Development of ultra-deep HDS catalyst for production of clean diesel fuels

Cosmo Oil has successfully developed a new CoMo HDS catalyst, C-606A, for production of ultra-low sulfur diesel fuels. This catalyst was prepared by an impregnation method using a solution containing Co, Mo, P, and citric acid on a HY-Al₂O₃. The resulting catalyst air-dried only without calcination. The HDS activity was measured with straight-run light gas oil feedstocks under industrial hydrotreating conditions. C-606A had a three times higher HDS activity compared with the conventional CoMoP/Al₂O₃ catalyst. Commercial operation with C-606A has successfully demonstrated high performance. This catalyst has superior activity, which enables <10-ppm sulfur content in products in a commercial hydrotreater designed to produce 500-ppm sulfur diesel fuels.     

On the formation of cobalt–molybdenum sulfides in silica‐supported hydrotreating model catalysts

Model catalysts, consisting of a conducting substrate with a thin SiO₂ layer on top of which the active catalytic phase is deposited by spincoating impregnation, were applied to study the formation of the active CoMoS phase in HDS catalysts. The catalysts thus prepared showed representative activity in the hydrodesulfurization of thiophene, confirming that these models of HDS catalysts are realistic. Combination of the sulfidation behaviour of Co and Mo studied by XPS and activity measurements shows that the key in the formation of the CoMoS phase is the retardation of the sulfidation of Co. Complexing Co to nitrilotriacetic acid complexes retarded the Co sulfidation, resulting in the most active catalyst. Due to the retardation of Co in these catalysts, the sulfidation of Mo precedes that of Co, thereby creating the ideal conditions for CoMoS formation. In the CoMo catalyst without NTA the sulfidation of Co is also retarded due to a Co–Mo interaction. However, the sulfidation of Mo still lags behind that of Co, resulting in less active phase and a lower activity in thiophene HDS. This revised version was published online in June 2006 with corrections to the Cover Date.     

Development of a high activity HDS catalyst for diesel fuel: from basic research to commercial experience

Cosmo Oil and Petroleum Energy Center (PEC) have developed a new hydrodesulfurization (HDS) catalyst of high activity, C-603A, to produce clean diesel fuel, whose sulfur content is less than 0.05 mass%. The preparation of this catalyst combines the use of zeolite technology and impregnation technology to provide excellent HDS activity. C-603A possesses significantly higher activity than conventional Co–Mo/alumina catalyst. Industrial operation with this catalyst has successfully proven its high performance.     

V-Mo based catalysts for oxidative desulfurization of diesel fuel

Catalytic oxidative desulfurization (ODS) of a Mexican diesel fuel on a spent HDS catalyst, deactivated by metal deposits, was carried out during several reactive-batch cycles in order to study the catalytic performance to obtain low sulfur diesel. To explain catalytic activity results, Mo and/or V oxides supported on alumina pellets were prepared and evaluated in the ODS of a model diesel using tert-butyl hydroperoxide (TBHP) or H₂O₂ as oxidant. The catalytic results show that V-Mo based catalysts are more active during several ODS cycles using TBHP. The performance of the catalysts was discussed in terms of reduced species of vanadium oxide, prevailing on the catalysts, which increase the sulfone yield of refractory HDS compounds (DBT, 4-MDBT and 4,6-DMDBT).     

Mixed Alcohol Synthesis from Syngas on K–Co–Mo/C Catalyst Prepared by a Sol–Gel Method

A kind of K–Co–Mo/C catalyst with homogenous components distribution and small particle size was prepared by sol–gel method with citric acid as complexant. Its structure and catalytic performance for mixed alcohol synthesis were investigated. By heat treating the dried gel in argon, the decomposition of citric acid resulted in the formations of amorphous carbon and low-valence MoO₂ species. The incorporation of potassium and cobalt increased significantly the alcohol synthesis activity, especially improved the C₂₊OH selectivity. The optimal atomic composition of catalyst was: 0.10 K: 0.50 Co: 1.0 Mo. Comparing with the similar catalysts reported in literatures, the sol–gel derived K–Co–Mo catalyst showed better performance, especially much higher C₂₊OH selectivity for mixed alcohol synthesis. A 150 h reaction test indicated that the catalyst had good stability during the entire experimental period. It suggested that the homogenous components distribution and small particle size enhanced the synergistic effect of promoters and created more active species, leading to a high catalytic performance. The formation of MoO₂ species was also favorable to improve the catalytic activity because the low-valence Mo⁴⁺ was known to be more active in CO hydrogenation.     

