A six-lump kinetic model for HDPE/VGO blend hydrocracking

A six lump-based kinetic model has been developed for the hydrocracking of high-density polyethylene (HDPE) blended with vacuum gas oil (VGO) over a PtPd/HY zeolite catalyst. The blend (20 wt% HDPE and 80 wt% VGO) has been hydrocracked in a semi-continuous stirred tank reactor under the following conditions: 400–440 °C; 80 H2 bar; catalyst to feed (C/F) weight ratio, 0.05–0.1 gcat gfeed−1; reaction time, 15–120 min; and stirring rate, 1300 rpm. The kinetic model, which is an approach to tackle the complex reaction mechanism behind the hydrocracking of a HDPE/VGO blend, predicts the evolution over time of product distribution (gas, naphtha, light cycle oil (LCO), heavy cycle oil (HCO), HDPE and coke). The kinetic model and its computed parameters have been used for the simulation of the HDPE/VGO hydrocracking establishing that a C/F ratio of 0.075 gcat gfeed−1 and temperature–time combinations of 430 °C–10 min and 440 °C–70 min are the optimal operating conditions. Under these conditions, a proper balance between the HCO conversion (>80 %), HDPE conversion (>60 %) and liquid fuel production index (>1.0) would be obtained. This kinetic model could serve as a basis for scaling-up in the valorization of waste plastics by co-feeding them to industrial hydrocracking units, within a Waste-Refinery strategy.This work has been carried out with the financial support of the Ministry of Science, Innovation and Universities (MICIU) of the Spanish Government (grant RTI2018-096981-B-I00), the European Union’s ERDF funds and Horizon 2020 research and innovation program under the Marie Skłodowska-Curie Actions (grant No 823745) and the Basque Government (grant IT1645-22). David Trueba thanks the University of the Basque Country UPV/EHU for his PhD grant (PIF 2018)

Modelling, simulation and multi-objective optimization of industrial hydrocrackers

Ph.DDOCTOR OF PHILOSOPH

Molecular management for refining operations

Molecular management targets the right molecules to be at the right place, at the right time and at the right price. It consists of molecular characterisation of refining streams, molecular modelling and optimisation of refining processes, as well as overall refinery optimisation integrating material processing system and utility system on the molecular level. The need to increase modelling details to a molecular level is not just a result of political regulations, which force refiners to managing the molecule properly, but also seems to be a very promising to increase the refining margin. In this work, four aspects of molecular management are investigated respectively. Molecular Type Homologous Series (MTHS) matrix framework is enhanced on both representation construction and transformation methodology. To improve the accuracy and adequacy of the representation model, different strategies are formulated separately to consider isomers for light and middle distillates. By introducing statistical distribution, which takes the composition distribution of molecules into account, the transformation approach is revolutionised to increase the usability, and tackle the challenge of possibly achieving significantly different compositions from the same bulk properties by the existing approaches. The methodology is also enhanced by applying extensive bulk properties. Case studies demonstrate the effectiveness and accuracy of the methodology. Based on the proposed characterisation method, refining processes are modelled on a molecular level, and then process level optimisation is preformed to have an insight view of economic performance. Three different processes, including gasoline blending, catalytic reforming, and diesel hydrotreating, are investigated respectively. Regarding gasoline blending, the property prediction of blending components, and the blending nonlinearity are discussed. To tightly control on the property giveaway, a molecular model of gasoline blending is developed, and then integrated into the recipe optimisation. As for the conversion processes, catalytic reforming and diesel hydrotreating, reactions and reactors are modelled separately, and then followed by the consideration of catalyst deactivation. A homogeneous rigorous molecular model of a semiregenerative catalytic reforming process, considering pressure drop, has been developed. In addition, a multi-period process optimisation model has been formulated. Regarding diesel hydrotreating, a molecular model of reactions with a three-phase trickle-bed reactor has been developed. The concept of reaction family is successfully applied. A structural contribution approach is used to obtain kinetics and adsorption parameters. A series of procedures are developed to solve the complex problem. Thereafter, a process optimisation model has been developed with the consideration of catalyst deactivation, with a new strategy on the division of catalyst life. Finally, a two-level decomposition optimisation method is extended to incorporate molecular modelling into the overall refinery optimisation, and then applied in two aspects. Firstly, with the integration of the process and the site-level models, a better perspective is obtained with regard to a material processing system. By molecular modelling of refining streams and processes, the integrated approach not only controls the molecules in products properly, but also increases the overall performance. In the second application, a framework integrating a hydrogen network with hydroprocesses is developed to target the maximum profit, rather than saving hydrogen. It allocates hydrogen on the hydrogen network level and utilise hydrogen efficiently on the process level by optimising operating conditions. Consequently, the extent of achieving the maximum profit could be fully exploited with optimal hydrogen utilisation.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Kinetic modelling simulation and optimal operation of fluid catalytic cracking of crude oil: Hydrodynamic investigation of riser gas phase compressibility factor, kinetic parameter estimation strategy and optimal yields of propylene, diesel and gasoline in fluid catalytic cracking unit

