Applied Catalysis A: General 458 (2013) 169182

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Review

Economic and technical impacts of replacing Co and Ni promotion in hydrotreating catalysts

S. Eijsbouts a, , G.H. Anderson b , J.A. Bergwerff a , S. Jacobi c
a

Albemarle Catalysts, Nieuwendammerkade 1-3, 1022AB Amsterdam, The Netherlands Albemarle Corporation, 2625 Bay Area Blvd., Suite 250, Houston, TX 77058, USA c Albemarle Corporation, Parc Scientique Einstein, Rue du Bosquet 9, 1348 Louvain-La-Neuve, Belgium
b

a r t i c l e

i n f o

a b s t r a c t
A vast majority of reneries uses alumina supported Co/NiMo/W catalysts in their hydrotreating units. As several Ni compounds are classied as carcinogens category 1A or 1B and some soluble Co compounds are classied as carcinogens category 1B and toxic to reproduction category 1B, catalyst manufacturers are required to look for suitable substitutes with a less severe hazard prole under the existing workplace legislation. There is extensive literature on alternatives to using Co and Ni in hydrotreating catalysts. Several compositions were reported to have high activities in various hydrotreating reactions. However, in reality, the options are limited as many alternative compositions are either very expensive, are not available in sufcient amounts for commercial use, or are known to be toxic. Most noble metal compositions proposed in the literature are several orders of magnitude more expensive than normal hydrotreating catalysts. Other compositions that are acceptable from the cost point of view do not show sufcient activity. This is illustrated by a series of ultra-low sulfur diesel (ULSD) and VGO FCC-pretreat tests. These tests use alumina supported single transition metals as well as combinations of rst row transition metals with Mo or W. All catalysts tested have much lower activities than the commercial catalysts. The consequences of using such low active catalysts in existing renery units are also discussed. To achieve the same product quality and cycle length a catalyst with half the activity of a reference catalyst requires a 50% reduction in space velocity, which is infeasible for virtually every renery. The rener can either signicantly increase reactor temperature or invest in additional reactors. Either way, the additional rening costs will increase the fuel price paid by the consumer at the pump and have a major negative impact on the competitiveness of many European reneries. 2013 Elsevier B.V. All rights reserved.

Article history: Received 5 February 2013 Received in revised form 27 March 2013 Accepted 29 March 2013 Available online 6 April 2013 Keywords: Transition metal suldes Hydrotreating Catalysts

Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. Regulatory context . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2. Considerations regarding the toxicity of the current and alternative catalyst components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3. Considerations regarding the price and availability of possible alternative transition metal components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. History of Co/NiMo/W hydrotreating catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Open literature on alternative catalyst compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Single transition metal suldes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Promotion of Group VI transition metal suldes by other transition metal suldes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3. Fe based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4. Transition metal carbides, nitrides and phosphides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Catalyst compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Activity testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170 170 170 171 172 172 172 172 173 174 174 175 175 175

2.

3.

Corresponding author. Tel.: +31 206347360; fax: +31 206347653. E-mail address: sonja.eijsbouts@albemarle.com (S. Eijsbouts). 0926-860X/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apcata.2013.03.043

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4.

5.

3.3. Test results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4. Conditions required to prepare ultra-low S diesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Translation of the results in terms of renery application and economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Hydroprocessing conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Renery drivers and constraints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3. Alternative catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4. Impacts on European reneries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5. Additional costs at the pump . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

175 176 177 177 177 177 178 179 179 179

1. Introduction 1.1. Regulatory context Compliance with EU Directives on Ambient Air Quality [14] requiring reduction of SOx and NOx emissions from fossil fuels, is dependent on the production of low S [5] and N containing fuels using hydrotreating catalysts. These catalysts enable the reduction of SOx and NOx emissions and contribute signicantly to the improvement of air quality. However, hydrotreating catalysts utilize combinations of Co/Ni and Mo/W compounds as active components. Several Ni compounds are classied as carcinogens category 1A or 1B [6] and some soluble Co compounds are classied as carcinogens category 1B and toxic to reproduction category 1B [6]. Moreover, Co carbonate, chloride, sulfate, nitrate and acetate are included in the Candidate List of Substances of Very High Concern of European Chemicals Agency (ECHA) [7]. (Other hazard classications of these compounds are not considered here.) Employers are required to substitute, as far as technically possible, carcinogens or mutagens at the workplace with less hazardous substances [812]. If this is not possible, the exposure needs to be well controlled, preferably by technical measures as opposed to personal protective equipment. The European Registration, Evaluation and Authorization of Chemicals (REACH) regulatory process [13] requires the producers and importers of chemicals to provide extensive data and documentation on the hazardous properties of these substances, as well as their uses and the potential of exposure of human beings and the environment. REACH also requires producers to recommend and apply appropriate risk reduction measures to ensure safe handling of chemicals throughout their life cycle. Most of the Co and Ni compounds of concern are used as intermediates in catalyst production, and the risk assessment in the REACH dossiers of these substances has shown that they can be safely used. Nevertheless further efforts have been made to explore potential substitutes for Ni and Co compounds of concern in catalyst production. The goal of this paper is to evaluate the economic and technical feasibility of Co/Ni-free hydroprocessing catalysts. Besides hydroprocessing, the substitution of Ni with less hazardous substances must be considered also in catalysts for steam reforming, hydrogenation, amination and sulfur trapping. However, that is outside the scope of the present study. 1.2. Considerations regarding the toxicity of the current and alternative catalyst components Most Ni and Co compounds used in the manufacturing of catalysts and some of those present in hydroprocessing catalysts are classied as carcinogenic or toxic to reproduction class 1A or 1B. Several Ni compounds have undergone an extensive risk assessment under the former EU existing substances regulation [14] and several Ni and Co compounds were registered under REACH in 2010. The European Scientic Committee on