基于镁铝水滑石的Mo/Al2O3-MgO催化剂制备及其加氢脱硫性能

生产低硫或无硫柴油是当今世界范围内清洁燃料发展的趋势,加氢脱硫（HDS）是大规模生产清洁柴油最为有效的技术之一,而研制高活性的HDS催化剂成为该技术的关键。以镁铝水滑石与氧化铝的复合氧化物为载体,通过等体积浸渍法制备了一系列Mo/Al₂O₃-MgO催化剂,以二苯并噻吩（DBT）的正庚烷溶液为原料,在固定床反应器上评价所得催化剂的HDS活性,考察了不同镁铝比的水滑石、焙烧温度和添加量对催化剂物化性质和催化性能的影响。研究结果表明,镁铝比、焙烧温度和添加量均影响催化剂的酸性、金属还原性、硫化性能和MoS₂片晶的堆垛度等,当镁铝摩尔比为3、焙烧温度为800℃、成型时水滑石加入量为10%（质量分数）时,所制备催化剂的HDS活性最高,其脱硫率可达96.2%。这是由于该催化剂的酸性较适宜,活性组分与载体间的相互作用力适中,活性组分更易硫化,有助于提高MoS₂片晶的堆垛度进而改善催化剂的HDS性能。     

Instability of zeolite Y supported cobalt sulfide hydrotreating catalysts in the presence of H2S

The influence of the sulfidation temperature of dehydrated ion exchanged CoNaY on the catalytic activity and structure was studied by thiophene HDS activity measurements, overall sulfur analysis, temperature programmed sulfidation, Xe adsorption measurements in combination with¹²⁹Xe NMR, EXAFS and ESR. It was shown that up to a sulfidation temperature of 573 K small highly active Co sulfide clusters were formed in the supercages. Sulfidation above 573 K led to decomposition of these Co sulfide particles by a protolysis reaction resulting in the formation of H₂Sand a blue colored Co compound having almost no HDS activity. This revised version was published online in July 2006 with corrections to the Cover Date.     

The functionalities of Pt/γ-Al2O3 catalysts in simultaneous HDS and HDA reactions

A Pt/γ-Al₂O₃ catalyst was tested in simultaneous hydrodesulfurization (HDS) of dibenzothiophene and hydrodearomatization (HDA) of naphthalene reactions. Samples of it were subjected to different pretreatments: reduction, reduction–sulfidation, sulfidation with pure H₂S and non-activation. The reduced catalyst presented the best performance, even comparable to that of Co(Ni)Mo catalysts. All catalyst samples were selective to the HDS reaction over HDA, and to the direct desulfurization pathway of dibenzothiophene HDS over the hydrogenation reaction pathway of HDS. The effect of H₂S partial pressure on the functionalities of the reduced Pt/γ-Al₂O₃ catalyst was studied. The results showed that an increase in H₂S partial pressure does not cause poisoning, but an inhibition effect, without changing the catalyst selectivity. Accordingly, the activity trends were ascribed to adsorption differences between the different reactive molecules over the same catalytic active site. TPR characterization along with a thermodynamics analysis showed that the active phase of reduced Pt/γ-Al₂O₃ is constituted by Pt⁰ particles. However, presulfidation of the catalyst leads to a mixture of PtS and Pt⁰ which has a negative effect on the catalytic performance without changing catalyst functionalities.     

MgO-supported Mo, CoMo and NiMo sulfide hydrotreating catalysts

The most common preparation of high surface area MgO (100–500 m² g⁻¹) is calcination of Mg(OH)₂ obtained either by precipitation or MgO hydration or sol–gel method. Preparation of MoO₃/MgO catalyst is complicated by the high reactivity of MgO to H₂O and MoO₃. During conventional aqueous impregnation, MgO is transformed to Mg(OH)₂, and well soluble MgMoO₄ is easily formed. Alternative methods, that do not impair the starting MgO so strongly, are non-aqueous slurry impregnation and thermal spreading of MoO₃. Mo species of MoO₃/MgO catalyst are dissolved as MgMoO₄ during deposition of Co(Ni) by conventional aqueous impregnation. This can be avoided by using non-aqueous impregnation. Co(Ni)Mo/MgO catalysts must be calcined only at low temperature because Co(Ni)O and MgO easily form a solid solution. Literature data on hydrodesulfurization (HDS) activity of MgO-supported catalysts are often contradictory and do not reproduced well. However, some results suggest that very highly active HDS sites can be obtained using this support. Co(Ni)Mo/MgO catalysts prepared by non-aqueous impregnation and calcined at low temperature exhibited strong synergism in HDS activity. Co(Ni)Mo/MgO catalysts are much less deactivated by coking than their Al₂O₃-supported counterparts. Hydrodenitrogenation (HDN) activity of Mo/MgO catalyst is similar to the activity of Mo/Al₂O₃. However, the promotion effect of Co(Ni) in HDN on Co(Ni)Mo/MgO is lower than that on Co(Ni)Mo/Al₂O₃.     

