acid-base property of ceria was also utilized to increase the SBA-15 support properties, and at 2.5 wt.% ceria, an optimum metal-support interaction, support acidity and active phase formation and dispersion was reported

160.

A curved fullerene-like

morphology due to 1) the excellent dispersion of MoS2 active phase on the Al- or Ti-modified SBA-15 support and 2) the stabilization of the Co-promoted MoS2. The latter effect is reported to impact on the HDS activity of the Al- or Ti-modified SBA-15 CoMo catalyst 161. Zirconia modification of SBA-15 was found to increase the promoter dispersion due to the Co-support interaction, and this enhanced the promotion effect of the Co on MoS2 active phase. Additionally, the inactive β-CoMoO4 phase, which is often detected in CoMo/SBA-15 catalyst, was not observed after support modification with ZrO2 162. Further studies on how to increase the dispersion of active phase through the Ti-Zr bi-heteroatom modification of SBA-15 support demonstrated that the electronegativity difference between the Ti and Zr further stabilized the inactive and undesirable MoO42- phase, which leads to low sulfidation

163.

Indeed, the poor performance of Ti-Zr bi-heteroatom modified SBA-15 supported CoMo catalyst has deterred further studies into the use of bi-heteroatom to modify the SBA-15 properties even though different heteroatom combination could likely result in different electronic and structural rearrangement. Gutiérrez et al. reported the effect of four different supports: γ-Al2O3, SBA-15, Zr-SBA15 and Ti-SBA-15 for the simultaneous HDS of DBT and hydrodenitrogenation (HDN) of o-


Page 33 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

propylaniline (OPA). The Zr and Ti modification of the SBA-15 considerably decreased the SBA-15 surface area; however, more active sites were observed (due to increased Lewis acid sites) in the Ni promoted Zr- and Ti-SBA-15-Mo catalysts than in the unmodified SBA-15-Mo catalyst 164,165. Dinh et al. optimized the loading of TiO2 on calcined SBA-15 support for CoMo catalyst 152. Within the range of 10-40 wt.% nanocrystallites TiO2 loading, an excellent dispersion of the active phase was observed at 20 wt.%. At lower TiO2 loading (below 20 wt.%), the inactive CoMoO4 phase was observed, and at higher loading, large aggregates of TiO2 were noticed. Both are detrimental to the HDS activity of the CoMo catalyst. The effect of Ti-SBA-15 and γ-Al2O3 hybrid as a support for NiMo catalysts was also compared with that of the Ti-SBA-15 and γ-Al2O3 counterparts in the HDS of DBT and 4,6-DMDBT, and it was reported that the incorporation of Ti-SBA-15 to alumina inhibits the formation of the inactive MoO4 phase 166. In addition, the hybrid supported NiMo catalysts performs 40% more than NiMo/γAl2O3 in the HDS of 4,6-DMDBT even though nearly the same conversion was recorded for the HDS of DBT.

Trimetallic catalysts have also been supported on SBA-15 to form highly active HDS

catalysts. The work of Mendoza-Nieto et al. compared the efficiency of NiMoW/SBA-15 catalysts over the bimetallic NiMo/SBA-15 and NiW/SBA-15 catalysts and discovered that the Mo(W)S2 active phases were better dispersed on the support than in the bimetallic systems

167.

More so, the highest

number of active phases are located on the edge sites of the catalyst, which afforded the catalysts highest DDS and HDS activity (Fig. 21).


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 34 of 100

Fig. 21. Comparison of the catalytic activity of NiMo, NiMoW and NiW catalysts supported on SBA-15 in HDS of DBT (◊) and 4,6-DMDBT (□). Open triangles correspond to the results obtained with trimetallic NiMo-NiW/SBA-15 catalyst prepared by mechanical mixing of corresponding bimetallic counterparts. Reprinted with permission from 167. Mechanically mixed SBA-15 and SBA-16 support for CoMoW catalyst has also proved to be better support than the individual SBA-15 or SBA-16. The mixed support contains mixed porosity, which may be the reason for the better diffusion of active phase precursor solution through the support medium (thus inhibit external mass transfer limitation) 168. KIT-6 and KIT-5 silica are another class of mesoporous molecular sieves that have shown great potential as HDS support catalyst 169–172. The three dimensional (3D) mesoporosity of KIT-6/KIT5 afford it an extra advantage of better catalyst dispersion, higher reducibility of the Mo oxides, and faster diffusion of reactants and products over other 2D molecular sieves (e.g., SBA-15) 173. Similar to SBA-15, modification of the KIT-6/KIT-5 properties by incorporating heteroatoms such 34 ACS Paragon Plus Environment

Page 35 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

as Al, the metal-support interaction and surface acidity have been enhanced, which in turn has increased the HDS performance of catalysts

174,175.

Zeolites are a class of materials with unique

pore architectures that can be made to fit almost any chemical conversion, and these materials have easily accessible active sites 176. As such, zeolites have also found application as support in HDS reaction 177,178. However, the small pore size of many zeolites hinders the diffusion of large sulfur molecules. For example, the molecular size of 4,6-DMDBT (0.78 × 1.13 nm by DFT calculations) was larger than the pores of BETA (0.65–0.68 nm) and ZSM-5 (0.55 nm) mesoporous zeolites 179. Furthermore, most zeolites are characterized with excessive acidity, which causes cracking more than the HDS activity 180. Therefore, the zeolites are mostly used as HDS support after their pores have been expanded and their acidity has been reduced. Tang et al. have developed parallel mesopore channels in the nanofiber of microporous mordenite and have efficiently dispersed the CoMo in both the micropores and mesopores of the mordenite support 181. The active phase in the micropores significantly affect the overall HDS activity of the mordenite supported CoMo catalyst by producing a large amount of spillover hydrogen that later diffuse onto a nearby CoMo active phase in the mesopores, consequently boosting the HYD pathway of the catalyst. An in-depth study into the HDS mechanism of thiophene over a zeolite L-supported CoMo catalyst using computational calculations revealed that the zeolite L acted as an electron donor and that its pore framework decreased the HYD energy barrier, which made the HYD pathway more favorable 182. The work of Quan Huo et al. demonstrated the modification of zeolite L by slowly adding the zeolite to a solution of CTAB in water and later adjusting the pH to 9.6 183. The solution was heated at 100 oC for 2 days in a Teflon-lined autoclave to yield the micro-meso molecular sieve composite with increased textural properties and moderate acidity, which resulted in better metal dispersion and HDS activity. Y-zeolite porosity and surface acidity was easily modulated by direct


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 36 of 100

incorporation of Ga in the Si-O-Al framework. Thus, some of the strong acid sites (Si–O(H)Al) in the Y-zeolite got substituted by weak acid sites (Si–O(H)Ga). Moreover, the Ga species promoted the sulfidation of both Ni and Mo species and changed the morphology of the active phases

184.

With small amounts of Ga species, more Ni atoms were easily doped into MoS2 crystals to form more NiMoS active phase. Composite materials made up of mixed supports of highly acidic microporous zeolites and weakly acidic mesoporous molecular sieves have been characterized with combined oxides properties such as presence of micro and meso porosity, moderate acidity, and hydrothermal stability. The combined effect of ZSM-5 and KIT-6 as mixed support lead to the formation of hierarchical porous structures that allows efficient diffusion of reactants and products 171.

Furthermore, the BrØnsted surface acidity of the NiMo/ZSM-5-KIT-6 catalyst was found

suitable for the efficient HDS of 4,6-DMDBT, especially via the isomerization pathway (Fig. 22). Similarly, improved textural properties, acidic strength and edge-cornered MoS2 sites were achieved when a mixed support of zeolite L and KIT-6 was used to support CoMo active metals 170.


Page 37 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 22. Comparison of GC peaks of the products in the HDS of 4,6-DMDBT over NiMo/Al2O3, NiMo/ZK-W, and NiMo/ZSM-5 at LHSV = 120 h−1. Reprinted with permission from 171. Series of composite supports (ZS) consisting of ZSM-15 and SBA-16 in specific ratios have been adopted as support for NiMo metals, and the support’s morphological properties as depicted in Fig. 23 were considered as a major determinant of the catalysts HDS activity

185.

The uniform

spherical aggregates morphology of ZS-3 consisted of uniform hexagonal-prismatic ZSM-5 monocrystals enabled the transfer of spillover hydrogen that had formed in the micropores of ZSM-5 onto nearby MoS2 active phases in the mesopores of SBA-16. Moreover, the enhanced reactants and products diffusion and active phase accessibility by reactants have been attributed to the ZS-3 uniform morphology. Further incorporation of cation additives (K+, Mg2+, Mn2+, Zn2+, and Cu2+) to the ZS series using inorganic salts of the cations changed the textural properties, acidity, metal-support interaction, and morphology of the supports 186. The NiMo/ZS-Mg catalyst presents exceptionally higher HDS activity than the other series of cation-modified ZS supported NiMo catalysts due to its desired catalytic properties, which include the distribution of pores, 37 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 38 of 100

acidity, and metal-support interaction. Similarly, a ZSM-5/KIT-6 composite mesoporous sieve had been developed with interesting support properties and more interestingly, the pore structure was successfully tuned by varying the mole ratio of support precursors 187.

Fig. 23. SEM images of the series ZS and pure SBA-16 supports: (a) ZSM-5; (b) SBA-16; (c) ZS-1; (d) ZS-2; (e) ZS-3; (f) ZS-4; (g) ZS-5; (h) ZS-Mechanical. Reprinted with permission from 185.

3.3. Carbon and carbon-based support 38 ACS Paragon Plus Environment

Page 39 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

The use of carbon supports in the preparation of hydrotreating catalysts for the upgrading of heavy oils has shown some fascinating results in recent years

188–195.

The advantages of using carbon

supports include its low cost, easy recovery of deposited metals from the catalyst, very high thermal and acid stability, and reasonably easily controlled pore structure

196,197.

However, with

the large amount of coke generated in the refineries, the use of carbon or carbon-based support may not be of special interest for practical industrial applications. Single-walled carbon nanotubes (SWCNTs) has recently been used as support for Ni and Yttrium metals, which were deposited via arc discharge method. Higher HDS activity was specifically observed when the Ni-Y/SWCNTs are oxidized by heat treatment at 200 oC 198. Single-layered nanocatalysts of CoMo supported on carbon nanotubes were also reported to have high HDS activity with the support properties inhibiting the formation of undesirable CoS2 phases

190.

Similarly, Ning et al. reported the

incorporation of MoS2 on graphene sheets (GS) (obtained after annealing of graphene oxide) via the microwave irradiation of functionalized GS (FGS) and ammonium tetrathiomolybdate (Fig. 24) for efficient HDS application 195.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 40 of 100

Fig. 24. Schematic representation of the preparation of M-MoS2/GS catalyst. Reprinted with permission from 195. The effect of nitrogen on mesoporous carbon support for HDS application was further studied by Hu et al. 193. The N-doped mesoporous carbon (NMC), prepared using urea and glucose as nitrogen and carbon precursors respectively, was used as MoS2 support with tunable pore structure (adjusted using various silica template) and nitrogen content (Fig. 25). The work of Nath and Verma discovered the use of activated carbon fiber as NiMo catalyst support for a tubular flow reactor 191. The small pore diffusion resistance and low pressure drop properties of the carbon fiber in addition to the general properties of carbon support was instrumental in the high HDS performance.

Fig. 25. Description of the synthesis process of MoS2/NMC catalyst. Reprinted with permission from 193.


Page 41 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

A nanohybrid of 3D graphene supported NiS-MoS2 catalyst was synthesized for HDS application. The 3D graphene layers inhibit the aggregation of NiS nanoparticles and MoS2 layers. Consequently, uniform distribution of NiS on the few layers of 3D MoS2/graphene hybrid was achieved as reported by Lonkar et al. 199. The promoter role of NiS served the MoS2 active sites with hydrogen via the hydrogen spillover mechanism presented in Fig. 26.

Fig. 26. Proposed hydrogen spillover mechanism during the HDS of DBT using 3D NiSMoS2/graphene nanohybrid catalysts. Reprinted with permission from 199.

Carbon-based materials have also been used in conjunction with other supports to improve the support properties. The modification of TiO2 support with graphene to enhance the HDS activity of NiMo/TiO2 catalysts was due to the hydrophobic property of graphene

200.

Li et al. observed

that the graphene-modified TiO2 supported NiMo catalyst has high hydrophobicity, which weakens the adsorption of polar molecules (e.g., H2S) and ultimately minimizes the catalyst deactivation

201.

The H2S gas quickly desorp from the catalyst’s surface as shown in Fig. 27.

Similarly, the HDS activity of MoCo/Alumina catalyst was enhanced after support modification 41 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 42 of 100

with carbon nanofiber. It was reported that the carbon nanofiber modification improves the support’s textural properties and the metal-support interaction, which result in better catalyst dispersion and HDS activity 202.

Fig. 27. Proposed mechanism for the HDS of NiMo/TGC-0.5 and H2S desorption rate (inset) detected by rapid gas detector tube. Reprinted with permission from 201. Based on the different supports discussed, it is quite clear that the choice of support plays a significant role in both the HDS activity and selectivity of the catalysts. With this background knowledge, the question that would come to our mind is, “Could there be new supports in the nearest future?” There still exist quite interesting mesoporous supports with excellent textural properties that have not yet found use in HDS. Large pore zeolites such as ITQ-44 and ITQ-33 are potential HDS catalyst supports, especially for sterically large refractory sulfur compounds 203–205. MOFs are another class of high surface area molecular sieve material that are increasingly gaining attention in all field of practical applications. Recently, there has been a huge success in developing highly stable MOFs that can withstand high thermal, chemical, and mechanical stabilities 206,207. 42 ACS Paragon Plus Environment

Page 43 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

The use of MOFs as catalyst or catalyst support for HDS application is therefore an area worthy of in-depth study. 4. Synthesis strategy The type of synthesis used for a catalyst has a significant impact on its physico-chemical properties and HDS activity. The synthesis approach covers a wide range of the step-by-step procedures that are followed to achieve the desired catalyst material. In this section, we intend to cover the major factors that can typically be expected to impact the physico-chemical properties of the catalysts during their synthesis. 4.1. Preparation method The most common method for preparing unsupported catalysts is the hydrothermal synthesis of the precursor solutions at high temperature 208,209. However, the nature of catalyst’s precursor can warrant the decomposition approach under the flow of H2 or Ar gas 210,211. For supported catalysts, the impregnation approach is the most common, but it is still probable that support synthesis may be via hydrothermal approach

212.

In the impregnation approach, the precursor solution of the

active metals is introduced into the support and later dried and calcined. When the precursor solution volume is exactly equal to the support pore volume (incipient wetness impregnation), better dispersion of active phase occurs under optimum mass transfer conditions within the support pores. However, the incipient wetness impregnation may limit the active metal loading due to the precursor’s solubility in the solution. In that case, the wet impregnation approach (using excess precursor solution) is a viable option

213.

