Hydrocracking Reactions Research Articles

Experimental Study of Iraqi Light Naphtha Isomerization over Ni-Pt/H-Mordenite

Hydroisomerization of Iraqi light naphtha was studied on prepared Ni-Pt/H-mordenite catalyst at a temperature range of 220-300°C, hydrogen to hydrocarbon molar ratio of 3.7, liquid hourly space velocity (LHSV) 1 hr-1 and at atmospheric pressure.
 The result shows that the hydrisomerization of light naphtha increases with the increase in reaction temperature at constant LHSV. However, above 270 0C the isomers formation decreases and the reaction is shifted towards the hydrocracking reaction, a higher octane number of naphtha was formed at 270 °C.

Synthesis And Characterization Of CoMo/Mordenite Catalyst For Hydrotreatment Of Lignin Compound Models

AbstractThe synthesis of CoMo/Mordenite (CoMo/MOR) catalysts was conducted using a co-impregnation method at a various Co/Mo ratios. The produced catalysts were then characterized by X-ray diffraction, total acidity analysis, and scanning electron microscopy. The activity of the catalyst in a hydrotreatment reaction was evaluated by applying the catalyst as a reduced-catalyst to the hydrocracking (HC) reaction of anisole molecules. Analysis of the diffraction data using the Le Bail refinement technique showed that the metal phase was successfully impregnated into the MOR. In addition, increasing the metal content resulted in an increase in the acidity of the catalysts and changed the morphology of the catalysts from homogeneous to heterogeneous with larger particle size. According to the data of GCMS, it is known that the catalysts successfully removed methyl group of anisole molecules. Hydrotreatment reaction with the prepared-catalyst produced 4.77% of phenols. It is 122 % higher than the reaction with MOR catalyst.

Effect of the catalytic system and operating conditions on BTX formation using tetralin as a model molecule

Light cycle oil (LCO) is an inexpensive feedstock for the production of high-added-commercial-value-mono-aromatic compounds such as benzene, toluene and xylenes (BTX). To extend the knowledge on the processing of LCO for BTX production, the hydrocracking reaction was studied using a commercial NiMo/Al2O3 catalyst, ZSM-5 zeolite and their mechanical mixtures (20/80, 30/70 and 50/50) for processing tetralin as model feedstock in a bench-scale-trickle-bed reactor at 450–500 °C, 3.9–5.9 MPa, 1.3 1/h and H2/feed volume ratio of 168–267 m3/m3. Accessible, well-dispersed and strong Brönsted acid sites eased the hydrocracking of tetralin to BTX and the metallic hydrogenation functions from nickel–molybdenum catalysts were also required to minimize deactivation. To achieve suitable tetralin conversions (86–95 wt%), high BTX selectivity in the liquid phase (44–70 wt%) and suitable catalytic activities for coke precursor hydrogenation (to reduce deactivation), NiMo/Al2O3//ZSM-5 mixtures (50–80 ZSM-5) were employed, which probed to be effective.

Designing a Mesoporous Zeolite Catalyst for Products Optimizing in n-Decane Hydrocraking

Mesoporous ZSM-5 zeolite is developed to enhance the catalytic performance in a hydrocracking reaction. The generated mesopores and mesoporous channels in the new catalyst supply more opportunities for reactant accessing the active sites according to the better mass transfer and diffusion. Meanwhile, the acidity of the mesoporous catalyst is also weakened because of the removal of Si and Al species from its MFI structure, which makes the products distribution drift to more valued chemicals such as olefins. In the modified mesoporous ZSM-5 zeolites via different metallic promoters, the olefins’ selectivity increases as the alkalinity of the catalyst increases. The reason for this is that the formed olefins will be further hydrogenated into corresponding alkanes immediately over the extremely acidic zeolite catalyst. Hence, the moderate alkalinity will limit this process, while at the same time the remaining olefins products will too. Furthermore, the Pd-based mesoporous ZSM-5 zeolite shows an excellent n-decane conversion and high propane selectivity due to the occurrence of hydrogen spillover via the Pd promoter. The phenomenon of hydrogen spillover supplies more chemisorbed sites of hydrogen atoms for hydrocracking and hydrogenating in this reaction. In short, this study explores the important effect factors in n-decane hydrocracking reaction activity and products distribution. It also shows a potential for the further industrial application of petroleum-derived fuel hydrocracking according to the optimized products distribution under metallic promoted mesoporous zeolite.