Effect of carbon black composite (CBC) support properties on hydrodesulfurization performance of sulfided Mo and Co, and carburized Mo, catalysts

Carbon black composites (CBCs) have been prepared by pyrolyzing mixture of a carbon black with polyfurfuryl alcohol and then pretreated by oxidation with nitric acid, gasification with water steam or ammoxidation. The effects of the chemical character of the carrier surface, nature of the active metal phase and pH value of the impregnation solution on the catalytic activity towards the hydrodesulfurization (HDS) of thiophene of the CBC supported Mo (Co) catalysts were determined. It was stated that the catalytic properties of the CBC supported sulfides of Mo or Co and of Mo carbides are affected by the chemical character of the carrier surface. Generally, catalysts supported over basic surface CBC exhibit higher activity than those ones supported over CBC possessing acidic surface character. Co catalysts supported on acidic surface show lower activity (per mol of active metal) than Mo based ones supported on the same carrier. In the case of catalysts supported on basic CBC, Co exhibits distinctly higher activity than Mo. At the experimental conditions adopted for this study, CBC surface properties, active phase nature, and catalyst impregnation pH were found to exert a relatively small influence on both HDS and hydrogenation activities.     

Support effects in the hydrotreatment of model molecules

The support effect on the activity of hydrotreating catalysts using model molecules was analyzed for catalysts supported on TiO₂, SiO₂ and MgO. The results reported in the literature indicate that adequate design of the characteristics of the catalytic support is of great importance in the development of better hydrotreating catalysts. It was shown that by means of an adequate support design it is possible to increase significantly the HDS, HYD and HDN functionalities of hydrotreating catalysts. Semiconducting supports like TiO₂ can improve the HDS and HYD activities by exerting electronic effects on the active phase, helping in this way the formation of sulfur vacancies. Alumina supports modified by SiO₂ can facilitate the sulfidation of the active species, leading to better-promoted type II active sites with increased HDS and HYD catalyst functionalities. The nature of the support affects the sulfidation and dispersion of the catalysts even when chelating agents are used during catalyst preparation.     

Preparation of Co–Mo/B2O3/Al2O3 catalysts for hydrodesulfurization: Effect of citric acid addition

The effect of citric acid (CA) addition was studied on the HDS of thiophene over Co–Mo/(B)/Al₂O₃ catalysts. The catalysts were characterized by means of LRS, Mo K-edge EXAFS, NO adsorption capacity measurements, and UV–vis spectra. The catalysts were subjected to a chemical vapor deposition (CVD) technique using Co(CO)₃NO as a precursor of Co in order to get deeper insights into the effect of citric acid addition. It was shown that the HDS activity was enhanced by the citric acid addition up to the CA/Mo mole ratio of around 1 and leveled off with further addition. The amount of Co anchored by the CVD was increased by the addition of citric acid, suggesting an increase in the dispersion of MoS₂ particles on the catalyst by the simultaneous presence of Co, Mo and citric acid, in conformity with the increase in the NO adsorption capacity. In contrast to Co–Mo catalysts, the edge dispersion of MoS₂ particles in Mo/B/Al₂O₃ was not affected by the addition of citric acid. The LRS, UV–vis spectra and Mo K-edge EXAFS showed that Co–CA and Mo–CA surface complexes are formed by the addition of citric acid. The Co–CA surface complex is more preferentially formed on CoMo/Al than on CoMo/B/Al, in agreement with a greater promoting effect of citric acid at a lower CA/Mo mole ratio for CoMo/Al than for CoMo/B/Al.     

