Characterization of Al2O3–ZrO2 Mixed Oxide Supported Mo Hydrotreating Catalyst

Abstract

A series of molybdenum catalysts supported on Al₂O₃–ZrO₂ mixed oxide containing 50% ZrO₂ and 50% Al₂O₃ were prepared by incipient wetness technique and characterized by BET surface area, X-ray diffraction, temperature programmed reduction and oxygen chemisorption. The catalytic activities for hydrodesulphurization (HDS), hydrogenation (HYD), and hydrocracking (HYC) were determined using thiophene, cyclohexene, and cumene as model compounds, respectively. Results indicate that up to 8 wt% Mo loading, the catalyst is well dispersed and crystallite growth occurred beyond this loading. Also both oxygen uptake and catalytic activities increase with Mo loading up to 8 wt% and then decreases at higher loading. A linear correlation was obtained between oxygen uptake and all catalytic activities and the correlation coefficients obtained suggest that the order of catalytic activities for HDS, HYD, and HYC is: HDS > HYD > HYC. Furthermore, the catalytic activities of the mixed oxide supported catalyst for HDS, HYD, and HYC were higher than those supported on pure alumina and pure zirconia. The incorporation of 3% Co on 8% Mo catalyst was determined to result in enhanced activity for HDS, HYD, and HYC.     

Hydrodesulfurization,Hydrodenitrogenation, Hydrodemetallization,and Hydrodeasphaltenization of Maya Crude over NiMo/Al2O3 Modified with Ti and P

Abstract

The effect of adding Ti (4.5 wt%) and P (～1.0 wt%) by several routes to a NiMo/ab Al₂O₃ catalyst on the hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM), and hydrodeasphaltenization (HDAs) of heavy Maya crude was investigated. The results show that not all the catalyst functionalities respond equally well to the addition of Ti and P to the catalyst formulation. There is not a single catalyst formulation that can achieve optimum performance in all the catalyst functionalities. For HDS, Ti incorporation increases activity but the route by which P is added afterwards can improve or be detrimental to HDS activity. For HDN, the incorporation of P to the catalyst can lead to significant improvements in catalytic activity and catalyst stability. Ti increases HDM activity but the addition of P to the catalyst is detrimental to this functionality. For the elimination of asphaltenes, the catalyst supported on pure alumina is the best. So for HDAs, no benefit is obtained by the addition of Ti or P to the catalyst. Textural properties are important and HDM and HDAs increase with catalyst average pore diameter. Hydrodemetallization activity increases with the acidity of the catalyst.     

COMBINED EFFECT OF FLUORINE AND ZINC INCORPORATION ON THE HDS ACTIVITY OF Co-Mo CATALYSTS

Abstract

Conventional HDS-catalysts consist of Co and Mo supported on Y-Al₂O₃. The addition of Zn as a second promoter or the alumina acidification with F increase the catalitye activity in HDS of commercial feeds (Fierro et al., 1984; Boorman et al., 1984). In this paper the combined effect of both Zn and F incorporation is discussed. A series of Zn-Co-Mo catalysts supported on fluorinated alumina (0.0 –2.0 wt% F) was prepared and tested for HDS activity using a commercial gas-oil. The data gathered showed a decrease in HDS activity for intermediate F contents (0.4 – 1.0 wt%). This result could be tentatively explained through alumina surface deterioration during impregnation with NH₄HF₂ solutions al low pH.     

Catalytic Coprocessing of Delayed Coker Light Naphtha with Light Straight-run Naphtha/FCC Gasoline

Abstract

Upgrading of delayed coker light naphtha (DCLN) is difficult due to its high diolefin and silicon content. Mixtures of light straight-run naphtha (LSRN) and DCLN fractions were hydrotreated in two stages over NiMo/Al₂O₃ and CoMo/Al₂O₃ catalysts (diolefin saturation followed by hydrodesulphurization (HDS). Naphtha fractions free of diolefins, olefins, sulfur, and silicon were produced, which are excellent feeds for naphtha isomerization. One-stage selective HDS tests were also conducted with blends of DCLN (up to 5 vol%) and fluid catalytic cracked (FCC) gasoline over CoMo/Al₂O₃. Diolefin-free products of <10 mg/kg sulfur could be produced with a research octene number (RON) loss of max. 3.     