Occupational Exposure Limits (SCOEL) has recently concluded that the available toxicological data suggest that Ni compounds can be regarded as carcinogens with a practical threshold acting via an indirect mode of action and safe occupational exposure levels can be derived, below which the effects are unlikely to occur [15,16]. A number of high quality genotoxicity studies, performed with several Cobalt compounds by the Cobalt REACH consortium and included in the registration dossiers for REACH, suggest that the Co ion is not genotoxic in mammalian cells in vitro and also does not cause chromosomal aberrations in vivo [17]. Consequently, the carcinogenic response observed with Co sulfate hexahydrate in a 2-year inhalation study in rats and mice [18] is also likely triggered by an indirect mode of action and a threshold effect is also likely to be applicable for Co ion triggered tumorigenic responses. In general, catalyst manufacturers have been successful in reducing workplace exposure below the safe occupational levels. However, because these Ni/Co compounds have been classied as carcinogenic, toxic to reproduction and/or mutagenic, catalyst manufacturers are required to look for suitable substitutes with a less severe hazard prole. Therefore, research initiatives have been launched to nd technically feasible replacements. Consequently, in the research described in this paper, compounds with hazardous properties causing some concern were excluded in a rst screening approach. Table 1 provides a short overview of the toxicity characteristics of selected transition metal compounds.1 More information is available in toxicology databases [21]. Most compounds of Fe, Mo and W considered in our analysis of alternatives are regarded as having a lower hazard than the Ni and Co compounds of concern, following the screening toxicity assessment. However, this may change as more toxicological information becomes available. Therefore, for any compound identied as promising on a technical basis, an in depth toxicological assessment, including testing for endpoints not yet addressed in the literature, needs to be performed.

1 Most Cr-VI compounds are classied inter alia as carcinogens category 1A or B [6]. Several Cr-VI compounds are also included in the REACH Candidate List of Substances of Very High Concern. Several Cd compounds are similarly classied inter alia as carcinogens category 1 B [6] and subject to several restrictions under the REACH regulation [13]. Hg compounds are regarded as critical due to their accumulation in the body and acute and chronic neurotoxic effects and kidney toxicity [256] as well as their environmental toxicity [6]. Os compounds, in particular OsO4 , are acutely very toxic and there is not much information available on other toxicological end points. OsO4 has been described as a substance with poor warning properties. Chronic exposure to OsO4 was reported to result in an accumulation of Os compounds in the liver and kidney and damage to these organs [21], Although there is at present no comparable carcinogenic hazard associated with Os compounds, their high acute toxicity also poses problems at the workplace. For Mn compounds, the impairment of neuromotoric functions after inhalation exposure has led to some concern. The Scientic Committee on Occupational Exposure Limits (SCOEL) [20] has recently derived a health based occupational exposure limit based on these effects.

S. Eijsbouts et al. / Applied Catalysis A: General 458 (2013) 169182 Table 1 Overview of toxicity data of selected transition metal compounds. Transition metal ion Cr Mn2+ Rh3+ Pd2+ Ag1+ Cd2+ Os3+ Pt2+ Pt4+ Au1+ Au3+ Hg2+
3+

171

Toxicity information Carcinogen category 1A/B Neurotoxic Sensitizing, genotoxic Sensitizing, toxic to spleen, liver and kidneys after repeated exposure Silver carbonate and nitrate: very toxic to aquatic organisms Carcinogen category 1B Toxic to liver and kidneys after repeated exposure, high acute toxicity Chloroplatinates: respiratory sensitizers, acutely toxic by inhalation Skin and respiratory allergen, causes hematological diseases after repeated exposure Accumulation in the body, neurotoxicity, nephrotoxicity, environmental toxicity

References [6,19] [20] [21] [2123] [24] [6,21] [21] [21,25] [21] [6]

1.3. Considerations regarding the price and availability of possible alternative transition metal components Since hydroprocessing catalysts are relatively inexpensive, a substitute metal would need to be less than 100 US$/kg in order to maintain the current pricing structure. That excludes most precious metals (Ru, Rh, Pd, Ag, Os, Ir, Pt and Au) as well as Sc and Hf as catalyst components (Fig. 1a, >1000 US$/kg metal).

Furthermore, the estimated world reserves of Pt and Pd metal groups are only about 70 thousand tons, which is an order of magnitude lower than the reserves of the currently used base metals (Fig. 1b; Co: 15 million tons; Ni: 130 million tons; Mo: 14 million tons; W: 3 million tons). This same argument, i.e. insufcient world reserves, holds true for Sc, Y, Ag, Cd, Ta, Re, Au and Hg. The rening industry consumes about 120 thousand tons of fresh hydrotreating catalysts per year [26]. Approximately 2530 thousand tons of

Fig. 1. Summary of (a) current prices [27] and (b) world reserves [28,29]. Elements with high price as well as those with insufcient reserves are highlighted in black.

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Fig. 2. Number of patent families designated as rening by elimination of heteroatoms without changing skeleton or cracking that utilize catalysts containing Co/NiMo/W published between 1920 and 2012. No patents were published before 1920. The 2010s consist of only 2.5 years. The peak in 2000s is caused by soaring number of Chinese patents and also by increases in US, EP and JP lings.

regenerated hydrotreating catalysts (from distillate service only) are re-used each year [26]. This leaves the catalyst manufacturers with a rather limited selection of alternative transition metals that are affordable (Fig. 1a), that are available in sufcient amounts (Fig. 1b) and that do not have critical hazardous properties. The following section presents a succinct review of available literature assessing the feasibility of using Co/Ni-free catalyst compositions. Section 3 presents a short experimental study, which evaluates some of the alternative compositions using real feedstocks and commercial reaction conditions. 2. Review 2.1. History of Co/NiMo/W hydrotreating catalysts Hydroprocessing is an established renery process that was rst practiced before World War II. Co promotion of Mo has been known and CoMo catalysts have been used for over 70 years [3037]. Bulk WS2 and NiSWS2 , WS2 /clay, and Mo/Al2 O3 as well as NiMo/Al2 O3 and NiW/Al2 O3 were already known as catalyst compositions for hydrogenation of oil fractions in 1946 [38]. Fig. 2 summarizes patent families associated with hydrotreating catalysts containing Co/NiMo/W that were published between 1920 and 2012. Alumina supported Co/NiMo/W hydroprocessing catalysts are still the industrys preferred catalysts. Patent literature related to alternative compositions is also very extensive. A summary of available patents on alternative compositions is shown in Fig. 3. 2.2. Open literature on alternative catalyst compositions Most transition metals have been tested as components in hydrotreating catalysts. They have been evaluated as active phases, promoters for Mo/W active phase, secondary promoters for Ni/CoMo/W active phase, dopants for -Al2 O3 or as catalyst supports. However, only catalyst compositions free of toxic components and acceptable from a cost and availability perspective are relevant within the constraints of the present study. 2.2.1. Single transition metal suldes Unpromoted Mo and W, both unsupported as well as supported on various carriers, have been extensively studied as catalysts for hydrotreating reactions (Table 2). The main appeal of these compositions is that their prices are similar to the current catalysts and commercial plants are already equipped to handle their production. However, the activities of these catalysts are comparable to those