For bi-, tri- and multi-metallic catalysts, the metal

precursors solution can be introduced to the support in a sequential or two-step impregnation method (one metal introduced at a time, and after drying, another metal is introduced)175 or in a


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 44 of 100

co-impregnation approach (all the metals precursor solutions added at once) 82. Recently, a singlepot approach, that involves hydrothermal synthesis of combined support and active metal precursors have been developed

157,214,

and effects of hydrothermal synthesis conditions and

molybdenum metal loadings have been studied extensively 158. Fig. 28 below shows the summary of procedure for (a) Co-impregnation approach and (b) single-pot hydrothermal synthesis approach.


Page 45 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(a)

(b)

Fig. 28. (a) Co-impregnation loading of active metals on Al2O3–SiO2 support

82.(b)

Single-Pot

(SP) synthesis of NiMo Supported on Metal-Modified SBA-15 Catalysts. Reprinted with permission from 157.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 46 of 100

In the sequential impregnation approach, it is worth mentioning that the sequence in which metal species are deposited on the catalyst support has a significant impact on both the catalyst activity and selectivity. In a typical example, addition of Ir to Pd/Al2O3 catalyst increases both HDS activity and C-S hydrogenolysis selectivity, but the addition of Pd to Ir/Al2O3 leads to a decrease in activity 38. A similar scenario was observed when Yttrium was used to enhance the HDS activity of palladium supported on alumina 39 and when P2O5 was used to modify the catalytic properties of NiMo/Al2O3 137. A colloidal chemistry approach has also been employed in the synthesis of HDS catalysts. Recently, nanosized islands of Pd were deposited on 12 nm colloidal iron oxide nanoparticles supported on alumina via the galvanic exchange reaction of Pd2+ to Pd0 by Fe0 and/or Fe2+ on preformed iron oxide seed 20. This approach greatly improved the dispersion of palladium islands on the support and ultimately resulted in a better (4-fold) activity than Pd/Al2O3 and Pd/Fe2O3 (commercial) catalysts. An ultrasound irradiation followed by non-thermal (glow discharge) plasma treatments of functionalized multiwalled carbon nanotubes supported NiMoW catalyst via coimpregnation were reported to enhance the phase structure, textural properties, and especially the dispersion of the active phases on the support 215. An anion-assisted approach, using CTAB has also been used to synthesize a dendritic mesoporous silica nanospheres (DMSNs) support with a large average pore diameter (26.4 nm) 216. The center-radial pore channels in the dendrimer-like silica support causes the large pore diameter, which is exceptionally good for sterically large sulfur compounds since they will have easy diffusion and access to and from the active sites. After Al modification of the DMSNs and further impregnation of Ni and Mo active phase, the average pore diameter is still more than 20 nm (Fig. 29). The interesting textural properties of the support result in high dispersion of NiO and MoO3 phases and together with Al modification lead to very high


Page 47 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

HDS activity. The type of metal and support precursor used in the catalyst preparation will also impact the catalytic properties of the developed catalyst as we shall see in the next sub-section.

Fig. 29. An illustration of NiMo/DMSNs and NiMo/Al-DMSNs catalysts’ synthesis. Reprinted with permission from 216. 4.2. Precursors The type of active metals and support precursors used to prepare catalysts can significantly impact the dispersion of the active phases, catalyst textural properties, reducibility of the oxides metals, and the HDS performance of the catalyst 217–219. Basically, the active metal precursors are sourced either from different salts each having a single representative active metal such as ammonium molybdate and copper nitrate polyoxometalate

220.

218

or from a single salt of all the active metals such as Keggin

In the former case, inconsequential counter ions are generated after

dissolution of the precursor salt, which might affect the catalyst properties, and it requires multipreparation of the precursor solutions for each active phase. However, it is best used for sequential 47 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 48 of 100

impregnation of active metals on support. The latter case has the advantage of only having single preparation of the active metal solution since all the active phase are in one compound (heteropoly compound or polyoxometalates). Moreover, better dispersion of the active phase due to intimate interaction from the all-metals-precursor solution is usually observed. Some precursors such as alkyltrimethylammonium-thiomolybdate-thiotungstate-cobaltate (II) comprised of trimetallic system plus the sulfur component required for metal sulfidation 221. It is important to consider the recent progress in the use of precursors for HDS reaction. The combined effect of pH and precursor on the morphology of (Co)MoS2 catalysts has been studied recently by Zhang et al.

222.

The pH

modulates the MoS2 nucleation rate, and precursors influence the slab length of the MoS2 catalyst (thus affect HDS of thiophene selectivity). At lower pH, fast nucleation was reported, which leads to the formation of large specific area small MoS2 crystallites with more active sites (Fig. 30). When the MoO3 and Na2S·9H2O precursor combination was used, shorter slab length occurred than in the case of (NH4)6Mo7O24·4H2O and CS(NH2)2 combination.


Page 49 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 30. An illustration of the synthesis procedure of MoS2 catalysts with different crystallite size and MoS2 catalysts with similar stacking number but different slab length. Reprinted with permission from 222. The work of Liang et al. reported the application of well-defined Strandberg polyoxometalates (Ni(NH4)2[(HPO3)2Mo5O15] and Ni[(HPO3)2Mo5O15]) as active phase precursors, which were supported on γ-Al2O3 via incipient wetness impregnation. The use of these well-defined crystal and molecular structured precursors significantly affect the nature of active phase dispersion, number of accessible sites, and ultimately HDS activity for the NiMoS- γ-Al2O3 catalyst

223.

Afterward, the same group adopted a ligand-induced self-assembly synthesis strategy using 4,4’bipyridine (4,4’-bipy) as the organic ligand (due to its coordinate and H-bonding properties) to 49 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 50 of 100

synthesize a new set of single crystals of Ni2(4,4’-bipy)Mo4(4,4’-bipy)2 and Ni(4,4’bipy)(H2O)3].2(4,4’-Hbipy).3H2O polyoxometalates and subsequently impregnated them on the γAl2O3 support (Fig. 31) 224. The framework, promotion, and ligand effect significantly impacted on the HDS performance of the catalysts.


Page 51 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 31. From small Ni–Mo–O clusters in solution to solid-state coordination frameworks of Mo2Ni and PMo11Ni via a ligand-induced self-assembly strategy. Reprinted with permission from 224. Nickel metal organic framework, [Ni2(dhtp)] (H4dhtp = 2,5-dihydroxyterephthalic acid), with well-defined crystallinity and molecular structure has also been used as a Ni precursor in the preparation of bulk NiMoS catalyst, while Mo was introduced into the pore structure of the [Ni2(dhtp)] via sublimation of Mo(CO)6 to form the [Ni2(dhtp)Mo(CO)3] MOF complex as shown in Fig. 32. The MOF complex was later decomposed under the flow of H2/H2S at 350 oC to form highly active HDS catalyst 225.

Fig. 32. Staggered (Left) and Eclipsed (Right) Conformers of [Ni2(dhtp)Mo(CO)3]. Reprinted with permission from 225. 51 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 52 of 100

4.3. Chelating agent Chelating agents are usually some organic ligands that can easily bind with the active metals (mostly the promoter) to form a stable complex. The formation of the stable co-promoter complex is particularly important in the gas-solid activation approach of the metal oxide catalysts. The sulfidation of Mo or W begin at a temperature around 150 oC while the sulfidation temperature for Ni or Co promoter is mostly within 50 oC. Obviously, it means the promoter gets sulfided prior to the formation of MoS2 active phase. Consequently, the amount of promoter on the MoS2 slabs will be significantly less, which leads to less active sites on the catalyst. However, by capping the promoter with a complexing agent, its sulfidation is typically delayed. This enables the formation of MoS2 slabs prior to the decomposition of the promoter complex, which later decomposes to release the promoter ion at the edges of the MoS2 slabs. Hence, there are increased active phases and HDS performance of catalyst

121.

Furthermore, the chelating agents have been identified as

facilitators of formation of octahedral polymolybdates, which are generally easier to sulfide

226.

The report of Santolalla-Vargas et al. presented that chelating agents also prevent strong metalsupport interaction between active metals and support 227. The method of introducing the chelating agent during catalyst preparation arguably impacts the catalyst performance. While Chen et al. considered co-impregnation of chelating agent as being the best performing method 228, the work of Li et al. considered the sequential impregnation of the chelating agent followed by active metal impregnation to be the most appropriate

229.

Several chelating ligands such as ethylene diamine

tetraacetic acid, citric acid, glycol, nitriloacetic acid, 1,2-cyclohexanediamine-tetraaceticacid, citric acid, and ethylenediamine have been tested

121.

More recently, trimesic acid

230

and

thioglycolic acid 231 have also been used as chelating agents in the preparation of HDS catalysts. 4.4. Surfactants and swelling agents 52 ACS Paragon Plus Environment

Page 53 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Advances in the synthesis of highly ordered, large porous material are typically based on the use of large molecular structure directing agent known as surfactant and/or utilization of suitable swelling agent

232.

While the surfactants primarily direct the material structure through its

templating property, the swelling agents typically tailor the pore diameter over a wide range by swelling the surfactants 233. Some of the prominent surfactants that are widely used in the synthesis of highly ordered support or catalyst materials for HDS applications include CTAB 183, P123 233 and P127 234. The role of surfactant has also been extended to acting as an active metal linker and disperser. In the work of Xu et al., polymolybdate anion from ammonium heptamolybdate tetrahydrate was stabilized using a gemini surfactant ((C16H33-N(CH3)2-C6H12-N(CH3)2C16H33)Br2)

235.

The gemini surfactant-linked polymolybdate was used as a precursor in the

preparation of the NiMo/SiO2-Al2O3 catalyst. The gemini surfactant modification of Mo species resulted in highly dispersed MoS2 phases with improved stacking. There are also large numbers of swelling agents that have been used in the literature to modulate the pore size of catalytic materials which include classes of both aliphatic 236,237, alicyclic233,238, and aromatics compounds 233,239. The use of 1,3,5-trimethylbenzene as a swelling agent for CTAB surfactant has been recently reported in the pore size controlled synthesis of meso-microporous zeolite Y, which was used to support NiMo active species for HDS of sterically hindered 4,6-DMDBT 240. In addition to enabling the diffusion of 4,6-DMDBT, it was further discovered that the larger pore size observed due to the swelling agent inhibited the polarization effect of Al3+ and decreases metal-support interaction, which enhances the degree of sulfidation of Ni and Mo species, increases stacking level, and decreases MoS2 slab length. 4.5. Catalyst activation methods


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 54 of 100

The active sites in HDS catalyst is mainly due to the MoS2 slabs, which may be surrounded by copromoter (such as Ni or Co) at the edges/corners or rims of the slabs. Generally, the prepared catalysts contain the metals in their oxide forms and will consequently require an activation step (sulfidation) to form the MoS2 prior to HDS application. The commonly adopted strategy for the oxide sulfidation of catalysts is the gas-solid phase approach that involves using H2 gas to reduce the metal oxides and then subsequent flowing H2S gas to do the sulfidation. This approach is performed at high temperature (usually above 350 oC) for over 5 h and can therefore be considered as harsh treatment of the catalysts oxides to form the sulfide form. It may also be connected with some health issues due to the risk of working in an environment with H2S. However, at the industrial scale, this approach has remained the best viable option due to the availability of excess H2S and the design of the hydrotreater plants. Interestingly, new approaches have been adopted to sulfide the catalysts without necessarily using direct H2S gas such as: 4.5.1. Decomposition of thiosalts Though slight modification of the direct flow of H2S, this particular approach involves thermal decomposition of the thiosalt to give a desired active catalysts ammonium

tetrathiotungstates,

thiomolybdate

242

tetraalkylammonium

211,241.

thiotunstate

Series of thiosalts such as 210,

alkyldiammonium

and alkyltrimethylammonium-thiomolybdate-thiotungstate-cobaltate (II)

221

have been synthesized and decomposed to form the active MoS2 catalysts. 4.5.2. In situ generation of MoS2 The synthesis of MoS2 active phase have also been performed via traditional wet chemistry approaches. For example, new synthesis strategy (Fig. 33) was developed recently based on the use of oleylamine as solvent, reducing agent, and surfactant in a one-pot containing Ni(acac)2/Co(acac)3 and Mo(CO)6 as


Page 55 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Ni/Co and Mo precursors respectively, and sulfur at 300 oC. This approach yielded a highly disordered monolayer of MoS2 with ultra-small lateral size (4.2 - 4.6 nm) and high density of active sites 243.

Fig. 33. An illustration of the one-step synthesis procedure to prepare MoS2, MoNiS and MoCoS catalysts. Reprinted with permission from 243. Another simple HDS catalyst synthesis strategy involves in situ generation of the NiS nanoparticles and MoS2 layers supported on graphene aerogel, and this approach is based on the hydrothermal synthesis of the metal thiosalts solutions and graphene support (Fig. 34) 199. The 3D NiS-MoS2/graphene assembly shows a promising interfacial interaction between the 3D highly porous graphene and the NiS and MoS2, which result in high dispersion of the actives phases.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 56 of 100

Fig. 34. Schematic representation for preparation of 3D NiS-MoS2/Graphene. Reprinted with permission from 199. Unsupported hierarchical porous NiMoS nanoflowers have also been synthesized via a simple hydrothermal approach that involves direct mixing of the elemental sulfur with as-prepared dried powder of Ni, Mo and Si mixture in various silica ratio 244. Silica that had been used to tune the NiMoS porosity was then removed by dissolving the formed silica supported NiMoS in HF. Typical ligand-directed colloidal synthesis strategy has recently been adopted to selectively grow dimensionally and shape-controlled NbS2 nanostructures

245.

In section 2.1, we highlighted the

challenge of niobium sulfidation using H2S. Interestingly, this reported approach has provided yet another viable option to not just sulfide Nb but also to modulate the shape and dimension of NbS2 by changing the reaction conditions such as molar ratio of reactants, capping ligand, and oleylamine solvent as depicted in Fig. 35 below.


Page 57 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 35. Schematic illustration of the colloidal synthesis protocol of NbS2 nanostructures. Reprinted with permission from 245. 4.6. Non MoS2 active phase HDS catalysts There is good amount of highly active and relatively stable non-MoS2 catalysts for HDS application that are more-or-less safe to deal with than the sulfides. The metal phosphides and silicides have shown some promising results 246,247. However, metal borides, carbides, and nitrides were found to first decompose and then form the respective metal sulfides under the harsh HDS reaction conditions

248.

The synthesis and HDS application of metal phosphides especially the

nickel phosphide (both bulk249,250 and supported251–254) have been extensively studied and recently reviewed 246,255. 4.6.1. Metal silicides


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 58 of 100

The metallic silicides have a long history of being widely used as catalyst256–260 and have recently gained relevance in the field of HDS due to their great resistance to sulfur poisoning and easy regeneration procedure 261–264. The resilience to sulfur poisoning by the Ni silicide was first investigated using the first-principle theoretical calculations where the nature of the ordered phases in the silicide was studied

265.

