Oil Hydrocracking Process Research Articles

Soft analyzer for sulfur content in tail oil of hydrocracking process based on adaptively regularized dynamic polynomial PLS

AbstractHydrocracking process is an essential and widely used means to remove impurities such as sulfur, nitrogen, and oxygen from heavy oil in refineries. The sulfur content in the tail oil of the hydrogenation process is a key quality index that must be strictly monitored and controlled. However, the traditional measurement ways of the sulfur content suffer from either large delays or high investment and maintenance costs. To this end, a predictive model named “adaptively regularized dynamic polynomial partial least squares (ARDPPLS)” is proposed to develop soft analyzer for sulfur content estimation. The ARDPPLS takes complicated characteristics of the hydrogenation process into consideration, including process dynamics, nonlinearities, and transportation delays of materials and energies. Specifically, the dynamics and nonlinearities are modeled by the finite impulse response paradigm and polynomial fitting, respectively, and the delays of explanatory variables are automatically determined using differential evolution. In particular, a Bayesian inference‐based adaptive regularization scheme for the polynomial partial least squares is designed to tackle overfitting that results from high‐order variable augmentation and high‐order polynomials. The performance of the ARDPPLS is evaluated by a real‐world industrial wax oil hydrocracking process, showing the effectiveness of the ARDPPLS.

Coprocessing Partially Hydrodeoxygenated Hydrothermal Liquefaction Biocrude from Forest Residue in the Vacuum Gas Oil Hydrocracking Process

Coprocessing Partially Hydrodeoxygenated Hydrothermal Liquefaction Biocrude from Forest Residue in the Vacuum Gas Oil Hydrocracking Process

Molecular transformation of heavy oil during slurry phase hydrocracking process: A comparison between thermal cracking and hydrocracking

To systematically investigate the reaction mechanism of heavy oil in the slurry phase hydrocracking process, comparative experiments of thermal cracking and slurry phase hydrocracking of a residual oil were carried out. The molecular composition of sulfur and nitrogen compounds in the feedstock and their products was comprehensively characterized by gas chromatography and electrospray ionization Orbitrap mass spectrometry. The participation of hydrogen makes the apparent cracking rate in hydrocracking process significantly lower than that in the thermal cracking process, leading to a more controllable cracking degree and higher liquid yield. Nitrogen- and sulfur-containing aromatics with high molecular condensation degree are the key refractory heteroatoms because of large steric hindrance. Aromatics with ring number over 4 have high saturation reactivity, as well as the exposed five-membered heteroaromatic rings. The mutual influence of cracking, aromatic saturation, and hydrodeheteroatom during hydrocracking were also discussed according to bulk properties and molecular composition. The results deepen the understanding of the complex reaction network and mechanism of heavy oil hydrocracking process from both thermal reaction and hydrogenation perspectives, which will be instructive for the catalyst design and the process optimization.

Nickel Supported Parangtritis Beach Sand (PP) Catalyst for Hydrocracking of Palm and Malapari Oil into Biofuel

Nickel supported Parangtritis beach sand (PP) catalyst for hydrocracking of palm and malapari oil into biofuel has been conducted. The impregnation process of Nickel (Ni) metal on PP was carried out through the dry impregnation method (blending) using a precursor salt of NiCl2.6H2O with variations of Ni metal as much as 10 and 15 wt% of PP which produced Ni(A) and Ni(B) catalysts. Each catalyst was tested for activity and selectivity through the hydrocracking process of oil into biofuel using a semi-batch system reactor at a temperature of 450 oC, a hydrogen gas flow rate of 20 mL/minute for 2 hours, and a weight ratio of 1:200 catalyst:feed (w/w). The results showed that the Ni(A)/PP catalyst had the highest activity and selectivity with the yield of liquid products and the total biofuel fraction (biohydrocarbons) obtained from hydrocracking of palm oil of 68.50 and 49.87 wt%, respectively. Ni(A)/PP catalyst has a total acidity, surface area, and crystal size of 0.051 mmol/g, 4.44 m2/g, 25.86 nm, respectively. The reusability test of the Ni(A)/PP catalyst in the hydrocracking process of palm oil into biofuel after the third use resulted in a liquid product and the total biofuel fraction obtained was 64.20 and 41.46 wt%, respectively. The yield of liquid product and the total fraction of biofuel (biohydrocarbon) in hydrocracking malapari oil were 66.10, 47.83 wt%, respectively. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Conversion of Nyamplung Oil (<i>Calophyllum inophyllum </i>L.<i>)</i> into Liquid Fuel by Hydrocracking Process Using NiMo/γ-Al<sub>2</sub>O<sub>3</sub> Bimetallic Based Catalyst