Production of bio-hydrogenated kerosene by catalytic hydrocracking from refined bleached deodorised palm/ palm kernel oils

In this work, refined bleached deodorised palm oil (RPO) and palm kernel oil (PKO) obtained from palm oil refinery, were used as feedstocks to investigate the production of bio-hydrogenated kerosene (BHK) via hydrocracking reaction. A statistical tool of box-behnken design (BBD) was applied to consider the effects of reaction temperature, pressure and liquid hourly space velocity (LHSV) on biofuel production from RPO. The results revealed that the temperature was strongly significant effect on the yield and the optimal condition was found at 477 °C, 5.6 MPa and 1.5 h−1 of LHSV. Subsequently, crude biofuel was separated by fractional distillation, the biofuel yield was obtained at approximately 90% and providing 49.59% kerosene selectivity. Curiously, another feedstock of PKO which has lauric acid as the main composition whereas RPO contained palmitic and oleic acids, was used to produce BHK by using operating condition based-on RPO optimal condition. The biofuel yield derived from PKO reached at the same quantity. On the other hand, kerosene selectivity obtained was higher than in case of RPO (55.35%). However, high oxygen content was found in PKO-derived BHK, and this affected to freezing point and total acid number.

Local Wood’s Bio-Oil Upgrading Using Non-sulfided (Co, Mo)/USY Catalyst

In this present study, the non-sulfided (Co, Mo)/USY has used as a catalyst on the hydrotreating and hydrocracking (HC) reactions for upgrading the quality of bio-oil. The bio-oils were obtained from sengon, coconut, meranti, and bangkirai woody biomass by pyrolysis method at a temperature of 300 °C and atmospheric pressure. Meanwhile, the hydrotreating and HC reactions were done with a flow reactor at 300 °C, under H2 gas flow (20 mL/min). The composition of bio-oil and upgrading bio-oil were analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). The resulted show that the main component of bio-oil is levoglucosan, while the main product of upgrading bio-oil is methyl format. Bio-oil with the highest yield obtained from meranti on the HC reaction that used Co-Mo/USY catalyst.

Kinetic study of thermal and catalytic hydrocracking of asphaltene

Abstract In this study, a five-lump model was proposed for kinetic modeling of asphaltene placed in a batch reactor with a commercial slurry-phase catalyst (Mo-octoate). Asphaltene was separated from vacuum residue using normal pentane. The kinetic experiments were carried out at 380∼430℃ for 1∼20 h together with a 1000 ppm concentration of Molybdenum in thermal and catalytic hydrocracking reaction modes. The results showed that the coke induction period and maximum maltene yield are changed with reaction temperature and time at thermal and catalytic hydrocracking. In addition, a linear relationship between coke and liquid (maltene + asphaltene remains) yields was shown so that the critical gas amount could be found as a criterion for determining the end of the coke induction period. Significantly, the kinetic model fit the experimental data well and, moreover, was found to be able to predict the moment when coke begins to form as well as maximum maltene yields.