DFT computational calculations revealed an overlap in the density of states of Si-sp

states and Ni states which leads to downshift of the d-band center in the Ni states. The resultant effect is difference in behavior between the Ni and the NiSi2, as explained in the d band theory of Norskov (Fig. 36a).

Fig. 36. (a) DOS of surface atoms of Ni (111) and NiSi2 (111); b) energy diagram for the H2S adsorption and dissociation on Ni (111) and NiSi2 (111) surfaces. Reprinted with permission from 266. Chen et al. reported that the adsorption energies of H2S, HS, and H on the NiSi2 phase was much lower than that of the Ni phase as presented in Fig. 36b and further reiterated that by using the Evans-Polanyi relationship, the decreased H2S adsorption can be explained by a higher energy barrier 266. This was further supported by experimental findings that showed an exceedingly higher turnover frequency for HDS of DBT by using NiSi2 as depicted in Fig. 37. The HDS activity of NiSi2 was further improved by the incorporation of additional metal to the NiSi2 structure.


Page 59 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 37. a) TOFs of DBT during HDS over the Ni–Si IMCs in comparison with metallic Ni catalysts at different reaction temperature. b) HDS TOFs of DBT as a function of time on the Ni–Si IMCs in comparison with Ni. Reprinted with permission from 266. The direct silicification of nickel cobalt oxide with SiH4 was created in order to synthesize Ni-Co silicide (Ni1-xCoxSi2). By optimization of Ni to Co molar ratio, the fluorite structured ferromagnetic Ni0.75Co0.25Si2 catalyst was formed, which also demonstrated higher HDS activity than the NiSi2 or CoSi2 catalysts. This approach also directed the reaction to the hydrogenation pathway by almost 32% 267.

Another modification of the NiSi2 catalyst with Fe to form Ni1-xFexSi2 catalysts was also reported

247.

The favorable binding of Fe with Ni to form Ni-Fe alloy and its further silicification to give Ni1-

xFexSi2

catalyst with high electron density at the metal sites was achieved at Ni:Fe molar ratio of

0.75:0.25 (Ni0.75Fe0.25Si2). These results are shown from the 57Fe Mossbauer spectroscopy and XPS analysis results. Because of the geometrical and electronic structure modification of the NiSi2 catalyst due to Fe substitution, the HDS activity was enhanced significantly (Fig. 38).


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 60 of 100

Fig. 38. Fe-substituted Ni-Si intermetallic catalysts (Ni1-xFeSi2). Reprinted with permission from 247.

Pd supported on carbon nanotubes (Pd/CNT) was also silicidized by addition of dichlorodimethylsilane solution to the Pd/CNT catalyst in a furnace at 500 oC via the chemical vapor deposition approach. The formed Pd2Si/CNT demonstrated strong resistance to sulfur poisoning, and the Pd modification with Si redirected the reaction pathway to DDS 268. The high sulfur tolerance is likely attributed to the formation of electron deficient Pd, due to the donation of electron to silicon (Pd-Si interaction) as depicted in Fig. 39 268.


Page 61 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Fig. 39. XPS of (a) the Pd3d region of the 3 wt% Pd/CNTs and the 3 wt% Pd2Si/CNTs. (b) XPS of the Si2p region, (c) the calculated electron localization function map, and (d) the calculated total electronic DOS of Pd2Si. Reprinted with permission from 268. 61 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 62 of 100

5. Conclusion The advancement of catalyst design and synthesis for HDS application is largely driven by its increasing demand for use as well as the quest for improved efficiency of catalysts. Over the last decade, there has been great advances in the design and synthesis of catalysts including (but not limited to) the choice of active metal, the support, and the preparation methods. Computational calculations have been a key player in the recent successes of improved catalysts. In this review, the discovery of new, cheaper base metals such as Zn, Fe and Cu as HDS catalysts has been discussed alongside the traditional Co(Ni) and Mo(W) species. Indeed, the ZnFe binary catalyst has shown high potential for HDS of DBT. Advancement in the use of expensive noble metals including the support effect studies, nanoparticles size modulation, co-promoter effect and so on, and how these impacted on the activity of the HDS per weight of catalyst have been elaborated. Non-metal (such as phosphorus, fluorine and boron) promoting effect and the use of multi-metallic catalysts have been explored. Advancement in the use of catalyst supports and the use of new supports, mixed supports, and support modifications have also been well-discussed. Indeed, catalyst support properties have a direct impact on the acidity, active phase dispersion, and HDS activity of the catalyst. The preparation approaches including the traditional co-impregnation and sequential impregnation and the single-pot approach for catalyst preparation have been carefully analyzed. The roles of other preparation parameters such as precursors, chelating agent, surfactants, and swelling agents on the textural properties, ease of reduction and sulfidation of metal oxides, and dispersion of active phases have been highlighted. The various catalyst activation approaches which typically involves the formation of active MoS2 phases have been discussed and the review was concluded with non-MoS2 active phase that have shown good potential as HDS catalysts such as the phosphides and silicides. 62 ACS Paragon Plus Environment

Page 63 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Acknowledgement Financial support from KFUPM through a project No. DSRNUS15105 is gratefully acknowledged. References (1)

Omer, A. M. Energy, Environment and Sustainable Development. Renew. Sustain. Energy Rev. 2008, 12 (9), 2265–2300.

(2)

Asif, M.; Muneer, T. Energy Supply, Its Demand and Security Issues for Developed and Emerging Economies. Renew. Sustain. Energy Rev. 2007, 11 (7), 1388–1413.

(3)

Arora, N. K. Environmental Sustainability—necessary for Survival. Environ. Sustain. 2018, 1 (1), 1–2.

(4)

Peters, G. P.; Andrew, R. M.; Boden, T.; Canadell, J. G.; Ciais, P.; Le Quéré, C.; Marland, G.; Raupach, M. R.; Wilson, C. The Challenge to Keep Global Warming below 2 °C. Nat. Clim. Chang. 2013, 3 (1), 4–6.

(5)

Han, Z.; Qi, F.; Wang, H.; Liu, B.; Shen, X.; Song, C.; Bao, Z.; Zhao, X.; Xu, Y.; Sun, D. Emission Characteristics of Volatile Sulfur Compounds (VSCs) from a Municipal Sewage Sludge Aerobic Composting Plant. Waste Manag. 2018, 77, 593–602.

(6)

Sadeghi Meresht, E.; Shahrabi Farahani, T.; Neshati, J. Failure Analysis of Stress Corrosion Cracking Occurred in a Gas Transmission Steel Pipeline. Eng. Fail. Anal. 2011, 18 (3), 963–970.

(7)

Srivastava, V. C. RSC Advances An Evaluation of Desulfurization Technologies for Sulfur Removal from Liquid Fuels. RSC Adv. 2012, 2 (3), 759–783. 63 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(8)

Page 64 of 100

Honeywell. ULTIMetTM | Honeywell UOP.

https://www.uop.com/products/catalysts/hydroprocessing/ultimet/ (accessed Dec 31, 2018). (9)

Bhaskar, M.; Valavarasu, G.; Sairam, B.; Balaraman, K. S.; Balu, K. Three-Phase Reactor Model to Simulate the Performance of Pilot-Plant and Industrial Trickle-Bed Reactors Sustaining Hydrotreating Reactions. Ind. Eng. Chem. Res. 2004, 43 (21), 6654–6669.

(10)

Babich, I. .; Moulijn, J. . Science and Technology of Novel Processes for Deep Desulfurization of Oil Refinery Streams: A Review. Fuel 2003, 82 (6), 607–631.

(11)

Stratas Advisors. A Global Overview and Outlook of On-Road Diesel Quality, Vehicle Emissions and Fuel Efficiency | Stratas Advisors.

https://stratasadvisors.com/Insights/110118-On-Road-Diesel-Quality (accessed Jan 15, 2019). (12)

Huang, T.; Xu, J.; Fan, Y. Effects of Concentration and Microstructure of Active Phases on the Selective Hydrodesulfurization Performance of Sulfided CoMo/Al2O3 Catalysts. Appl. Catal. B Environ. 2018, 220, 42–56.

(13)

Khan, M. R.; Sayed, E. Sulfur Removal from Heavy and Light Petroleum Hydrocarbon by Selective Oxidation. In Advances in Clean Hydrocarbon Fuel Processing: Science and Technology; Woodhead Publishing, 2011; pp 243–261.

(14)

Guo, K.; Gu, M.; Yu, Z. Carbon Nanocatalysts for Aquathermolysis of Heavy Crude Oil: Insights into Thiophene Hydrodesulfurization. Energy Technol. 2017, 5 (8), 1228–1234.

(15)

Lai, W.; Chen, Z.; Zhu, J.; Yang, L.; Zheng, J.; Yi, X.; Fang, W. A NiMoS Flower-like Structure with Self-Assembled Nanosheets as High-Performance Hydrodesulfurization Catalysts. Nanoscale 2016, 8 (6), 3823–3833. 64 ACS Paragon Plus Environment

Page 65 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(16)

Liu, H.; Li, Y. P.; Yin, C. L.; Wu, Y. L.; Chai, Y. M.; Dong, D. M.; Li, X. H.; Liu, C. G. One-Pot Synthesis of Ordered Mesoporous NiMo-Al2O3 Catalysts for Dibenzothiophene Hydrodesulfurization. Appl. Catal. B-Environmental 2016, 198, 493–507.

(17)

Egorova,

M.;

Prins,

R.

Hydrodesulfurization

of

Dibenzothiophene

and

4,6-

Dimethyldibenzothiophene over Sulfided NiMo/γ-Al2O3, CoMo/γ-Al2O3, and Mo/γ-Al2O3 Catalysts. J. Catal. 2004, 225 (2), 417–427. (18)

Liu, H.; Yin, C.; Liu, B.; Li, X.; Li, Y.; Chai, Y.; Liu, C. Effect of Calcination Temperature of Unsupported NiMo Catalysts on the Hydrodesulfurization of Dibenzothiophene. Energy & Fuels 2014, 28 (4), 2429–2436.

(19)

Zepeda, T. A. Comparison and Performance of Different Sulphided Ti-Loaded Mesostructured Silica-Supported CoMo Catalysts in Deep HDS. Appl. Catal. A Gen. 2008, 347 (2), 148–161.

(20)

Mansouri, A.; Semagina, N. Palladium Islands on Iron Oxide Nanoparticles for Hydrodesulfurization Catalysis. Catal. Sci. Technol. 2018, 8 (9), 2323–2332.

(21)

Soares, R. R.; Simonetti, D. A.; Dumesic, J. A. Glycerol as a Source for Fuels and Chemicals by Low-Temperature Catalytic Processing. Angew. Chemie 2006, 118 (24), 4086–4089.

(22)

He, Z.; Qian, Q.; Ma, J.; Meng, Q.; Zhou, H.; Song, J.; Liu, Z.; Han, B. Water-Enhanced Synthesis of Higher Alcohols from CO2 Hydrogenation over a Pt/Co3O4 Catalyst under Milder Conditions. Angew. Chemie Int. Ed. 2016, 55 (2), 737–741.

(23)

Taylor, M. J.; Durndell, L. J.; Isaacs, M. A.; Parlett, C. M. A.; Wilson, K.; Lee, A. F.;


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 66 of 100

Kyriakou, G. Highly Selective Hydrogenation of Furfural over Supported Pt Nanoparticles under Mild Conditions. Appl. Catal. B Environ. 2016, 180, 580–585. (24)

Michaud, P.; Lemberton, J. .; Pérot, G. Hydrodesulfurization of Dibenzothiophene and 4,6Dimethyldibenzothiophene: Effect of an Acid Component on the Activity of a Sulfided NiMo on Alumina Catalyst. Appl. Catal. A Gen. 1998, 169 (2), 343–353.

(25)

Fu, W.; Zhang, L.; Tang, T.; Ke, Q.; Wang, S.; Hu, J.; Fang, G.; Li, J.; Xiao, F.-S. Extraordinarily

High

Activity

in

the


of

4,6-

Dimethyldibenzothiophene over Pd Supported on Mesoporous Zeolite Y. J. Am. Chem. Soc. 2011, 133 (39), 15346–15349. (26)

Sun, Y.; Prins, R. Hydrodesulfurization of 4,6-Dimethyldibenzothiophene over Noble Metals Supported on Mesoporous Zeolites. Angew. Chemie 2008, 120 (44), 8606–8609.

(27)

Nasri, N. S.; Jones, J. M.; Dupont, V. A.; Williams, A. A Comparative Study of Sulfur Poisoning and Regeneration of Precious-Metal Catalysts. Energy & Fuels 1998, 12 (6), 1130–1134.

(28)

Alfonso, D. R. First-Principles Studies of H2S Adsorption and Dissociation on Metal Surfaces. Surf. Sci. 2008, 602 (16), 2758–2768.

(29)

Farmer, J. A.; Campbell, C. T. Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding. Science (80-. ). 2010, 329 (5994), 933–936.

(30)

Bock, C.; Paquet, C.; Couillard, M.; Botton, G. A.; MacDougall, B. R. Size-Selected Synthesis of PtRu Nano-Catalysts: Reaction and Size Control Mechanism. J. Am. Chem. Soc. 2004, 126 (25), 8028–8037.


Page 67 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(31)

Sun, Y.; Wang, H.; Prins, R. Hydrodesulfurization with Classic Co-MoS2 and Ni-MoS2/γAl2O3 and New Pt-Pd on Mesoporous Zeolite Catalysts. Catal. Today 2010, 150 (3–4), 213– 217.

(32)

Sun, Y.; Prins, R. Hydrodesulfurization of 4,6-Dimethyldibenzothiophene over Noble Metals Supported on Mesoporous Zeolites. Angew. Chemie 2008, 120 (44), 8606–8609.

(33)

Vít, Z.; Gulková, D.; Kaluža, L.; Bakardieva, S.; Boaro, M. Mesoporous Silica–alumina Modified by Acid Leaching as Support of Pt Catalysts in HDS of Model Compounds. Appl. Catal. B Environ. 2010, 100 (3–4), 463–471.

(34)

Prins, R.; Niquille-ro, A. Hydrodesulfurization of 4 , 6-Dimethyldibenzothiophene over Pt , Pd , and Pt – Pd Catalysts Supported on Amorphous Silica – Alumina. Catal. Today 2007, 123, 198–207.

(35)

Xu, W.; Wang, X.; Zhou, Q.; Meng, B.; Zhao, J.; Qiu, J.; Gogotsi, Y. Low-Temperature Plasma-Assisted Preparation of Graphene Supported Palladium Nanoparticles with High Hydrodesulfurization Activity. J. Mater. Chem. 2012, 22 (29), 14363.

(36)

Xu, J.; Guo, Y.; Huang, T.; Fan, Y. Decamethonium Bromide-Dispersed Palladium Nanoparticles on Mesoporous HZSM-5 Zeolites for Deep Hydrodesulfurization. Chem. Eng. J. 2018, 333, 206–215.

(37)

Shen, J.; Semagina, N. Palladium Nanoparticle Size Effect in Hydrodesulfurization of 4,6Dimethyldibenzothiophene (4,6-DMDBT). ChemCatChem 2016, 8 (15), 2565–2571.

