Hydroprocessing Catalysts Containing Noble Metals: Deactivation

Review pubs.acs.org/EF

Hydroprocessing Catalysts Containing Noble Metals: Deactivation, Regeneration, Metals Reclamation, and Environment and Safety Meena Marafi† and Edward Furimsky*,‡ †

Petroleum Refining, Petroleum Research and Studies Centre, Kuwait Institute for Scientific Research, P.O. Box 24885, 13109 Safat, Kuwait ‡ IMAF Group, 184 Marlborough Avenue Ottawa, Ontario K1N 8G4, Canada ABSTRACT: Interest in the use of catalysts containing noble metals (NMs) in various hydroprocessing (HPR) applications is the result of an increasing volume of unconventional feeds and a continuous change in performance parameters of petroleum products. Conventional HPR catalysts can only partially fulfill new requirements. The high price of NMs and their high activity under both reducing and oxidative atmospheres require some modifications of the strategies that have been used for the handling of spent conventional HPR catalysts. Because of their higher activity, the deactivation of NMs-containing catalysts during HPR occurs under less severe conditions compared with that of conventional HPR catalysts. However, adverse effects of sulfur, nitrogen, oxygenates, and metals in feeds may require a higher severity to achieve HPR objectives. The activity of spent NMscontaining catalysts can be almost completely recovered by regeneration. The oxidative regeneration of spent NMs-containing catalysts has been performed commercially, while reductive and extractive regenerations offer alternative routes. The high value of NMs dictates that metal recovery is the only option if an adequate catalyst activity recovery cannot be achieved by regeneration. The methods are available for NMs recovery on an industrial scale. Also, the research aiming at improvement of metals recovery via existing methods as well as development novel methods has been noted.

1. INTRODUCTION Conventional hydroprocessing (HPR) catalysts comprise active metals such as Mo and W combined with Co and Ni promoters on various supports, among which γ-Al2O3 has been by far predominant. Gradually, novel supports that vary widely in surface acidity and textural properties have been incorporated for the preparation of conventional HPR catalysts. An extensive database covering all aspects of conventional HPR catalysts is available in the literature.1−8 Special attention has been paid to the spent conventional HPR catalysts.9−13 In this case, the focus has been on deactivation, regeneration, and environmental and safety aspects, as well as metal reclamation. HPR of unconventional feeds, i.e., biofeeds, the syncrude from Fischer−Tropsch synthesis (FTS), light tight oils, and coal-derived liquids (CDLs), requires catalyst formulations that differ from those of conventional catalysts. Thus, for the former, primary reactions occurring during HPR differ from those occurring during the HPR of conventional feeds. While hydro-desulfurization (HDS), hydro-denitrogenation (HDN), and hydrogenation (HYD) are the main reactions during the HPR of conventional distillate feeds, hydro-deoxygenation (HDO), hydroisomerization (HIS), hydrocracking (HCR), and ring opening (RO) are the primary reactions occurring during the HPR of novel feeds.8 Typical HPR conditions that have been observed in most of the studies conducted over conventional HPR catalysts include the temperature range of 250−400 °C and H2 pressure range of 1−10 MPa.1−9 Because of the higher activity of HPR catalysts containing noble metals (NMs), lower operating severity, i.e., 100−350 °C and 0.1−5 MPa, has been noted.13−16 The main focus of this Review is on NMs-containing catalysts on various supports used for the HPR of distillate feeds to produce fuels © 2017 American Chemical Society

and lubricants. Information on the use of NMs-containing catalysts for the HYD of various reactants below 100 °C and atmospheric H2 is rather extensive. This includes NMssupported catalysts, NMs alloys, and organometallic NMscontaining catalysts. The primary objective has been the production of chemicals with a wide range of commercial applications. Contrary to HPR, the use of NMs in organic chemistry has been receiving attention for decades as indicated by early books published by Rylander17 and Bond.18 In most of these studies, rather mild conditions (e.g., less than 100 °C, atmospheric H2) have been employed. Such catalysts are not the objective of this Review. Unconventional catalysts used for the HPR of novel feeds, which are the focus of the present Review, contain NMs combined with supports varying widely in surface acidity. The NMs used for the preparation of unconventional HPR catalysts include platinum group metals (PGMs), i.e., platinum, palladium, ruthenium, rhodium, iridium, and osmium as well as rhenium, which is not a PGM. It should be noted that in various discussions, NMs are referred to as “precious metals”, while the term “noble metals” has been adopted for the purpose of this Review. So far, gold and silver have not been used as active metals under HPR conditions. However, interest in these metals may be anticipated in the future. Information on the development and testing of the NMscontaining catalysts is rather extensive.14−16 This includes bifunctional catalysts on acidic supports (e.g., silica−alumina, zeolites, etc.) and those on traditional supports such as γ-Al2O3 Received: February 16, 2017 Revised: May 8, 2017 Published: May 9, 2017 5711

DOI: 10.1021/acs.energyfuels.7b00471 Energy Fuels 2017, 31, 5711−5750

Review

Energy & Fuels

For such bifunctionality, the catalyst must facilitate deHYD/ HYD functions and, at the same time, supply protons necessary for the HIS, HCR, and RO reactions.23−31 The mechanism in Figure 1 is used to illustrate the role of catalytic sites over bifunctional catalysts.31 In this scheme, C

and SiO2. Neutral carbon supports have been actively evaluated particularly for the preparation of NMs-containing catalyst for the HPR of biofeeds. In this case, the catalyst stability in the presence of water requires a special attention. The patent literature showed that some lanthanides (e.g., ytterbium, holmium, yttrium, cerium, and europium) were used in combination with NMs. 19−22 But, no information on corresponding spent catalysts was published. A great variety of NMs-containing catalyst formulations have been evaluated for HPR applications. In the present Review, these catalysts are divided into four groups: 1. NMs on acidic supports (bifunctional catalysts) 2. NMs on γ-Al2O3 support 3. NMs on other oxidic supports 4. NMs on carbon supports In spite of the extensive database on various aspects of the NMs containing HPR catalysts, a comprehensive review focusing on their deactivation as well as properties of the corresponding spent catalysts, utilization options of spent catalysts, and environmental and safety aspects has not yet been published. Because of the high value of the metals present in these catalysts, regeneration for reuse and reclamation of metals from the spent catalysts appear to be the only options. However, other aspects (e.g., toxicity, flammability, leachability, etc.) require attention as well.11 Therefore, the safety during storage and transportation of the spent unconventional HPR catalysts has to be addressed in accordance with the regulations issued by environmental and safety authorities.

Figure 1. Mechanism of hydroisomerization of n-hexane. Reprinted with permission from ref 31. Copyright 1887 Elsevier B.V.

and O denote alkanes and olefins, respectively. The mechanism was based on the results obtained during the HCR-HIS of straight chain hydrocarbons over several Pt catalysts on acidic supports. In this case, the deHYD/HYD steps 1 and 5 occur on Pt metals, whereas acidic support supplied proton for step 2. The deHYD step occurring on Pt is necessary to initiate protonation of intermediate. The transformation of carbocation via step 3 was assumed to be the rate limiting step. The final stabilization of intermediate via HYD occurs on Pt as part of the step 5. During HCR-HIS, the acidity of bifunctional catalysts (supplied by acidic support) must be properly balanced to maintain the HCR at an optimal level and to ensure a desirable level of HIS. The approach used for preparation of bifunctional catalysts to obtain an optimal acid sites distribution was described in detail in the studies published by Samad et al.32,33 A bifunctional catalyst exhibiting a good activity and selectivity for simultaneous HIS and HCR requires the optimization of the acidic sites. For example, a catalyst with predominantly medium and weak acid sites may exhibit a high activity for HIS, but its activity for HCR may be rather low.34 To various degrees, other HPR reactions occur in parallel with HIS and HCR reactions. This suggests that the origin of the feed and the properties of anticipated products have to be taken into consideration while designing bifunctional catalysts for HIS/HCR. A wide range of catalysts have been developed and tested for the HIS of n-paraffins and n-olefins.8 These catalysts were dominated by different combinations of active metals (e.g., Pt and Pd) with zeolites, although during the early stages of research amorphous silica−alumina (ASA) and active clays were also receiving attention. Silica−alumina phosphate (SAPO) molecular sieves, SZ- and tungstated zirconia (TZ)supported catalysts have been attracting interests as well.8 The chlorinated conventional γ-Al2O3 exhibited bifunctionality as well.30 The shape selectivity of acidic supports must ensure that unbranched n-alkanes and n-alkenes can enter pores of a medium size, while the diffusion rate of branched paraffins into pores should be low. For example, during the HPR of heavy vacuum gas oil over Pt/zeolite-β, diffusion limitations became insignificant when diameter of channels approached 50 nm.35 Under such conditions, the effective diffusion coefficient inside the crystals of the zeolite was 2 × 10−14 cm2/g. Detailed accounts on preparation, characterization, and testing of bifunctional Pt catalysts on various acidic supports were given by Miller et al.36 with attention being payed to activity, shape selectivity, and surface acid sites distribution.

2. PROPERTIES AND APPLICATIONS OF HYDROPROCESSING CATALYSTS CONTAINING NOBLE METALS Unconventional HPR catalysts containing NMs have been developed and used in various petroleum refining techniques. In this regard, in the most advanced stages are bifunctional catalysts as well as the catalysts supported on γ-Al2O3 and carbons. Among the metals, Pt and Pd have attracted the most attention. To a lesser extent, other NMs in combination with a wide range of different supports have been included in the research on novel unconventional HPR catalysts. The HYD activity of all NMs metals exceeds that of conventional metals. However, a desirable activity and selectivity for other HPR reactions, e.g., HCR, HIS, RO, and HDO, requires a combination with suitable support. In this regard, the acidity and stability of supports are of primary interest. For the catalyst preparation, a wide range of acidity such as exhibited by neutral carbon supports on one hand and very acidic supports, e.g., silica−alumina, zeolites, sulfated zirconia (SZ), etc., on the other have been evaluated. In addition, the type of support is crucial for ensuring stability of NMs-supported catalysts in the presence of water. Rather extensive data on the properties and applications of HPR catalysts containing NMs can be found in the scientific literature.23−31 Because this database can be readily accessed, only brief account of relevant information is given. 2.1. Bifunctional Catalysts. Bifunctional catalysts have been used for the HIS of n-alkanes and n-alkenes to corresponding isomers as well as for the HCR of large molecules (e.g., waxes, resins, and asphaltenes) to distillates. Also, hydro-dearomatization (HDAr) via RO has attracted attention.8 Bifunctionality of any catalyst can be achieved if an acidic support is combined with either transition metal or NMs. 5712