Fig. 3. Number of patent families designated as rening by elimination of heteroatoms without changing skeleton or cracking using catalysts with transition metals other than Co, Ni, Mo or W published between 1920 and 2012. Numerous patents include multiple elements. Cr and Fe may be over represented as these elements are often mentioned together with the other Group VIb (Mo and W) and Group VIII (Co and Ni) transition metals.

used in the 1940s and 1950s, which is inadequate for current fuel specications. This will be illustrated by Mo/Al2 O3 and W/Al2 O3 examples in Section 3. The studies on the so-called periodic trends in the activities of transition metal suldes in various hydrotreating reactions include experimental studies [6265,8590] as well theoretical studies [91100]. The experimental studies comprise testing bulk transition metal suldes [85,88,101] as well as transition metal suldes supported on carbon [6265,86,87,102], -Al2 O3 [90,103], and SiO2 [89,103] in various model reactions. The most important periodic trends can be summarized as follows [6264,85,87,88,102]: There is a performance maximum at Co or Ni in the 1st row of transition metal suldes. There can be a 2nd maximum at V or Cr in the 1st row of transition metal suldes. There is a performance maximum at Ru or Rh in the 2nd row of transition metal suldes. There is a performance maximum at Os or Ir in the 3rd row of transition metal suldes.
Table 2 Examples of unpromoted Mo and W catalysts. Mo Unsupported -Al2 O3 -Al2 O3 modied by addition of Zn, Ti, Fe, Mn, Mg, or Ca SiO2 MCM-41 SBA-15 TiO2 Carbon Nb2 O5 ZrO2 SiO2 Al2 O3 TiO2 Al2 O3 Nb2 O5 Al2 O3 TiO2 ZrO2 ZrO2 Al2 O3 ZrO2 SiO2 ZrO2 -doped MCM-41 TiO2 -doped SBA-15 Phosphated Nb2 O5 Pillared clays Y-zeolite [3944] [44,4851] [57] W [40,4347] [44,5256]

[44,58,59] [60] [60] [50,58,61] [6266] [69,70] [71,72] [50,51] [7376] [70] [78] [79] [79] [80] [81] [69] [82,83]

[44]

[6264,67,68]

[77]

[84]

S. Eijsbouts et al. / Applied Catalysis A: General 458 (2013) 169182 Table 3 Examples of noble metal catalysts. Ru Unsupported -Al2 O3 SiO2 Carbon SiO2 Al2 O3 Zeolite [42,85,88,93,101,104,105] [51,106111] [117] [6264,87,102] [51] [106,110,119124] Rh [88,101,105] [111114] [6264,87,102,118] Pd [88,101] [115] [6264,87,102] [115,121] Os [85,88] [117] [6264,87,102] Ir [88] [116] [117] [6264,87,102] Pt [88]

173

[6264,87,102]

Table 4 Examples of single transition metal catalysts other than Co, Ni, Mo or W. V Unsupported -Al2 O3 SiO2 Carbon SiO2 Al2 O3 TiO2 ZrO2 Zeolite [88,101,127] Cr [88,101] [103,111,134] [103] [6264,87,102] [137] Mn [88,101] [103] [103] [6264,87,102] [137] Zn [101] [103,135] [103] [87] [137] Nb [88,101,128131] Cd [101] Re [43,101,132,133] [49,136] [6264,87,102] [136] [136] [138] [138] [138]

[6264]

[87]

[87]

Among the high activity noble metal suldes at the top of the respective volcano curves (Ru, Rh, Os and Ir), RuS2 is most similar to MoS2 and WS2 and was consequently investigated in detail [42,88,93,101,104,105]. Further examples of noble metal suldes tested in hydrotreating reactions are shown in Table 3. The reported activities of Ru, Rh, Os and Ir suldes in model reactions [6264,85,87,88,102] are usually higher than those of conventional Co/NiMo/W catalysts. These high activities were mostly obtained for bulk suldes or for supported catalysts with relatively high metal loadings (Fig. 4). With very few experimental data published [125,126], it is uncertain if these catalysts also perform well with real feedstocks. However, most importantly, the metal costs of these catalysts are several orders of magnitude higher than those of a commercial CoMo catalyst (Fig. 4). For example, a stacked bed of a conventional CoMo catalyst [90 vol.% 80 wt.%; compacted bulk density (CBD) of about 0.8 g/cm3 ] and RuS2 bulk catalyst (10 vol.% 20 wt.%; CBD assumed to be twice that of the conventional CoMo catalyst) has outperformed a full bed of CoMo catalyst by a factor of 1.64 in HDS [126]. However, the price of this CoMo + RuS2 stacked bed is 79.5 times higher than that of a full bed of CoMo catalyst. The price of a full bed of 15 wt.% Ir on C (the best performing catalyst in [6264], CBD assumed to be