(38)

Ziaei-Azad, H.; Semagina, N. Iridium Addition Enhances Hydrodesulfurization Selectivity in 4,6-Dimethyldibenzothiophene Conversion on Palladium. Appl. Catal. B Environ. 2016,


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 68 of 100

191, 138–146. (39)

Mansouri, A.; Semagina, N. Enhancement of Palladium-Catalyzed Direct Desulfurization by Yttrium Addition. Appl. Catal. A Gen. 2017, 543, 43–50.

(40)

Vít, Z.; Gulková, D.; Kaluža, L.; Kupčík, J. Pd–Pt Catalysts on Mesoporous SiO2–Al2O3 with Superior Activity for HDS of 4,6-Dimethyldibenzothiophene: Effect of Metal Loading and Support Composition. Appl. Catal. B Environ. 2015, 179, 44–53.

(41)

Venezia, A. M.; La Parola, V.; Nicolı̀, V.; Deganello, G. Effect of Gold on the HDS Activity of Supported Palladium Catalysts. J. Catal. 2002, 212 (1), 56–62.

(42)

Venezia, A. M.; La Parola, V.; Deganello, G.; Pawelec, B.; Fierro, J. L. G. Synergetic Effect of Gold in Au/Pd Catalysts during HDS Reaction of Benzothiophene. In Elsevier; 2003; p 936.

(43)

Herzing, A. A.; Carley, A. F.; Edwards, J. K.; Hutchings, G. J.; Kiely, C. J. Microstructural Development and Catalytic Performance of Au−Pd Nanoparticles on Al2O3 Supports: The Effect of Heat Treatment Temperature and Atmosphere. Chem. Mater. 2008, 20 (4), 1492– 1501.

(44)

Suo, Z.; Ma, C.; Liao, W.; Jin, M.; Lv, H. Structure and Activity of Au–Pd/SiO2 Bimetallic Catalyst for Thiophene Hydrodesulfurization. Fuel Process. Technol. 2011, 92 (8), 1549– 1553.

(45)

La Parola, V.; Testa, M. L.; Venezia, A. M. Pd and PdAu Catalysts Supported over 3MPTES Grafted HMS Used in the HDS of Thiophene. Appl. Catal. B Environ. 2012, 119– 120, 248–255.


Page 69 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(46)

Liao, F.; Lo, T. W. B.; Tsang, S. C. E. Recent Developments in Palladium-Based Bimetallic Catalysts. ChemCatChem 2015, 7 (14), 1998–2014.

(47)

Ishihara, A.; Dumeignil, F.; Lee, J.; Mitsuhashi, K.; Qian, E. W.; Kabe, T. Hydrodesulfurization of Sulfur-Containing Polyaromatic Compounds in Light Gas Oil Using Noble Metal Catalysts. Appl. Catal. A Gen. 2005, 289 (2), 163–173.

(48)

Kolpin, A.; Jones, G.; Jones, S.; Zheng, W.; Cookson, J.; York, A. P. E.; Collier, P. J.; Tsang, S. C. E. Quantitative Differences in Sulfur Poisoning Phenomena over Ruthenium and Palladium: An Attempt To Deconvolute Geometric and Electronic Poisoning Effects Using Model Catalysts. ACS Catal. 2017, 7 (1), 592–605.

(49)

Infantes-Molina, A.; Romero-Pérez, A.; Finocchio, E.; Busca, G.; Jiménez-López, A.; Rodríguez-Castellón, E. HDS and HDN on SBA-Supported RuS2 catalysts Promoted by Pt and Ir. J. Catal. 2013, 305, 101–117.

(50)

Romero-Pérez, A.; Infantes-Molina, A.; Jiménez-López, A.; Jalil, E. R.; Sapag, K.; Rodríguez-Castellón, E. Al-Pillared Montmorillonite as a Support for Catalysts Based on Ruthenium Sulfide in HDS Reactions. Catal. Today 2012, 187 (1), 88–96.

(51)

Kaluža, L.; Vít, Z.; Zdražil, M. Support Effect in the Hydrodesulfurization of Thiophene over Rhodium Sulfide. React. Kinet. Mech. Catal. 2010, 101 (1), 63–72.

(52)

Lee, J.; Ishihara, A.; Dumeignil, F.; Miyazaki, K.; Oomori, Y.; Qian, E. W.; Kabe, T. Novel Hydrodesulfurization Catalysts Derived from a Rhodium Carbonyl Complex. J. Mol. Catal. A Chem. 2004, 209 (1–2), 155–162.

(53)

Giraldo, S. A.; Pinzón, M. H.; Centeno, A. Behavior of Catalysts with Rhodium in


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 70 of 100

Simultaneous Hydrodesulfurization and Hydrogenation Reactions. Catal. Today 2008, 133–135 (1–4), 239–243. (54)

Pecoraro, T. A.; Chianelli, R. R. Hydrodesulfurization Catalysis by Transition Metal Sulfides. Stud. Surf. Sci. Catal. 1981, 7 (2), 1426–1427.

(55)

Quartararo, J.; Mignard, S.; Kasztelan, S. Hydrodesulfurization and Hydrogenation Activities of Alumina-Supported Transition Metal Sulfides. J. Catal. 2000, 192 (2), 307– 315.

(56)

Karroua, M.; Ladrie`re, J.; Matralis, H.; Grange, P.; Delmon, B. Characterisation of Unsupported FeMoS Catalysts: Stability during Reaction and Effect of the Sulfiding Temperature. J. Catal. 1992, 138 (2), 640–658.

(57)

Bezverkhyy, I.; Afanasiev, P.; Danot, M. Preparation of Highly Dispersed Pentlandites (M,M′)9S 8 (M, M′ = Fe, Co, Ni) and Their Catalytic Properties in Hydrodesulfurization. J. Phys. Chem. B 2004, 108 (23), 7709–7715.

(58)

Rodriguez, J. A.; Hrbek, J. Interaction of Sulfur with Well-Defined Metal and Oxide Surfaces: Unraveling the Mysteries behind Catalyst Poisoning and Desulfurization. Acc. Chem. Res. 1999, 32 (9), 719–728.

(59)

Heine, V. S − d Interaction in Transition Metals. Phys. Rev. 1967, 153 (3), 673–682.

(60)

Anderson, P. W. (Philip W. . A Career in Theoretical Physics; World Scientific, 1994.

(61)

Phillips, J. C. Optical Spectra of Transition and Noble Metals. J. Appl. Phys. 1968, 39 (2), 755–761.

(62)

Pinto, S.; D’Ornelas, L.; Betancourt, P. Synthesis and Characterization of Vanadium 70 ACS Paragon Plus Environment

Page 71 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Nanoparticles on Activated Carbon and Their Catalytic Activity in Thiophene Hydrodesulphurization. Appl. Surf. Sci. 2008, 254 (17), 5390–5393. (63)

Chen, T.-M.; Wang, C.-M.; Wang, I.; Tsai, T.-C. Promoter Effect of Vanadia on Co/Mo/Al2O3 Catalyst for Deep Hydrodesulfurization via the Hydrogenation Reaction Pathway. J. Catal. 2010, 272 (1), 28–36.

(64)

Li, H.; Liu, J.; Li, J.; Hu, Y.; Wang, W.; Yuan, D.; Wang, Y.; Yang, T.; Li, L.; Sun, H.; et al. Promotion of the Inactive Iron Sulfide to an Efficient Hydrodesulfurization Catalyst. ACS Catal. 2017, 7 (7), 4805–4816.

(65)

Allali, N.; Marie, A. M.; Danot, M.; Geantet, C.; Breysse, M. Carbon-Supported and Alumina-Supported Niobium Sulfide Catalysts. J. Catal. 1995, 156 (2), 279–289.

(66)

Geantet, C.; Afonso, J.; Breysse, M.; Allali, N.; Danot, M. Niobium Sulfides as Catalysts for Hydrotreating Reactions. Catal. Today 1996, 28 (1–2), 23–30.

(67)

Hermann, N.; Brorson, M.; Topsøe, H. Activities of Unsupported Second Transition Series Metal

Sulfides

for


of

Sterically

Hindered

4,6-

Dimethyldibenzothiophene and of Unsubstituted Dibenzothiophene. Catal. Letters 2000, 65 (4), 169–174. (68)

C., G.; M., V.; V., G.; M., D.; N., A.; M., B.; Gaborit, V.; Allali, N.; Geantet, C.; Breysse, M.; et al. Niobium Sulfide as a Dopant for HPC NiMo Catalysts. Catal. Today 2000, 57, 267–273.

(69)

Wachs, I. E.; Chen, Y.; Jehng, J. M.; Briand, L. E.; Tanaka, T. Molecular Structure and Reactivity of the Group V Metal Oxides. In Catalysis Today; 2003; Vol. 78, pp 13–24.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(70)

Page 72 of 100

Dash, J. K.; Chen, L.; Dinolfo, P. H.; Lu, T.; Wang, G. A Method Toward Fabricating Semiconducting 3R-NbS2 Ultrathin Films. J. Phys. Chem. C 2015, 119 (34), 19763–19771.

(71)

Mansouri, A.; Semagina, N. Promotion of Niobium Oxide Sulfidation by Copper and Its Effects on Hydrodesulfurization Catalysis. ACS Catal. 2018, 8 (8), 7621–7632.

(72)

Aray, Y.; Zambrano, D.; Cornejo, M. H.; Ludeña, E. V.; Iza, P.; Vidal, A. B.; Coll, D. S.; Jímenez, D. M.; Henriquez, F.; Paredes, C. First-Principles Study of the Nature of Niobium Sulfide Catalyst for Hydrodesulfurization in Hydrotreating Conditions. J. Phys. Chem. C 2014, 118 (48), 27823–27832.

(73)

Méndez, F. J.; Franco-López, O. E.; Bokhimi, X.; Solís-Casados, D. A.; Escobar-Alarcón, L.; Klimova, T. E. Dibenzothiophene Hydrodesulfurization with NiMo and CoMo Catalysts Supported on Niobium-Modified MCM-41. Appl. Catal. B Environ. 2017, 219, 479–491.

(74)

Palcheva, R.; Kaluža, L.; Dimitrov, L.; Tyuliev, G.; Avdeev, G.; Jirátová, K.; Spojakina, A. NiMo Catalysts Supported on the Nb Modified Mesoporous SBA-15 and HMS: Effect of Thioglycolic Acid Addition on HDS. Appl. Catal. A Gen. 2016, 520, 24–34.

(75)

Ali, S. A.; Ahmed, S.; Ahmed, K. W.; Al-Saleh, M. A. Simultaneous Hydrodesulfurization of Dibenzothiophene and Substituted Dibenzothiophenes over Phosphorus Modified CoMo/Al2O3 catalysts. Fuel Process. Technol. 2012, 98, 39–44.

(76)

Kim, H.; Lee, J. J.; Koh, J. H.; Moon, S. H. Effect of Fluorine Addition on the Poisoning of NiMo/Al2O3 Catalysts by Nitrogen Compounds during the Hydrodesulfurization of Dibenzothiophene Compounds. Appl. Catal. B Environ. 2004, 50 (1), 17–24.

(77)

Guo, X.; Song, M.; Zhao, X.; Zhao, L. Effect of Fluoride Promoter on the Catalytic Activity


Page 73 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

of NiWF/γ-Al2O3 for Hydrodenitrogenation and Hydrodesulfurization of Coal Tar. J. Fuel Chem. Technol. 2016, 44 (11), 1326–1333. (78)

Zhou, T.; Yin, H.; Han, S.; Chai, Y.; Liu, Y.; Liu, C. Influences of Different Phosphorus Contents on NiMoP/Al2O3 Hydrotreating Catalysts. J. Fuel Chem. Technol. 2009, 37 (3), 330–334.

(79)

Saleh, T. A.; AL-Hammadi, S. A.; Al-Amer, A. M. Effect of Boron on the Efficiency of MoCo Catalysts Supported on Alumina for the Hydrodesulfurization of Liquid Fuels. Process Saf. Environ. Prot. 2019, 121, 165–174.

(80)

Rashidi, F.; Sasaki, T.; Rashidi, A. M.; Nemati Kharat, A.; Jozani, K. J. Ultradeep Hydrodesulfurization of Diesel Fuels Using Highly Efficient Nanoalumina-Supported Catalysts: Impact of Support, Phosphorus, and/or Boron on the Structure and Catalytic Activity. J. Catal. 2013, 299, 321–335.

(81)

Ferdous, D.; Dalai, A.K.; and Adjaye, J. Hydrodenitrogenation and Hydrodesulfurization of Heavy Gas Oil Using NiMo/Al2O3 Catalyst Containing Boron: Experimental and Kinetic Studies. 2005.

(82)

Cui, W.; Li, W.; Gao, R.; Ma, H.; Li, D.; Niu, M.; Lei, X. Hydroprocessing of LowTemperature Coal Tar for the Production of Clean Fuel over Fluorinated NiW/Al2O3 –SiO2 Catalyst. Energy & Fuels 2017, 31 (4), 3768–3783.

(83)

Dorneles de Mello, M.; de Almeida Braggio, F.; da Costa Magalhães, B.; Zotin, J. L.; da Silva, M. A. P. Effects of Phosphorus Content on Simultaneous Ultradeep HDS and HDN Reactions over NiMoP/Alumina Catalysts. Ind. Eng. Chem. Res. 2017, 56 (37), 10287– 10299. 73 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(84)

Page 74 of 100

Stanislaus, A.; Marafi, A.; Rana, M. S. Recent Advances in the Science and Technology of Ultra Low Sulfur Diesel (ULSD) Production. Catal. Today 2010, 153 (1–2), 1–68.

(85)

Mendoza-Nieto, J. A.; Vera-Vallejo, O.; Escobar-Alarcón, L.; Solís-Casados, D.; Klimova, T. Development of New Trimetallic NiMoW Catalysts Supported on SBA-15 for Deep Hydrodesulfurization. Fuel 2013, 110, 268–277.

(86)

Huang, Y.; Zhou, Z.; Qi, Y.; Li, X.; Cheng, Z.; Yuan, W. Hierarchically Macro/Mesoporous Structured Co–Mo–Ni/γ-Al2O3 Catalyst for the Hydrodesulfurization of Thiophene. Chem. Eng. J. 2011, 172 (1), 444–451.

(87)

Wang, H.; Xiao, B.; Cheng, X.; Wang, C.; Zhao, L.; Zhu, Y.; Zhu, J.; Lu, X. NiMo Catalysts Supported

on

Graphene-Modified

Mesoporous

TiO2

toward

Highly

Efficient

Hydrodesulfurization of Dibenzothiophene. Appl. Catal. A Gen. 2015, 502, 157–165. (88)

Arias, S.; Licea, Y. E.; Soares, D.; Eon, J. G.; Palacio, L. A.; Faro, A. C. Mixed NiMo, NiW and NiMoW Sulfides Obtained from Layered Double Hydroxides as Catalysts in Simultaneous HDA and HDS Reactions. Catal. Today 2017, 296, 187–196.