Bio-kerosene and Bio-gasoil from Coconut Oils via Hydrocracking Process over Ni-Fe/HZSM-5 Catalyst

In this study, hydrocracking of coconut oil over Ni-Fe/HZSM-5 catalyst was carried out in a batch reactor under different reaction temperature. Coconut oil is proposed as one of the potential feedstock for biofuel production. The Ni-Fe/HZSM-5 catalyst was prepared by incipient wetness impregnation method. The characterization of Ni-Fe/HZSM-5 catalyst by X-Ray Diffraction (XRD), Scanning Electron Microscopy-Energy Dispersive X-ray (SEM-EDAX), and Brunauer-Emmett-Teller (BET). The chemical composition of biofuel was analyzed by Gas-Chromatography-Mass Spectrometry (GC-MS). The results from the GC-MS analysis showed that the hydrocracking reaction over 10 % (Ni-Fe)/HZSM-5 catalyst at temperature of 375 oC obtained the highest hydrocarbon content (contained 49.4% n-paraffin, 26.93 % isoparaffin, 3.58 % olefin) and the highest yield of bio-gasoil 38.6 % in the biofuel liquid hydrocarbon. Pentadecane (n-C15) and heptadecane (n-C17) were the most abundant hydrocarbon compounds in biofuel liquid hydrocarbon. Decarboxylation and/or decarbonylation was the dominant reaction pathways in this process. Based on the result, the reaction temperature had a significant effect on the distribution of biofuel composition and yield of biofuel from coconut oil.

Hydrodesulfurization activity of Ni-containing unsupported Ga(x)WS2 catalysts

Nickel addition in the unsupported Ga-containing WS2 catalysts of varying Ga-content on their catalytic performance for the hydrodesulfurization of dibenzothiophene was studied. Nickel addition caused a drastic enhancement of the catalytic activity of the samples. The catalyst with 1.5 wt% Ni addition showed the highest activity. Besides, all Ga-loaded catalysts enhanced the hydrogenation pathway of dibenzothiophene transformation, starting with the hydrocracking reactions of the aromatic rings prior to their hydrogenation. FTIR studies of NO adsorption showed that Ga-addition increased both the dispersion of Ni and W species and the interaction of Ni species with W.

Modified Vermiculite for Hydrocracking of Athabasca Bitumen

A series of catalysts were synthesized by incorporating Mo and W active phases promoted with Co, Ni, or Fe, on a mesoporous delaminated vermiculite. The resulting solids were characterized by X-ray diffraction, temperature-programmed reduction with H2 (TPR-H2), temperature-programmed desorption of ammonia (TPD-NH3), N2 adsorption/desorption isotherms, and transmission electron microscopy. The catalytic performance of the materials was evaluated in the hydrocracking reaction of Athabasca Bitumen. The results indicate that the delaminated vermiculite is a promising material as catalytic support with acidity properties and texture which are appropriate for the synthesis of successful catalysts in the hydrocracking reaction of heavy crudes. The redox properties of the catalysts are important in the catalytic performance, the catalysts with the Mo active phase promoted with Ni and Fe being those that exhibit better activity in the hydrocracking of Bitumen.

Effect of the Texture and Acidity of a Zeolite-Containing Support on the Activity and Selectivity of NiMoS Catalysts in Hydrogenation and Hydrocracking Reactions

Supports based on pseudoboehmite, ultrastable zeolite Y, and ZSM-5 with different silica ratio and concentration of acid sites are prepared. NiMoS catalysts are synthesized by the incipient wetness impregnation of the prepared supports by the joint solution of H3PMo12O40 and nickel citrate. The composition and properties of the supports and catalysts are studied by low-temperature nitrogen adsorption, ammonia temperature-programmed desorption, IR spectroscopy of pyridine adsorption, and high-resolution transmission electron microscopy. Catalytic properties are investigated in dibenzothiophene hydrodesulfurization (HDS), naphthalene hydrogenation (HYD), and hexadecane hydrocracking (HC) concurrent reactions in a flow unit equipped with a microreactor. It is shown that the HDS activity of the synthesized samples declines as the dispersity of active-phase particles decreases in correlation with a change in the surface area of support mesopores. It is shown that the NiMo/ZSM-5/23 catalyst exhibits a high activity in naphthalene HYD and subsequent reactions of tetralin and decalin naphthene ring opening and hexadecane HC. It is found that the activity of zeolite-containing catalysts in naphthalene HYD grows with the proportion of Bronsted acid sites.