Hydrocracking of Vacuum Gasoil on NiMoW/AAS-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Trimetallic Catalysts: Effect of the W : Mo Ratio

The effect of the W: (W + Mo) atomic ratio in NiMoW trimetallic catalysts on their catalytic and physicochemical properties is studied. The catalysts are prepared by impregnating a carrier containing amorphous aluminosilicate (AAS) and aluminium oxide with an aqueous solution containing Ni, Mo, W compounds, and citric acid. They are studied via XRF, TEM, NH₃ TPD, and low-temperature nitrogen adsorption and are tested in the hydrocracking of vacuum gasoil (VGO). The average length of a sulfide active component layer shrinks as the amount of Mo increases and the amount of W in the catalyst is reduced. XPS data indicate that the degree of sulfidation of tungsten in NiMoW trimetallic catalysts is lower than in NiW catalyst. Testing of the catalysts in hydrocracking of a straight-line VGO at 390–420°C, 16 MPa, a feedstock hourly space velocity (FHSV) of 0.71 h^?1, and a H₂: VGO ratio of 1200 L/L shows the activities of hydrodesulfurization, hydrodenitrogenation, hydrogenation, and hydrocracking grow along with the W: (W + Mo) ratio. When the process pressure is high and the amount of sulfur in the NiW feedstock is low, the catalysts have higher activity in the target reactions of VGO hydrocracking than NiMo catalyst.     

Elucidation of hydrodesulfurization mechanism using S radioisotope pulse tracer methods

The sulfidation state in a series of Co-promoted Mo/Al₂O₃ catalysts was investigated using a ³⁵S pulse tracer method. ³⁵S-labeled H₂S ([³⁵S]H₂S) pulses were introduced into catalysts in a nitrogen stream until the radioactivity in the recovered pulse approached the radioactivity of the introduced pulse. From the amount of introduced [³⁵S]H₂S, the amount of sulfur accumulated on the catalyst was estimated. The result indicated that the amounts of sulfur accumulated on the catalysts increased with increasing temperature for all catalysts. Only molybdenum was sulfided in both Co–Mo/Al₂O₃ and Mo/Al₂O₃ catalysts below 300°C, but the sulfided states of the catalysts at 400°C were very close to the stoichiometric states where Co and Mo are present as Co₉S₈ and MoS₂. Further, hydrodesulfurization (HDS) reactions of radioactive ³⁵S labeled dibenzothiophene were carried out over the series of Co-promoted Mo/Al₂O₃ catalysts. The amount of labile sulfur and the release rate constant of H₂S were determined. The promotion effect of cobalt on activity of the molybdenum catalyst was attributed to the formation of more active sites. Moreover, the increase in the catalytic activity with Co/Mo ratio among the promoted catalysts was due to increase in the number of the sites with the same activity.     

Molybdate catalysts prepared by a novel impregnation method: Effect of citric acid as a ligand on the catalytic activities

Molybdate, nickel-molybdate and cobalt-molybdate/γ-alumina catalysts were prepared by an impregnation method using citric acid as well as ammonia as ligands. Molybdenum structures in the impregnating solutions and on the sulfided catalysts were characterized by EXAFS and XPS. Agglomerated molybdenum octahedra existed in the impregnating solutions containing citric acid, in contrast to the monomeric molybdenum tetrahedra obtained when using ammonia. The nickel-molybdenum catalyst prepared by using citric acid was inferior to the one prepared by using ammonia in terms of both hydrogenation and HDN activities, which might be due to a decrease in the amount of active Ni-Mo-S phase. On the other hand, the cobalt-molybdenum catalyst prepared using citric acid was superior to the one prepared using ammonia in terms of HDS activity. A decrease in the lateral size of MoS₂-like crystallites might attribute to an increase in the HDS activity.     

络合剂对加氢精制催化剂影响的研究进展

络合剂作为一种常用的助剂,由于其能提高加氢催化剂的性能而得到了研究者的重视。本文综述了络合剂对加氢催化剂加氢性能的影响,总结了引入络合剂后催化剂硫化行为方面的研究进展。简要介绍了络合剂的加入对金属浸渍液性质与催化剂加氢活性的影响,及采用共浸渍和分步浸渍引入络合剂时络合剂不同的作用机理。总体来看,络合剂的添加可以延迟助剂Ni(Co)的硫化,降低Mo(W)的硫化温度,进而提高Mo(W)的硫化程度,减弱活性组分与载体的相互作用,增强了活性组分的分散性,最终提高了催化剂的加氢脱硫活性。最后指出对络合剂改性的加氢脱硫催化剂在作用机理、工业催化领域等方面的研究是未来的研究方向。     

Activated Carbon‐Supported Mo‐Co‐K Sulfide Catalysts for Synthesizing Higher Alcohols from CO2

Activated carbon‐supported Mo‐Co‐K sulfide catalysts, prepared by stepwise impregnation, were used in the synthesis of higher alcohols via CO₂ hydrogenation. The catalysts with varying Mo contents and defined K/Mo and Co/Mo molar ratios exhibited relatively high CO₂ conversions and high selectivity to total alcohols and C₂₊ alcohols. Moreover, the influence of calcination conditions on the sulfidation states and catalytic performance was studied. The surface sulfur runoff of the supported catalysts can be effectively suppressed by online calcination. As a result, the selectivity to total alcohols and C₂₊ alcohols can be improved.     