half that of the conventional CoMo catalyst) is 465 times higher than that of a full bed of CoMo catalyst. Even a 1 wt.% addition of noble metals to the catalyst composition results in a huge increase in metal costs (Fig. 4). Consequently, the price/performance ratio of noble metal-containing catalysts is extremely unfavorable. That is why, to our knowledge, none of these compositions have been applied in commercial hydroprocessing applications. In addition to noble metal suldes, several other transition metal compositions were investigated as alternative active components in hydrotreating catalysts because of their appealing catalytic properties such as specic selectivity in certain reactions (Table 4). For example, NbS3 and NbS2 are potentially attractive because of their acidic properties [128131]. Cr2 S3 has the ability to perform well under high H2 S partial pressure [111]. ReS2 had a high selectivity for unsaturated reaction products in HDN [6264] etc. However, the overall activities of these compositions are too low to be considered for commercial application. This will be illustrated by a few examples (1st row transition metals on Al2 O3 ) in Section 3. 2.2.2. Promotion of Group VI transition metal suldes by other transition metal suldes Since the discovery of the promotion effects of Co and Ni on the activity of MoS2 and WS2 , numerous studies have been conducted to unravel the cause of this phenomenon and to identify other transition metals that would have similar effect as Co and Ni [89,139,140] (Table 5). The promoting effect was attributed to the
Table 5 Examples of Group VI metals promoted by other transition metals than Co/Ni. Cr Ti V Cr Mn Fe Cu Zn Nb Ru Rh Pd La W Re Ir Pt Mo [90,95,146] [90,95,147,148] [90,95,151] [90,95,148] [90,95,152] [44,72,90,95,151,153,154] [155,156] [107,148,157160] [114,148,159,160] [148,160] [161164] [165,166] [148] [148,160] [148,160,167170] W [89] [89] [89] [89] [89] [89] [44,89]

[149,150] [149,150] [149,150] [149,150]

[113]

Fig. 4. Estimated metal costs of noble metal sulde catalysts as the function of catalyst metal content. The prices of carbon supported catalysts [6264], bulk catalysts [88] as well as catalysts containing 1 wt.% noble metal are indicated by the points on the respective lines. The horizontal dashed line corresponds to metal price of a conventional CoMo catalyst.

174 Table 6 Examples of Fe containing catalysts. Fe Unsupported -Al2 O3 SiO2 TiO2 Cr2 O3 Carbon SiO2 Al2 O3 Zeolite [172176] [66,186] [188]

S. Eijsbouts et al. / Applied Catalysis A: General 458 (2013) 169182

FeMo [147,173,177185] [186,187] [187,189] [147] [190,191] [137,193]

FeW [147,173,177185]

FeV [150]

FeCr [150]

Fenoble metal

[66] [137] [138,194]

[192]

removal of metal-S anti-bonding electrons from Co and Ni and their transfer to Mo, i.e. the ability of Co and Ni to formally reduce Mo in the binary oxides [95,98]. None of the other 3d transition metals has this ability. In contrast, Cu can formally oxidize Mo and functions as a poison [95]. An alternative explanation of the promoting effect involves spillover of activated hydrogen from the promoter sulde phase Co9 S8 or Ni3 S2 to MoS2 or WS2 [141]. This effect was observed in catalysts where the active phase was segregated but also in physical mixtures and stacked beds [141]. Co and Ni promotion is also effective for RuS2 [141143]. The promotion effect was also linked to the optimum stability of a S atom bound to the transition metals [99] as well as to optimum average heat of formation of the corresponding suldes [93]. In this respect, the promoted CoMoS and NiMoS systems have similar characteristics as the noble metal suldes on the top of the volcano curves. Further theories propose that the role of Co and Ni is simply to increase the structural disorder of the MoS2 phase [144,145]. Co and Ni free combinations tested in hydrotreating reactions include unsupported suldes [89,90,95,113,146,147,153, 156,165,166], several Chevrel compounds [152,162164,170] as well as compositions supported on Al2 O3 [44,107,114,134, 135,148,151,155,157161,167169], SiO2 [44,89], carbon [154] and ZrO2 [72]. As discussed above, while noble metals containing compositions have an improved activity, this does not compensate for the huge increase in catalyst cost price. The other transition metals are more likely to only change the catalyst selectivity but at a low activity level. This will be illustrated by a number of examples (1st row transition metals + Mo or W) in Section 3. That is why, to our knowledge, none of these compositions has been applied commercially in hydrotreating. 2.2.3. Fe based catalysts Fe exhibits low activity but is an economical solution for use in disposable catalysts. Fe based catalysts have been used in coal liquefaction for many years. Inherent mineral matter in coal (mainly pyrite) acts as a catalyst during liquefaction. Approximately 10% FeSO4 7H2 O on Grude (coke obtained by carbonization of brown coal in a Winkler generator) was identied as a catalyst for hydrogenation of oil fractions in 1946 [38]. Another example of a cheap coal liquefaction catalyst is red mud (solid waste from rening of bauxite, containing up to 60% Fe2 O3 as well as silica, alumina and
Table 7 Examples of catalysts based on carbides, nitrides and phosphides. Carbide Ti V ZnMo Nb ZrMo NbMo VMo MIMIIOC, with Mo/W + V/Nb/Cr/Fe/Co/Ni MIMIIOxNy, with Mo/W + V/Nb/Cr/Mn/Co Fe [200] [202,203] [204] [202] [207] [208]

