A Review of Modelling of the FCC Unit. Part I: The Riser

Heavy petroleum industries, including the fluid catalytic cracking (FCC) unit, are useful for producing fuels but they are among some of the biggest contributors to global greenhouse gas (GHG) emissions. The recent global push for mitigation efforts against climate change has resulted in increased legislation that affects the operations and future of these industries. In terms of the FCC unit, on the riser side, more legislation is pushing towards them switching from petroleum-driven energy sources to more renewable sources such as solar and wind, which threatens the profitability of the unit. On the regenerator side, there is more legislation aimed at reducing emissions of GHGs from such units. As a result, it is more important than ever to develop models that are accurate and reliable, that will help optimise the unit for maximisation of profits under new regulations and changing trends, and that predict emissions of various GHGs to keep up with new reporting guidelines. This article, split over two parts, reviews traditional modelling methodologies used in modelling and simulation of the FCC unit. In Part I, hydrodynamics and kinetics of the riser are discussed in terms of experimental data and modelling approaches. A brief review of the FCC feed is undertaken in terms of characterisations and cracking reaction chemistry, and how these factors have affected modelling approaches. A brief overview of how vaporisation and catalyst deactivation are addressed in the FCC modelling literature is also undertaken. Modelling of constitutive parts that are important to the FCC riser unit such as gas-solid cyclones, disengaging and stripping vessels, is also considered. This review then identifies areas where current models for the riser can be improved for the future. In Part II, a similar review is presented for the FCC regenerator system.

Catalytic Hydrothermal Liquefaction of Penicillin Residue for the Production of Bio-Oil over Different Homogeneous/Heterogeneous Catalysts

In this study, penicillin residue (PR) was used to prepare bio-oil by hydrothermal liquefaction. The effects of homogeneous (organic acid and alkaline catalysts) and heterogeneous catalysts (zeolite molecular sieve) on the yield and properties of bio-oil were investigated. The results show that there are significant differences in the catalytic performance of the catalysts. The effect of homogeneous catalysts on the bio-oil yield was not significant, which only increased from 26.09 (no catalysts) to 31.44 wt.% (Na2CO3, 8 wt.%). In contrast, heterogeneous catalysts had a more obvious effect, and the oil yield reached 36.44 wt.% after adding 5 wt.% MCM-48. Increasing the amount of catalyst enhanced the yield of bio-oil, but excessive amounts of catalyst led to a secondary cracking reaction, resulting in a reduction in bio-oil. Catalytic hydrothermal liquefaction reduced the contents of heteroatoms (oxygen, mainly), slightly increased the contents of C and H in the bio-oil and increased the higher heating value (HHV) and energy recovery (ER) of bio-oil. FTIR and GC-MS analyses showed that the addition of catalysts was beneficial in increasing hydrocarbons and oxygen-containing hydrocarbons in bio-oil and reducing the proportion of nitrogen-containing substances. Comprehensive analyses of the distribution of aromatic, nitrogen-containing and oxygen-containing components in bio-oil were also performed. This work is beneficial for further research on the preparation of bio-oil by hydrothermal liquefaction of antibiotic fermentation residue.

Effect of Temperature on Gas and Liquid Products Distribution in Thermal Cracking of Nigerian Bitumen

The increasing population growth resulting in the tremendous increase in consumption of fuels, energy, and petrochemical products and coupled with the depletion in conventional crude oil reserves and production make it imperative for Nigeria to explore her bitumen reserves so as to meet her energy and petrochemicals needs. Samples of Agbabu bitumen were subjected to thermal cracking in a tubular steel reactor operated at 10 bar pressure to investigate the effect of temperature on the cracking reaction. The gas produced was analyzed in a Gas Chromatograph while the liquid products were subjected to Gas Chromatography-Mass Spectrometry (GC-MS) analysis. Heptane was the dominant gas produced in bitumen cracking at all temperatures and the reaction products show a distribution of lighter hydrocarbons most of which are in the gasoline range. The product distribution of bitumen conversion depends strongly on the cracking temperature and the oil produced contains the valuable liquid fractions. The products of thermal cracking of bitumen can be classified into the following groups; alkanes, alkenes, amines, aromatics, alkanoic acids, alkanols, esters, ethers, ketones, sulphur compounds, and nitrogen compounds. The activation energies of the products formed were determined. The LNG produced all have unusually low values activation energy (hence easily converted) pointing to the high quality of Agbabu crude The conversion process was affected by the reaction time and suggests that the transformation of bitumen into smaller fractions follows a definite reaction scheme in which the heavy oil transformed to lower fractions and was subsequently converted to smaller liquid fractions and gases.

Molecular simulation on mechanism of thiophene hydrodesulfurization on surface of Ni2P

Hydrodesulfurization reaction, as the last step of hydrothermal cracking reaction, is of great significance for the reduction of viscosity and desulfurization of heavy oil. Based on Density Functional Theory and using Dmol3 module of Materials Studio, this research simulated the adsorption and hydrodesulfurization of thiophene on Ni2P (001) surface, and discussed the hydrodesulfurization reaction mechanism of thiophene on Ni2P (001) surface. It was found that the direct hydrodesulfurization of thiophene had more advantages than the indirect hydrodesulfurization of thiophene. Finally, the optimal reaction path was determined: C4H4S+H2→C4H6.

Molecular-level reaction network in delayed coking process based on structure-oriented lumping

Based on the structure-oriented lumping method, a molecular-level reaction kinetic model of the delayed coking process, which adopted 24 structural increments to construct the feed molecular matrix containing 2,944 molecules, was established with a reaction network containing 74,581 reactions using MATLAB. The reliability of the model was verified by experimental results. According to the discriminant rules of structural increments, 173 structural vectors in gasoline and 1,132 structural vectors in diesel were classified into different group compositions, respectively. The model could track the reaction path of any specific molecule in the complex thermal cracking reaction network. The influences of operation conditions such as recycle ratio on the product distribution could be discovered through the calculation of the molecular-level model, which is helpful for the process optimization and precise regulation of product composition for the delayed coking plants.