Selectivity enhancement of Co-Mo/Al2O3 FCC gasoline hydrodesulfurization catalysts via incorporation of mesoporous Si-SBA-15

Mesoporous Si-SBA-15 was applied to enhance the FCC gasoline selective hydrodesulfurization (HDS) performance of conventional Co-Mo/Al₂O₃ catalysts and the physicochemical properties of the resulting catalyst were compared with those of Co-Mo/Al₂O₃ catalysts incorporated with macroporous kaolin, mesoporous Si-MCM-41 and microporous Si-ZSM-5. The selective HDS performances of all the catalysts were assessed with different FCC gasolines as feedstocks. The results showed that the HDS selectivity of the catalysts was closely related to the Mo sulfidation that depends on catalyst surface area and metal-support interaction. With the superior Mo sulfidation, the Co-Mo/Si-SBA-15-Al₂O₃ catalyst had the optimal HDS selectivity for not only the full-range FCC gasolines but also the heavy fractions thereof. The present article demonstrates the significance of enhancing Mo sulfidation in improving HDS selectivity and thus sheds a light on the development of highly selective HDS catalysts.     

Modification of the preparation procedure for increasing the hydrodesulfurisation activity of the CoMo/γ-alumina catalysts

In this work we have examined whether the re-impregnation of CoMo/γ-alumina catalysts or the replacement of the conventional non-dry impregnation step by “equilibrium deposition filtration” (EDF) may be used for improving their surface characteristics and thus their catalytic activity.

Two samples were prepared. In the first sample (EDF) the molybdenum species were mounted by “equilibrium deposition filtration” whereas in the second sample these species were mounted by non-dry impregnation (NDI). In both cases the Co was deposited on the calcined Mo/γ-Al₂O₃ precursor solid by simple dry impregnation. An aliquot of each sample was impregnated again with an amount of pure water equal to its pore volume and then it underwent drying and calcination.

The catalysts prepared were characterized using N₂ adsorption measurements (BET), UV–vis diffuse reflectance spectroscopy (DRS), laser Raman spectroscopy (LRS) and NO chemisorption. The hydrodesulfurization (HDS) activities over the catalysts studied were determined using a continuous-flow tubular fixed-bed microreactor operating in a differential mode at atmospheric pressure.

It was confirmed that the replacement of the conventional impregnation by equilibrium deposition filtration results to catalysts with relatively high active surface and high portion of the well-dispersed octahedral cobalt and thus, to catalysts with 30% higher HDS activity. The re-impregnation resulted to partial dissolution and re-dispersion of the Mo and Co supported oxidic phases. Concerning the NDI catalyst re-impregnation resulted to an increase of the active surface and of the portion of the well-dispersed octahedral cobalt and thus to 25% higher catalytic activity. The opposite effects were observed for the EDF catalyst which exhibited almost 7% lower activity after re-impregnation.     

Effects of carbon on the sulfidation and hydrodesulfurization of CoMo hydrating catalysts

The effects of carbon addition on CoMo catalyst performance for sulfidation and hydrodesulfurization (HDS) were investigated. The carbon-containing catalyst was prepared by impregnation of γ-Al₂O₃ support with NH₃ aqueous solution containing Co(NO₃)₂·6H₂O, (NH₄)₆Mo₇O₂₄·4H₂O and ethylenediamine. The results indicated that the incorporation of proper carbon on CoMo catalyst can improve its HDS performance. The carbon species on the catalyst were characterized by temperature-programmed oxidation and reduction, temperature-programmed desorption of ammonia and ultraviolet-visible diffuse reflectance spectra. Two forms of carbon species were differentiated: one is spread over the catalyst surface, similar to coke formed from reaction; the other interacts with active phase as an intermediate support. The carbon species acting as intermediate support may decrease the interaction of active metals with support, which enhances the sulfidation and HDS activities of CoMo catalyst. This work was presented at the 7th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.