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catalysts for the HPR of residual feeds may not be justified because of the high cost of NMs and rapid catalyst deactivation.47 2.2. Noble Metals Supported on γ-Al2O3. Besides acidic supports discussed above, γ-Al2O3 has been used most frequently. Because of their relatively low acidity, the bifunctionality of the NMs-containing catalysts supported on γ-Al2O3 is less evident compared with those on the acidic supports. The NMs-containing catalysts supported on γ-Al2O3 have been used commercially in petroleum refining applications.48 For example, during the lubricants production, the primary product of dewaxing may require additional hydrofinishing and/or dehazing to ensure that the properties of base oil are in line with specifications of commercial lubricants. Because of their high HYD activity, the unconventional catalysts containing NMs are the most suitable for the final refining step. Therefore, besides conventional and bifunctional HPR catalysts, other types of catalysts are being part of the integrated dewaxing operations as part of a multistage process, i.e., catalytic reactors comprising several layers of different catalysts, several sections in the same vessel, or several reactors connected in a series.8,49 During the production of transportation fuels, a final step may be required to attain the content of aromatics prescribed by specifications. Pt and Pd catalysts supported on γ-Al2O3 are suitable for such applications. Similarly, the removal of aromatics followed by RO may be necessary to attain performance parameters of fuels. In the case of a multistage process, the HYD of feed must precede the RO step usually conducted over bifunctional catalysts. Pt and Pd catalysts supported on γ-Al2O3 have been tested during the HPR of various biofeeds and corresponding Ocontaining model compounds.48 For most part, the tests were of a relatively short duration. Thus, a long-term performance of these catalysts has not been determined in spite of the fact that the presence of H2O (either in the biofeed or as the HDO product) and other oxygenates (e.g., CO and CO2) may affect the catalyst’s stability. Thus, potential deactivation due to the hydrolysis of γ-Al2O3 to boehmite requires attention. Nevertheless, it has been noted that the information on properties of spent Pt and Pd catalysts supported on γ-Al2O3 used during the HPR of biofeeds has been part of several studies. This includes the factors causing catalyst deactivation. Also, the conditions for catalyst regeneration for reuse have been receiving attention. 2.3. Noble Metals on Other Oxidic Supports. In an attempt to improve the performance of the NMs-containing catalysts, other oxides (e.g., SiO2, TiO2, ZrO2, MgO, etc.) have been evaluated as potential supports. It has been generally observed that NMs-containing catalysts on these supports have been evaluated together with the NMs supported on γ-Al2O3. It is believed that with respect to catalyst stability, particularly the resistance to hydrolysis of support, some of these oxides may be more suitable supports than γ-Al2O3. However, so far, little attention has been paid to corresponding spent catalysts. Apparently, the novel NMs-containing catalysts are still in a stage of development rather than being evaluated on a larger scale. 2.4. Noble Metals on Carbon Supports. Various forms of carbon (e.g., activated carbon (AC), carbon blacks, carbon nanomaterials, graphene, etc.) have been used as supports for the preparation of the NMs-containing catalysts. The information on the use of carbon-supported catalysts in a

During the testing of bifunctional catalysts, activity and selectivity were determined using both model compounds and real feeds. For comparison, the studies in which different types of catalysts were tested under identical conditions are of a particular importance.37,38 The H2 pressure varied between atmospheric and ∼6 MPa, whereas temperatures varied between 100 and 400 °C. Among zeolites, a high selectivity was achieved using the medium pore size ZSM-5 zeolite and Pt/MOR.39,40 In practical situation, bifunctional catalysts have been used for improving the performance parameters of diesel fuel and lube base oil.41,42 Having the highest cetane number and viscosity index, n-paraffins are desirable components of diesel fuels and lubricants, respectively. Unfortunately, n-paraffins have to be removed from both fuels and lubricants because of their undesirable cold flow behavior, i.e., high cloud point, pour point, and freezing point. By converting n-paraffins to iparaffins cetane number of diesel fuel and viscosity index of lube base oil are affected, but they are still much higher than those of aromatic and naphthenic compounds. At the same time, the melting point of n-paraffins is significantly decreased, i.e., from +35 to −15 °C for C20 n-paraffin and the C20 isoparaffin containing a 5-methyl substituent, respectively. Figure 2 shows similar trends in the decreasing freezing points of nalkanes to corresponding iso-alkanes during the HIS over bifunctional catalysts.8

Figure 2. Freezing point of linear (□), 2-methyl (■), 3-methyl (●), 4methyl (▲), and dimethyl (×) branched C9−C15 alkanes. Reprinted with permission from ref 8. Copyright 2010 Royal Society of Chemistry.

Bifunctional catalysts are also used for catalytic reforming of heavy naphtha.43,44 On a commercial scale, Pt and Re on acidic supports such as SiO2-Al2O3 and chlorinated γ-Al2O3 have been used as catalysts. However, the operating temperature approaching 500 °C is far too high compared with the HPR conditions that are the subject of this Review. The production of fuels from unconventional feeds (light tight oils, FTS syncrude, biofeeds, CDLs, etc.) via HPR requires bifunctional catalysts as it was emphasized by Ruddy et al.45 The intermediate long-chain alkanes and alkenes produced during the HPR of some biofeeds, e.g., those derived from algae and vegetable oils, must be converted to corresponding isomers. RO in aromatics is required to decrease the content of aromatics in CDL and biocrude obtained from lignocellulosic sources. In this regard, detailed accounts of bifunctional catalysts in biofeeds upgrading applications were given recently by Robinson et al.46 It is believed that using NMs-containing 5713


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Energy & Fuels Table 1. Compositions of Tight Oils and Reference Conventional Crudes (wt%) tight oils C H H/C S N O a

biocrude

FT syncrude

Bekkam

Eagle Ford

algae liquefaction

algae pyrolysis

vegetable oil origin

wood pyrolysis

low-temp FTS

high-temp FTS

CDLa

85.4 13.6 1.92 0.19 0.04 374 °C and >221 bar), carbon became soluble in the supercritical water, while inorganics remained insoluble. The commercial process is based on Chematur Engineering’s SCWO process, Aqua Critox.253,254 In this process, the slurry enters the reactor where high-pressure oxygen is injected to reach temperature of ∼600 °C. The organic material is converted to CO2 and H2O. At the same time, metals are converted to their oxides. After cooling and separation of combustion products, solids are sent for further processing, which may involve a treatment with NaBH4 to obtain metallic Pt or Pd. The flowchart of the current version of the process, referred to as the AquaCat process, is shown in Figure 38.253 The commercial process such as Tetronics’ DC Plasma Arc is one of the most advanced pyrometallurgical technology for the recovery of NMs from spent catalysts.255 In this case, spent catalyst is mixed with a melting-point-lowering additive and melted in a furnace to give a mixed bath of molten slag, molten metals droplets, and solid metal particles. The droplets and particles of metal sink under gravity and settle out to form a pool of molten metal at the base of the furnace. The Umicore process in a commercial operation in Belgium can recover NMs from various solid wastes including spent catalysts.229,256,257 The essential part of this process is the smelter, where NMs in spent catalysts are separated from other metals. In the smelter, a submerged lanced combustion technology is applied. In this case, the oxygen enriched air is injected into the molten bath of metals. This follows by copper leaching and electrowinning. The residue containing highly concentrated NMs is further processed to recover more than 95% of NMs content in spent catalysts.

metallurgical process developed by Batista and Afonso.251 It involved fusion of the de-coked and ground spent catalysts with KHSO4 at about 450 °C for 3 h using the spent catalyst/flux mass ratio of 1/10. The fused mass obtained under these conditions was dissolved in water, while all Pt remained concentrated in the insoluble solid residue. More than 99% of Pt present in spent catalysts could be recovered using this method. 5.2.5. Metal Recovery by Chlorination. Other metal reclamation process is based on the gas-phase volatilization of precious metals using the Cl-containing agents such as AlCl3, CCl4, mixture of CO + Cl2, and phosgene.233 In this method, Pt and Pd are selectively chlorinated to volatile products, which on cooling condense. Apparently, the main constraints of this method is the handling of toxic agents and products. Piskulov and Chiu252 described the process for the isolation of NMs from spent catalysts by chlorination in the presence of polyamine resin. In this case, NMs were dissolved on chlorination and adsorbed on the resin, while other metals remained in solution. The metal loaded resin was then separated from the solution, combusted to isolate NMs in high purity. In another approach, NMs were separated from transition metals present in a complex solution by precipitation using tetramethylammonium chloride. 5.2.6. Commercial Processes. The processes used for commercial recovery of NMs from spent catalysts employ a wide variety of equipment and procedures, i.e., rotary and crucible furnaces, kilns, roasters, pulverizers, granulators, screens, blenders, dissolvers, precipitators, electrolytic cells, etc. Using state-of-the art technology, up to 95% of the NMs content of spent catalysts and other NMs-containing spent materials can be recovered. In this regard, an extensive experience and/or information on metal reclamation from automotive catalysts and similar solids have been noted. After some modifications, these methods can be applied to the spent NMs-containing HPR catalysts after some modifications.10,230 The commercial recovery of Pd and Pt from spent catalysts on carbon supports involved the preparation of water slurry with dispersed catalysts particles of 5−800 μm size.220 The

6. SAFETY AND ENVIRONMENT The environmental and safety aspects of spent conventional HPR catalysts removed from catalytic reactors at the end of operation were discussed in details in the Handbook of Spent Hydroprocessing Catalysts.11 Similarly, after being unloaded from the reactor, spent NMs-containing catalysts must be handled 5742