(89)

Gómez-Orozco, S. Y.; Huirache-Acuña, R.; Pawelec, B.; Fierro, J. L. G.; Rivera-Muñoz, E. M.; Lara-Romero, J.; Alonso-Nuñez, G. Characterizations and HDS Performances of Sulfided NiMoW Catalysts Supported on Mesoporous Titania-Modified SBA-15. Catal. Today 2018, 305, 152–161.

(90)

Olivas, A.; Zepeda, T. A. Impact of Al and Ti Ions on the Dispersion and Performance of Supported NiMo(W)/SBA-15 Catalysts in the HDS and HYD Reactions. Catal. Today 2009, 143 (1–2), 120–125.


Page 75 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(91)

Van Haandel, L.; Bremmer, M.; Kooyman, P. J.; Van Veen, J. A. R.; Weber, T.; Hensen, E. J. M. Structure–Activity Correlations in Hydrodesulfurization Reactions over NiPromoted Mox W(1– x ) S2/Al2O3 Catalysts. ACS Catal. 2015, 5 (12), 7276–7287.

(92)

Thomazeau, C.; Lacroix, M.; Danot, M.; Harlé, V.; Raybaud, P. Predictive Approach for the Design of Improved HDT Catalysts: γ-Alumina Supported (Ni, Co) Promoted Mo1−xWxS2 Active Phases. Appl. Catal. A Gen. 2007, 322, 92–97.

(93)

Cervantes-Gaxiola, M. E.; Arroyo-Albiter, M.; Pérez-Larios, A.; Balbuena, P. B.; EspinoValencia, J. Experimental and Theoretical Study of NiMoW, NiMo, and NiW Sulfide Catalysts Supported on an AlTiMg Mixed Oxide during the Hydrodesulfurization of Dibenzothiophene. Fuel 2013, 113, 733–743.

(94)

Aguirre-Gutiérrez, A.; de la Fuente, J. A. M.; de los Reyes, J. A.; del Angel, P.; Vargas, A. Palladium Effect over Mo and NiMo/Alumina–titania Sulfided Catalysts on the Hydrodesulfurization of 4,6-Dimethyldibenzothiophene. J. Mol. Catal. A Chem. 2011, 346 (1–2), 12–19.

(95)

Navarro, R. M.; Castaño, P.; Álvarez-Galván, M. C.; Pawelec, B. Hydrodesulfurization of Dibenzothiophene and a SRGO on Sulfide Ni(Co)Mo/Al2O3 Catalysts. Effect of Ru and Pd Promotion. Catal. Today 2009, 143 (1–2), 108–114.

(96)

Ding, S.; Li, A.; Jiang, S.; Zhou, Y.; Wei, Q.; Zhou, W.; Huang, Y.; Yang, Q.; Fan, T. Niobium Modification Effects on Hydrodesulfurization of 4,6-DMDBT Catalyzed on NiMo-S Active Sites: A Combination of Experiments and Theoretical Study. Fuel 2019, 237, 429–441.

(97)

Sharma, G.; Kumar, D.; Kumar, A.; Al-Muhtaseb, A. H.; Pathania, D.; Naushad, M.; Mola, 75 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 76 of 100

G. T. Revolution from Monometallic to Trimetallic Nanoparticle Composites, Various Synthesis Methods and Their Applications: A Review. Mater. Sci. Eng. C 2017, 71, 1216– 1230. (98)

Wang, L.; Zhang, Y.; Zhang, Y.; Liu, P.; Han, H.; Yang, M.; Jiang, Z.; Li, C. Hydrodesulfurization of 4,6-DMDBT on a Multi-Metallic Sulfide Catalyst with Layered Structure. Appl. Catal. A Gen. 2011, 394 (1–2), 18–24.

(99)

Chen, Y.; Wang, L.; Zhang, Y.; Liu, T.; Liu, X.; Jiang, Z.; Li, C. A New Multi-Metallic Bulk Catalyst with High Hydrodesulfurization Activity of 4,6-DMDBT Prepared Using Layered Hydroxide Salts as Structural Templates. Appl. Catal. A Gen. 2014, 474, 69–77.

(100) Chen, Y.; Wang, L.; Liu, X.; Liu, T.; Huang, B.; Li, P.; Jiang, Z.; Li, C. Hydrodesulfurization of 4,6-DMDBT on Multi-Metallic Bulk Catalyst NiAlZnMoW: Effect of Zn. Appl. Catal. A Gen. 2015, 504, 319–327. (101) Huirache-Acuña, R.; Nava, R.; Peza-Ledesma, C.; Lara-Romero, J.; Alonso-Núez, G.; Pawelec, B.; Rivera-Muñoz, E. SBA-15 Mesoporous Silica as Catalytic Support for Hydrodesulfurization Catalysts—Review. Materials (Basel). 2013, 6 (9), 4139–4167. (102) Egorova, M.; Prins, R. The Role of Ni and Co Promoters in the Simultaneous HDS of Dibenzothiophene and HDN of Amines over Mo/γ-Al2O3 Catalysts. J. Catal. 2006, 241 (1), 162–172. (103) Sundaramurthy, V.; Eswaramoorthi, I.; Dalai, A. K.; Adjaye, J. Hydrotreating of Gas Oil on SBA-15 Supported NiMo Catalysts. Microporous Mesoporous Mater. 2008, 111 (1–3), 560–568.


Page 77 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(104) Badoga, S.; Mouli, K. C.; Soni, K. K.; Dalai, A. K.; Adjaye, J. Beneficial Influence of EDTA on the Structure and Catalytic Properties of Sulfided NiMo/SBA-15 Catalysts for Hydrotreating of Light Gas Oil. Appl. Catal. B Environ. 2012, 125, 67–84. (105) Gutiérrez, O. Y.; Singh, S.; Schachtl, E.; Kim, J.; Kondratieva, E.; Hein, J.; Lercher, J. A. Effects of the Support on the Performance and Promotion of (Ni)MoS2 Catalysts for Simultaneous Hydrodenitrogenation and HydrodesulfurizationEffects of the Support on the Performance

and

Promotion

of

(Ni)MoS2

Catalysts

for

Simultaneous

Hydrodenitrogenation. ACS Catal. 2014, 4 (5), 1487–1499. (106) Fan, Y.; Xiao, H.; Shi, G.; Liu, H.; Bao, X. A Novel Approach for Modulating the Morphology of Supported Metal Nanoparticles in Hydrodesulfurization Catalysts. Energy Environ. Sci. 2011, 4 (2), 572–582. (107) Wang, X.; Zhao, Z.; Zheng, P.; Chen, Z.; Duan, A.; Xu, C.; Jiao, J.; Zhang, H.; Cao, Z.; Ge, B. Synthesis of NiMo Catalysts Supported on Mesoporous Al2O3 with Different Crystal Forms

and

Superior

Catalytic

Performance

for

the


of

Dibenzothiophene and 4,6-Dimethyldibenzothiophene. J. Catal. 2016, 344, 680–691. (108) Méndez, F. J.; Llanos, A.; Echeverría, M.; Jáuregui, R.; Villasana, Y.; Díaz, Y.; LiendoPolanco, G.; Ramos-García, M. A.; Zoltan, T.; Brito, J. L. Mesoporous Catalysts Based on Keggin-Type Heteropolyacids Supported on MCM-41 and Their Application in Thiophene Hydrodesulfurization. Fuel 2013, 110, 249–258. (109) Liu, F.; Xu, S.; Chi, Y.; Xue, D. A Novel Alumina-Activated Carbon Composite Supported NiMo Catalyst for Hydrodesulfurization of Dibenzothiophene. Catal. Commun. 2011, 12 (6), 521–524. 77 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 78 of 100

(110) Zhang, L.; Dai, Q.; Fu, W.; Tang, T.; Dong, P.; He, M.; Chen, Q. CoMo Catalyst on Zeolite TS-1 Nanorod Assemblies with High Activity in the Hydrodesulfurization of 4,6Dimethyldibenzothiophene. J. Catal. 2018, 359, 130–142. (111) Soni, K.; Rana, B. S.; Sinha, A. K.; Bhaumik, A.; Nandi, M.; Kumar, M.; Dhar, G. M. 3-D Ordered Mesoporous KIT-6 Support for Effective Hydrodesulfurization Catalysts. Appl. Catal. B Environ. 2009, 90 (1–2), 55–63. (112) Vázquez-Garrido, I.; López-Benítez, A.; Berhault, G.; Guevara-Lara, A. Effect of Support on the Acidity of NiMo/Al2O3-MgO and NiMo/TiO2-Al2O3 Catalysts and on the Resulting Competitive Hydrodesulfurization/Hydrodenitrogenation Reactions. Fuel 2019, 236, 55– 64. (113) Han, W.; Nie, H.; Long, X.; Li, M.; Yang, Q.; Li, D. Effects of the Support Brønsted Acidity on the Hydrodesulfurization and Hydrodenitrogention Activity of Sulfided NiMo/Al2O3 Catalysts. Catal. Today 2017, 292, 58–66. (114) Yashnik, S. A.; Urzhuntsev, G. A.; Stadnichenko, A. I.; Svintsitskiy, D. A.; Ishchenko, A. V.; Boronin, A. I.; Ismagilov, Z. R. Effect of Pd- Precursor and Support Acid Properties on the Pd Electronic State and the Hydrodesulfurization Activity of Pd-Zeolite Catalysts. Catal. Today 2019, 323, 257–270. (115) Zhang, M.; Fan, J.; Chi, K.; Duan, A.; Zhao, Z.; Meng, X.; Zhang, H. Synthesis, Characterization, and Catalytic Performance of NiMo Catalysts Supported on Different Crystal Alumina Materials in the Hydrodesulfurization of Diesel. Fuel Process. Technol. 2017, 156, 446–453. (116) Dong, Y.; Xu, Y.; Zhang, Y.; Lian, X.; Yi, X.; Zhou, Y.; Fang, W. Synthesis of 78 ACS Paragon Plus Environment

Page 79 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Hierarchically Structured Alumina Support with Adjustable Nanocrystalline Aggregation towards Efficient Hydrodesulfurization. Appl. Catal. A Gen. 2018, 559, 30–39. (117) Shan, S.; Yuan, P.; Han, W.; Shi, G.; Bao, X. Supported NiW Catalysts with Tunable Size and Morphology of Active Phases for Highly Selective Hydrodesulfurization of Fluid Catalytic Cracking Naphtha. J. Catal. 2015, 330, 288–301. (118) Liu, J.; Li, Y.; Li, Y.; Sang, S.; Li, S. Effects of Pore Structure on Thermal Conductivity and Strength of Alumina Porous Ceramics Using Carbon Black as Pore-Forming Agent. Ceram. Int. 2016, 42 (7), 8221–8228. (119) Cao, F.; Ren, L.; Li, X. Synthesis of High Strength Monolithic Alumina Aerogels at Ambient Pressure. RSC Adv. 2015, 5 (23), 18025–18028. (120) Qu, L.; Zhang, W.; Kooyman, P. J.; Prins, R. MAS NMR, TPR, and TEM Studies of the Interaction of NiMo with Alumina and Silica-Alumina Supports. J. Catal. 2003, 215 (1), 7–13. (121) Badoga, S.; Dalai, A. K.; Adjaye, J.; Hu, Y. Combined Effects of EDTA and Heteroatoms (Ti, Zr, and Al) on Catalytic Activity of SBA-15 Supported NiMo Catalyst for Hydrotreating of Heavy Gas Oil. Ind. Eng. Chem. Res. 2014, 53 (6), 2137–2156. (122) Díaz de León, J. N. Binary γ-Al2O3–α-Ga2O3 as Supports of NiW Catalysts for Hydrocarbon Sulfur Removal. Appl. Catal. B Environ. 2016, 181, 524–533. (123) Zhou, W.; Zhang, Y.; Tao, X.; Zhou, Y.; Wei, Q.; Ding, S. Effects of Gallium Addition to Mesoporous Alumina by Impregnation on Dibenzothiophene Hydrodesulfurization Performances of the Corresponding NiMo Supported Catalysts. Fuel 2018, 228, 152–163.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 80 of 100

(124) Díaz de León, J. N.; Picquart, M.; Massin, L.; Vrinat, M.; de los Reyes, J. A. Hydrodesulfurization of Sulfur Refractory Compounds: Effect of Gallium as an Additive in NiWS/γ-Al2O3 Catalysts. J. Mol. Catal. A Chem. 2012, 363–364, 311–321. (125) Díaz de León, J. N.; Picquart, M.; Villarroel, M.; Vrinat, M.; Gil Llambias, F. J.; Murrieta, F.; de los Reyes, J. A. Effect of Gallium as an Additive in Hydrodesulfurization WS2/γAl2O3 Catalysts. J. Mol. Catal. A Chem. 2010, 323 (1–2), 1–6. (126) Altamirano, E.; de los Reyes, J. A.; Murrieta, F.; Vrinat, M. Hydrodesulfurization of 4,6Dimethyldibenzothiophene over Co(Ni)MoS2 Catalysts Supported on Alumina: Effect of Gallium as an Additive. Catal. Today 2008, 133–135, 292–298. (127) Giraldo, S. A.; Centeno, A. Isomerization and Cracking under HDS Conditions Using γAlumina Modified with Boron as Catalysts Support. Catal. Today 2008, 133–135, 255–260. (128) Saih, Y.; Segawa, K. Catalytic Activity of CoMo Catalysts Supported on Boron-Modified Alumina

for

the

Hydrodesulphurization

of

Dibenzothiophene

and

4,6-

Dimethyldibenzothiophene. Appl. Catal. A Gen. 2009, 353 (2), 258–265. (129) Andonova, S.; Vladov, C.; Pawelec, B.; Shtereva, I.; Tyuliev, G.; Damyanova, S.; Petrov, L. Effect of the Modified Support γ-Al2O3-CaO on the Structure and Hydrodesulfurization Activity of Mo and Ni-Mo Catalysts. Appl. Catal. A Gen. 2007, 328 (2), 201–209. (130) Maity, S. K.; Flores, L.; Ancheyta, J.; Fukuyama, H. Carbon-Modified Alumina and Alumina−Carbon-Supported Hydrotreating Catalysts. Ind. Eng. Chem. Res. 2009, 48 (3), 1190–1195. (131) Nikulshin, P. A.; Salnikov, V. A.; Mozhaev, A. V.; Minaev, P. P.; Kogan, V. M.; Pimerzin,


Page 81 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

A. A. Relationship between Active Phase Morphology and Catalytic Properties of the Carbon–alumina-Supported Co(Ni)Mo Catalysts in HDS and HYD Reactions. J. Catal. 2014, 309, 386–396. (132) Cui, F.; Li, G.; Li, X.; Lu, M.; Li, M. Enhancement of Hydrodesulfurization of 4,6Dimethyldibenzothiophene Catalyzed by CoMo Catalysts Supported on Carbon-Covered γAl2O3. Catal. Sci. Technol. 2015, 5 (1), 549–555. (133) Fukuyama, H.; Terai, S.; Uchida, M.; Cano, J. L.; Ancheyta, J. Active Carbon Catalyst for Heavy Oil Upgrading. In Catalysis Today; 2004; Vol. 98, pp 207–215. (134) Jalilov, A. S.; Tanimu, A.; Ganiyu, S. A.; Alhooshani, K. Kinetic and Mechanistic Analysis of Dibenzothiophene Hydrodesulfurization on Ti-SBA-15–NiMo Catalysts. Energy & Fuels 2018, 32 (11), 11383–11389. (135) Maity, S. K.; Ancheyta, J.; Rana, M. S.; Rayo, P. Effect of Phosphorus on Activity of Hydrotreating Catalyst of Maya Heavy Crude. Catal. Today 2005, 109 (1–4), 42–48. (136) Rayo,

P.;

Ramírez,

J.;

Ancheyta,

J.;

Rana,

M.

