Hydroprocessing Catalysts Containing Noble Metals - American

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

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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

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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

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