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conventional HPR catalysts should be noted. First of all, milder operating conditions during HPR and only trace quantities of contaminants (sulfur, nitrogen, asphaltenes and metals) in the feeds, combined with a high HYD activity of NMs as active metals, ensure a much higher reactivity of coke on spent NMs-containing catalysts compared with conventional HPR catalysts. Thus, the coke on spent catalyst surface, particularly in the vicinity of active NMs might be very reactive because of a low aromaticity.93 Most likely, such coke possesses a high concentration of sites that are very active for oxygen chemisorption.258 Consequently, the pyrophoric nature of coke is much greater than that of the coke on spent conventional HPR catalysts. The portion of NMs in spent catalysts may be in a reduced form. In such a form, metals can act as active sites for oxygen chemisorption. Therefore, both coke and metals in spent NMscontaining HPR catalysts exhibit a high reactivity to oxygen. On the other extreme, i.e., under reducing conditions, NMs can form clusters with hydrogen.179 Such clusters may be present in spent catalyst unless they were subjected to a special pretreatment. Then, if present, these structures would react rapidly on the exposure to air. Therefore, much more precautions have to be taken during handling, storage, transportation, and disposal and particularly during the unloading of such catalysts from reactor, compared with spent conventional HPR catalysts. For example, the flammability of spent Pd/Al2O3 catalyst was significantly decreased by a treatment with steam and air after process streams were removed and the reactor was flushed with an inert gas.201 Similarly as for pyrophoric properties, there is little information on the behavior of spent NMs-containing catalysts during the contact with water alone and/or in combination with air and water. The standard methods for determining the leachability of spent NMs-containing catalysts and their toxicity levels while in an aqueous solution have not yet been applied.259 This may be attributed to the high value of NMs. Thus, rather than to dispose of, such spent catalysts are of a much greater interest to both refining companies and metal reclaiming companies compared with spent conventional HPR catalysts. From environmental and safety points of view, special attention must be paid during pyrometallurgical treatment of spent catalysts that contain highly volatile metallic components. Also, some components formed on oxidation may have high vapor pressures. In such cases, pyrometallurgical process must be equipped with complex system for the removal of unwanted volatile components from gaseous stream before they are discharged to environment. If an incineration to destroy carbonaceous portion of spent catalysts is part of the overall NMs recovery process, the subsequent scrubbing of waste gases to remove environmentally hazardous species (e.g., dioxins) is necessary. The need for such system was identified in the case of the commercial NMs reclamation process such as AquaCat process employing SCWO for removing organic carry-overs from spent catalysts.253,254

according to the procedures prescribed by environmental and health authorities. Compared with spent conventional HPR catalysts, the high recyclability of the spent NMs-containing catalysts reduces their environmental impacts by orders of magnitude. For example, the amount of the latter generated by petroleum refineries is much smaller compared with that of the spent conventional HPR catalysts. In addition, a much higher economic value of NMs than that of conventional metals is the reason for some differences between the handling of corresponding spent catalysts. For example, disposal in landfills sometimes practiced for spent conventional HPR catalysts has never been considered for spent NMs-containing catalysts. Nevertheless, these catalysts are considered as an important resource of NMs rather than the solid waste. Thus, the inventory of spent NMs-containing catalysts has been always thoroughly maintained. A reputable company should be selected for all stages of handling of spent NMs-containing catalysts to ensure environmental acceptance and safety.217,218 First of all, the records must show that the company has been obeying all applicable environmental laws and regulations, before the selection is made. In the United States, these requirements are spelled out by the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA), also known as the Superfund Act. This Act emphasizes joint petroleum refiner-metal reclaimer responsibility as well as the future liability to avoid serious financial and legal consequences. For example, a NMs reclaiming company must operate contaminants removal equipment, e.g., 1. Thermal oxidation systems with properly scaled afterburners to ensure complete combustion of organic contaminant effluents. 2. Neutralizing equipment for liquid effluents including water-treatment plant. 3. Pollution-control systems to minimize discharge of pollutants to atmosphere. In practical situation, the shut-down of operation is the beginning of the handling of spent NMs-containing catalysts. This step can be performed in the reactor by replacing feed streams with a suitable solvent for spent catalyst de-oiling. At the end of de-oiling step, the flow of solvent is replaced by the flow of an inert gas (e.g., N2). In situ passivation of spent catalyst, i.e., treatment with diluted air and steam, may enhance safety during the next handling stages.201 At a safe temperature, the reactor is opened, and the spent catalyst is removed and transferred into specially designed containers. Depending on the agreement between petroleum refinery and regeneration and/or metal reclamation company, an accurate analysis of the metal content in spent NMs-containing catalyst is performed either on the refinery site or by the latter. Special requirements for transboundary transportation of spent NMs-containing HPR catalysts have been in effect.216 These regulations are spelled out as part of the Basel Convention agreement, where waste solids are listed as either green or amber. Green listed spent catalysts comprise only NMs, while amber listed spent catalysts contain additional solid contaminants. For the transportation of green listed catalysts, only notification to the authorities of the country involved is needed, whereas for the amber listed materials, the consent of the relevant authority must be obtained. With respect to safety, the difference between the properties of spent NMs-containing HPR catalysts and those of

7. CONCLUSIONS Decades of utilization of catalysts containing noble metals (NMs) for reforming of distillate feeds provides a basis for understanding aspects of deactivation and regeneration of the spent hydroprocessing (HPR) catalysts containing NMs. For conventional distillate feeds, NMs on various supports have been used commercially. For such feeds, coke deposition on the 5743


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Energy & Fuels catalyst surface and the presence of sulfur, nitrogen, and aromatics are the main causes of catalyst deactivation. Because of the high cost of NMs, regeneration and metals reclamation are the only two options for utilization of the corresponding spent catalysts. An extensive database of scientific literature confirmed that supported NMs-containing catalysts can play a major role during the HPR of unconventional feeds (e.g., biofeeds, FTS syncrude, light tight oil, etc.) to gasoline and diesel fractions. Advancement in improving the resistance and/or stability of the NMs-containing catalysts in the presence of oxygenates (e.g., H2O, CO, and CO2) have been made. Spent catalysts from these applications can be regenerated for reuse in the same or different operations. However, catalyst deactivation due to the agglomeration as well as leaching of NMs requires attention. Research has shown that such adverse effects can be minimized by the alloying of NMs with either another NM or transition metals. Also, the method of catalyst preparation and selection of support can enhance the stability of HPR catalysts containing NMs. Higher reactivity and solubility of coke on spent NMscontaining catalysts favor non-oxidative regeneration. Thus, the catalyst activity recovery can be achieved by reductive and extractive regenerations. Efficiency of the latter can be enhanced significantly under supercritical conditions. In spite of promising results found in the literature, these methods have not yet been utilized industrially.

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TGA = thermal gravimetric analysis TPD = temperature-programmed desorption TPO = temperature-programmed oxidation TPR = temperature-programmed reduction TZ = tungstated zirconia WHSV = weight hourly space velocity XRD = X-ray diffraction

REFERENCES

(1) Topsoe, H.; Clausen, B. S.; Massoth, F. E. Hydrotreating Catalysis. In Catalysis: Anderson, J. R., Boudart, M., Eds.; Science and Technology Vol. 11; Springer-Verlag: Berlin Heidelberg, 1996; p 1. (2) Massoth, F. E. Characterization of molybdena catalysts. Adv. Catal. 1979, 27, 265. (3) Prins, R. Catalytic hydrodenitrogenation. Adv. Catal. 2001, 46, 399. (4) Furimsky, E. Catalytic hydrodeoxygenation. Appl. Catal., A 2000, 199, 147. (5) Stanislaus, A.; Cooper, B. H. Aromatics hydrogenation catalysis: Review. Catal. Rev.: Sci. Eng. 1994, 36, 75. (6) Trimm, D. L. Stud. Surf. Sci. Catal. 1989, 53, 41. (7) Furimsky, E.; Massoth, F. E. Hydrodenitrogenation of petroleum. Catal. Rev.: Sci. Eng. 2005, 47, 297. (8) De Klerk, A.; Furimsky, E. Catalysis in Refining Fischer−Tropsch Syncrude; RSC Publishing: Cambridge, UK, 2010. (9) Furimsky, F.; Massoth, F. E. Regeneration of hydroprocessing catalysts. Catal. Today 1993, 17, 537. (10) Furimsky, F. Spent refinery catalysts: Environment, Safety and Utilization. Catal. Today 1996, 30, 223. (11) Marafi, M.; Stanislaus, A.; Furimsky, E. Handbook of Spent Hydroprocessing Catalysts; Elsevier: Amsterdam, The Netherlands, 2010. (12) Marafi, M.; Stanislaus, A. Resources, Spent catalyst waste management: A review: Part IDevelopments in hydroprocessing catalyst waste reduction and use. Conserv. Recyc. J. 2008, 52, 859−873. (13) Marafi, M.; Stanislaus, A. Resources, Spent hydroprocessing catalyst management: A review: Part II. Advances in metal recovery and safe disposal methods. Conserv. Recyc. J. 2008, 53, 1. (14) Houzvicka, J.; Ponec, V. Skeletal isomerization of n-butene. Catal. Rev.: Sci. Eng. 1997, 39, 319−344. (15) Travers, C. In Petroleum Refining, Vol. 3: Conversion Processes; Leprince, P., Ed.; Technip: Paris, 2001; p 229. (16) Cusher, N. A. In Handbook of Petroleum Refining Processes; Meyers, R. A., Ed.; McGraw-Hill: New York, 2004. (17) Rylander, P. N. Catalytic hydrogenation over platinum metals; Academic Press: San Diego, CA, 1967. (18) Bond, G. C. Metal-catalysed reactions of hydrocarbons; Springer: Berlin, 2005. (19) Gillespie, R. D. Isomerization catalyst and processes. U.S. Patent 6,818,589, Nov 2004. (20) Gillespie, R. D. Solid-acid isomerization catalyst and process. U.S. Patent 7,041,866, May 2006. (21) Gillespie, R. D. Isomerization catalyst and processes. U.S. Patent 6,977,322, Dec 2005. (22) Vassilakis, J. G.; Rosin, R. R.; Bradley, S. A.; Gillespie, R. D.; Cohn, M. J.; Xu, F. High-activity isomerization catalyst and process. U.S. Patent 7,015,175, May 2006. (23) Schulz, H. F.; Weitkamp, J. Prospects for obtaining high quality fuels from the hydrocracking of a hydrotreated scrap tires pyrolysis oil. Ind. Eng. Chem. Prod. Res. Dev. 1972, 11, 46−53. (24) Santos, R. C. R.; Valentini, A.; Lima, C. L.; Filho, J. M.; Oliveira, J. M. Modifications of an HY zeolite for n-octane hydroconversion. Appl. Catal., A 2011, 403, 65−74. (25) Shakun, A. N.; Fedorova, M. L. Isomerization of light gasoline fractions: The efficiency of different catalysts and technologies. Catal. Industry 2014, 6, 298. (26) Tijsebaert, B.; Henry, M.; Gies, H.; Xiao, F.-S.; Zhang, W.; Bao, X.; Imai, H.; Tatsumi, T.; Müller, U.; Yilmaz, B.; Jacobs, P.; De Vos, D.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Edward Furimsky: 0000-0003-1150-9067 Notes

The authors declare no competing financial interest.