The Fluidized Catalytic Cracking (FCC) is known for its ability to convert refinery wastes into useful fuels such as gasoline, diesel and some lighter products such as ethylene and propylene, which are major building blocks for the polyethylene and polypropylene production. It is the most important unit of the refinery. However, changes in quality, nature of crude oil blends feedstock, environmental changes and the desire to obtain higher profitability, lead to many alternative operating conditions of the FCC riser. There are two major reactors in the FCC unit: the riser and the regenerator. The production objective of the riser is the maximisation of gasoline and diesel, but it can also be used to maximise products like propylene, butylene etc. For the regenerator, it is for regeneration of spent or deactivated catalyst. To realise these objectives, mathematical models of the riser, disengage-stripping section, cyclones and regenerator were adopted from the literature and modified, and then used on the gPROMS model builder platform to make a virtual form of the FCC unit. A new parameter estimation technique was developed in this research and used to estimate new kinetic parameters for a new six lumps kinetic model based on an industrial unit. Research outputs have resulted in the following major products’ yields: gasoline (plant; 47.31 wt% and simulation; 48.63 wt%) and diesel (plant; 18.57 wt% and simulation; 18.42 wt%) and this readily validates the new estimation methodology as well as the kinetic parameters estimated. The same methodology was used to estimate kinetic parameters for a new kinetic reaction scheme that considered propylene as a single lump. The yield of propylene was found to be 4.59 wt%, which is consistent with published data. For the first time, a Z-factor correlation analysis was used in the riser simulation to improve the hydrodynamics. It was found that different Z factor correlations predicted different riser operating pressures (90 – 279 kPa) and temperatures as well as the riser products. The Z factor correlation of Heidaryan et al. (2010a) was found to represent the condition of the riser, and depending on the catalyst-to-oil ratio, this ranges from 1.06 at the inlet of the riser to 0.92 at the exit. Optimisation was carried out to maximise gasoline, propylene in the riser and minimise CO2 in the regenerator. An increase of 4.51% gasoline, 8.93 wt.% increase in propylene as a single lump and 5.24 % reduction of carbon dioxide emission were achieved. Finally, varying the riser diameter was found to have very little effect on the yields of the riser products

Kinetic Modelling Simulation and Optimal Operation of Trickle Bed Reactor for Hydrotreating of Crude Oil. Kinetic Parameters Estimation of Hydrotreating Reactions in Trickle Bed Reactor (TBR) via Pilot Plant Experiments; Optimal Design and Operation of an Industrial TBR with Heat Integration and Economic Evaluation.