The limitations of fossil fuels as one of the non-renewable energy sources in Indonesia make the discourse to create alternative and renewable sources. This research studies the effect of reaction temperature on the hydrocracking process of nyamplung oil into biofuel based on conversion parameters and component selectivity of biofuel products, as well as studying the reaction kinetics of the nyamplung oil hydrocracking process. The research was conducted in two stages, namely the catalyst preparation and the nyamplung oil hydrocracking process. The γ-Al2O3 catalyst was prepared for Ni and Mo metals using the dry impregnation method and then characterized by Energy Dispersion X-Ray Spectroscopy (EDX) showing that the levels in γ-Al2O3 (8.78 wt%) and Ni metals (1.47 wt%), Mo (1.44 wt%), for the surface area of γ-Al2O3 obtained from the Brunauner Emmet Teller (BET) analysis, which is 120.765-185.491 m2.g-1 and the average pore size is 0.229 cc/g. The hydrocracking reaction is carried out in a stirred batch reactor (Model 4563 Parr Instrument Company, 600 mL size) which is a catalyst by 10% of the volume of oil and the reactor is coated with a heating element. Then 300 mL nyamplung oil is put into a batch reactor. Temperature variations between 300-350 °C, reactor pressure 10 bar after gas H2 injected and the reaction time is 2 hours. The best catalyst performance is the NiMo/γ-Al2O3 catalyst 15% ratio of 2:2 with the resulting conversion of 97. 18%. The highest selectivity of bio-gasoline, bio-kerosene, and bio-gasoil was 1.25, 6.07, and 92.68% using a NiMo/γ-Al2O3 catalyst of 15% 2:1 ratio at 350 °C. The main composition of compounds in the bio-gasoil fraction includes n-paraffin, namely pentadecane (C15), heptadecane (C17), and hexadecane (C16), an increase in temperature seems to reduce carboxylic acid compounds and other oxygenated compounds.

Low-oxygenated biofuels production from palm oil through hydrocracking process using the enhanced Spent RFCC catalysts

Utilization of the enhanced Spent Residue Fluid Catalytic Cracking (SRFCC) catalysts through the acid treatment was conducted for the palm oil hydrocracking process to produce biofuels. The catalysts were characterized using Pyridine-probed Fourier Transform Infrared (Pyridine-FTIR) spectroscopy and Brunauer−Emmett−Teller-Barrett−Joyner−Halenda (BET-BJH) method. The higher number of Brønsted acid sites on the enhanced SRFCC catalysts leads to the lower conversion of palm oil as well as lower deoxygenation activity because of the slower carbocations formation process as the initiation reaction. On the other hand, the Lewis acid sites on the enhanced SRFCC catalysts have a significant role in the deoxygenation reaction mechanism. Meanwhile, the catalysts surface area and pore size are responsible for tailoring the diffusion mechanism of the mass transfer process of reactant molecules. The introduction of hydrogen gas in the reaction system has a significant role in deoxygenation, double bond cleavage, and de-coking process mechanisms.