The surface properties of aluminated meso–macroporous silica and its catalytic performance as hydrodesulfurization catalyst support

Aluminated mesoporous silica was prepared by multiple post-grafting of alumina onto uniform mesoporous SiO_2 ,which was assembled from monodisperse SiO_2 microspheres.Hydrodesulfurization(HDS)catalyst was prepared by loading Ni and Mo active components onto the aluminated uniform mesoporous SiO_2 ,and its HDS catalytic performance was evaluated using hydrodesulfurization of dibenzothiophene as the probe reaction at 300°C and 6.0 MPa in a tubular reactor.The samples were characterized by N_2 physisorption,scanning electronic microscopy,Fourier transform infrared spectrum,X-ray diffraction(XRD),temperature-programmed desorption of ammonia(NH_3-TPD),~(27)Al nuclear magnetic resonance(~(27)Al-NMR)and high-resolution transmission electron microscopy(HRTEM).The results showed that the Si–OH group content of SiO_2 was mainly dependent on the pretreatment conditions and had significant influence on the activity of the Ni Mo catalyst.The surface properties of the aluminated SiO_2 varied with the Al_2O_3-grafting cycles.Generally after four cycles of grafting,the aluminated SiO_2 behaved like amorphous alumina.In addition,plotting of activity of Ni Mo catalysts supported on aluminated meso–macroporous silica materials against the Al_2O_3-grafting cycle yields a volcano curve.     

Effect of Vanadium Introduction on the Activity of NiMo/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts in the Hydrotreating of Diesel Fractions

The influence of the introduction of V₂O₅ into NiMo/Al₂O₃ catalysts on their activity in hydrodesulfurization (HDS) and hydrogenation reactions of the components of petroleum fractions has been studied. The activity of the synthesized catalysts has been determined in the straight-run diesel and light coker gas oil hydrotreating processes in a flow-through unit under hydrogen pressure. The most active catalyst for HDS and hydrogenation of polycyclic aromatic hydrocarbons has been synthesized using VMo₁₂ heteropoly compounds: the activity increases by 6–10 and 11–13 wt % in HDS and PAH hydrogenation, respectively, at different temperatures. It has been shown that the activity of the regenerated catalyst further impregnated with the vanadium compound in HDS and PAH hydrogenation increases by 2–5 rel. %, as compared to the regenerated catalyst.     

钒作为加氢催化剂活性组分的研究 Ⅱ 钒对NiMo/Al2O3催化剂渣油加氢活性的影响

 采用浸渍法制备了一系列含V的NiMo/Al₂O₃催化剂。对硫化态含V的NiMo/Al₂O₃催化剂进行了XPS和TEM表征;以科威特常压渣油为原料,考察了V对NiMo/Al₂O₃催化剂渣油加氢活性的影响。结果表明,由于渣油中金属和硫的存在形态不同,并且V-Mo-S相和V-S相对于加氢脱金属的催化作用大于加氢脱硫的催化作用,因此V能引起NiMo/Al₂O₃催化剂上渣油脱金属率的增加;但是V含量较高时,V会造成NiMo/Al₂O₃催化剂上渣油脱硫率的降低。     

A Comparative Study of Surface Characteristics of Nickel Supported on Silica Gel, γ-Alumina,Aluminosilicate

Abstract

Surface characteristics of the prepared nickel catalysts containing 7, 10, and 13 wt% Ni w/w over different supports—silica gel, γ-alumina, and aluminosilicate—were investigated. Surface areas, total pore volumes, and average pore radii were determined for all catalysts. Pore analysis was discussed based on V_l-t plots and pore size distribution. The measured surface areas and pore volumes of pure supports increased in the following order: γ-alumina < aluminosilicate < silica gel. Pore analysis showed that SiO₂ and Al₂O₃-SiO₂ and their supported Ni samples were characterized by presence of narrower mesopores of ink-bottle type. Al₂O₃ was distinguished by presence of two distinct pore types, both showing continual increase in fraction with a shift to larger dimensions upon loading with nickel. Penetration and/or incorporation process of Ni particles took place at the expense of their interaction with Al⁺³. SiO₂ revealed a gradual increase in surface parameters upon loading with nickel. For Al₂O₃-SiO₂—supported samples, the result proposed the interaction of Ni with both alumina and silica contents of the support regardless of the penetration process.     