Catalytic hydrotreating (HDT) is a mature process technology practiced in the petroleum refining industries to treat oil fractions for the removal of impurities (such as sulfur, nitrogen, metals, asphaltene). Hydrotreating of whole crude oil is a new technology and is regarded as one of the more difficult tasks that have not been reported widely in the literature. In order to obtain useful models for the HDT process that can be confidently applied to reactor design, operation and control, the accurate estimation of kinetic parameters of the relevant reaction scheme are required. This thesis aims to develop a crude oil hydrotreating process (based on hydrotreating of whole crude oil followed by distillation) with high efficiency, selectivity and minimum energy consumption via pilot plant experiments, mathematical modelling and optimization. To estimate the kinetic parameters and to validate the kinetic models under different operating conditions, a set of experiments were carried out in a continuous flow isothermal trickle bed reactor using crude oil as a feedstock and commercial cobaltmolybdenum on alumina (Co-Mo/¿-Al2O3) as a catalyst. The reactor temperature was varied from 335°C to 400°C, the hydrogen pressure from 4 to10 MPa and the liquid hourly space velocity (LHSV) from 0.5 to 1.5 hr-1, keeping constant hydrogen to oil ratio (H2/Oil) at 250 L/L. The main hydrotreating reactions were hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeasphaltenization (HDAs) and hydrodemetallization (HDM) that includes hydrodevanadization (HDV) and hydrodenickelation (HDNi). An optimization technique is used to evaluate the best kinetic models of a trickle-bed reactor (TBR) process utilized for HDS, HDAs, HDN, HDV and HDNi of crude oil based on pilot plant experiments. The minimization of the sum of the squared errors (SSE) between the experimental and estimated concentrations of sulfur (S), nitrogen (N), asphaltene (Asph), vanadium (V) and nickel (Ni) compounds in the products, is used as an objective function in the optimization problem using two approaches (linear (LN) and non-linear (NLN) regression). The growing demand for high-quality middle distillates is increasing worldwide whereas the demand for low-value oil products, such as heavy oils and residues, is decreasing. Thus, maximizing the production of more liquid distillates of very high quality is of immediate interest to refiners. At the same time, environmental legislation has led to more strict specifications of petroleum derivatives. Crude oil hydrotreatment enhances the productivity of distillate fractions due to chemical reactions. The hydrotreated crude oil was distilled into the following fractions (using distillation pilot plant unit): light naphtha (L.N), heavy naphtha (H.N), heavy kerosene (H.K), light gas oil (L.G.O) and reduced crude residue (R.C.R) in order to compare the yield of these fractions produced by distillation after the HDT process with those produced by conventional methods (i.e. HDT of each fraction separately after the distillation). The yield of middle distillate showed greater yield compared to the middle distillate produced by conventional methods in addition to improve the properties of R.C.R. Kinetic models that enhance oil distillates productivity are also proposed based on the experimental data obtained in a pilot plant at different operation conditions using the discrete kinetic lumping approach. The kinetic models of crude oil hydrotreating are assumed to include five lumps: gases (G), naphtha (N), heavy kerosene (H.K), light gas oil (L.G.O) and reduced crude residue (R.C.R). For all experiments, the sum of the squared errors (SSE) between the experimental product compositions and predicted values of compositions is minimized using optimization technique. The kinetic models developed are then used to describe and analyse the behaviour of an industrial trickle bed reactor (TBR) used for crude oil hydrotreating with the optimal quench system based on experiments in order to evaluate the viability of large-scale processing of crude oil hydrotreating. The optimal distribution of the catalyst bed (in terms of optimal reactor length to diameter) with the best quench position and quench rate are investigated, based upon the total annual cost. The energy consumption is very important for reducing environmental impact and maximizing the profitability of operation. Since high temperatures are employed in hydrotreating (HDT) processes, hot effluents can be used to heat other cold process streams. It is noticed that the energy consumption and recovery issues may be ignored for pilot plant experiments while these energies could not be ignored for large scale operations. Here, the heat integration of the HDT process during hydrotreating of crude oil in trickle bed reactor is addressed in order to recover most of the external energy. Experimental information obtained from a pilot scale, kinetics and reactor modelling tools, and commercial process data, are employed for the heat integration process model. The optimization problem is formulated to optimize some of the design and operating parameters of integrated process, and minimizing the overall annual cost is used as an objective function. The economic analysis of the continuous whole industrial refining process that involves the developed hydrotreating (integrated hydrotreating process) unit with the other complementary units (until the units that used to produce middle distillate fractions) is also presented. In all cases considered in this study, the gPROMS (general PROcess Modelling System) package has been used for modelling, simulation and parameter estimation via optimization process.Tikrit University, Ira