titania) [171,172], which was used in the German Kohle l process. Additional examples of Fe catalysts are shown in Table 6. Fe only has a slight positive impact on the HDS activity of Mo and W but signicantly increases the HDN selectivity [177,184]. While FeMo/W catalysts are attractive from the health and cost perspective, their activity is too low for commercial application. This will be illustrated by Fe/Al2 O3 and FeMo/Al2 O3 examples in Section 3. 2.2.4. Transition metal carbides, nitrides and phosphides Co, Ni, Mo and W carbides [195,196], nitrides [195,197], and phosphides [198,199] as well as a number of compositions containing other transition metals (Table 7) have been evaluated as potential catalyst components in hydrotreating reactions. Mo and W carbides, nitrides and phosphides have been reported to have equal to or higher activity than their sulde counterparts [195199,204,216223]. Ni2 P [214,215,224226] (having the same toxicity issues as other Ni-containing catalysts) is more active than phosphides of Fe [198], Co [198,227], Mo [198,214,215,228] and W [198,214,215,228]. Most of the activity data originate from short tests (not exceeding 11 days) using model compounds [195198,212,214,215,224235] as well as real feedstocks [195,204,216223]. To compensate for the lower numbers of active sites (determined by CO chemisorption), carbides, nitrides and phosphides were often compared in terms of turnover frequency per active site [220,224,228,229] or larger catalyst volumes were loaded [220,224,229]. The performance comparison is less favorable on reactor volume basis, using CoMo or NiMo suldes as reference catalysts. For example, the relative volume activities (RVA; 1st order kinetics) of Mo nitride are RVA HDS/HDN = 47/104 compared to low activity CoMo sulde (4 wt.% CoO and 16 wt.% MoO3 , RVA = 100) on vacuum gas oil (VGO; 8 h) [219]. Moreover, Mo nitride (RVA HDS/HDN = 1419/2249) and Mo carbide (RVA HDS/HDN = 2428/4267) have much lower activities than the commercial NiMo catalyst (RVA = 100) on coal gas oil and coal resid (11 days) [220]. The preparations of transition metal carbides, nitrides and phosphides, using oxide precursors reacted with CH4 H2 (carbides [204,216218,236]), NH3 (nitrides [204,212,218,222,236]) or H2 (phosphides [214,215]) at temperatures typically above 600 C, yield materials with relatively high surface areas. However, the

Oxycarbide

Nitride [201,202] [202]

Oxynitride

Phosphide

[205] [206] [209] [208] [202,209212] [198,213215]

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combination of high temperature with the use of CH4 H2 , NH3 or H2 reactant make it necessary to carry out these treatments offsite, which increases the catalyst cost prize signicantly. These materials are often praised for their high stability [224,229,237,238]. However, to exhibit any HDS activity, carbides, nitrides and phosphides must be able to form surface suldes. The formation of carbosuldes [230232], phosphosuldes [224229,233,234,239] as well partial suldation of the nitride phase [220,231,232,235,240] have actually been observed already in materials originating from short tests. The possibility that the suldation of these phases is progressive and that all of the material might eventually be transformed into suldes after prolonged use in commercial units (cycle length > 13 years) should certainly be considered. Rapid deactivation due to S or coke deposition was indeed observed in several studies [197,225,227,232]. For the above reasons, carbides, nitrides and phosphides have yet not been applied commercially in hydrotreating.

Table 8 Overview of catalyst compositions. Single transition metals on -Al2 O3 Mixed 1st row transition metals + 20 wt.% MoO3 3.1 wt.% V2 O3 3.2 wt.% Cr2 O3 3.0 wt.% MnO2 4.0 wt.% Fe2 O3 3.1 wt.% CoO 3.1 wt.% NiO 3.3 wt.% CuO 4.0 wt.% ZnO Mixed 1st row transition metals + 29 wt.% WO3 4.8 wt.% Cr2 O3 5.4 wt.% MnO2 5.0 wt.% Fe2 O3 4.7 wt.% CoO 4.7 wt.% NiO 2.5 wt.% CuO 5.1 wt.% ZnO

21.9 wt.% Cr2 O3 24.2 wt.% MnO2 22.7 wt.% Fe2 O3 21.6 wt.% CoO 21.6 wt.% NiO 22.7 wt.% CuO 23.0 wt.% ZnO 25.2 wt.% Nb2 O5 34.7 wt.% MoO3 45.3 wt.% WO3

alternative for Co or Ni but was included in the testing to obtain more complete trends. 3.2. Activity testing

3. Experimental The following experiments were conducted to investigate whether the trends reported in the literature for model catalysts and test reactions are also valid for ultra-low sulfur diesel (ULSD) and vacuum gasoil (VGO) hydrotreating applications. The catalysts utilized in the experiments were prepared using state-ofthe-art commercial preparation methods. Although pore volume impregnation is the method of choice in both industry and academia, catalyst preparations in both contexts are distinctly different. In academic studies, the prepared catalysts often serve as well-dened model systems with low metal loadings and high dispersion. In this approach, turn-over frequencies can be calculated and catalysts can be compared on this basis. In industry, the aim is to maximize volumetric activity. As a result, high metal loadings are applied and losses in dispersion are accepted. The present set of catalysts was evaluated in micro ow reactors using real diesel and VGO feedstocks under actual commercial hydrotreating conditions. The ULSD and VGO results can then be utilized to calculate the economic feasibility of alternative catalyst compositions in a renery. In academic studies, model feeds are often applied for the evaluation of HDS and HDN performance, which makes it difcult to extrapolate to commercial conditions. In particular, the high concentration of inhibitors present in real feedstocks cannot be simulated easily using model feeds. A low metal loading noble metal catalyst may exhibit impressive activity per metal-atom in a model reaction, once faced with a surplus of H2 S, aromatics and N-containing compounds, this may be a completely different story.

The catalysts were sulded in situ in the liquid phase, using straight run gas oil (SRGO) spiked with dimethyl disulde (DMDS) to a total S content of 2.5 wt.% (P = 45 bar, LHSV = 3, H2 /oil = 300 Nl/l). The following temperature program was used: 1. The catalysts were soaked at RT for 3 h, 2. The temperature was then increased with 30 C/h to 250 C and held at 250 C for 15.6 h, 3. The temperature was then increased with 20 C/h to 320 C and held at 320 C for 8.5 h. The catalysts were then tested in ULSD or FCC-pretreatment (FCC-PT) applications using conditions listed in Table 9. The light gasoil (LGO) feed (BP5% = 228 C; BP95% = 399 C) contained 0.79 wt.% S, 169 ppm N and 33 wt.% aromatics. The VGO feed (BP5% = 350 C; BP95% = 556 C) contained 1.99 wt.% S, 1600 ppm N and 54 wt.% aromatics. The RVAs in ULSD and FCC-PT were calculated relative to CoMo and NiMo commercial catalyst, respectively. 3.3. Test results Results of single transition metals on alumina (ULSD) are summarized in Fig. 5. Mo has mostly the highest HDS and HDN activities, followed by W, Cr and Co. (The only exception is that W has a slightly higher HDN activity than Mo in condition 3.) While Mo is more active than the other catalysts in this series it is still much less active than the commercial CoMo reference catalyst (RVA = 100). The RVAs increase from condition 1 to condition 3 in this ULSD test. (The only exception is that Mo has a slightly higher HDN activity in condition 1 than in condition 2.) However, the activity ranking remains essentially the same in all conditions. The observed trends (Fig. 5) in the 1st row of transition metal suldes, i.e. somewhat higher activities for Cr and Co and very low activities for Mn, Cu and Zn, agree well with what was previously observed [6265,8590]. Also the low activity of Nb and somewhat higher activities of Mo and W are as expected.
Table 9 ULSD test conditions using LGO feed. No. Feed P (bar) 45 45 45 LHSV (1/h) 3.00 2.50 1.00 1.20 H2 /oil (Nl/l) 300 300 300 400 T ( C) 315 350 350 360