Reaction Kinetics Model for a Slurry Hydrocracking Process Using Limonite Catalyst

Kobe Steel, Ltd. and Chiyoda Corp. developed the KOBELCO Slurry Phase Hydrocracking (SPH) process for the ultimate heavy oil upgrading, both at upstream wells and refineries with a cracking rate higher than 90 %. Generally, with the heavy oil hydrocracking process, a higher cracking rate is associated with a greater sludge formation rate due to a radical reaction, large molecular condensation and polymerization induced by thermal cracking. This research objective is to apply optimized operation conditions, obtained through experimental results, to the new process system’s development for the pilot and commercial plants by achieving a more than 95 wt% VR cracking rate, more than 80 wt% of oil yield, and minimizing sludge generation. For this purpose, the reaction time, amount of limonite content, reaction pressure, and reaction temperature in the 1 L autoclave are tested to find the optimal reaction point. To scale up the SPH process to pilot plants and commercial plants, a new reaction model, for which reaction conditions are theorized, must be developed. This study proposes a new reaction model by simulating the autoclave tests, verifying its validity, and discussing future challenges and plans.

Modeling and Evaluating Zeolite and Amorphous Based Catalysts in Vacuum Gas Oil Hydrocracking Process

Abstract Hydrocracking is a significant process in a refinery which is commonly used for converting heavy fractions such as vacuum gas oil (VGO) to the valuable products such as naphtha and diesel. In this research, VGO hydrocracking process was studied in a pilot scale plant in the presence of a zeolite and two amorphous based commercial catalysts called RK-NiY, RK-MNi and KF-101, respectively. In order to study the effect of support on the yield of the process, a discrete 4-lump kinetic model, including feed (vacuum gas oil and unconverted materials), distillate (diesel and kerosene), naphtha and gas was proposed for each catalyst. At first, each network had six reaction paths and twelve kinetic coefficients, and then by using the model reduction methodology, only four main routes for RK-MNi and RK-NiY, and three ones for KF-101 were designated. Results showed that the absolute average deviation (AAD%) of reduced models decreased from 5.11 %, 10.1 % and 21.8 % to 4.54 %, 8.9 % and 19.67 % for RK-MNi, KF-101 and RK-NiY, respectively. Moreover, it was confirmed that amorphous and zeolite catalysts could be selected for producing middle distillate and naphtha products, respectively.

Hydrocracking of Vacuum Gas Oil on Bimetallic Ni-Mo Sulfide Catalysts Based on Mesoporous Aluminosilicate Al-HMS

The activity and selectivity of a bimetallic Ni-Mo sulfide catalyst based on mesoporous aluminosilicate Al-HMS with Si/Al ratio of 10 in the vacuum gas oil hydrocracking process in a reactor with a fixed catalyst bed was studied. The dependence of the activity and selectivity of the NiS-MoS2/Al-HMS (Si/Al = 10) catalyst on the process parameters (temperature, hydrogen pressure, volume stock feed rate, etc.) was investigated. It was shown that in the 380-450°C range at 5 MPa hydrogen pressure the catalyst ensures conversion of the heavy part of the hydrocarbon stock into fuel fractions with high selectivity in the middle distillates and makes it possible to reduce the sulfur content of the liquid hydrocracking products.

Molecular-Level Modeling and Simulation of Vacuum Gas Oil Hydrocracking

Advancing the capabilities of refinery process models requires fundamental knowledge of hydrocarbon composition and processing behavior at the molecular level. In common practice, however, the main obstacle to reaching such a level of understanding is the difficulty to characterize the molecular composition of petroleum and its derived products with current analytical methods. A different approach is through the use of hydrocarbon composition modeling techniques to derive the molecular make up of petroleum fractions, thus enabling the development of molecular reaction models. The purpose of this study is to illustrate the application of this concept to model and simulate the vacuum gas oil hydrocracking process at the molecular level. At first the analytical characterization of the feed sample is transformed into a computational mixture of hydrocarbon molecules that is consistent with the chemistry of the actual oil sample. This molecular representation is then used as input to model the chemical transformations occurring in the hydrocracking reactor. The reaction network is organized in terms of reaction families, and reactivity parameters are modeled with quantitative structure/reactivity correlations. The developed model is tuned using experimental data obtained from a bench-scale hydrocracking reactor. Simulations showed that the model reproduces the product distribution by boiling range and hydrocarbon type, relevant product properties (e.g., API gravity), and process parameters such as hydrogen consumption and hydrocarbon vaporization, over a wide range of operating conditions.