Product distribution and catalytic performance of nano-sized H-ZSM-5 zeolites in the methanol-to-aromatics (MTA) reaction

A study of the effect of SiO₂/Al₂O₃ molar ratio on the activity and selectivity of H-ZSM-5 catalyst in the reaction of methanol to aromatics (MTA) has been carried out in this work. Aluminosilicate zeolite (ZSM-5) zeolites with different SiO₂/Al₂O₃ molar ratios were successfully synthesized by the hydrothermal method. The SiO₂/Al₂O₃ molar ratio of the prepared ZSM-5 zeolite particles could be easily controlled by changing the ratio of tetraethylorthosilicate to aluminum nitrate nonahydrate. The effect of SiO₂/Al₂O₃ molar ratio on the activity of nano-sized H-ZSM-5 zeolites in the MTA reaction was studied. The H-ZSM-5 zeolite catalyst with low SiO₂/Al₂O₃ molar ratios shows remarkable selectivity toward aromatics and benzene, toluene, and xylene (BTX) in the MTA reaction.     

Desulfurization of FCC Gasoline Over Mordenite Modified with Al2O3

Abstract

Mordenite modified with Al₂O₃ (Al₂O₃/mordenite) was synthesized and used for the desulfurization of FCC gasoline. The influences of operating parameters on the results were studied for the model solution composed of dibenzothiophene (DBT) and isooctane. Al₂O₃/mordenite exhibits higher sulfur capacity than other kinds of chemisorbents. The suitable composition of the chemisorbent is 30 wt% Al₂O₃ to 70 wt% mordenite. The optimal operating parameters are: temperature 160°C; velocity 3 h^?1 (WHSV). Under the stated conditions, desulfurization was carried out for the FCC gasoline with sulfur content of 220.4 μg/g. The chemisorbent can maintain the sulfur content under 50 μg/g for 40 h and has good regeneration ability after desorption using benzene.     

Synthesis,Characterization, and Evaluation of Mesoporous MCM-41-supported Molybdenum Hydrotreating Catalysts

Abstract

Mesoporous MCM-41 material with high surface area and narrow pore size distribution was synthesized and used as a support for Mo, CoMo, and NiMo catalysts. The molybdenum loading was varied from 2–14 wt% on MCM-41. On 10 wt% Mo/MCM-41, the promoter Co or Ni concentration was varied from 1–5 wt%. All the catalyst samples were characterized by surface area, low temperature oxygen chemisorption, x-ray diffraction (XRD), and temperature programmed reduction methods. Characterization results show that Mo is well dispersed on MCM-41 up to 10 wt%. The catalytic activities were evaluated for thiophene hydrodesulphurization (HDS), cyclohexene hydrogenation (HYD), and furan hydrodeoxygenation (HDO). All three catalytic functionalities vary in a similar manner to that of oxygen chemisorption as a function of Mo loading, indicating that there is a correlation between oxygen uptake and catalytic sites. The activities of these catalysts were compared with γ-Al₂O₃- and amorphous SiO₂-supported catalysts. It was found that MCM-41-supported Mo catalysts displayed superior activities.     

Nanocatalysts: Effect of Active-phase and Promoter on Catalytic Properties and Performance in the Hydrodesulfurization Reaction

The influence of various amounts of phosphorus addition on performance of NiMoP/Al₂O₃ and CoMoP/Al₂O₃ nanocatalysts was examined in hydrodesulfurization of thiophene. The nanocatalysts were synthesized via sonochemical technique. The prepared samples were characterized by XRD, FESEM, BET, and FTIR analysis. The catalytic activity in hydrodesulfurization reaction was investigated in a batch stirred slurry reactor at 160°C and atmospheric pressure. The characterizations confirmed highly dispersion of active phase and formation of amorphous AlPO₄ species on the support surface. The results obtained from thiophene hydrodesulfurization showed the nanocatalysts contained 1 wt% of phosphorus had the highest activity. The CoMoP/Al₂O₃ and NiMoP/Al₂O₃ nanocatalysts with optimum phosphorus loading nearly gave 100% conversion of thiophene, so that the sulfur compound concentration in final solution was less than 50 ppm.     