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ABBREVIATIONS AC = activated carbon ASA = amorphous silica−alumina BT = benzothiophene CDL = coal-derived liquid DBT = dibenzothiophene FTS = Fischer−Tropsch synthesis HCR = hydrocracking HDAr = hydro-dearomatization HDCl = hydro-dechlorination HDN = hydro-denitrogenation HDO = hydro-deoxygenation HDS = hydro-desulfurization HIS = hydroisomerization HMS = hexagonal molecular sieve HPR = hydroprocessing HYD = hydrogenation MOR = mordenite NM = noble metal PGM = platinum group metal RO = ring opening SAPO = silica−alumina phosphate (molecular sieves) SCWO = supercritical water oxidation STEM = scanning transmission electron microscopy SZ = sulfated zirconia TEM = transmission electron microscopy 5744


Review

Energy & Fuels

(50) Serp, P.; Figueiredo, J. L. Carbon materials for catalysis; Wiley: Weinheim, 2009. (51) Furimsky, E. Carbons and carbon supported catalysts in hydroprocessing; RSC Publishing: Cambridge, UK, 2008. (52) Pérez-Mayoral, E.; Calvino-Casilda, V.; Soriano, E. Metalsupported carbon-based materials: opportunities and challenges in the synthesis of valuable products. Catal. Sci. Technol. 2016, 6, 1265−1291. (53) Hita, I.; Cordero-Lanzac, T.; Gallardo, A.; Arandes, J. M.; Rodríguez-Mirasol, J.; Bilbao, J.; Cordero, T.; Castaño, P. Phosphoruscontaining activated carbon as acid support in a bifunctional Pt−Pd catalyst for tire oil hydrocracking. Catal. Commun. 2016, 78, 48−51. (54) Furimsky, E. Properties of tight oils and selection of catalysts for hydroprocessing. Energy Fuels 2015, 29, 2043−2058. (55) Lemus, J.; Bedia, J.; Calvo, L.; Simakova, I. L.; Murzin, D. Y.; Etzold, B. J. M.; Rodriguez, J. J.; Gilarranz, M. A. Improved synthesis and hydrothermal stability of Pt/C catalysts based on size-controlled nanoparticles. Catal. Sci. Technol. 2016, 6, 5196−5206. (56) Breysse, M.; Furimsky, E.; Kasztelan, S.; Lacroix, M.; Perot, G. Hydrogen activation by transition metals sulfides. Catal. Rev.: Sci. Eng. 2002, 44, 651. (57) Harvey, T. G.; Matheson, T. W. Hydroprocessing catalysis by supported ruthenium sulphide. J. Catal. 1986, 101, 253−261. (58) Eijsbouts, S.; de Beer, V. H. J.; Prins, R. Periodic trends in the hydrodenitrogenation activity of carbon-supported transition metal sulfide catalysts. J. Catal. 1988, 109, 217−220. (59) Eijsbouts, S.; de Beer, V. H. J.; Prins, R. Hydrodenitrogenation of quinoline over carbon-supported transition metal sulfides. J. Catal. 1991, 127, 619−630. (60) Eijsbouts, S.; Sundhakar, C.; de Beer, V. H. J.; Prins, R. Hydrodenitrogenation of decahydroquinoline, cyclohexylamine and Opropylaniline over carbon-supported transition metal sulfide catalysts. J. Catal. 1991, 127, 605−618. (61) Cattenot, M.; Portefaix, J. L.; Afonso, J.; Breysse, M.; Lacroix, M.; Perot, G. Mechanism of carbon-nitrogen bond scission on unsupported transition metal sulfides. J. Catal. 1998, 173, 366−373. (62) Portefaix, J. L.; Cattenot, M.; Guerriche, M.; Breysse, M. Mechanism of carbon-nitrogen bond cleavage during amylamine hydrodenitrogenation over a sulphided NiMo/Al2O3 catalyst. Catal. Lett. 1991, 9, 127−132. (63) Chianelli, R. R.; Berhault, G.; Raybaud, P.; Kasztelan, S.; Hafner, J.; Toulhoat, H. Periodic trends in hydrodesulfurization: in support of the Sabatier principle. Appl. Catal., A 2002, 227, 83−96. (64) Raje, A. P.; Liaw, S. J.; Srinivansan, R.; Davis, B. H. Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha I. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen. Appl. Catal., A 1997, 150, 297−318. (65) Liaw, S. J.; Raje, A. P.; Thomas, G. A.; Davis, B. H. Second row transition metal sulfides for the hydrotreatment of coal derived naphtha III. Removal of individual nitrogen compounds. Appl. Catal., A 1997, 150, 343−364. (66) Liaw, S. J.; Lin, R.; Raje, A. P.; Davis, B. H. Hydrotreatment of coal- derived naphtha. Properties of zeolite-supported Ru sulfide catalysts. Appl. Catal., A 1997, 151, 423−435. (67) Hart, A.; Omajali, J. B.; Murray, A. J.; Macaskie, L. E.; Greaves, M.; Wood, J. Comparison of the effects of dispersed noble metal (Pd) biomass supported catalysts with typical hydrogenation (Pd/C, Pd/ Al2O3) and hydrotreatment catalysts (CoMo/Al2O3) for in-situ heavy oil upgrading with Toe-to-Heel Air Injection (THAI). Fuel 2016, 180, 367−376. (68) Furimsky, E. Hydroprocessing in aqueous phase. Ind. Eng. Chem. Res. 2013, 52, 17695−17713. (69) Bailón-García, E.; Carrasco-Marín, F.; Pérez-Cadenas, A. F.; Maldonado-Hodar, F. J. Influence of the Pt-particle size on the performance of carbon supported catalysts used in the hydrogenation of citral. Catal. Commun. 2016, 82, 36−40. (70) Zeng, Y.; Wang, Z.; Lin, W.; Song, W.; Christensen, J. M.; Jensen, A. D. Hydrodeoxygenation of phenol over Pd catalysts by in-

Exploring the void structure and activity of RUB-39 based expanded materials using the hydroconversion of decane. J. Catal. 2011, 282, 47. (27) Larsen, G.; Petkovic, L. M. Effect of preparation method and selective poisoning on the performance of platinum supported on tungstated zirconia catalysts for alkane isomerization. Appl. Catal., A 1996, 148, 155. (28) Larsen, G.; Lotero, E.; Raghavan, S.; Parra, R. D.; Querini, C. A. A study of platinum supported on tungstated zirconia catalysts. Appl. Catal., A 1996, 139, 201. (29) Liu, Y.; Murata, K.; Sakanishi, K. A study of platinum supported on tungstated zirconia catalysts. Fuel 2011, 90, 3056. (30) Skotak, M.; Karpinski, Z. C6-alkane conversion over γ-alumina supported palladium and platinum catalysts. Chem. Eng. J. 2002, 90, 89. (31) Allain, J. F.; Magnoux, P.; Schulz, P.; Guisnet, M. Hydroisomerization of n-hexane over platinum mazzite and platinum mordenite catalysts kinetics and mechanism. Appl. Catal., A 1997, 152, 221−235. (32) Samad, J. E.; Blanchard, J.; Sayag, C.; Louis, C.; Regalbuto, J. R. Mechanism of carbon-nitrogen bond scission on unsupported transition metal sulfides. J. Catal. 2016, 342, 203−212. (33) Samad, J. E.; Blanchard, J.; Sayag, C.; Louis, C.; Regalbuto, J. R. The controlled synthesis of metal-acid bifunctional catalysts: Selective Pt deposition and nanoparticle synthesis on amorphous aluminosilicates. J. Catal. 2016, 342, 213−225. (34) Pines, H. Chemistry of catalytic hydrocarbon conversion; Academic Press: New York, 1981. (35) Landau, M. V.; Vradman, L.; Valtchev, V.; Lezervant, J.; Liubich, E.; Talianker, M. Hydrocracking of heavy vacuum gas oil with a Pt/Hbeta−Al2O3 catalyst: Effect of zeolite crystal size in the nanoscale range. Ind. Eng. Chem. Res. 2003, 42, 2773−2782. (36) Miller, S. J.; Lacheen, H. S.; Chen, C.-Y. Determining the strength of Brønsted acid sites for hydrodewaxing over shape-selective catalysts. Ind. Eng. Chem. Res. 2016, 55, 6760−6767. (37) Girgis, M. J.; Tsao, Y. P. Impact of catalyst metal-acid balance in n-hexadecane hydroisomerization and hydrocracking. Ind. Eng. Chem. Res. 1996, 35, 386−396. (38) O’Young, C. L.; Xu, W. Q.; Simon, M.; Suib, S. L. Stud. Surf. Sci. Catal. 1994, 84, 1671−1676. (39) Bendoraitis, J. G.; Chester, A. W.; Dwyer, F. G.; Garwood, W. E. Proceedings of the 7th International Zeolite Conference, Tokyo, 1986; p 669. (40) Chen, N. Y.; Garwood, W. E. High boiling and premium quality jet fuels by catalytic dewaxing and hydrogenation. Ind. Eng. Chem. Prod. Res. Dev. 1986, 25, 641−645. (41) Bertram, R.; Danzinger, F. NPRA Annual Meeting, San Antonio, TX, March 1994; M-94−50. (42) Furimsky, E. Catalysts for upgrading heavy petroleum feeds. Stud. Surf. Sci. Catal. 2007, 169, 12. (43) Sterba, M.J.; Haensel, V. Catalytic reforming. Ind. Eng. Chem. Prod. Res. Dev. 1976, 15, 2−17. (44) Lapinski, M.; Baird, L.; James, J. In Handbook of Petroleum Refining Processes; Meyers, R. A., Ed.; McGraw-Hill: New York, 2004; p 4.3. (45) Ruddy, D. A.; Schaidle, J. A.; Ferrell, J. R., III; Wang, J.; Moens, L.; Hensley, J. E. Recent advances in heterogeneous catalysts for biooil upgrading via “ex situ catalytic fast pyrolysis”: catalyst development through the study of model compounds. Green Chem. 2014, 16, 454− 490. (46) Robinson, A. M.; Hensley, J. E.; Medlin, J. W. Bifunctional catalysts for upgrading of biomass-derived oxygenates: A Review. ACS Catal. 2016, 6, 5026−5043. (47) Dik, P. P.; Klimov, O. V.; Danilova, I. G.; Leonova, K. A.; Pereyma, V. Y.; Budukva, S. V.; Uvarkina, D. D.; Kazakov, M. O.; Noskov, A. S. Composition of stack bed for VGO hydrocracking with maximum diesel yield. Catal. Today 2016, 271, 154. (48) Furimsky, E. Hydroprocessing challenges in bio-fuels production. Catal. Today 2013, 217, 13. (49) Weitkamp, J. Erdoel Kohle Erdgas. Petrochem. 1978, 31, 13. 5745