3.1. Catalyst compositions The preparation of the catalysts was carried out using pore volume impregnation and coimpregnation techniques with nitrates, acetates, acetylacetonates and carbonates of 1st row transition metals in combination with oxides, ammonium salts or heteropoly compounds of Mo and W. The cosolutions were further stabilized with phosphoric and/or citric acid. The catalysts were dried at 120 C after each impregnation. Three series of catalysts were prepared (Table 8). For each metal or metals combination studied, several catalysts with different metal loadings were prepared, using different methods (composition of impregnation solution, single impregnation or several consecutive steps, drying versus calcination). The catalyst set in Table 8 includes samples with the highest activity for each metal or metals combination, i.e. not all of the samples have the same metal surface loading. Cr is not a viable

ULSD test (LGO feed) SRGO 1 2 SRGO SRGO 3

FCC-PT test (VGO feed) VGO 70 1

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Fig. 5. RVA HDN and HDS (versus CoMo reference catalyst; RVA = 100) for single transition metals in ULSD (conditions 13, Table 9). The product S levels for this series of catalysts were 45507525 ppm S in condition 1, 18155725 ppm S in condition 2 and 4304675 ppm S in condition 3. The product S levels for the CoMo reference catalyst were 720 ppm S, 115 ppm S and 5 ppm S in conditions 1, 2 and 3, respectively.

Fig. 7. RVA HDN and HDS (versus NiMo reference catalyst; RVA = 100) for mixed 1st row transition metals + W on alumina in VGO FCC-PT (conditions see Table 9). Their product S levels were between 1840 and 14680 ppm S as compared to 1180 ppm S for the NiMo reference catalyst.

The results of mixed 1st row transition metals + Mo on alumina in VGO FCC-PT are summarized in Fig. 6. The highest performing catalysts in this series were composed of CoMo and NiMo. As expected, the performance of NiMo was similar to the commercial NiMo reference catalyst, while CoMo exhibited a similar HDN and a higher HDS activity than the commercial NiMo reference catalyst (RVA = 100). The FeMo catalyst was the best HDS catalyst (RVA HDS = 48) among the Co- and Ni-free compositions. The observed trend in Fig. 6 (somewhat higher HDS activity for FeMo and very low activity for CuMo) agrees well with what was previously observed [89,139,140]. The VMo was the best HDN catalyst (RVA HDN = 58) among the Co- and Ni-free compositions. However, its RVA HDS was only 28. The FeMo catalyst was also tested in ULSD where it had RVA HDS between 20 and 31 and RVA HDN between 36 and 46 in conditions 13, compared to the CoMo reference catalyst (RVA = 100). The FeMo catalysts achieved between 1395 and 5005 ppm S in the ULSD test while the CoMo reference catalyst achieved between 60 and 850 ppm S. Results of mixed 1st row transition metals + W on alumina in VGO FCC-PT are summarized in Fig. 7. The highest performing catalysts in this series are composed of CoW and NiW. As expected, NiW performed somewhat better than CoW, but both were less active than the commercial NiMo reference catalyst. All other compositions had very low activities. The FeW composition performed slightly better (RVA HDS = 16; RVA HDN = 32) than the other Co and Ni free compositions. The observed trend in Fig. 7 (somewhat higher HDS

activity for FeW and very low activity for CuW) agrees well with what was previously observed [89]. The above results (Figs. 57) indicate that the performance trends known from model reactions and catalysts are also valid for catalysts prepared using state-of-the-art commercial preparation methods and tested under ULSD and VGO FCC-PT conditions. All Co and Ni-free compositions that were tested (Figs. 57) had much lower activities than the commercial reference catalysts in ULSD and FCC-PT applications. The product S levels were much higher for the Co- and Ni-free catalysts than for the reference catalysts, which leads to large RVA differences when comparing the catalysts under xed reaction conditions. As will be shown in the following section, the RVA differences become even larger when all catalysts are compared at xed product S level of 10 ppm, which is the normal ULSD product S target. 3.4. Conditions required to prepare ultra-low S diesel FeMo/Al2 O3 and Mo/Al2 O3 catalysts are the best performing Co and Ni-free compositions in this series of ULSD and FCC-PT tests. However, their activities are much lower than those of the CoMo and NiMo reference catalysts. Since catalysts were compared at equal reaction conditions, conversions were low for the FeMo/Al2 O3 and Mo/Al2 O3 catalysts. This makes it difcult to accurately determine the activity of these catalysts relative to the reference catalyst at constant conversion. To determine the relative activity of these catalysts, one would ideally test the low activity catalysts at high conversion as well. However, limitations in the hardware that was available made that we were not able to do this experimentally. (The pumps in the test units cannot operate at LHSV below 0.8 for the given catalyst volume. Increasing the T too much is also not desirable.) In an alternative approach, the available test data were processed using an application model, which is able to t the experimental data and predict the catalyst performance over a broad range of conditions. This model has been optimized using data of numerous high and low activity CoMo and NiMo catalysts and various sets of reaction conditions. The data used for extrapolations to very high and very low conversion levels were generated in reactor units operating over a broad range of LHSVs. This model has been successfully used to predict performance of, among others, commercial units. The model is based on HDN and HDS reaction chemistry and uses a Langmuir Hinshelwood kinetic model, including Ninhibition [241244]. In this way, the HDS and HDN conversions as a function of LHSV were reconstructed at 350 C, 45 bar. By extrapolating to the low S diesel condition (10 ppm S, Fig. 8a), the LHSV that

Fig. 6. RVA HDN and HDS (versus NiMo reference catalyst; RVA = 100) for mixed 1st row transition metals + Mo on alumina in VGO FCC-PT (conditions see Table 9). The Co- and Ni-free compositions had product S levels between 3860 and 7365 ppm S as compared to 1300 ppm S for the NiMo reference catalyst.