S.

Hydrodesulfurization,

Hydrodenitrogenation, Hydrodemetallization, and Hydrodeasphaltenization of Maya Crude over NiMo/Al2O3 Modified with Ti and P. Pet. Sci. Technol. 2007, 25 (1–2), 215–229. (137) Rayo, P.; Ramírez, J.; Torres-Mancera, P.; Marroquín, G.; Maity, S. K.; Ancheyta, J. Hydrodesulfurization and Hydrocracking of Maya Crude with P-Modified NiMo/Al2O3 Catalysts. In Fuel; 2012; Vol. 100, pp 34–42. (138) Díaz de León, J. N.; Zavala-Sánchez, L. A.; Suárez-Toriello, V. A.; Alonso-Núñez, G.; Zepeda, T. A.; Yocupicio, R. I.; de los Reyes, J. A.; Fuentes, S. Support Effects of NiW


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 82 of 100

Catalysts for Highly Selective Sulfur Removal from Light Hydrocarbons. Appl. Catal. B Environ. 2017, 213, 167–176. (139) Kelly, S. D.; Yang, N.; Mickelson, G. E.; Greenlay, N.; Karapetrova, E.; Sinkler, W.; Bare, S. R. Structural Characterization of Ni–W Hydrocracking Catalysts Using in Situ EXAFS and HRTEM. J. Catal. 2009, 263 (1), 16–33. (140) Kasztelan, S.; Toulhoat, H.; Grimblot, J.; Bonnelle, J. P. A Geometrical Model of the Active Phase of Hydrotreating Catalysts. Appl. Catal. 1984, 13 (1), 127–159. (141) Díaz de León, J. N.; Antunes-García, J.; Alonso-Nuñez, G.; Zepeda, T. A.; Galvan, D. H.; de los Reyes, J. A.; Fuentes, S. Support Effects of NiW Hydrodesulfurization Catalysts from Experiments and DFT Calculations. Appl. Catal. B Environ. 2018, 238, 480–490. (142) Fujikawa, T.; Idei, K.; Ohki, K.; Mizuguchi, H.; Usui, K. Kinetic Behavior of Hydrogenation of Aromatics in Diesel Fuel over Silica-Alumina-Supported Bimetallic PtPd Catalyst. Appl. Catal. A Gen. 2001, 205 (1–2), 71–77. (143) Wan, G.; Duan, A.; Zhao, Z.; Jiang, G.; Zhang, D.; Li, R.; Dou, T.; Chung, K. H. Al2O3−TiO2/Al2O3−TiO2−SiO2 Composite-Supported Bimetallic Pt−Pd Catalysts for the Hydrodearomatization and Hydrodesulfurization of Diesel Fuel. Energy & Fuels 2009, 23 (1), 81–85. (144) Petzold, F. G.; Jasinski, J.; Clark, E. L.; Kim, J. H.; Absher, J.; Toufar, H.; Sunkara, M. K. Nickel Supported on Zinc Oxide Nanowires as Advanced Hydrodesulfurization Catalysts. Catal. Today 2012, 198 (1), 219–227. (145) Kaluža,

L.;

Zdražil,

M.

Relative

Activity

of

Niobia-Supported

CoMo


Page 83 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Hydrodesulphurization Catalyst Prepared with NTA: A Kinetic Approach. Catal. Commun. 2018, 107, 62–67. (146) Palcheva, R.; Dimitrov, L.; Tyuliev, G.; Spojakina, A.; Jiratova, K. TiO2 Nanotubes Supported NiW Hydrodesulphurization Catalysts: Characterization and Activity. Appl. Surf. Sci. 2013, 265, 309–316. (147) Cruz Pérez, A. E.; Torrez Jiménez, Y.; Velasco Alejo, J. J.; Zepeda, T. A.; Frías Márquez, D. M.; Rivera Ruedas, M. G.; Fuentes, S.; Díaz de León, J. N. NiW/MgO–TiO2 Catalysts for Dibenzothiophene Hydrodesulfurization: Effect of Preparation Method. Catal. Today 2016, 271, 28–34. (148) Jiao, F.; Frei, H. Nanostructured Cobalt Oxide Clusters in Mesoporous Silica as Efficient Oxygen-Evolving Catalysts. Angew. Chemie Int. Ed. 2009, 48 (10), 1841–1844. (149) Li, Y.; Wang, W.-N.; Zhan, Z.; Woo, M.-H.; Wu, C.-Y.; Biswas, P. Photocatalytic Reduction of CO2 with H2O on Mesoporous Silica Supported Cu/TiO2 Catalysts. Appl. Catal. B Environ. 2010, 100 (1–2), 386–392. (150) Joo, S. H.; Park, J. Y.; Tsung, C.-K.; Yamada, Y.; Yang, P.; Somorjai, G. A. Thermally Stable Pt/Mesoporous Silica Core–shell Nanocatalysts for High-Temperature Reactions. Nat. Mater. 2009, 8 (2), 126–131. (151) Zhou, X.; Duan, A.; Zhao, Z.; Gong, Y.; Wu, H.; Li, J.; Wei, Y.; Jiang, G.; Liu, J.; Zhang, Y. Synthesis of Hierarchically Porous Silicas with Mesophase Transformations in a FourComponent

Microemulsion-Type

System

and

the

Catalytic

Performance

for

Dibenzothiophene Hydrodesulfurization. J. Mater. Chem. A 2014, 2 (19), 6823–6833.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 84 of 100

(152) Nguyen Dinh, M. T.; Rajbhandari, P.; Lancelot, C.; Blanchard, P.; Lamonier, C.; Bonne, M.; Royer, S.; Dumeignil, F.; Payen, E. Tuning Hydrodesulfurization Active-Phase Dispersion Using Optimized Mesoporous Titania-Doped Silica Supports. ChemCatChem 2014, 6 (1), 328–338. (153) Danforth, S. J.; Liyanage, D. R.; Hitihami-Mudiyanselage, A.; Ilic, B.; Brock, S. L.; Bussell, M. E. Probing Hydrodesulfurization over Bimetallic Phosphides Using Monodisperse Ni2XMxP

Nanoparticles Encapsulated in Mesoporous Silica. Surf. Sci. 2016, 648, 126–135.

(154) Rayo, P.; Ramírez, J.; Rana, M. S.; Ancheyta, J.; Aguilar-Elguézabal, A. Effect of the Incorporation of Al, Ti, and Zr on the Cracking and Hydrodesulfurization Activity of NiMo/SBA-15 Catalysts. Ind. Eng. Chem. Res. 2009, 48 (3), 1242–1248. (155) Lizama, L. Y.; Klimova, T. E. SBA-15 Modified with Al, Ti, or Zr as Supports for Highly Active NiW Catalysts for HDS. In Journal of Materials Science; 2009; Vol. 44, pp 6617– 6628. (156) Biswas, P.; Narayanasarma, P.; Kotikalapudi, C. M.; Dalai, A. K.; Adjaye, J. Characterization and Activity of ZrO2 Doped SBA-15 Supported NiMo Catalysts for HDS and HDN of Bitumen Derived Heavy Gas Oil. Ind. Eng. Chem. Res. 2011, 50 (13), 7882– 7895. (157) Ganiyu, S. A.; Alhooshani, K.; Ali, S. A. Single-Pot Synthesis of Ti-SBA-15-NiMo Hydrodesulfurization Catalysts: Role of Calcination Temperature on Dispersion and Activity. Appl. Catal. B Environ. 2017, 203, 428–441. (158) Ganiyu, S. A.; Ali, S. A.; Alhooshani, K. Synthesis of a Ti-SBA-15-NiMo Hydrodesulfurization Catalyst: The Effect of the Hydrothermal Synthesis Temperature of 84 ACS Paragon Plus Environment

Page 85 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

NiMo and Molybdenum Loading on the Catalytic Activity. Ind. Eng. Chem. Res. 2017, 56 (18), 5201–5209. (159) Jiang, S.; Zhou, Y.; Ding, S.; Wei, Q.; Zhou, W.; Shan, Y. Effect of Direct Synthesis Al– SBA-15 Supports on the Morphology and Catalytic Activity of the NiMoS Phase in HDS of DBT. RSC Adv. 2016, 6 (108), 106680–106689. (160) Tanimu, A.; Ganiyu, S. A.; Adamu, S.; Alhooshani, K. Synthesis, Application and Kinetic Modeling of CeOx –Si–CoMo Catalysts for the Hydrodesulfurization of Dibenzothiophene. React. Chem. Eng. 2019. (161) Suresh, C.; Cabrera, L. P.; Aliaga, J. A.; de León, J. N. D.; Zepeda, T. A.; Fuentes, S.; Berhault, G.; Alonso-Núñez, G. Formation of Co-Promoted MoS2 Fullerene-Like Nanostructures on SBA-15 as Effective Hydrodesulfurization Catalyst. Catal. Letters 2017, 147 (1), 46–57. (162) Valencia, D.; Klimova, T. Effect of the Support Composition on the Characteristics of NiMo and CoMo/(Zr)SBA-15 Catalysts and Their Performance in Deep Hydrodesulfurization. Catal. Today 2011, 166 (1), 91–101. (163) Chandra Mouli, K.; Mohanty, S.; Hu, Y.; Dalai, A.; Adjaye, J. Effect of Hetero Atom on Dispersion of NiMo Phase on M-SBA-15 (M = Zr, Ti, Ti-Zr). In Catalysis Today; Elsevier, 2013; Vol. 207, pp 133–144. (164) Gutiérrez, O. Y.; Singh, S.; Schachtl, E.; Kim, J.; Kondratieva, E.; Hein, J.; Lercher, J. A. Effects of the Support on the Performance and Promotion of (Ni)MoS2 Catalysts for Simultaneous Hydrodenitrogenation and Hydrodesulfurization. ACS Catal. 2014, 4 (5), 1487–1499. 85 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 86 of 100

(165) Ganiyu, S. A.; Alhooshani, K. Catalytic Performance of NiMoS Supported on (Zr)SBA-15 for Hydrodesulfurization of Diesel: Insight into a One-Step Calcination and Reduction Strategy during Sulfidation. Energy & Fuels 2019, acs.energyfuels.8b04536. (166) Morales-Ortuño, J. C.; Klimova, T. E. Development of New Hydrodesulfurization NiMo Catalysts Supported on Al2O3-TiSBA-15 Hybrid Materials. Fuel 2017, 198, 99–109. (167) Mendoza-Nieto, J. A.; Vera-Vallejo, O.; Escobar-Alarcón, L.; Solís-Casados, D.; Klimova, T. Development of New Trimetallic NiMoW Catalysts Supported on SBA-15 for Deep Hydrodesulfurization. Fuel 2013, 110, 268–277. (168) López-Mendoza, M. A.; Nava, R.; Peza-Ledesma, C.; Millán-Malo, B.; Huirache-Acuña, R.; Skewes, P.; Rivera-Muñoz, E. M. Characterization and Catalytic Performance of CoMo-W Sulfide Catalysts Supported on SBA-15 and SBA-16 Mechanically Mixed. Catal. Today 2016, 271, 114–126. (169) Suresh, C.; Pérez-Cabrera, L.; Díaz de León, J. N.; Zepeda, T. A.; Alonso-Núñez, G.; Moyado, S. F. Highly Active CoMo/Al (10) KIT-6 Catalysts for HDS of DBT: Role of Structure and Aluminum Heteroatom in the Support Matrix. Catal. Today 2017, 296, 214– 218. (170) Duan, A.; Li, T.; Zhao, Z.; Liu, B.; Zhou, X.; Jiang, G.; Liu, J.; Wei, Y.; Pan, H. Synthesis of Hierarchically Porous L-KIT-6 Silica–alumina Material and the Super Catalytic Performances for Hydrodesulfurization of Benzothiophene. Appl. Catal. B Environ. 2015, 165, 763–773. (171) Wu, H.; Duan, A.; Zhao, Z.; Li, T.; Prins, R.; Zhou, X. Synthesis of NiMo Hydrodesulfurization Catalyst Supported on a Composite of Nano-Sized ZSM-5 Zeolite 86 ACS Paragon Plus Environment

Page 87 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Enwrapped with Mesoporous KIT-6 Material and Its High Isomerization Selectivity. J. Catal. 2014, 317, 303–317. (172) Gao, Q.; Zhang, Y.; Zhou, K.; Wu, H.; Guo, J.; Zhang, L.; Duan, A.; Zhao, Z.; Zhang, F.; Zhou, Y. Synthesis of ZSM-5/KIT-6 with a Tunable Pore Structure and Its Catalytic Application in the Hydrodesulfurization of Dibenzothiophene and Diesel Oil. RSC Adv. 2018, 8 (51), 28879–28890. (173) Soni, K.; Rana, B. S.; Sinha, A. K.; Bhaumik, A.; Nandi, M.; Kumar, M.; Dhar, G. M. 3-D Ordered Mesoporous KIT-6 Support for Effective Hydrodesulfurization Catalysts. Appl. Catal. B Environ. 2009, 90 (1–2), 55–63. (174) Suresh, C.; Pérez-Cabrera, L.; Díaz de León, J. N.; Zepeda, T. A.; Alonso-Núñez, G.; Moyado, S. F. Highly Active CoMo/Al (10) KIT-6 Catalysts for HDS of DBT: Role of Structure and Aluminum Heteroatom in the Support Matrix. Catal. Today 2017, 296, 214– 218. (175) Fan, J.; Duan, A.; Xu, C.; Zhao, Z.; Zheng, P.; Wang, X.; Li, H.; Xiao, C.; Mei, J.; Jiang, G. Hydrodesulfurization Properties of Dibenzothiophene over NiMo Catalysts Supported on Cubic Fm 3 m Mesoporous Structure and High-Framework Aluminum-Modified AlKIT5. Energy & Fuels 2018, 32 (9), 9793–9803. (176) Shi, J.; Wang, Y.; Yang, W.; Tang, Y.; Xie, Z. Recent Advances of Pore System Construction in Zeolite-Catalyzed Chemical Industry Processes. Chem. Soc. Rev. 2015, 44 (24), 8877–8903. (177) Bataille, F.; Lemberton, J. L.; Leyrit, P.; Cseri, T.; Marchal, N.; Kasztelan, S. Sulfided Mo and CoMo Supported on Zeolite as Hydrodesulfurization Catalysts : Transformation Of. 87 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 88 of 100