Review

Energy & Fuels situ generated hydrogen from aqueous reforming of formic acid. Catal. Commun. 2016, 82, 46−49. (71) Raut, A. N.; Nandanwar, S. U.; Suryawanshi, Y. R.; Chakraborty, M.; Jauhari, S.; Mukhopadhyay, S.; Shenoy, K. T.; Bajaj, H. C. Liquid phase selective hydrogenation of phenol to cyclohexanone over Ru/ Al2O nanocatalyst under mild conditions. Kinet. Catal. 2016, 57, 39− 46. (72) De Souza, P. M.; Rabelo-Neto, R. C.; Borges, L. E. P.; Jacobs, G.; Davis, B. H.; Graham, U. M.; Resasco, D. E.; Noronha, F. B. Effect of zirconia morphology on hydrodeoxygenation of phenol over Pd/ ZrO2. ACS Catal. 2015, 5, 7385−7398. (73) Roy, S.; Datta, S. Hydrogenation of toluene on zirconiummodified hexagonal molecular sieves-supported platinum and palladium catalysts. Ind. Eng. Chem. Res. 2013, 52, 17360−17368. (74) González, H.; Castillo, O. S.; Rico, J. L.; Gutiérrez-Alejandre, A.; Ramírez, J. Hydroconversion of 2-methylnaphthalene on Pt/ Mordenite catalysts. Reaction study and mathematical modeling. Ind. Eng. Chem. Res. 2013, 52, 2510−2519. (75) Zhou, L.; Lawal, A. Hydrodeoxygenation of microalgae oil to green diesel over Pt, Rh and presulfided NiMo catalysts. Catal. Sci. Technol. 2016, 6, 1442−1454. (76) Sanchez, S. I.; Moser, M. D.; Bradley, S. A. Mechanistic study of Pt− Re/γ-Al2O3 catalyst deactivation by chemical imaging of carbonaceous deposits using advanced X-ray detection in scanning transmission electron microscopy. ACS Catal. 2014, 4, 220−228. (77) De Souza, P. M.; Rabelo-Neto, R. C.; Borges, L. E. P.; Jacobs, G.; Davis, B. H.; Resasco, D. E.; Noronha, F. B. Hydrodeoxygenation of phenol over Pd catalysts. Effect of support on reaction mechanism and catalyst deactivation. ACS Catal. 2017, 7, 2058−2073. (78) Regali, F.; Liotta, L. F.; Venezia, A. M.; Montes, V.; Boutonnet, M.; Järås, S. Effect of metal loading on activity, selectivity and deactivation behavior of Pd/silica−alumina catalysts in the hydroconversion of n- hexadecane. Catal. Today 2014, 223, 87−96. (79) Busto, M.; Grau, J. M.; Sepulveda, J. H.; Tsendra, O. M.; Vera, C. R. Hydrocracking of long paraffins over Pt−Pd/WO3−ZrO2 in the presence of sulfur and aromatic impurities. Energy Fuels 2013, 27, 6962−6972. (80) Busto, M.; Grau, J. M.; Canavese, S.; Vera, C. R. Simultaneous hydroconversion of n-hexane and benzene over Pt/WO3−ZrO2 in the presence of sulfur impurities. Energy Fuels 2009, 23, 599−606. (81) Lenoi, C.; Rohr, F.; Allahverdiev, A.; Stocker, M.; Ruiz, P. Stud. Surf. Sci. Catal. 2004, 154, 2371. (82) Foo, G. S.; Rogers, A. K.; Yung, M. M.; Sievers, C. Steric effect and evolution of surface species in the hydrodeoxygenation of bio-oil model compounds over Pt/HBEA. ACS Catal. 2016, 6, 1292−1307. (83) Pichaikaran, S.; Arumugam, P. Vapour phase hydrodeoxygenation of anisole over ruthenium and nickel supported mesoporous aluminosilicate. Green Chem. 2016, 18, 2888−2899. (84) Campelo, J. M.; Lafont, F.; Marinas, J. M. Hydroconversion of n- dodecane over Pt/SAPO-11 catalyst. Appl. Catal., A 1998, 170, 139−144. (85) Castaño, P.; Gutiérrez, A.; Hita, I.; Arandes, J. M.; Aguayo, A. T.; Bilbao, J. Deactivating species deposited on Pt−Pd catalysts in the hydrocracking of light-cycle oil. Energy Fuels 2012, 26, 1509−1519. (86) Gutiérrez, A.; Arandes, J. M.; Castaño, P.; Aguayo, A. T.; Bilbao, J. Role of acidity in the deactivation and steady hydroconversion of light cycle oil on noble metal supported catalysts. Energy Fuels 2011, 25, 3389−3399. (87) Hita, I.; Rodríguez, E.; Olazar, M.; Bilbao, J.; Arandes, J. M.; Castano, P. Prospects for obtaining high quality fuels from the hydrocracking of a hydrotreated scrap tires pyrolysis oil. Energy Fuels 2015, 29, 5458−5466. (88) Kuznetsova, L. N.; Kazbanova, A. V.; Kuznetsov, P. N.; Tarasova, L. S. Activity of the Pt/WO42−/ZrO2 catalyst in hydroisomerization reaction of n-heptane-benzene mixture. Pet. Chem. 2015, 55, 57−62. (89) Galiasso-Tailleur, R. Catalyst deactivation during upgrade of light catalytic cracking gas oil to ultralow-sulfur and low-aromatic diesel. Energy Fuels 2008, 22, 1509−1518.

(90) Galiasso Tailleur, R. Low-emission diesel production by upgrading LCO plus SR diesel fractions. Catal. Today 2008, 130, 492−500. (91) Galiasso Tailleur, R. Deactivation of WNiPd/TiO2Al2O3 catalyst during the upgrading of LCO. Fuel 2008, 87, 2551−2562. (92) Zhou, L.; Lawal, A. Evaluation of presulfided NiMo/γ-Al2O3 for hydrodeoxygenation of microalgae oil to produce green diesel. Energy Fuels 2015, 29, 262−272. (93) Zanuttini, M. S.; Peralta, M. A.; Querini, C. A. Deoxygenation of m-cresol: Deactivation and regeneration of Pt/γ-Al2O3 catalysts. Ind. Eng. Chem. Res. 2015, 54, 4929−4939. (94) González, C.; Marin, P.; Díez, F. V.; Ordóñez, S. Hydrodeoxygenation of acetophenone over supported precious metal catalysts at mild conditions: Process optimization and reaction kinetics. Energy Fuels 2015, 29, 8208−8215. (95) González, C.; Marín, P.; Díez, F. V.; Ordoñez, S. Gas-Phase hydrodeoxygenation of benzaldehyde, benzyl alcohol, phenyl acetate, and anisole over precious metal catalysts. Ind. Eng. Chem. Res. 2016, 55, 2319−2327. (96) Speight, J. G. The Chemistry and Technology of Petroleum; CRC Press: Boca Raton, FL, 2014. (97) Ravanchi, M. T.; Sahebdelfar, S. Pd-Ag/Al2O3 catalyst: Stages of deactivation in tail-end acetylene selective hydrogenation. Appl. Catal., A 2016, 525, 197−203. (98) Hollak, S. A. W.; de Jong, K. P.; van Es, D. S. Catalytic deoxygenation of fatty acids: Elucidation of the inhibition process. ChemCatChem 2014, 6, 2648−2655. (99) Ftouni, J.; Muñoz-Murillo, A.; Goryachev, A.; Hofmann, J. P.; Hensen, E. J. M.; Lu, L.; Kiely, C. J.; Bruijnincx, P. C. A.; Weckhuysen, B. M. ZrO2 is preferred over TiO2 as support for the Ru-catalyzed hydrogenation of levulinic acid to γ-valerolactone. ACS Catal. 2016, 6, 5462−5472. (100) Di, L.; Yao, S.; Li, M.; Wu, G.; Dai, W.; Wang, G.; Li, L.; Guan, N. Selective catalytic hydrogenolysis of carbon-carbon σ bonds in primary aliphatic alcohols over supported metals. ACS Catal. 2015, 5, 7199−7207. (101) Nimmanwudipong, T.; Aydin, C.; Lu, J.; Runnebaum, R. C.; Brodwater, K. C.; Browning, N. D.; Block, D. E.; Gates, B. C. Selective hydrodeoxygenation of guaiacol catalyzed by platinum supported on magnesium oxide. Catal. Lett. 2012, 142, 1190−1196. (102) Di, L.; Yao, S.; Song, S.; Wu, G.; Dai, W.; Guan, N.; Li, L. Robust ruthenium catalysts for the selective conversion of stearic acid to diesel- range alkanes. Appl. Catal., B 2017, 201, 137−149. (103) Savage, P. E. J. Supercrit. Fluids 2009, 47, 407−414. (104) Liu, B. Y.; Bai, F.; Zhu, C.-C.; Yuan, P. Q.; Cheng, Z.-M.; Yuan, W.-K. Upgrading of residual oil in sub- and supercritical water: An experimental study. Fuel Process. Technol. 2013, 106, 281. (105) Huber, C. G. W.; Cortright, R. D.; Dumesic, J. A. Renewable Alkanes by Aqueous-Phase Reforming of Biomass-Derived Oxygenates. Angew. Chem., Int. Ed. 2004, 43, 1549−1551. (106) Gao, D.; Schweitzer, C.; Hwang, H. T.; Varma, A. Conversion of guaiacol on noble metal catalysts: Reaction performance and deactivation studies. Ind. Eng. Chem. Res. 2014, 53, 18658−18667. (107) Ledoux, M. J.; Djellouli, D. Hydrodenitrogenation activity and selectivity of well-dispersed transition metal sulfides of the second row on activated carbon. J. Catal. 1989, 115, 580−590. (108) Chang, J.; Danuthai, T.; Dewiyanti, S.; Wang, C.; Borgna, A. Hydrodeoxygenation of guaiacol over carbon-supported metal catalysts. ChemCatChem 2013, 5, 3041−3049. (109) Madsen, A. T.; Rozmysłowicz, B.; Mäki-Arvela, P.; Simakova, I. L.; Eränen, P.; Murzin, D. Y.; Fehrmann, R. Deactivation in continuous deoxygenation of C18-Fatty feedstock over Pd/Sibunit. Top. Catal. 2013, 56, 714−724. (110) Wang, H.; Wang, Y. Characterization of deactivated bio-oil hydrotreating catalysts. Top. Catal. 2016, 59, 65−72. (111) Wang, Z.; Adhikari, S.; Valdez, P.; Shakya, R.; Laird, C. Upgrading of hydrothermal liquefaction biocrude from algae grown in municipal wastewater. Fuel Process. Technol. 2016, 142, 147. 5746