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The results (Table 10) show that the FeMo/Al2 O3 and Mo/Al2 O3 catalysts would have to operate at extremely low LHSV (0.2 and 0.3) to achieve 10 ppm S under normal ULSD conditions (350 C, 45 bar and H2 :oil = 300). By assuming constant activation energy, the T increase required to reach 10 ppm S at equal LHSV and P was determined as well (Table 10). Alternatively, FeMo/Al2 O3 and Mo/Al2 O3 catalysts would need to operate at extremely high temperatures (390 and 430 C, respectively) to achieve 10 ppm S at LHSV = 1, 45 bar and H2 :oil = 300. 4. Translation of the results in terms of renery application and economics There are many different renery congurations and types of hydroprocessing units, which complicates any quantitative analysis of the impacts of changing catalyst types. Nonetheless, a qualitative assessment is possible. To do so, it is important to understand where hydroprocessing ts into the overall rening complex. Crude oils, even after distillation, are not suitable for direct use. The most notable specication that is exceeded by raw crude cuts is sulfur content, but specications for product nitrogen and aromatics contents, as well as product density, must also be met by rened products. Hydroprocessing is instrumental in producing nal rened products, such as jet/kerosene and diesel fuel as well as feeds for other processes, such as FCC, hydrocracking and naphtha reforming (Fig. 9). 4.1. Hydroprocessing conditions The majority of hydroprocessing units are downow xed bed units. The operating conditions are designed to achieve product specications for the given process application and type of feed. More severe operating conditions must be applied as feedstocks become heavier (Table 11). The higher severity of operating conditions is achieved via reduction of liquid hourly space velocity (LHSV) and/or increases in hydrogen partial pressure (ppH2 ), weighted average bed temperature (WABT), and H2 /oil ratio. In addition to the heaviness of the feedstock, the operating conditions and achievable cycle length are also affected by the amounts of cracked feed components (from FCC and/or Coking). For example, coker naphtha hydrotreaters often operate at >40 bar ppH2 with >250 Nm3 /m3 H2 /oil ratio and still only achieve a 0.51 year cycle length, which is related to catalyst poisons in the feed. 4.2. Renery drivers and constraints Reneries earn money by converting crude oils into nished products and chemical feedstocks. The total investments for process equipment in individual reneries add up to billions of US$. Reneries use two economic indices for measuring their economic performance: (1) net operating prot, which is the difference between total income and total expenses, and (2) return on capital employed (ROCE), which measures net prot as a percentage of capital investment. Consequently, reneries are reluctant to increase capital investment in new equipment unless it is absolutely necessary, and they strive to limit any controllable costs. 4.3. Alternative catalysts As shown in our experiments, FeMo/Al2 O3 and Mo/Al2 O3 catalysts are the only Co- and Ni-free alternative compositions exhibiting appreciable activity, but the activity levels are substantially lower than those of the Co- and Ni-promoted catalysts. Although we nd a relative activity well below this value in our experiments, we will assume a catalyst activity of 50% versus a

Fig. 8. Extrapolation of the ULSD activity data of FeMo/Al2 O3 and Mo/Al2 O3 catalysts: (a) product S level and (b) N product level. Data points were tted with an application model (solid lines) and by assuming a reaction order of 1.0 for HDN and 1.4 for HDS (dotted lines). The FeMo/Al2 O3 and Mo/Al2 O3 catalysts have much lower activity than the CoMo reference. The differences become substantial at S concentrations of 10 ppm S in the reaction product.

is required to produce low S diesel could be estimated (Table 10). The removal of the inhibiting N-compounds (Fig. 8b) is the prerequisite for achieving such low product S levels. The most refractive S-species are only removed in the bottom of the reactor. As a result, the reaction rate slows down toward higher HDS conversion and very low LHSVs are required to obtain 10 ppm S. Since considerable extrapolation is necessary, the LHSV required for 10 ppm S can only be estimated with a substantial margin of about 20%. A simpler approach would be to assume a reaction order for the HDS and HDN reactions, with 1.4 and 1.0 being typical reaction orders for HDS and HDN, respectively [243,244]. The dotted lines in Fig. 8 represent the t that can be obtained using this method. The conclusions remain more or less the same regardless of the approach.

Table 10 Catalyst comparison in ULSD. Catalyst RVA HDS [%] LHSV [1/h] required to reach 10 ppm S at 350 C, 45 bar and H2 :oil = 300 Temperature [ C] required to reach 10 ppm S at LHSV = 1, 45 bar and H2 :oil = 300, CoMo reference 100 1.72 FeMo 22 0.31 Mo 14 0.19

337

390

430

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Fig. 9. Block process diagram example of a generic renery producing fuel products.

NiMo or CoMo reference catalyst for an estimation of the implications of Co- and Ni-free catalysts, The following should therefore be interpreted as a best case scenario, assuming substantial improvements in the activity of Co- and Ni-free catalysts to be made in the coming years. Catalyst activity is linked to the LHSV and WABT required to achieve target performance. For example, to achieve the same product quality and cycle length for a given feed and set of operating conditions (i.e., the same ppH2 , WABT and H2 /oil ratio), a catalyst with half the activity of a reference catalyst would require that the space velocity be reduced by 50%. This would not only severely upset the operations balances between the hydroprocessing units and other processes in the renery but it would be infeasible for virtually every renery from an overall protability standpoint. There are two ways to restore the process feed rates back to their normal levels. Firstly, the WABT could be increased in order to increase the throughput. This would, however, signicantly reduce the unit cycle length, due to the higher throughput across the less active catalyst and the increased rate of coke deactivation caused by higher operating temperatures [245,246]. For example, the CoMo reference catalyst operating at start of run (SOR) temperature WABT = 350 C achieves a unit cycle length = 33 months in ULSD hydrotreater. It can be calculated using empiric models that, the SOR WABT would have to be increased to 363 C for a catalyst with 50% RVA, which would reduce the unit cycle length to about
Table 11 Typical range of hydroprocessing unit operating conditions for a variety of feeds. Feedstock Application/condition LHSV (1/h) ppH2 (bar) WABT ( C, @SOR) H2 /oil (Nm3 /m3 ) Cycle length (years) Naphtha NHT (pre-treat) 210 620 275290 35100 46 Kerosene Jet HT/ULSK KHT 25 1230 275290 100200 35