In-situ upgrading and enhanced recovery of heavy oil from carbonate reservoirs using nano-catalysts: Upgrading reactions analysis

Exploitation of heavy/extra heavy oil is becoming challenging as it conventionally requires injection of steam in high proportions, making it not environmentally friendly. In-situ upgrading technology (ISUT) is a novel alternative to the current heavy oil and bitumen production methods, which gives the benefits of both oil recovery and upgrading in one single stage. In this method, recovered vacuum residue (VR) from produced oil along with nano-catalyst and hydrogen will be injected in the reservoir, where upgrading reactions take place. For the first time, a comprehensive kinetic analysis of mild hydrocracking reactions inside a carbonate rock is implemented, which considerably enhances predictive simulations of the technology. With the aid of a continuous experimental setup, nano-catalyst deposition into the rock is also assessed in carbonate cores. Furthermore, a five-lumped kinetic model is developed and matched against experimental data with an average error of 6%. Significant viscosity reduction of 99.8% and API gravity increase of 8 °API are observed for the most severe condition with 35% VR conversion, while asphaltene stability criterion is met. It is recurrently omitted in most in-reservoir upgrading reports and the literature the essentially relevant information about oil stability limits. Non-catalytic conversion of heavy oils, disregarding the energy source employed, is most certain to produce unstable asphaltenes and/or coke before reaching surface transportability viscosity requirements, with additional mid-long term reservoir impairment consequences. It is included in this paper the required confirmation that the in-situ upgraded oil is fully stable when transportable viscosity values are reached.

Modeling, simulation, and parametric sensitivity analysis of a commercial slurry-phase reactor for heavy oil hydrocracking

Modeling and simulation of a commercial size unit for hydrocracking of an atmospheric residue (312 °C+) in a slurry-phase reactor are reported. The model of the industrial reactor is formulated taking into account axial and radial gradients of the state variables: composition and temperature. The mathematical model was partially discretized with finite central differences in the positional derivatives generating a matrix system of ordinary differential equations which was solved by a Runge-Kutta method. The hydrocracking reaction kinetic model is based on lumping technique and hydrotreating reactions kinetics are described by Langmuir-Hinshelwood and power-law approaches. All the intrinsic kinetic parameters and correlations used in the simulations were taken from the literature. Dynamic and steady-state simulations were performed with the objective to find a distribution of composition and temperature in the reactor as a function of time. Also a parametric sensitivity study was elaborated in order to analyze the effects of uncertainties of model parameters in the dynamic and steady-state model responses.

Catalytic hydrotreatment of pyrolysis-oil with bimetallic Ni-Cu catalysts supported by several mono-oxide and mixed-oxide materials

Catalytic hydrotreatment of pyrolysis-oil from biomass is an important process to improve oil characteristics for use as liquid fuel. Bimetallic NiCu catalysts are currently attractive for use in hydrotreatment process due to its highly active for hydrogenation, hydrodeoxygenation and hydrocracking reactions. In this study, NiCu catalyst supported by several mono-oxide (i.e. γ-Al2O3, ZrO2, SBA-15 and MCM-41) and mixed-oxide (ZrO2-SBA-15 and ZrO2-MCM-41) materials was tested for hydrotreatment of guaiacol (as pyrolysis-oil model compound) and pyrolysis-oil from eucalyptus under several reaction temperatures (200–350 °C) and times (1–6 h). Among all catalysts, NiCu/ZrO2-SBA-15 showed the highest activity toward the hydrotreatment of guaiacol, from which hydrodeoxygenation yield of 87.3% with relatively low carbon deposition (3.4 wt%) was achieved from the reaction at 325 °C for 2 h. For the hydrotreatment of pyrolysis-oil in the presence of NiCu/ZrO2-SBA-15, ungraded oil with favorable qualities (i.e. high H/C ratio and low thermogravimetric residue) was obtained from the reaction at 350 °C for 3 h. After reaction test, catalyst regeneration and reusability were also studied. The regeneration of spent NiCu/ZrO2-SBA-15 by oxidation with O2 at 600 °C for 3 h can remove most of carbon species from catalyst surface with insignificant change in catalyst surface properties. In addition, the regenerated catalyst can be reused for at least 5 reaction cycles without significant deactivation observed.