Review

Energy & Fuels (112) Ahmadi, S.; Yuan, Z.; Rohani, S.; Xu, C. Effects of nanostructured CoMo catalysts on hydrodeoxygenation of fast pyrolysis oil in supercritical ethanol. Catal. Today 2016, 269, 182−194. (113) Mäki-Arvela, P.; Martin, G.; Simakova, I.; Tokarev, A.; Wärnå, J.; Hemming, J.; Holmbom, B.; Salmi, T.; Murzin, D. Y. Chem. Eng. J. 2009, 154, 45. (114) Vonortas, A.; Papayannakos, N. Upgrading of hydrothermal liquefaction biocrude from algae grown in municipal wastewater. Fuel Process. Technol. 2016, 150, 126. (115) York, A. P. E.; Pham-Huu, C.; Del Gallo, P.; Blekkan, A. E.; Ledoux, M. J. Comparative effect of organosulfur compounds on catalysts for the n- heptane isomerization reaction at medium pressure: Mo2C-oxygen- modified, MoO3-carbon-modified, Pt/γ-Al2O3, and Pt/ β-zeolite catalysts. Ind. Eng. Chem. Res. 1996, 35, 672−682. (116) Chorfa, N.; Hamoudi, S.; Arul, J.; Belkacemi, K. Sulfur promotion in conjugated isomerization of safflower oil over bifunctional structured Rh/SBA-15 catalysts. ChemCatChem 2013, 5, 1917− 1934. (117) Kim, H. J.; Song, C. Enhancing sulfur tolerance of Pd catalysts by hydrogen spillover with two different zeolite supports for lowtemperature hydrogenation of aromatics. Energy Fuels 2014, 28, 6788− 6792. (118) He, T.; Wang, Y.; Miao, P.; Li, J.; Wu, J.; Fang, Y. Fuel 2013, 106, 365. (119) Martínez, A.; Arribas, M. A.; Pergher, S. B. C. Bifunctional noble metal/zeolite catalysts for upgrading low-quality diesel fractions via selective opening of naphthenic rings. Catal. Sci. Technol. 2016, 6, 2528−2542. (120) Del Gallo, P.; Pham-Huu, C.; York, A. P. E.; Ledoux, M. J. Comparison of the effects of nitrogen poisoning on molybdenum oxycarbide and Pt/β-zeolite catalysts in the isomerization of n-heptane. Ind. Eng. Chem. Res. 1996, 35, 3302−3310. (121) Yu, Y.; Fonfe, B.; Jentys, A.; Haller, G. L.; van Veen, J. A. R.; Gutiérrez, O. Y.; Lercher, J. A. Bimetallic Pt−Pd/silica−alumina hydrotreating catalysts − Part I: Physicochemical characterization. J. Catal. 2012, 292, 1−12. (122) Yu, Y.; Fonfé, B.; Jentys, A.; Haller, G. L.; van Veen, J. A. R.; Gutierrez, O. Y.; Lercher, J. A. Bimetallic Pt−Pd/silica−alumina hydrotreating catalysts. Part II: Structure−activity correlations in the hydrogenation of tetralin in the presence of dibenzothiophene and quinolone. J. Catal. 2012, 292, 13−25. (123) Williams, M. F.; Fonfé, B.; Jentys, A.; Breitkopf, C.; van Veen, J. A. R.; Lercher, J. A. J. Phys. Chem. C 2010, 114, 14532. (124) Gutiérrez, O. Y.; Yu, Y.; Kolvenbach, R.; Haller, G. L.; Lercher, J. A. Hydrogenation of tetralin over Pt catalysts supported on sulfated zirconia and amorphous silica alumina. Catal. Sci. Technol. 2013, 3, 2365−2372. (125) Miller, S. J. Studies on Wax Isomerization for Lubes and Fuels. Stud. Surf. Sci. Catal. 1994, 84, 2319−2326. (126) Vallés, V. A.; Ledesma, B. C.; Pecchi, G. A.; Anunziata, O. A.; Beltramone, A. R. Hydrogenation of tetralin in presence of nitrogen using a noble-bimetallic couple over a Ti-modified SBA-15. Catal. Today 2017, 282, 111−122. (127) Guedes, A. S.; Fontaine, C.; Bouchy, C.; Brunet, S. Inhibiting effect of decan-1-ol on the transformation of n-hexadecane over a Pt/ SiO2-Al2O3 catalyst. Appl. Catal., B 2010, 100, 165−172. (128) Guedes, A. S.; Bouchy, C.; Brunet, S. Inhibiting effect of decanoic acid and its by-products on the transformation of nhexadecane over a Pt/SiO2- Al2O3 catalyst. Appl. Catal., B 2016, 192, 311−324. (129) Pritchard, J.; Ciftci, A.; Verhoeven, M. W. G. M.; Hensen, E. J. M.; Pidko, E. A. Supported Pt-Re catalysts for the selective hydrogenation of methyl and ethyl esters to alcohols. Catal. Today 2017, 279, 10−18. (130) Sun, K.; Wilson, A. R.; Thompson, S. T.; Lamb, H. H. Catalytic Deoxygenation of octanoic acid over supported palladium: Effects of particle size and alloying with gold. ACS Catal. 2015, 5, 1939−1948.

(131) Yoon, J. S.; Choi, J.-W; Suh, D. J.; Lee, K.; Lee, H.; Ha, J.-M. Water- assisted selective hydrodeoxygenation of lignin-derived guaiacol to monooxygenates. ChemCatChem 2015, 7, 2669−2674. (132) Narita, T.; Miura, M.; Ohira, M.; Hondou, H.; Sugiyama, K.; Matsuda, T.; Gonzalez, R. D. The effect of reduction temperature on the chemisorptive properties of Ru/Al2O3: Effect of chlorine. Appl. Catal. 1987, 32, 185−190. (133) Martin-Martinez, M.; Á lvarez-Montero, A.; Gómez-Sainero, L. M.; Baker, R. T.; Palomar, J.; Omar, S.; Eser, S.; Rodriguez, J. J. Deactivation behavior of Pd/C and Pt/C catalysts in the gas-phase hydrodechlorination of chloromethanes: Structure−reactivity relationship. Appl. Catal., B 2015, 162, 532−543. (134) Martin-Martinez, M.; Gómez-Sainero, M.; Palomar, J.; Omar, S.; Rodriguez, J. J. Dechlorination of dichloromethane by hydrotreatment with bimetallic Pd-Pt/C catalyst. Catal. Lett. 2016, 146, 2614− 2621. (135) Infantes-Molina, A.; Moretti, E.; Segovia, E.; Lenarda, A.; Rodríguez-Castellón, E. Pd-Nb binfunctional catalysts supported on silica and zirconium phosphate heterostructures for O-removal of dibenzofurane. Catal. Today 2016, 277, 143−151. (136) Vicerich, M. A.; Sánchez, M. A.; Benitez, V. M.; Pieck, C. L. Pretreatment temperature influence on the selective ring opening of decalin on Pt− Ir/TiO2 catalysts. Catal. Lett. 2017, 147, 758−764. (137) Patil, N. M.; Bhanage, B. M. Greener, recyclable, and reusable ruthenium(III) chloride/polyethylene glycol/water system for the selective hydrogenation of biomass-derived levulinic acid to γvalerolactone. ChemCatChem 2016, 8, 3458−3462. (138) Pushkarev, V. V.; An, K.; Alayoglu, S.; Beaumont, S. K.; Somorjai, G. A. Hydrogenation of benzene and toluene over size controlled Pt/SBA-15 catalysts: Elucidation of the Pt particle size effect on reaction kinetics. J. Catal. 2012, 292, 64−72. (139) Simakova, I.; Simakova, O.; Mäki-Arvela, P.; Simakov, A.; Estrada, M.; Murzin, D. Y. Deoxygenation of palmitic and stearic acid over supported Pd catalysts: Effect of metal dispersion. Appl. Catal., A 2009, 355, 100−106. (140) Shen, J.; Semagina, N. Palladium nanoparticle size effect in hydrodesulfurization of 4,6-dimethyldibenzothiophene (4,6-DMDBT). ChemCatChem 2016, 8, 2565−2571. (141) París, R. S.; L’Abbate, M. E.; Liotta, L. F.; Montes, V.; Barrientos, J.; Regali, F.; Aho, A.; Boutonnet, M.; Järås, S. Hydroconversion of paraffinic wax over platinum and palladium catalysts supported on silica− alumina. Catal. Today 2016, 275, 141− 148. (142) Priya, S. S.; Bhanuchander, P.; Kumar, V. P.; Dumbre, D. K.; Periasamy, S. R.; Bhargava, S. K.; Kantam, M. L.; Chary, K. V. R. Platinum Supported on H-Mordenite: A Highly Efficient Catalyst for Selective Hydrogenolysis of Glycerol to 1,3-Propanediol. ACS Sustainable Chem. Eng. 2016, 4, 1212−1222. (143) Priya, S. S.; Bhanuchander, P.; Kumar, V. P.; Bhargava, S. K.; Chary, K. V. R. Activity and selectivity of platinum-copper bimetallic catalysts supported on mordenite for glycerol hydrogenolysis to 1,3propanediol. Ind. Eng. Chem. Res. 2016, 55, 4461−4472. (144) De Souza, P. M.; Rabelo-Neto, R. C.; Borges, L. E. P.; Jacobs, G.; Davis, B. H.; Sooknoi, T.; Resasco, D. E.; Noronha, F. B. Role of keto intermediates in the hydrodeoxygenation of phenol over Pd on oxophilic supports. ACS Catal. 2015, 5, 1318−1329. (145) Luo, J.; Monai, M.; Yun, H.; Arroyo-Ramírez, L.; Wang, C.; Murray, C. B.; Fornasiero, P.; Gorte, R. J. The H2 pressure dependence of hydrodeoxygenation selectivities for furfural over Pt/ C catalysts. Catal. Lett. 2016, 146, 711−717. (146) Besse, X.; Schuurman, Y.; Guilhaume, N. Appl. Catal., A 2016, 524, 139. (147) Meng, Q.; Zheng, H.; Zhu, Y.; Li, Y. J. Mol. Catal. A: Chem. 2016, 421, 76. (148) Duyckaerts, N.; Trotuş, I.-T.; Swertz, A.-C.; Schüth, F.; Prieto, G. In situ hydrocracking of Fischer−Tropsch hydrocarbons: COprompted diverging reaction pathways for paraffin and α-olefin primary products. ACS Catal. 2016, 6, 4229−4238. 5747