Elsevier 2001, 220, 191–205. (178) Taniguchi, M.; Imamura, D.; Ishige, H.; Ishii, Y.; Murata, T.; Hidai, M.; Tatsumi, T. Hydrodesulfurization of Benzothiophene over Zeolite-Supported Catalysts Prepared from Mo and Mo-Ni Sulfide Clusters. J. Catal. 1999, 187 (1), 139–150. (179) Fu, W.; Zhang, L.; Tang, T.; Ke, Q.; Wang, S.; Hu, J.; Fang, G.; Li, J.; Xiao, F.-S. Extraordinarily

High

Activity

in

the


of

4,6-

Dimethyldibenzothiophene over Pd Supported on Mesoporous Zeolite Y. J. Am. Chem. Soc. 2011, 133 (39), 15346–15349. (180) Al-Khattaf, S. Catalytic Transformation of Toluene over a High-Acidity Y-Zeolite Based Catalyst. Energy and Fuels 2006, 20 (3), 946–954. (181) Tang, T.; Zhang, L.; Fu, W.; Ma, Y.; Xu, J.; Jiang, J.; Fang, G.; Xiao, F.-S. Design and Synthesis of Metal Sulfide Catalysts Supported on Zeolite Nanofiber Bundles with Unprecedented Hydrodesulfurization Activities. J. Am. Chem. Soc. 2013, 135 (31), 11437– 11440. (182) Liu, B.; Zhao, Z.; Wang, D.; Liu, J.; Chen, Y.; Li, T.; Duan, A.; Jiang, G. A Theoretical Study on the Mechanism for Thiophene Hydrodesulfurization over Zeolite L-Supported Sulfided CoMo Catalysts: Insight into the Hydrodesulfurization over Zeolite-Based Catalysts. Comput. Theor. Chem. 2015, 1052, 47–57. (183) Huo, Q.; Gong, Y.; Dou, T.; Zhao, Z.; Pan, H.; Deng, F. Novel Micro- and Mesoporous Composite Molecular Sieve Assembled by Zeolite L Nanocrystal and Its Performance for the Hydrodesulfurization (HDS) of Fluid Catalytic Cracking (FCC) Gasoline. Energy & Fuels 2010, 24 (7), 3764–3771. 88 ACS Paragon Plus Environment

Page 89 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(184) Zhou, W.; Liu, M.; Zhang, Q.; Wei, Q.; Ding, S.; Zhou, Y. Synthesis of NiMo Catalysts Supported on Gallium-Containing Mesoporous Y Zeolites with Different Gallium Contents and Their High Activities in the Hydrodesulfurization of 4,6-Dimethyldibenzothiophene. ACS Catal. 2017, 7 (11), 7665–7679. (185) Wang, X.; Mei, J.; Zhao, Z.; Zheng, P.; Chen, Z.; Gao, D.; Fu, J.; Fan, J.; Duan, A.; Xu, C. Self-Assembly of Hierarchically Porous ZSM-5/SBA-16 with Different Morphologies and Its High Isomerization Performance for Hydrodesulfurization of Dibenzothiophene and 4,6Dimethyldibenzothiophene. ACS Catal. 2018, 8 (3), 1891–1902. (186) Wang, X.; Li, Y.; Chi, K.; Zhao, Z.; Du, P.; Mei, J.; Zheng, P.; Fan, J.; Duan, A.; Xu, C. Optimal Synthesis of Hierarchical Porous Composite ZSM-5/SBA-16 for Ultradeep Hydrodesulfurization of Dibenzothiophene and 4,6-Dimethyldibenzothiophene. Part 1: The Influence of Inorganic Salt on the Properties of NiMo Catalysts. Energy & Fuels 2018, 32 (5), 6204–6212. (187) Gao, Q.; Zhang, Y.; Zhou, K.; Wu, H.; Guo, J.; Zhang, L.; Duan, A.; Zhao, Z.; Zhang, F.; Zhou, Y. Synthesis of ZSM-5/KIT-6 with a Tunable Pore Structure and Its Catalytic Application in the Hydrodesulfurization of Dibenzothiophene and Diesel Oil. RSC Adv. 2018, 8 (51), 28879–28890. (188) Yang, L.; Wang, X.; Liu, Y.; Yu, Z.; Liang, J.; Chen, B.; Shi, C.; Tian, S.; Li, X.; Qiu, J. Monolayer MoS2 Anchored on Reduced Graphene Oxide Nanosheets for Efficient Hydrodesulfurization. Appl. Catal. B Environ. 2017, 200, 211–221. (189) Abubakar, U. C.; Alhooshani, K. R.; Adamu, S.; Al Thagfi, J.; Saleh, T. A. The Effect of Calcination Temperature on the Activity of Hydrodesulfurization Catalysts Supported on 89 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 90 of 100

Mesoporous Activated Carbon. J. Clean. Prod. 2019, 211, 1567–1575. (190) Whelan, J.; Katsiotis, M. S.; Stephen, S.; Luckachan, G. E.; Tharalekshmy, A.; Banu, N. D.; Idrobo, J.-C.; Pantelides, S. T.; Vladea, R. V.; Banu, I.; et al. Cobalt-Molybdenum Single-Layered Nanocatalysts Decorated on Carbon Nanotubes and the Influence of Preparation Conditions on Their Hydrodesulfurization Catalytic Activity. Energy & Fuels 2018, 32 (7), 7820–7826. (191) Nath Prajapati, Y.; Verma, N. Hydrodesulfurization of Thiophene on Activated Carbon Fiber Supported NiMo Catalysts. Energy & Fuels 2018, 32 (2), 2183–2196. (192) Hajjar, Z.; Kazemeini, M.; Rashidi, A.; Bazmi, M. Graphene Based Catalysts for Deep Hydrodesulfurization of Naphtha and Diesel Fuels: A Physiochemical Study. Fuel 2016, 165, 468–476. (193) Hu, J.; Zhang, Z.; Wang, F.; Zheng, S.; Cai, J.; Qin, J.; Liu, W.; Liang, S.; Jiang, X. A Controllable Synthesis of Nitrogen-Doped Mesoporous Carbon Supported MoS 2 Catalysts for Hydrodesulfurization of Thiophene. RSC Adv. 2016, 6 (103), 101544–101551. (194) Puello-Polo, E.; Ayala-G, M.; Brito, J. L. Sulfidability and Thiophene Hydrodesulfurization Activity of Supported NiMo Carbides. Catal. Commun. 2014, 53, 9–14. (195) Liu, N.; Wang, X.; Xu, W.; Hu, H.; Liang, J.; Qiu, J. Microwave-Assisted Synthesis of MoS2/Graphene Nanocomposites for Efficient Hydrodesulfurization. Fuel 2014, 119, 163– 169. (196) Rankel, L. A. Hydroprocessing of Heavy Oil over Cobalt-Molybdenum/Carbon Supported Catalysts. Energy & Fuels 1993, 7 (6), 937–942.


Page 91 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(197) Farag, H.; Mochida, I.; Sakanishi, K. Fundamental Comparison Studies on Hydrodesulfurization of Dibenzothiophenes over CoMo-Based Carbon and Alumina Catalysts. Appl. Catal. A Gen. 2000, 194, 147–157. (198) Xu, K.; Li, Y.; Xu, X.; Zhou, C.; Liu, Z.; Yang, F.; Zhang, L.; Wang, G.; Gao, J.; Xu, C. Single-Walled Carbon Nanotubes Supported Ni–Y as Catalyst for Ultra-Deep Hydrodesulfurization of Gasoline and Diesel. Fuel 2015, 160, 291–296. (199) Lonkar, S. P.; Pillai, V. V.; Alhassan, S. M. Three-Dimensional NiS-MoS2 /Graphene Heterostructured Nanohybrids as High-Performance Hydrodesulfurization Catalysts. ACS Appl. Nano Mater. 2018, 1 (7), 3114–3123. (200) Li, L.; Zhu, Y.; Lu, X.; Wei, M.; Zhuang, W.; Yang, Z.; Feng, X. Carbon Heterogeneous Surface Modification on a Mesoporous TiO2-Supported Catalyst and Its Enhanced Hydrodesulfurization Performance. Chem. Commun. 2012, 48 (94), 11525–11527. (201) Wang, H.; Xiao, B.; Cheng, X.; Wang, C.; Zhao, L.; Zhu, Y.; Zhu, J.; Lu, X. NiMo Catalysts Supported

on

Graphene-Modified

Mesoporous

TiO2

toward

Highly

Efficient

Hydrodesulfurization of Dibenzothiophene. Appl. Catal. A Gen. 2015, 502, 157–165. (202) AL-Hammadi, S. A.; Al-Amer, A. M.; Saleh, T. A. Alumina-Carbon Nanofiber Composite as a Support for MoCo Catalysts in Hydrodesulfurization Reactions. Chem. Eng. J. 2018, 345, 242–251. (203) Bai, R.; Sun, Q.; Wang, N.; Zou, Y.; Guo, G.; Iborra, S.; Corma, A.; Yu, J. Simple Quaternary

Ammonium

Cations-Templated

Syntheses

of

Extra-Large

Pore

Germanosilicate Zeolites. Chem. Mater. 2016, 28 (18), 6455–6458.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 92 of 100

(204) Chen, F.-J.; Xu, Y.; Du, H.-B. An Extra-Large-Pore Zeolite with Intersecting 18-, 12-, and 10-Membered Ring Channels. Angew. Chemie Int. Ed. 2014, 53 (36), 9592–9596. (205) Petkov, P. St.; Aleksandrov, H. A.; Valtchev, V.; Vayssilov, G. N. Framework Stability of Heteroatom-Substituted Forms of Extra-Large-Pore Ge-Silicate Molecular Sieves: The Case of ITQ-44. Chem. Mater. 2012, 24 (13), 2509–2518. (206) Mouchaham, G.; Wang, S.; Serre, C. The Stability of Metal-Organic Frameworks. In MetalOrganic Frameworks; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2018; pp 1–28. (207) Guillerm, V.; Ragon, F.; Dan-Hardi, M.; Devic, T.; Vishnuvarthan, M.; Campo, B.; Vimont, A.; Clet, G.; Yang, Q.; Maurin, G.; Ferey, G.; Vittadini, A.; Gross, S; Serre, C. A Series of Isoreticular, Highly Stable, Porous Zirconium Oxide Based Metal-Organic Frameworks. Angew. Chemie Int. Ed. 2012, 51 (37), 9267–9271. (208) Song, W.; Lai, W.; Chen, Z.; Cao, J.; Wang, H.; Lian, Y.; Yang, W.; Jiang, X. Fabrication of 3D Porous Hierarchical NiMoS Flowerlike Architectures for Hydrodesulfurization Applications. ACS Appl. Nano Mater. 2018, 1 (1), 442–454. (209) Zhang, C.; Li, P.; Liu, X.; Liu, T.; Jiang, Z.; Li, C. Morphology-Performance Relation of (Co)MoS2 Catalysts in the Hydrodesulfurization of FCC Gasoline. Appl. Catal. A Gen. 2018, 556, 20–28. (210) Romero-Rivera, R.; Berhault, G.; Alonso-Núñez, G.; Del Valle, M.; Paraguay-Delgado, F.; Fuentes, S.; Salazar, S.; Aguilar, A.; Cruz-Reyes, J. Tungsten Disulfide Catalysts from Tetraalkylammonium Thiotungstates by Ex Situ Activation, Their Properties and HDS Activity. Appl. Catal. A Gen. 2012, 433–434, 115–121. 92 ACS Paragon Plus Environment

Page 93 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(211) Yi, Y.; Zhang, B.; Jin, X.; Wang, L.; Williams, C. T.; Xiong, G.; Su, D.; Liang, C. Unsupported NiMoW Sulfide Catalysts for Hydrodesulfurization of Dibenzothiophene by Thermal Decomposition of Thiosalts. J. Mol. Catal. A Chem. 2011, 351, 120–127. (212) Zhou, W.; Wei, Q.; Zhou, Y.; Liu, M.; Ding, S.; Yang, Q. Hydrodesulfurization of 4,6Dimethyldibenzothiophene over NiMo Sulfide Catalysts Supported on Meso-Microporous Y Zeolite with Different Mesopore Sizes. Appl. Catal. B Environ. 2018, 238, 212–224. (213) Naboulsi, I.; Lebeau, B.; Aponte, C. F. L.; Brunet, S.; Mallet, M.; Michelin, L.; Bonne, M.; Carteret, C.; Blin, J.-L. Selective Direct Desulfurization Way (DDS) with CoMoS Supported over Mesostructured Titania for the Deep Hydrodesulfurization of 4,6Dimethydibenzothiophene. Appl. Catal. A Gen. 2018, 563, 91–97. (214) Huang, T.; Chang, J.; He, S.; Wen, C.; Fan, Y. Efficient Hydrodesulfurization of 4,6Dimethyldibenzothiophene via Ni4Mo12/Al2O3 Catalysts Prepared by a One-Step Hydrothermal

Polyoxometalate

Dispersion

Method.

Energy

&

Fuels

2018,

acs.energyfuels.8b03423. (215) Ashenaeian, S.; Haghighi, M.; Rahemi, N. Hybrid Plasma-Sono-Coprecipitation Dispersion of NiMo Nanocatalyst over Functionalized Multiwall Carbon Nanotube Used in Hydrodesulfurization of Thiophene. Adv. Powder Technol. 2018. (216) Jiao, J.; Fu, J.; Wei, Y.; Zhao, Z.; Duan, A.; Xu, C.; Li, J.; Song, H.; Zheng, P.; Wang, X.; et al. Al-Modified Dendritic Mesoporous Silica Nanospheres-Supported NiMo Catalysts for the Hydrodesulfurization of Dibenzothiophene: Efficient Accessibility of Active Sites and Suitable Metal–support Interaction. J. Catal. 2017, 356, 269–282. (217) Shan, S.; Liu, H.; Yue, Y.; Shi, G.; Bao, X. Trimetallic WMoNi Diesel Ultra-Deep 93 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 94 of 100

Hydrodesulfurization Catalysts with Enhanced Synergism Prepared from Inorganic– organic Hybrid Nanocrystals. J. Catal. 2016, 344, 325–333. (218) Vít, Z.; Gulková, D.; Kaluža, L.; Boaro, M. Effect of Catalyst Precursor and Its Pretreatment on the Amount of β-Pd Hydride Phase and HDS Activity of Pd-Pt/Silica-Alumina. Appl. Catal. B Environ. 2014, 146, 213–220. (219) Hein, J.; Gutiérrez, O. Y.; Albersberger, S.; Han, J.; Jentys, A.; Lercher, J. A. Towards Understanding Structure-Activity Relationships of Ni-Mo-W Sulfide Hydrotreating Catalysts. ChemCatChem 2017, 9 (4), 629–641. (220) Alsalme, A.; Alzaqri, N.; Alsaleh, A.; Siddiqui, M. R. H.; Alotaibi, A.; Kozhevnikova, E. F.; Kozhevnikov, I. V. Efficient Ni–Mo Hydrodesulfurization Catalyst Prepared through Keggin Polyoxometalate. Appl. Catal. B Environ. 2016, 182, 102–108. (221) Espinoza-Armenta, Y.; Cruz-Reyes, J.; Paraguay-Delgado, F.; Del Valle, M.; Alonso, G.; Fuentes, S.; Romero-Rivera, R. CoMoW Sulfide Nanocatalysts for the HDS of DBT from Novel Ammonium and Alkyltrimethylammonium-Thiomolybdatethiotungstate-Cobaltate (II) Precursors. Appl. Catal. A Gen. 2014, 486, 62–68. (222) Zhang, C.; Li, P.; Liu, X.; Liu, T.; Jiang, Z.; Li, C. Morphology-Performance Relation of (Co)MoS2 Catalysts in the Hydrodesulfurization of FCC Gasoline. Appl. Catal. A Gen. 2018, 556, 20–28. (223) Liang, J.; Wu, M.; Wei, P.; Zhao, J.; Huang, H.; Li, C.; Lu, Y.; Liu, Y.; Liu, C. Efficient Hydrodesulfurization Catalysts Derived from Strandberg P–Mo–Ni Polyoxometalates. J. Catal. 2018, 358, 155–167.