Acid-modified phonolite and foamed zeolite as supports for NiW catalysts for deoxygenation of waste rendering fat

Acid-modified phonolite material, Al2O3/foam zeolite and foam zeolite were used as supports for NiW catalysts. The zeolite type materials were prepared by a novel procedure from natural clinoptilolite. Phonolite materials were loaded with 5, 7.5 and 10 wt% of Ni containing 10, 7.5 and 5 wt% of W. Al2O3/foam zeolite contained 4 and 13 wt% of Ni and W and pure foamed zeolite was effectively loaded with 5 and 16 wt% of Ni and W. NiW/Al2O3 catalyst (3 wt% Ni and 11 wt% of W) was used for comparison of catalytic properties of synthesized materials. Catalytic tests were carried out in an autoclave pressurized at 7 MPa (H2) at room temperature and then heated to 365 °C for 1 h. Catalysts were characterized by N2 physisorption, XRD, XRF, NH3-TPD, CO2-TPD and H2-TPR. Catalyst properties were compared for the HDO of rendering fat into hydrocarbons. The liquid products were analyzed by simulated distillation, C, H, N, S elemental analysis, ATR and density (15 °C). Gaseous products were characterized by RGA-GC. Used catalysts were also analyzed by N2-TGA and O2-TGA. Novel phonolite modified solids and NiW/foam zeolite type materials were tested for the first time as catalysts being in some cases more active than NiW/Al2O3 material. Ni(5%)W(10%)/Acid phonolite and NiW/Foamed Zeolite resulted to be the most active materials for the HDO and hydrocracking reactions. The lowest amount of carbonaceous species on the surface of tested catalyst was found for the Ni(5%)W(10%)/Acid phonolite solid.

Hydrotreating of Light Cycle Oil over Supported on Porous Aromatic Framework Catalysts

The hydroprocessing of substituted naphthalenes and light cycle oil (LCO) over bimetallic Ni-W-S and Ni-Mo-S catalysts that were obtained by decomposition of [N(n-Bu)4]2[Ni(MeS4)2] (Me = W, Mo) complexes in situ in the pores of mesoporous aromatic frameworks (PAFs) during the reaction, was studied. The promotion of acid-catalyzed processes by PAF-AlCl3, synthesized by impregnation of a PAF with AlCl3 from its toluene solution, was investigated. It has been found that Ni-W-S catalytic systems were more active in the hydrodearomatization reactions, while Ni-Mo-S catalytic systems were more active in hydrodesulfurization and hydrocracking reactions. The introduction of sulfur into the reaction medium enhanced the activity of the catalysts and the presence of PAF-AlCl3 led to an acceleration of the hydrocracking processes.

Triglycerides Hydrocracking Reaction of Nyamplung Oil with Non-sulfided CoMo/γ-Al2O3 Catalysts

The purpose of this research are to study the temperature influence in hydrocracking process of the nyamplung oil (Calophyllum inophyllum) using a non-sulfided CoMo/γ-Al2O3 catalyst and to develop a simple kinetic model in interpreting the data of hydrocracking products. The experiment was carried out in a pressurized batch reactor operated pressure up 30 bar. The CoMo catalyst supported with γ-Al2O3 was prepared through impregnation method without sulfidation process. The operating temperature varied from 200 to 350 oC. The results show that the non-sulfided CoMo/γ-Al2O3 catalysts, nyamplung oil triglycerides can converted into gasoil and gasoline-like hydrocarbons. The triglyceride hydrocracking reaction of nyamplung oil followed a several stages, i.e., hydrogenation, dehydrogenation, and cracking. Based on the compounds contained in liquid product, hydrocracking reaction was dominated by decarboxylation. The products obtained in hydrocracking process of nyamplung oil are classified to gasoil (C11-C18) and gasoline (C5-C10). The triglycerides hydrocracking reaction of nyamplung oil was assumed by following a series reaction mechanism and a simple kinetic model used for determined the kinetics constants. The highest reaction conversion is 99.10% obtained at temperature of 350 °C for 160 minutes reaction time.