Review

Energy & Fuels (149) Brosius, R.; Fletcher, J. C. Q. Hydrocracking under Fischer− Tropsch conditions; the effect of CO on the mass transfer resistance by metal clusters. J. Catal. 2014, 317, 318−325. (150) Luo, Z.; Zheng, Z.; Wang, Y.; Sun, G.; Jiang, H.; Zhao, C. Hydrothermally stable Ru/HZSM-5-catalyzed selective hydrogenolysis of lignin-derived substituted phenols to bio-arenes in water. Green Chem. 2016, 18, 5845−5858. (151) Yang, J.; Li, S.; Zhang, L.; Liu, X.; Wang, J.; Pan, X.; Li, N.; Wang, A.; Cong, Y.; Wang, X.; Zhang, T. Hydrodeoxygenation of furans over Pd- FeOx/SiO2 catalyst under atmospheric pressure. Appl. Catal., B 2017, 201, 266−277. (152) Lu, M.; Zhu, J.; Li, M.; Shan, Y.; He, M.; Song, C. TiO2Modified Pd/SiO2 for catalytic hydrodeoxygenation of guaiacol. Energy Fuels 2016, 30, 6671−6676. (153) Kaylor, N.; Xie, J.; Kim, Y.-S.; Pham, H. N.; Datye, A.-K.; Lee, Y.-K.; Davis, R. J. Vapor phase deoxygenation of heptanoic acid over silica- supported palladium and palladium-tin catalysts. J. Catal. 2016, 344, 202−212. (154) Martínez, N.; García, R.; Fierro, J. L. G.; Wheeler, C.; Austin, R. N.; Gallagher, J. R.; Miller, J. T.; Krause, T. R.; Escalona, N.; Sepúlveda, C. Effect of Cu addition as a promoter on Re/SiO2 catalysts in the hydrodeoxygenation of 2-methoxyphenol as a model bio oil compound. Fuel 2016, 186, 112−121. (155) Zhang, J.; Zhao, C. Development of a bimetallic Pd-Ni/ HZSM-5 catalyst for the tandem limonene dehydrogenation and fatty acid deoxygenation to alkanes and arenes for use as biojet fuel. ACS Catal. 2016, 6, 4512−4525. (156) Luo, J.; Yun, H.; Mironenko, A. V.; Goulas, K.; Lee, J. D.; Monai, M.; Wang, C.; Vorotnikov, V.; Murray, C. B.; Vlachos, D. G.; Fornasiero, P.; Gorte, R. J. Mechanisms for high selectivity in the hydrodeoxygenation of 5-hydroxymethylfurfural over PtCo nanocrystals. ACS Catal. 2016, 6, 4095−4104. (157) Pamphile-Adrián, A. J.; Florez-Rodriguez, P. P.; Pires, M. H. M.; Perez, G.; Passos, F. B. Selective hydrogenolysis of glycerol over IrNi bimetallic catalysts. Catal. Today 2017, 289, 302−308. (158) Liu, X.; Wang, X.; Liu, Q.; Xu, G.; Li, X.; Mu, X. A sustainable process for the production of 2-methyl-1,4-butanediol by hydrogenation of biomass-derived itaconic acid. Catal. Today 2016, 274, 88−93. (159) Ye, F.; Zhang, D.; Xue, T. G.; Wang, Y.; Guan, Y. Enhanced hydrogenation of ethyl levulinate by Pd−AC doped with Nb2O5. Green Chem. 2014, 16, 3951−3957. (160) Yohe, S. L.; Choudhari, H. J.; Mehta, D. D.; Dietrich, P. J.; Detwiler, M. D.; Akatay, C. M.; Stach, E. A.; Miller, J. T.; Delgass, W. N.; Agrawal, R.; Ribeiro, F. H. High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization. J. Catal. 2016, 344, 535−552. (161) Cordero-Lanzac, T.; Palos, R.; Arandes, J. M.; Castano, P.; Rodríguez- Mirasol, J.; Cordero, T.; Bilbao, J. Stability of an acid activated carbon based bifunctional catalyst for the raw bio-oil hydrodeoxygenation. Appl. Catal., B 2017, 203, 389−399. (162) Sádaba, I.; López Granados, M.; Riisager, A.; Taarning, E. Deactivation of solid catalysts in liquid media: the case of leaching of active sites in biomass conversion reactions. Green Chem. 2015, 17, 4133−4145. (163) Besson, M.; Gallezot, P. Deactivation of metal catalysts in liquid phase organic reactions. Catal. Today 2003, 81, 547−559. (164) García-Sancho, C.; Rubio-Caballero, J. M.; Mérida-Robles, J. M.; Moreno-Tost, R.; Santamaría-González, J.; Maireles-Torres, P. Mesoporous Nb2O5 as solid acid catalyst for dehydration of D-xylose into furfural. Catal. Today 2014, 234, 119−124. (165) Agirrezabal-Telleria, I.; Requies, J.; Güemez, M. B.; Arias, P. L. Dehydration of d-xylose to furfural using selective and hydrothermally stable arenesulfonic SBA-15 catalysts. Appl. Catal., B 2014, 145, 34− 42. (166) Xiong, H.; Pham, H. N.; Datye, A. K. Hydrothermally stable heterogeneous catalysts for conversion of biorenewables. Green Chem. 2014, 16, 4627−4643.

(167) Panpranot, J.; Pattamakomsan, K.; Praserthdam, P. Deactivation of silica supported Pd catalysts during liquid-phase hydrogenation. React. Kinet. Catal. Lett. 2005, 86, 141−147. (168) Kamari, Y.; Ghiaci, M. Incorporation of TiO2 coating on a palladium heterogeneous nanocatalyst. A new method to improve reusability of a catalyst. Catal. Commun. 2016, 84, 16−20. (169) Pham, T. N.; Samikannu, A.; Rautio, R.; Juhasz, K. L.; Konya, Z.; Wärnå, J.; Kordas, K.; Mikkola, J.-P. Catalytic Hydrogenation of DXylose Over Ru Decorated Carbon Foam Catalyst in a SpinChem® Rotating Bed Reactor. Top. Catal. 2016, 59, 1165−1177. (170) Xiao, Y.; Varma, A. ACS Energy Lett. 2016, 1, 963. (171) Jęczmionek, Ł.; Kozak, M.; Badura, X.; Stępień, Z.; Ziemiański, L.; Ż ak, G.; Krasodomski, W.; Wcisło, G. Trace elements in vegetable oils after hydroconversion into advanced-generation biocomponents. Energy Fuels 2017, 31, 1536−1543. (172) Elliott, D. C.; Wang, H.; Rover, M.; Whitmer, L.; Smith, R.; Brown, R. Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover. ACS Sustainable Chem. Eng. 2015, 3, 892−902. (173) Su, W.-B.; Chen, W.-R.; Chang, J.-R. Impact of iron deposition on Pd/δ-Al2O3 in selective hydrogenation of pyrolysis gasoline. Ind. Eng. Chem. Res. 2000, 39, 4063−4069. (174) Hart, A.; Omajali, J. B.; Murray, A. J.; Macaskie, L. E.; Greaves, M.; Wood, J. Noble-bimetallic supported CMK-3 as a novel catalyst for hydrogenation of tetralin in the presence of sulfur and nitrogen. Fuel 2016, 180, 367−376. (175) Gopal, S.; Smirniotis, P. G. Deactivation behavior of bifunctional Pt/H- zeolite catalysts during cyclopentane hydroconversion. J. Catal. 2002, 205, 231−243. (176) Bauer, F.; Ficht, K.; Bertmer, M.; Einicke, W.-D.; Kuchling, T.; Gläser, R. Hydroisomerization of long-chain paraffins over nano-sized bimetallic Pt−Pd/H-beta catalysts. Catal. Sci. Technol. 2014, 4, 4045− 4054. (177) Zhu, X.; Nie, L.; Lobban, L. L.; Mallinson, R. G.; Resasco, D. E. Efficient conversion of m-cresol to aromatics on a bifunctional Pt/ HBeta catalyst. Energy Fuels 2014, 28, 4104−4111. (178) Chen, L.; Li, H.; Fu, J.; Miao, C.; Lv, P.; Yuan, Z. Catalytic hydroprocessing of fatty acid methyl esters to renewable alkane fuels over Ni/HZSM-5 catalyst. Catal. Today 2016, 259, 266−276. (179) Li, Y.; Zhang, C.; Liu, Y.; Hou, X.; Zhang, R.; Tang, X. Coke Deposition on Ni/HZSM-5 in bio-oil hydrodeoxygenation processing. Energy Fuels 2015, 29, 1722−28. (180) Yeh, T.; Linic, S.; Savage, P. E. ACS Sustainable Chem. Eng. 2014, 2, 2399. (181) Jocz, J. N.; Savage, P. E. Behavior of cholesterol and catalysts in supercritical water. Energy Fuels 2016, 30, 7937−7946. (182) Fu, J.; Lu, X.; Savage, P. E. Energy Environ. Sci. 2010, 3, 311. (183) Mao, J.; Jiang, D.; Fang, Z.; Wu, X.; Ni, J.; Li, X. Efficient hydrothermal hydrodeoxygenation of triglycerides with in situ generated hydrogen for production of diesel-like hydrocarbons. Catal. Commun. 2017, 90, 47−50. (184) Zeng, Y.; Wang, Z.; Lin, W.; Song, W.; Christensen, J. M.; Jensen, A. D. Hydrodeoxygenation of phenol over Pd catalysts by insitu generated hydrogen from aqueous reforming of formic acid. Catal. Commun. 2016, 82, 46−49. (185) Wambach, J.; Schubert, M.; Döbeli, M.; Vogel, F. Chimia 2012, 66, 706. (186) Chen, J.; Xu, Q. Hydrodeoxygenation of biodiesel-related fatty acid methyl esters to diesel-range alkanes over zeolite-supported ruthenium catalysts. Catal. Sci. Technol. 2016, 6, 7239−7251. (187) Guo, Y.; Li, Y.; Chen, J.; Chen, L. Hydrogenation of levulinic acid into γ-valerolactone over ruthenium catalysts supported on metalorganic frameworks in aqueous medium. Catal. Lett. 2016, 146, 2041− 2052. (188) Jiang, Z.; Lan, G.; Liu, X.; Tang, H.; Li, Y. Solid state synthesis of Ru− MC with highly dispersed semi-embedded ruthenium nanoparticles in a porous carbon framework for benzoic acid hydrogenation. Catal. Sci. Technol. 2016, 6, 7259−7266. 5748