Cracking Callophyllum Innophyllum L. Oil to Bio-gasoline by Micro-porous Based Zeolite and Al2O3 Catalysts

Natural minerals such as zeolite are local natural resources in the various regions in Indonesia which has application as a filler, bleaching agent, or dehydration agent. It also has function as green catalysts material for biomass conversion into bio-fuel. The trend movement of green and sustainable chemistry research that designing environmentally friendly chemical processes from renewable raw materials to produce innovative products derived biomass for bio-fuel. Callophyllum innophyllum L.seeds can be used as raw material for bio-energy because of its high oil content. The fatty acid and triglyceride compounds of these seeds can be cracked into bio-gasoline, which does not contain oxygen in the hydrocarbon structure. This paper focused on the preparation and formulation of the catalyst NiMo/Al2O3 and NiMo/H-Zeolite which was used in hydro-cracking process of oil from Callophyllum innophyllum L. seeds to produce bio-gasoline. The catalysts were characterized using XRD, BET and FTIR-adsorbed pyridine method. The results of hydro-cracking products mostly were paraffin (C10-C19) straight chain, with 59.5% peak area based on GC-MS analysist.

Preparation of Co–Mo supported multi-wall carbon nanotube for hydrocracking of extra heavy oil

In this study, multi-wall carbon nanotube (MWCNT) supported Co–Mo nanocatalysts with changes in synthesis steps, one and two-step, were prepared through impregnation to be used in extra heavy oil hydrocracking process. In both of the synthesized nanocatalysts, the Co/Mo weight ratio was 1/3. The nanocatalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and accelerated surface area and porosimetry (ASAP) methods. The results showed that the nanocatalysts prepared through a two-step impregnation method had higher surface area and pore volume than the other synthesized nanocatalysts.The nanocatalysts were used in hydrocracking process under mild operating conditions, 260–300°C and at H2 initial pressure of 5MPa. Hydrocracking of extra heavy oil was conducted in an autoclave reactor. The results indicated that both nanocatalysts were capable of hydrocracking heavy oil at mild operating conditions. However, the nanocatalysts synthesized through the two-step impregnation exhibited higher performance, better heavy oil to light oil conversion, and better sulfur removal than the other methods. This superiority is due to the nanocatalyst's structure and better distribution of metal clusters on the support.

Investigation of the mechanism of sediment formation in residual oil hydrocracking process through characterization of sediment deposits

In deep conversion of petroleum residues by hydrocracking, the refiners often face the problem of sediment or sludge formation, which causes equipment fouling and catalyst deactivation and leads to enormous financial burden in terms of increased costs of operation, maintenance and shutdown. The primary objective of the present study was to obtain information on the composition and structure of the sediments and to understand the mechanism of their formation. Two samples of coke-like sediments, one collected from an industrial vacuum residue hydrocracking unit, and the other produced in pilot plant experiments with the same industrially used feedstock (VR from Kuwait export crude), were analyzed by chemical analysis as well as by various other techniques, such as TGA, NMR, and FT-IR. Prior to analyses, the sediments were fractionated by sequential extraction with heptane, toluene, and tetrahydrofuran. Structural characterization of the sediment material showed the presence of a variety of polyaromatic structures with different degrees of condensation and alkyl substitution. Presentations of average molecular structures were constructed for a number of fractions, such as heptane soluble (HS, 38 wt.%), heptane insoluble–toluene soluble (HIS–TS, 31 wt.%) and tetrahydrofuran insoluble (THFIS, 28 wt.%), separated from the pilot plant sediment. The HIS–TS fraction contained a modified asphaltene-like material. It was more aromatic and contained shorter aliphatic chains than the asphaltenes obtained from VR. The presence of a large amount of HIS–TS modified asphaltenes in the pilot plant sediment suggests that asphaltenes play a key role in the initial stage of sediment formation. The industrial sediment, which underwent severe cracking and condensation reactions on prolonged exposure to high temperature conditions, was highly carbonized (THFIS, 82 wt.%).

Mathematical modeling of gas oil hydrocracking process

Mathematical modeling of gas oil hydrocracking process