Co-hydrotreating of straight-run diesel fraction and vegetable oil on Co(Ni)-PMo/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

The process of co-hydrotreatment of straight-run diesel fraction (DF) and vegetable oil (VO) on Co(Ni)-PMo/Al₂O₃ catalysts prepared from H₃PMo₁₂O₄₀ and cobalt (nickel) citrate has been studied. It has been shown that under conditions close to those in the industry, the complete conversion of fatty acid triglycerides (FATG) is achieved on the catalysts of both types to give an ultraclean hydrotreating product in a 97% yield and a cetane number of 5 points above that of the hydrotreating product of the DF alone. The degree of hydrodesulfurization (HDS) is reduced more significantly on the Co-PMo/Al₂O₃ catalyst than in the case of Ni-PMo/Al₂O₃. The catalysts are more susceptible to deactivation in the hydrotreating of the blended feedstock containing VO. The Co-PMo/Al₂O₃ sample is less stable than Ni-PMo/Al₂O₃. Examination of the spent catalysts by transmission electron microscopy has shown that the average particle length of the active phase of Co-PMo/Al₂O₃ increases, whereas this increment for Ni-PMo/Al₂O₃ is insignificant, indicating higher stability of particles of the NiMoS phase. Thus, the co-hydrotreating of petroleum fractions and vegetable oil is more reasonable to carry out on NiMo/Al₂O₃ catalysts.     

The Support Effect on Hydrogenolysis of Thiophene and Gas–Oil

Abstract

Results are reported on the support effect on the catalytic activity in thiophene hydrodesulfurization (HDS) of sulfided Ni-Mo catalysts supported on pure niobia, mixed oxides of Nb₂O₅-TiO₂ prepared by sol-gel method, and Nb₂O₅/TiO₂ and Nb₂O₅/Al₂O₃ prepared by surface deposition. The prepared samples were characterized using N₂ adsorption at ?196°C, X-ray diffraction (XRD), and temperature-programmed reduction (TPR) techniques. This study showed activity variation as a function of support composition. The activity of niobia-rich catalysts was no longer promoted by the synergy between Ni and Mo. The absence of synergy between molybdenum and nickel on niobia can be explained by the strong interaction of each metal with niobia at the expense of interaction with each other. It was found that 5 wt% Nb₂O₅/TiO₂-supported catalyst was the better catalyst for thiophene HDS. It was shown that by means of an adequate support design it is possible to significantly increase the functionalities of HDS catalysts. Semiconducting supports like TiO₂ can improve the HDS activity by exerting electronic effects on the active phase, helping in this way the formation of sulfur vacancies. The 5 wt% Nb₂O₅/TiO₂ was also tested at high pressure with gas oil feedstock. It is observed with the hydrogeolysis of sulfur compounds against time-on-stream that the activity of this catalyst decreases fast with time.     

复合SiO2-WO3催化剂的制备、表征及氧化脱除苯并噻吩性能

 采用溶胶-凝胶法制备了SiO₂-WO₃催化剂,并采用XRD、FT-IR、BET、TG-DTA等方法对催化剂进行表征。以苯并噻吩(BT)为模型化合物,H₂O₂为氧化剂,考察了催化剂的活性元素、制备方法、n(W)/n(Si)和焙烧温度对其催化氧化脱硫活性的影响。结果表明,W的引入降低了SiO₂的比表面积,SiO₂-WO₃催化剂中W的主物相为WO₃。在以W为活性组元,且n(W)/n(Si)为0.1时,500℃焙烧得到的SiO₂-0.1WO₃催化剂具有最好的催化脱硫活性。在模拟油20 mL、催化剂SiO₂-0.1WO₃用量0.04 g、n(H₂O₂)/n(S)为15.9、乙腈/模拟油体积比0.3、65℃反应60 min的条件下,苯并噻吩模拟油脱硫率可达99.3%。     

Mathematical modeling of catalytic behavior of catalyst pellets in crude oils after blocking by liquid sulfur

The sulfur recovery unit converts H₂S to elemental sulfur by the Claus process. The process occurs during two combustion and catalytic reactions. Alumina (γ-Al₂O₃) and bauxite (Al₂O₃H₂O) are the main Claus catalysts in crude oils. The volume distribution of micro- and macropores and the parameter of Bethe lattice representing the complex structure of catalyst pellets pores are the most important parameters affecting catalyst performance. This research is aimed at evaluating these parameters impact on effective efficiency of catalyst bed after blocking by liquid sulfur for the second and third reactors. It can be done by considering micro- and macropores as a function of pellet diameter. The results show that pellets with a minimum coordination number or Bethe lattice parameter of 6 are more suitable to use in catalytic reactors. There is a great consistency between the modeling results and the industrial ones. In addition, a catalytic pellet with a diameter of 4.55 mm has the most optimal performance for sulfur recycling processes in industrial crude oil.     