Review

Energy & Fuels

(214) Loferski, P. J. Platinum Group Metals. Mineral Commodity Summaries 2014; U.S. Geological Survey: Catonsville, MD, 2014 (215) Loferski, P. J.Platinum Group Metals. Mineral Commodity Summaries 2015; U.S. Geological Survey: Catonsville, MD, 2015 (216) Hagelüken, C. In Handbook of Heterogeneous Catalysis; Ertl, G., Knozinger, H., Schuth, F., Weitkamp, G., Eds.; Wiley-VCH: Weinheim, 2008. (217) DeSantis, R. Hydroc. Proc. 2000, 79, 100-M. (218) Cook, B. M. Maximize precious metals returns from spent process catalysts. Hydroc. Proc. 2015, 94, 2. (219) Beirne, K. M. Recovery of precious metals in spent process catalysts. PharmTech.com, Aug 1, 2007; http://www.pharmtech.com/ recovery-precious-metals-spent-process-catalysts. (220) Grumett, P. Precious Metal Recovery from Spent Catalysts. Platinum Metals Rev. 2003, 47, 163−166. (221) Beirne, K. M. How to choose a refiner for your precious metals catalyst. Hydroc. Proc. 2013, 2, 9. (222) Super, J. D. The precious metal loop, costs from an operating company perspective. Top. Catal. 2010, 53, 1138−1141. (223) Rosso, J. P. Chem. Eng. Progr. 1992, 12, 66. (224) Rosso, J. P.; El Guindy, M. E. In Catalytic Naphtha Reforming; Antos, G. J., Aitani, A. M., Parera, J. M., Eds.; Marcel Dekker: New York, 1995; p 395. (225) Ondrey, G. A new petroleum-refining catalysts makes its commercial debut in reforming. Chem. Eng. 2004, 111, 13. (226) Park, K. H.; Mohapatra, D.; Reddy, B. R.; Nam, C. W. Hydrometallurgical processing and recovery of molybdenum trioxide from spent catalyst. Int. J. Miner. Process. 2006, 80, 261−265. (227) Park, K. H.; Mohapatra, D.; Reddy, B. R. Selective recovery of molybdenum from spent HDS catalyst using oxidative soda ash leach/ carbon adsorption method. J. Hazard. Mater. 2006, 138, 311−316. (228) Dong, H.; Zhao, J.; Chen, J.; Wu, Y.; Li, B. Recovery of platinum group metals from spent catalysts: A review. Int. J. Miner. Process. 2015, 145, 108−113. (229) Um ic ore Pr ecious Me ta ls Canada Inc., www. umicorepreciousmetals.com. (230) Yoo, J. S. Metal recovery and rejuvenation of metal-loaded spent catalysts. Catal. Today 1998, 44, 27−46. (231) Jha, M. K.; Lee, J.-C.; Kim, M.-S.; Jeong, J.; Kim, B.-S.; Kumar, V. Hydrometallurgical recovery/recycling of platinum by the leaching of spent catalysts: A review. Hydrometallurgy 2013, 133, 23−32. (232) Scholtz, P. Chem. Technol. 1988, 40, 451. (233) Mishra, R. K. Proceedings of the 17th Precious Metals Conference, Newport, Rhode Island, 1993; p 449. (234) Tyson, D. R.; Bautista, R. G. Leaching Kinetics of Platinum and Palladium from Spent Automotive Catalysts. Sep. Sci. Technol. 1987, 22, 1149−1167. (235) Mastny, L.; Bumbova, M.; Kalalova, E.; Svajgl, O.; Prazak, V. Chem. Prum. 1986, 36, 243. (236) Sibrell, P. L.; Atkinson, G. B. U.S. Bureau of Mines Report PB95-18172/XAB, 1995. (237) Awadalla, F. T.; Molnar, R. E., Ritcey, G. M. U.S. Patent 5,304,233, 1994. (238) de Boer, G. B. J.; Hausselaar, M. U.S. Patent 5,302,183, 1994. (239) Ezawa, N.; Inoue, H.; Takada, S.; Masuda, H. U.S. Patent 5,252,305, 1993. (240) Li, G. Q.; Konishi, S.; Saito, K.; Sugo, T. High collection rate of Pd in hydrochloric acid medium using chelating microporous membrane. J. Membr. Sci. 1994, 95, 63−69. (241) Mladenova, E.; Karadjova, I.; Tsalev, D. L. Solid-phase extraction in the determination of gold, palladium, and platinum. J. Separ. Sci. 2012, 35, 1249−1265. (242) Motaghed, M.; Mousavi, S. M.; Rastegar, S. O.; Shojaosadati, S. A. Platinum and rhenium extraction from a spent refinery catalyst using Bacillus megaterium as a cyanogenic bacterium: Statistical modeling and process optimization. Bioresour. Technol. 2014, 171, 401−409. (243) Jacobsen, R. T. Proceedings of the AIChE Spring National Meeting, Houston, TX 1993; Pep. 69c, p 12.

(189) Xu, G.; Zhang, Y.; Fu, Y.; Guo, Q. Efficient hydrogenation of various renewable oils over Ru-HAP catalyst in water. ACS Catal. 2017, 7, 1158. (190) Murata, K.; Liu, Y.; Watanabe, M. M.; Inaba, M.; Takahara, I. Hydrocracking of algae oil into aviation fuel-range hydrocarbons using a Pt−Re catalyst. Energy Fuels 2014, 28, 6999−7006. (191) Ahmadi, M.; Macias, E. E.; Jasinski, J. B.; Ratnasamy, P.; Carreon, M. A. Decarboxylation and further transformation of oleic acid over bifunctional, Pt/SAPO-11 catalyst and Pt/chloride Al2O3 catalysts. J. Mol. Catal. A: Chem. 2014, 386, 14−19. (192) Zhang, Y.; Yao, M.; Sun, G.; Gao, S.; Xu, G. Characteristics and kinetics of coked catalyst regeneration via steam gasification in a micro fluidized bed. Ind. Eng. Chem. Res. 2014, 53, 6316−6324. (193) Zhou, L.; Lawal, A. Kinetic study of hydrodeoxygenation of palmitic acid as a model compound for microalgae oil over Pt/γ-Al2O3. Appl. Catal., A 2017, 532, 40−49. (194) Marecot, P.; Peyrovi, S.; Bahloul, D.; Barbier, J. Regeneration by hydrogen treatment of bifunctional catalysts deactivated by coke deposition. Appl. Catal. 1990, 66, 181−190. (195) Dabek, L.; Swiatkowski, A.; Dziaduszek, J. Adsorption 2005, 11, 781. (196) Vallés, V.; Ledesma, B.; Juárez, J.; Gómez Costa, M.; Anunziata, O.; Beltramone, A. Noble-bimetallic supported CMK-3 as a novel catalyst for hydrogenation of tetralin in the presence of sulfur and nitrogen. Fuel 2017, 188, 155−165. (197) De Sousa, F. P.; Cardoso, C. C.; Pasa, V. M. D. The regeneration of Pt promoted SO42−−ZrO2 catalysts. Fuel Process. Technol. 2016, 143, 35−42. (198) Zhang, X.; Zong, B.; Qiao, M. AIChE J. 2009, 55, 2382. (199) Sagdeev, K. A.; Khazipov, M. R.; Galimova, A. T.; Sagdeev, A. A.; Gumerov, F. M.; Yarullin, R. S. Regeneration of an alumopalladium hydrogenation catalyst in the process of supercritical CO2 fluid extraction. Catal. Ind. 2016, 8, 1−8. (200) Dabek, L.; Swiatkowski, A.; Dziaduszek, J. Environ. Prog. 2007, 26, 360. (201) Wan, H.; Chaudhari, R. V.; Subramaniam, B. Catalytic hydroprocessing of p-cresol: Metal, solvent and mass-transfer effects. Top. Catal. 2012, 55, 129−139. (202) Zhang, J.; Zhao, C. Development of a bimetallic Pd-Ni/ HZSM-5 catalyst for the tandem limonene dehydrogenation and fatty acid deoxygenation to alkanes and arenes for use as biojet fuel. ACS Catal. 2016, 6, 4512−4525. (203) Lee, C.-L.; Jou, C.-J. G. Using low energy-consuming microwave technology to regenerate high carbon-containing Pt catalyst. Environ. Pollut. 2014, 3, 41−47. (204) Keogh, R. A.; Srinivasan, R.; Sparks, D. E.; Khorfan, S.; Davis, B. H. The regeneration of Pt promoted SO42−−ZrO2 catalysts. Fuel 1999, 78, 721−727. (205) Maslyanskii, G. N.; Bursian, N. R.; Shipikin, V. V.; Zharkov, B. B. Regeneration of platinized alumina reforming catalysts by the use of chlorine. Chem. Technol. Fuels Oils 1966, 2, 145−149. (206) D’Aniello, M. J., Jr.; Monroe, D. R.; Carr, C. J.; Krueger, H. H. The redispersion of sintered Pt, Rh, and Pt-Rh catalysts. J. Catal. 1988, 109, 407−422. (207) Fung, S. C. Am. Chem. Soc. Div. Petr. Chem. Prepr. 1993, 38, 1. (208) Beltraminin, J. N. In Catalytic Naphtha; Refortming, G. J., Antos, A. M., Aitani, Pertera, J. M., Eds. Marcel Dekker: New York, 1995. (209) Pherson, N. Phenol refiners focus on catalyst. Oil Gas J. 1988, 46. (210) Blashka, S. R.; Welch, J. G.; Nite, K.; Furfaro, A. P. Catalyst separation method reduces Platformer turnaround costs. Oil Gas J. 1995, 62−63. (211) Jacobsen, R. T. Catalyst Recovery - Part 3: Removing contaminants from spent catalysts. Chem. Eng. Progr. 2005, 4, 41−43. (212) Jacobsen, R. T. Catalyst Recovery - Part 2: Ensure fair market value through accurate sampling. Chem. Eng. Progr. 2005, 3, 22−27. (213) Jacobsen, R. T. Catalyst Recovery - Part 1: Recovering precious metals from catalysts - The Basics. Chem. Eng. Progr. 2005, 2, 20−23. 5749


Review

Energy & Fuels (244) Sarioglan, S. Recovery of Palladium from Spent Activated Carbon- Supported Palladium Catalysts. Platinum Met. Rev. 2013, 57, 289−296. (245) Sharma, S.; Rajesh, N. Augmenting the adsorption of palladium from spent catalyst using a thiazole ligand tethered on an amine functionalized polymeric resin. Chem. Eng. J. 2016, 283, 999−1008. (246) Tong, T.; Wang, C.; Huang, Y.; Yang, Y. Extraction and Stripping of Platinum from Hydrochloric Acid Medium by Mixed Imidazolium Ionic Liquids. Ind. Eng. Chem. Res. 2015, 54, 705−711. (247) Jafarifar, D.; Daryanavard, M. R.; Sheibani, S. Ultra fast microwave-assisted leaching for recovery of platinum from spent catalyst. Hydrometallurgy 2005, 78, 166−171. (248) Wang, S.; Chen, A.; Zhang, Z.; Peng, S. Leaching of palladium and rhodium from spent automobile catalysts by microwave roasting. Environ. Prog. Sustainable Energy 2014, 33, 913−917. (249) Brown, S. Catalysis in the refining of Fischer−Tropsch syncrude. Platinum Met. Rev. 2011, 55, 263−267. (250) Ferella, F.; Innocenzi, V.; Maggiore, F. Oil refining spent catalysts: A review of possible recycling technologies. Res. Conserv. & Recyc. 2016, 108, 10. (251) Batista, S. G., Jr.; Afonso, J. C. Processing of spent platinumbased catalysts via fusion with potassium hydrogenosulfate. J. Hazard. Mater. 2010, 184, 717−723. (252) Piskulov, M.; Carol, C. Structure Control of Noble Metal Nano- and Microparticles. Platinum Met. Rev. 2013, 57, 143−147. (253) Filter media. Filtration Separation 2003, 40, 16. (254) Frankham, J. Precious metals recovery. Chem. Ind. 2004, 5, 18−19. (255) Johnson, T. P.; Deegan, D. E. The recovery of PGMs from spent catalysts. Tetronics International, http://tetronics.com/oursolutions/resource-recovery-solutions/spent-catalysts/. (256) Page Bailey, M. New Products. Chem. Eng. 2016, 123, 28−32. (257) www.umicore.com (258) Furimsky, F.; Duguay, D. D.; Houle, J. Chemisorption of oxygen by coke deposited on catalyst surface. Fuel 1988, 67, 182−185. (259) U.S. EPA. Hazardous Waste Management System: Petroleum Refining Process Wastes; Identification of Characteristically Hazardous Self-Heating Solids; Land Disposal Restrictions: Treatment Standards for Spent Hydrorefining Catalyst (K172) Hazardous Waste. Federal Register 2003, 68, 59935−59940.

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