Page 95 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(224) Liang, J.; Wu, M.; Wang, J.; Wei, P.; Sun, B.; Lu, Y.; Sun, D.; Liu, Y.; Liu, C. A New Approach to Construct a Hydrodesulfurization Catalyst from a Crystalline Precursor: Ligand-Induced Self-Assembly, Sulfidation and Hydrodesulfurization. Catal. Sci. Technol. 2018, 8 (24), 6330–6345. (225) Larabi, C.; Nielsen, P. K.; Helveg, S.; Thieuleux, C.; Johansson, F. B.; Brorson, M.; Quadrelli, E. A. Bulk Hydrodesulfurization Catalyst Obtained by Mo(CO)6 Grafting on the Metal–Organic Framework Ni2(2,5-Dihydroxoterephthalate). ACS Catal. 2012, 2 (4), 695– 700. (226) Badoga, S.; Mouli, K. C.; Soni, K. K.; Dalai, A. K.; Adjaye, J. Beneficial Influence of EDTA on the Structure and Catalytic Properties of Sulfided NiMo/SBA-15 Catalysts for Hydrotreating of Light Gas Oil. Appl. Catal. B Environ. 2012, 125, 67–84. (227) Santolalla-Vargas, C. E.; Suárez Toriello, V. A.; de los Reyes, J. A.; Cromwell, D. K.; Pawelec, B.; Fierro, J. L. G. Effects of PH and Chelating Agent on the NiWS Phase Formation in NiW/γ-Al2O3 HDS Catalysts. Mater. Chem. Phys. 2015, 166, 105–115. (228) Chen, J.; Maugé, F.; El Fallah, J.; Oliviero, L. IR Spectroscopy Evidence of MoS2 Morphology Change by Citric Acid Addition on MoS2/Al2O3 Catalysts – A Step Forward to Differentiate the Reactivity of M-Edge and S-Edge. J. Catal. 2014, 320, 170–179. (229) Li, H.; Li, M.; Chu, Y.; Liu, F.; Nie, H. Essential Role of Citric Acid in Preparation of Efficient NiW/Al2O3 HDS Catalysts. Appl. Catal. A Gen. 2011, 403 (1–2), 75–82. (230) Santolalla-Vargas, C. E.; Santes, V.; Ortega-Niño, C.; Hernández-Gordillo, A.; SanchezMinero, F.; Lartundo-Rojas, L.; Borja-Urby, R.; López-Curiel, J. C.; Goiz, O.; PadillaMartinez, I. I. Effect of Trimesic Acid as Chelating Agent in Sulfided CoMoP/γ-Al2O3 95 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 96 of 100

Catalyst for Hydrodesulfurization of Straight-Run Gas Oil. Catal. Today 2018. (231) Palcheva, R.; Kaluža, L.; Dimitrov, L.; Tyuliev, G.; Avdeev, G.; Jirátová, K.; Spojakina, A. NiMo Catalysts Supported on the Nb Modified Mesoporous SBA-15 and HMS: Effect of Thioglycolic Acid Addition on HDS. Appl. Catal. A Gen. 2016, 520, 24–34. (232) Kruk, M. Access to Ultralarge-Pore Ordered Mesoporous Materials through Selection of Surfactant/Swelling-Agent Micellar Templates. Acc. Chem. Res. 2012, 45 (10), 1678–1687. (233) Song, S.; Zhou, X.; Duan, A.; Zhao, Z.; Chi, K.; Zhang, M.; Jiang, G.; Liu, J.; Li, J.; Wang, X. Synthesis of Mesoporous Silica Material with Ultra-Large Pore Sizes and the HDS Performance of Dibenzothiophene. Microporous Mesoporous Mater. 2016, 226, 510–521. (234) Zhao, J.; Yin, Y.; Li, Y.; Chen, W.; Liu, B. Synthesis and Characterization of Mesoporous Zeolite Y by Using Block Copolymers as Templates. Chem. Eng. J. 2016, 284, 405–411. (235) Xu, J.; Huang, T.; Fan, Y. Highly Efficient NiMo/SiO2-Al2O3 Hydrodesulfurization Catalyst Prepared from Gemini Surfactant-Dispersed Mo Precursor. Appl. Catal. B Environ. 2017, 203, 839–850. (236) Zhang, H.; Sun, J.; Ma, D.; Weinberg, G.; Su, D. S.; Bao, X. Engineered Complex Emulsion System: Toward Modulating the Pore Length and Morphological Architecture of Mesoporous Silicas. J. Phys. Chem. B 2006, 110 (51), 25908–25915. (237) Chandra Mouli, K.; Soni, K.; Dalai, A.; Adjaye, J. Effect of Pore Diameter of Ni–Mo/AlSBA-15 Catalysts on the Hydrotreating of Heavy Gas Oil. Appl. Catal. A Gen. 2011, 404 (1–2), 21–29. (238) Mandal, M.; Kruk, M. Versatile Approach to Synthesis of 2-D Hexagonal Ultra-Large-Pore 96 ACS Paragon Plus Environment

Page 97 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Periodic Mesoporous Organosilicas. J. Mater. Chem. 2010, 20 (35), 7506. (239) Zhou, X.; Song, S.; Duan, A.; Zhao, Z.; Gong, Y.; Wang, X.; Li, J.; Wei, Y.; Jiang, G.; Liu, J. Synthesis of Al-Containing Spherical Mesocellular Silica Foams with Different Pore Sizes and Their Applications as Catalyst Supports for Hydrodesulfurization of Dibenzothiophene. ChemCatChem 2015, 7 (13), 1948–1960. (240) Zhou, W.; Wei, Q.; Zhou, Y.; Liu, M.; Ding, S.; Yang, Q. Hydrodesulfurization of 4,6Dimethyldibenzothiophene over NiMo Sulfide Catalysts Supported on Meso-Microporous Y Zeolite with Different Mesopore Sizes. Appl. Catal. B Environ. 2018, 238, 212–224. (241) Huirache-Acuña, R.; Alonso-Núñez, G.; Paraguay-Delgado, F.; Lara-Romero, J.; Berhault, G.; Rivera-Muñoz, E. M. Unsupported Trimetallic CoMoW Sulfide HDS Catalysts Prepared by in Situ Decomposition of Sulfur-Containing Precursors. Catal. Today 2015, 250, 28–37. (242) Romero, L.; Del Valle, M.; Romero-Rivera, R.; Alonso, G.; Ávalos-Borja, M.; Fuentes, S.; Paraguay-Delgado,

F.;

Cruz-Reyes,

J.

MoS2catalysts

Derived

from

N-

Methylenediammonium Thiomolybdates during HDS of DBT. Catal. Today 2015, 250, 66– 71. (243) Guo, K.; Ding, Y.; Yu, Z. One-Step Synthesis of Ultrafine MoNiS and MoCoS Monolayers as High-Performance Catalysts for Hydrodesulfurization and Hydrodenitrogenation. Appl. Catal. B Environ. 2018, 239, 433–440. (244) Song, W.; Lai, W.; Chen, Z.; Cao, J.; Wang, H.; Lian, Y.; Yang, W.; Jiang, X. Fabrication of 3D Porous Hierarchical NiMoS Flowerlike Architectures for Hydrodesulfurization Applications. ACS Appl. Nano Mater. 2018, 1 (1), 442–454. 97 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 98 of 100

(245) Mansouri, A.; Semagina, N. Colloidal Synthesis Protocol of Shape- and DimensionallyControlled Transition-Metal Chalcogenides and Their Hydrodesulfurization Activities. ACS Appl. Nano Mater. 2018, 1 (9), 4408–4412. (246) Oyama, S. T.; Gott, T.; Zhao, H.; Lee, Y.-K. Transition Metal Phosphide Hydroprocessing Catalysts: A Review. Catal. Today 2009, 143 (1–2), 94–107. (247) Chen, X.; Wang, J.; Yang, K.; Meng, C.; Williams, C. T.; Liang, C. Structure Investigation and Dibenzothiophene Hydrodesulfurization Properties of Fe-Substituted Ni–Si Intermetallics. J. Phys. Chem. C 2015, 119 (52), 29052–29061. (248) Skrabalak, S. E.; Suslick, K. S. On the Possibility of Metal Borides for Hydrodesulfurization. Chem. Mater. 2006, 18 (13), 3103–3107. (249) Song, L.; Zhang, S.; Wei, Q. A New Route for Synthesizing Nickel Phosphide Catalysts with High Hydrodesulfurization Activity Based on Sodium Dihydrogenphosphite. Catal. Commun. 2011, 12 (12), 1157–1160. (250) Guan, Q.; Cheng, X.; Li, R.; Li, W. A Feasible Approach to the Synthesis of Nickel Phosphide for Hydrodesulfurization. J. Catal. 2013, 299, 1–9. (251) Layan Savithra, G. H.; Muthuswamy, E.; Bowker, R. H.; Carrillo, B. A.; Bussell, M. E.; Brock, S. L. Rational Design of Nickel Phosphide Hydrodesulfurization Catalysts: Controlling Particle Size and Preventing Sintering. Chem. Mater. 2013, 25 (6), 825–833. (252) Wang, K.; Yang, B.; Liu, Y.; Yi, C. Preparation of Ni2P/TiO2−Al2O3 and the Catalytic Performance for Hydrodesulfurization of 3-Methylthiophene. Energy & Fuels 2009, 23 (9), 4209–4214.


Page 99 of 100 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(253) Cecilia, J. A.; Infantes-Molina, A.; Rodríguez-Castellón, E.; Jiménez-López, A. The Influence of the Support on the Formation of Ni2P Based Catalysts by a New Synthetic Approach. Study of the Catalytic Activity in the Hydrodesulfurization of Dibenzothiophene. J. Phys. Chem. C 2009, 113 (39), 17032–17044. (254) Chen, T.; Yang, B.; Li, S.; Wang, K.; Jiang, X.; Zhang, Y.; He, G. Ni 2 P Catalysts Supported on Titania-Modified Alumina for the Hydrodesulfurization of Dibenzothiophene. Ind. Eng. Chem. Res. 2011, 50 (19), 11043–11048. (255) Bussell, M. E. New Methods for the Preparation of Nanoscale Nickel Phosphide Catalysts for Heteroatom Removal Reactions. React. Chem. Eng. 2017, 2 (5), 628–635. (256) Chen, X.; Li, M.; Guan, J.; Wang, X.; Williams, C. T.; Liang, C. Nickel–Silicon Intermetallics with Enhanced Selectivity in Hydrogenation Reactions of Cinnamaldehyde and Phenylacetylene. Ind. Eng. Chem. Res. 2012, 51 (9), 3604–3611. (257) Chen, X.; Zhao, A.; Shao, Z.; Li, C.; Williams, C. T.; Liang, C. Synthesis and Catalytic Properties for Phenylacetylene Hydrogenation of Silicide Modified Nickel Catalysts. J. Phys. Chem. C 2010, 114 (39), 16525–16533. (258) Zhao, A.; Zhang, X.; Chen, X.; Guan, J.; Liang, C. Cobalt Silicide Nanoparticles in Mesoporous Silica as Efficient Naphthalene Hydrogenation Catalysts by Chemical Vapor Deposition. J. Phys. Chem. C 2010, 114 (9), 3962–3967. (259) Vlasenko, N. V.; Ilchenko, N. I. Catalytic Activity of Transition Metal Silicides in Hydrogen Oxidation. React. Kinet. Catal. Lett. 1988, 36 (1), 189–193. (260) Imamura, H.; Wallace, W. E. Methanation Activity of Catalysts Formed by Treating


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 100 of 100

Intermetallic Compounds Nickel-Silicon (Ni5Si2), Nickel-Silicon (Ni2Si), and CobaltSilicon (Co2Si) with Oxygen. J. Phys. Chem. 1979, 83 (25), 3261–3264. (261) Yoo, J. S. Metal Recovery and Rejuvenation of Metal-Loaded Spent Catalysts. Catal. Today 1998, 44 (1–4), 27–46. (262) A. W. Searcy, D. V. R. and U. C. Chemical and Mechanical Behavior of Inorganic Materials, Ed.; Wiley-Interscience , New York, 1970. (263) Garten, J. J. B. and R. L. R. B. Levy, in Advanced Materials in Catalysis, Ed.; Academic Press, New York, 1977. (264) Dufresne, P. Hydroprocessing Catalysts Regeneration and Recycling. Appl. Catal. A Gen. 2007, 322 (SUPPL.), 67–75. (265) Connétable, D.; Thomas, O. First-Principles Study of Nickel-Silicides Ordered Phases. J. Alloys Compd. 2011, 509 (6), 2639–2644. (266) Chen, X.; Liu, X.; Wang, L.; Li, M.; Williams, C. T.; Liang, C. High Sulfur Tolerance of Ni–Si Intermetallics as Hydrodesulfurization Catalysts. RSC Adv. 2013, 3 (6), 1728–1731. (267) Chen, X.; Wang, X.; Xiu, J.; Williams, C. T.; Liang, C. Synthesis and Characterization of Ferromagnetic Nickel–Cobalt Silicide Catalysts with Good Sulfur Tolerance in Hydrodesulfurization of Dibenzothiophene. J. Phys. Chem. C 2012, 116 (47), 24968– 24976. (268) Yang, K.; Chen, X.; Qi, J.; Bai, Z.; Zhang, L.; Liang, C. A Highly Efficient and SulfurTolerant Pd2Si/CNTs Catalyst for Hydrodesulfurization of Dibenzothiophenes. J. Catal. 2019, 369, 363–371. 100 ACS Paragon Plus Environment

Advanced hydrodesulfurization catalysts: A review of design and

Recommend Documents