Hydrodesulfurization of Dibenzothiophenic Compounds in a Light Cycle Oil

Abstract

A hydrotreating study was conducted in a bench-scale hydroprocessing reactor, over a wide range of operating conditions of industrial interest, to look in detail at hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and aromatics hydrogenation, and the interactions between these reactions. This article focuses on preliminary HDS results and some general findings. The feed used was a fluid catalytic cracking (FCC), light cycle oil (LCO) and the catalyst was a commercial NiMo/Al₂O₃ hydrotreating catalyst. The HDS results were analyzed by focusing on individual dibenzothiophenic sulfur species in the feedstock and products. Some of those species were positively identified while others were grouped into classes. It was observed that above 385°C, the assumption of irreversible pseudo-first-order reaction is not applicable for both total sulfur removal and sulfur removal of individual dibenzothiophenic species. All HDS reactions involving dibenzothiophenic structures reach a point where they are affected by hydrogenation/dehydrogenation equilibrium. Among all the 14 difficult-to-remove sulfur species identified in this work 4-methyldibenzothiophene (4-MDBT) has the highest HDS reactivity, while 4,6-dimethyldibenzothiophene (4,6-DMDBT) has the lowest HDS reactivity attributable to steric hindrance by methyl substitutes at 4 and 6 positions. It was also found that H₂S significantly reduces the reaction rates of HDS. However, this effect reaches a plateau as H₂S concentration in the gas phase increases. At low reactor temperature, HDS rates linearly increase with the increase in hydrogen partial pressure. At high temperature it reaches the limit of complete conversion.     

介孔CuO/SiO2用于汽油氧化-吸附脱硫

 利用[(C₁₆H₃₃) N(CH₃)₃]₃-[PW₁₂O₄₀]双亲催化剂与H₂O₂组成的催化氧化体系对汽油进行氧化后,以介孔SiO₂为载体等体积浸渍法制备的介孔CuO/SiO₂为吸附剂,采用固定床连续流动式吸附脱硫评价装置,考察了CuO/SiO₂的CuO负载量、焙烧温度、焙烧时间和吸附温度对汽油脱硫率的影响,并对介孔CuO/ SiO₂吸附剂性质进行了XRD表征。结果表明,采用在焙烧温度为400℃、焙烧时间为2.0 h、CuO负载量为2%制备的CuO/SiO₂, 在吸附温度为120℃时,汽油氧化-脱硫的脱硫效果较好,汽油脱硫率可达56.82%。     

Hydrotreating of Maya Crude Oil: I. Effect of Support Composition and Its Pore-diameter on Asphaltene Conversion

Abstract

A systematic study for a concept governing support effect in heavy oil hydrotreating (HDT) catalysts is performed. Different Al₂O₃ and its mixed oxides supports were prepared and CoMo supported catalysts were tested for Maya heavy crude oil hydrotreating. Fresh and spent catalysts are characterized with N₂ adsorption-desorption, element analysis, and scanning electron microscopy-energy dispersion analysis by x-ray (SEM-EDAX), which confirms that coke and metals deposition on the surface of catalyst is most probably near the pore mouth. It is also demonstrated from these results that asphaltene conversion depends on the pore diameter of the catalyst, while other hydrotreating conversions (hydrodesulfurization (HDS), hydrodenitogenation (HDN), and in some extent hydrodemetallization (HDM)) are more likely affected by the nature of active metal distribution. The evaluation of alumina mixed oxide (TiO₂, ZrO₂, B₂O₃, and MgO) supported catalysts indicates that supports with basic nature have better stability than the acid ones.     

Hydrogen production by catalytic gasification of petroleum residue

The liquid fuel gasification to obtain a clean flue gas for power generation and produce chemicals such as methanol is a most promising attempt to reduce the greenhouse gas emissions and air pollutants. In this paper, an equilibrium model of liquid fuel gasification was developed by the method of Gibbs free energy minimization. Two kinds of catalysts: Ni/CeO₂/Al₂O₃ and Ni/Al₂O₃ were used to explore the influence of catalysts and operating conditions on hydrogen yield and char conversion. Over the ranges of operating conditions studied, the maximum hydrogen yield reached 52.47 vol%, whereas the char conversion varied between 45.2% and 98.5%. The results indicated that an appropriate reaction temperature is favorable for higher hydrogen production and char conversion. The model was validated with experimental data obtained from a fluidized bed gasifier.