Comprehensive Residual Oil Hydrocracking Reaction Kinetic Modeling Combined with Effective Phase Equilibrium Calculation

A model for a residual hydrocracking unit combining a comprehensive kinetic model with efficient phase equilibrium calculation has been created. For chemical reactions the model uses actual well-defined chemical components (base components) and kinetically limited stoichiometric reactions. For the phase equilibrium calculations base components are combined to lumps in order to accelerate the calculations. The physical properties of lumped component are based on those of the base components. The novelty involved in the model is that the physical properties of the lumps are continuously updated when the composition of the base components changes. The advantage of the model is that it avoids the tedious iteration of phase equilibrium with the full base component set, whereas allows full component set in kinetics calculation. The model is computationally very efficient and is demonstrated to work with a system of 19 444 base components and 486 079 reactions. For vapor–liquid equilibrium (VLE) calculations the...

Hydrocracking of algae oil to aviation fuel-ranged hydrocarbons over NiMo-supported catalysts

An algae oil from Botryococcus braunii (CnH2n–10, n = 29–34) and its model compound (squalene, C30H50) were hydrocracked to light hydrocarbons over NiMo-supported catalysts in batch reactors. Polyoxocation [AlO4Al12(OH)24(H2O)12]7+-pillared montmorillonite (denoted by Al13-Mont) was prepared as a support for NiMo catalyst in the hydrocracking reaction. Al13-Mont had large micropores, large BET surface area, high temperature stability, and properly weak solid acidity. For the hydrocracking of squalene at 300 °C for 6 h under 4 MPa H2, NiMo/SiO2 formed squalane (C30H62) as a main product; NiMo/H-ZSM-5 formed C1−C4 gas hydrocarbons as main products; NiMo/H-Y and NiMo/SiO2-Al2O3 formed C5−C9 gasoline-ranged hydrocarbons as main products; NiMo/Al13-Mont formed C10−C15 aviation fuel-ranged hydrocarbons as main products. The catalysts containing NiMo and solid acids acted as bifunctional catalysts in the squalene hydrocracking reaction: squalene (C30H50) was firstly hydrogenated to squalane (C30H62) on the NiMo sites, and then the formed squalane was cracked to light hydrocarbons on the solid acids. The NiMo/Al13-Mont catalyst achieved a C10−C15 aviation fuel-ranged hydrocarbons yield of 52% for the hydrocracking of Botryococcus braunii oil at 300 °C for 6 h.

Effect of reaction temperature and time on the products and asphaltene dispersion stability in slurry-phase hydrocracking of vacuum residue

The effect of reaction temperature and time on the products and the asphaltene dispersion according to the residue conversion was investigated in a slurry-phase hydrocracking reaction. The experiments were carried out with two different approaches to control the hydrocracking reaction, which the reaction time was changed from 4 h to 20 h (at 410 °C) and the reaction temperature from 430 °C to 453 °C (for 1 h) at 100 bar (at 80 °C) of initial hydrogen pressure and 500 wt.ppm of molybdenum concentration. As a result, it was found that the control of the reaction time and reaction temperature may give different effect to the stability of the asphaltene in the liquid phase in spite of the same VR conversion. In order to understand this, the dipole moments of the liquid product and structural change of the asphaltene was compared. And it was found that enhancing hydrogenation reaction by increasing reaction time at low temperature delayed the time of decreasing point for dipole moments of the liquid phase and increased the length of alkyl chain of remaining asphaltene. Therefore, it is considered that the dispersibility of asphaltene with high polarity is increased. Additionally, it was found that enhancing hydrogenation can also improve the catalyst dispersion in the liquid phase below 80% of residue conversion.