Kinetic modeling of the hydrocracking of polystyrene blended with vacuum gasoil

The kinetic modeling of the hydrocracking of a mixture of polystyrene (PS) and vacuum gasoil (VGO) over a PtPd/HY catalyst has been carried out. The reactions have been performed in a batch reactor under the following conditions: 380–420 °C; 80 bar; content of PS in the feed, 10 wt%; catalyst/feed ratio, 0.1 in mass; and time, 30–300 min. Different reaction networks and kinetic models have been studied, in which the evolution of product distribution (unconverted PS, dry gas, liquefied petroleum gases, naphtha, light cycle oil, heavy cycle oil and coke) with the extent of time has been quantified by considering three different simultaneous deactivation mechanisms (plastic fouling, coke deposition and metal poisoning). The kinetic model selected (based on a 7-lump reaction network) has been used for performing a parametric study, determining that 400 °C and 180 min are the optimal conditions for maximizing the yield of naphtha (35 wt%) at the same time that PS is totally converted. This original kinetic model may act as a basis for scaling-up studies focused on the large-scale valorization of waste plastics by co-feeding them into a hydrocracking unit of a Waste-Refinery.This work has been carried out with the financial support of the Ministry of Science, Innovation and Universities (MICIU) of the Spanish Government (grant RTI2018-096981-B-I00), the European Union’s ERDF funds and Horizon 2020 research and innovation program under the Marie Skłodowska-Curie Actions (grant No 823745) and the Basque Government (grant IT1645-22). David Trueba thanks the University of the Basque Country UPV/EHU for his PhD grant (PIF 2018). The authors thank for technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). The authors also acknowledge Petronor refinery for providing the feed used in the work

Accelerating kinetic parameter identification by extracting information from transient data : a hydroprocessing study case

Hydroprocessing reactions require several days to reach steady-state, leading to long experimentation times for collecting sufficient data for kinetic modeling purposes. The information contained in the transient data during the evolution toward the steady-state is, at present, not used for kinetic modeling since the stabilization behavior is not well understood. The present work aims at accelerating kinetic model construction by employing these transient data, provided that the stabilization can be adequately accounted for. A comparison between the model obtained against the steady-state data and the one after accounting for the transient information was carried out. It was demonstrated that by accounting for the stabilization, combined with an experimental design algorithm, a more robust and faster manner was obtained to identify kinetic parameters, which saves time and cost. An application was presented in hydrodenitrogenation, but the proposed methodology can be extended to any hydroprocessing reaction

Fuel production by hydrocracking of non-olefinic plastics and vacuum gasoil blends

306 p.The catalytic hydrocracking of different blends of non-olefinic polymers (polystyrene, polymethylmethacrylate and polyethylene terephthalate) with vacuum gasoil has been studied to produce fuel streams suitable for inclusion in refinery pools. For this purpose, a catalyst synthesized in the laboratory composed of Pt and Pd supported on a zeolite Y has been used. For all the mixtures, the influence of the operating conditions (time, temperature, pressure) and the effect they have on the yields of the fractions of interest (naphtha and light cycle oil), as well as on their composition, have been tested. In addition, special attention has been paid to the physicochemical phenomena that take place during the reactions in order to analyze the catalyst behaviour and the different causes of its deactivation with a view to its implementation in industrial units. The use of advanced analytical techniques has allowed to establish the compositional framework of all samples regardless of their heavy nature, which has allowed to determine the mechanisms of hydrocracking of plastics, as well as the routes of elimination of different families of compounds. Finally, kinetic modelling of these systems has been carried out for the optimization of the operating conditions by performing simulations aiming at the maximum conversion of the plastics and maximum yield of the target fractions, while minimizing the products of less interest