11 months. Cycle length shorter than 11 months is untenable from an operations availability viewpoint in most reneries. The second option is to invest in an additional reactor and to expand ancillary equipment capacities in order to halve the LHSV with the normal feed rate. The metal costs per kilogram catalyst for Mo/Al2 O3 catalyst (35 wt.% MoO3 ) and FeMo/Al2 O3 (4 wt.%. Fe2 O3 and 24 wt.% MoO3 ) are approximately 1.55 times and 0.56 times, respectively, those of the commercial CoMo catalyst. While the metal costs are not prohibitive, the shorter cycle length as well as adding more reactor volume make that the price/performance ratio is very unfavorable in the end. 4.4. Impacts on European reneries EU reneries, if forced to utilize catalysts that have <50% RVA compared to the currently used CoMo or NiMo catalysts, would have to choose between cutting throughputs to <50% of todays rates, or reducing cycle lengths to possibly unacceptable levels, or making large investments to recover lost processing capacity. If the total cost is considered too high, many reneries would be forced to shut down at least a portion of their renery complex. European reneries would not be able to compete with reneries elsewhere. It would be cheaper to import fuels (and chemical feedstocks or products) from outside Europe and this could mean the closure for

Diesel ULSD DHT 0.54 1570 325350 90300 15

VGO FCC-PT/MHC/HC-PT 0.52 40100 (FCC-PT/MHC) 100160(HC-PT) 335360 200450 13

Resid E-bed, xed bed 0.20.6 100170 350380 5001100 12

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many European reneries. Already now, many reners in Europe [247], the Caribbean region [248] and the U.S. East Coast [249] are facing tenuous economic outlooks. This is evidenced by the high number of renery sales and closures that have occurred in 2011 and 2012 in all three of these regions. Because these reneries are relatively old, they have dated hardware, are equipped to treat relatively clean high priced crudes, and do not have access to lower cost sources of hydrogen supply. As a result, the average European (gross) rening margin, which was almost 7 US$/bbl2 (0.044 US$/l) from 2004 to 2008, has decreased to below 3 US$/bbl (0.019 US$/l) for the period 2009 through 2012 [250,251]. The latter gross margin is consistent with the gross margins experienced over the previous decades. Out of the gross margin, the reneries must pay for xed operating costs (e.g., wages/salaries) and variable operating costs (e.g., catalysts, chemicals, utilities), which often add up to at least 5 US$/bbl. The consequence is that, while some European reneries are able to make up to 23 US$/bbl net income, others actually lose more than this per day. For a renery processing 150,000 bbl/day, this could translate into a net income or loss of up to 450,000 US$/day. One renery on the U.S. East Coast cited prolonged losses of 1 million US$/day when they announced their closure early in 2012 [252]. In the example in Section 4.3, catalyst change-outs would have to occur annually rather than once every three years. For a European ULSD unit, the turnaround costs for spent catalyst unloading/handing and fresh catalyst loading/activation/start-up are in the order of 1 million US$. Multiplying these increased variable costs by the number of hydroprocessing units in the renery, gives a very rough estimate of the extra costs for each renery. Alternatively, the reneries could invest in additional reactors to maintain throughput without reducing cycle length. Finding reliable data on investment costs for various types of hydroprocessing units is difcult. Investments required for ULSD revamp projects quoted 710 years ago were in the range of 140450 US$ per barrelper-stream-day (bbl/SD) for a high pressure unit [253,254]. Thus, for a ULSD hydrotreater processing 25,000 bbl/SD feed rate, the investment is expected to be in the range of 3.511.2 MM US$. Many European reneries are already at a competitive disadvantage when compared to foreign reneries supplying export fuel products. On the order of 70 EU reneries were noted to be at risk for possible future shut-down [255]. Even if the absolute number would be lower, the shut-down of 15 EU reneries would already be a major setback to the EU economy. 4.5. Additional costs at the pump Ultimately, all the additional rening costs will be paid by the consumer at the pump. In addition, if substantial European hydroprocessing capacity is closed, there will be a very signicant impact on rened product supply at least in the near-term. It is conceivable that some fuel wholesale prices could double or triple and that fuel distribution and availability could experience severe shortages until foreign renery capacity has expanded to where it can replace the supply of products no longer being produced in Europe. 5. Concluding remarks The options to replace Co and Ni in hydrotreating catalysts are limited since many alternative compositions are very expensive, are not available in sufcient amounts or are known to be toxic. Most noble metal compositions proposed in the literature

are several orders of magnitude more expensive than normal hydrotreating catalysts. Other compositions do not show sufcient activity when tested with real feedstocks and when their activities are compared to those of the current commercial catalysts on a reactor volume basis. The latter was illustrated by a series of ultralow sulfur diesel (ULSD) and VGO FCC-pretreat tests using alumina supported single transition metals as well as combinations of 1st row transition metals with Mo or W. All catalysts that were tested exhibited much lower activities than the commercial catalysts. There would be serious consequences for reneries forced to use such low active catalysts in existing units. To achieve the same product quality and cycle length the space velocity would have to be signicantly reduced, which is infeasible for virtually every renery. To restore the process feed rates back to their normal levels, the rener can either signicantly increase reactor temperature or make a large investment in additional reactors. Both would dramatically increase the rening costs. This will not only be felt by the consumer at the pump but would mean a major competitive disadvantage for European reneries, increasing the risk for possible future shut-downs.

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