Deactivation of Catalysts and Reaction Kinetics for Upgrading of Renewable Oils

The transport sector is one of the main contributors of greenhouse gas emissions in the world. Advanced biofuels from renewable oils can play a decisive role in reducing carbon emissions from the transport sector. Advanced biofuels from waste streams like tall oil, used cooking oil etc. can lower the CO2 emissions in a range of up to 90% making our future and society more sustainable. Catalytic hydrodeoxygenation (HDO) is a process in which oxygen is selectively removed from renewable oils to produce advanced biofuels. These biofuels are drop-in hydrocarbons which can substitute fossil-based fuels without infrastructure or vehicle changes. This thesis focuses on aspects of catalyst deactivation and reaction kinetics during the production of such biofuels via HDO reactions.Renewable oils can be sourced from varied streams like tall oil (paper industry residue), animal fats, used cooking oil etc. due to which their composition and innate contaminants can vary significantly. Phosphorus, alkali metals like potassium or sodium, iron, silicon, chlorides etc. are some of the common poisons present in renewable feedstocks which can cause catalyst deactivation during the upgrading process. In the first section of this thesis, the influence of iron (Fe), phosphorus (from phospholipid) and potassium (K) as poisons during HDO of fatty acids over molybdenum based sulfided catalysts was investigated. A range of concentration of poisons was evaluated to show that these poisons severely impacted the activity of catalysts. A change in selectivity was also seen, which is an important parameter to consider during the industrial production of biofuels. Different characterization techniques were employed to study the poison distribution on catalyst samples from lab experiments as well as from a refinery. It was suggested that Fe deposits preferentially near Ni-rich sites which deteriorated the ability of these catalysts to create active sites i.e. via sulfur vacancies. However, phosphorus resulted in irreversible phase transformation of the support to aluminum phosphate (AlPO4) which resulted in catalyst deactivation via pore blockage. In the comparative experiments, with spherical catalyst particles (1.8 mm), the Fe caused the strongest deactivation among P and K, based on the quantity added to feed oil. Although, considering the decrease in surface area per unit of deposited element after the experiment, then P caused the most deactivation. It was concluded that Fe deposited mostly near to the outer surface irrespective of concentration while P and K penetrated deeper in catalyst particles such that the distribution profile was dependent on the concentration.Reaction kinetics of HDO of fatty acids provides critical knowledge which could be applied at the refining scale in process design and optimization. The activity and selectivity of NiMo catalyst during HDO of stearic acid was studied by varying reaction conditions like temperature, pressure, feed concentration and batch-reactor stirring rate and using intermediates like octadecanal and octadecanol. A deeper understanding of the reaction scheme and selectivities was developed based on the experimental results. A Langmuir–Hinshelwood-type mechanism was used to develop a kinetic model which well-predicted the changes in selectivities at varying reaction conditions

Catalytic Upgrading of Waste Oils to Advanced Biofuels – Deactivation and Kinetic Modelling Study

The demand for liquid hydrocarbons as transportation fuels is enormous and ever growing.Advanced biofuels is one of the promising solutions to keep pace with the global transitionto cleaner energy by reducing greenhouse gas emissions from the transport sector. It ispossible to selectively remove oxygen from waste oils like tall oil, used cooking oil etc. viaa catalytic hydrodeoxygenation (HDO) process to produce advanced biofuels. Thesebiofuels have similar molecules as in the traditional fossil-based fuels and exhibit improvedperformance. This thesis focuses on aspects of catalyst deactivation and kinetic modellingof HDO reactions.\ua0In the first study, the influence of iron (Fe) as a poison during HDO of a model compoundfor renewable feeds (Oleic acid) over molybdenum based sulfided catalysts wasinvestigated. Fe is a potential contaminant in renewable feeds due to corrosion duringtransportation and storage in iron vessels. A series of experiments with varying Fe-oleateconcentration in the feed over MoS2/Al2O3 and NiMoS/Al2O3 catalysts. There was a salientdrop in the activity of the catalysts. At higher Fe concentration, for the NiMoS catalyst, theselectivity for the direct hydrodeoxygenation product (C18 hydrocarbons) increased.However, it was opposite for the MoS2 catalyst. There was a decrease in the yield of directhydrodeoxygenation products and an increase in yield of decarbonated products. It wasproposed that Fe interacted with these two catalyst systems differently. Fe influenced thecritical step of creation of sulfur vacancies in a negative way which resulted in loweractivity. Microscopic analysis indicated that Fe was preferentially deposited close oraround the nickel promoted phase, which explained why the role of Ni as a promoter forthe decarbonation route was subdued for the NiMoS catalyst.\ua0In the second study, the kinetics during HDO of stearic acid (SA) over a sulfidedNiMo/Al2O3 catalyst were explored to investigate the reaction scheme. Model compoundslike octadecanal (C18=O) and octadecanol (C18-OH) were employed to understand thereaction steps and quantify the selectivity. A Langmuir–Hinshelwood-type kinetic modelwas used to investigate the kinetics. The results from the proposed kinetic model werefound to be in good agreement with experimental results. In addition, the model couldeffectively reproduce the observed experimental profiles of different intermediates likeC18=O and C18-OH and illustrate phenomena like inhibiting effects of the fatty acid

Brain Tumor Segmentation of MRI Images Using Processed Image Driven U-Net Architecture

Brain tumor segmentation seeks to separate healthy tissue from tumorous regions. This is an essential step in diagnosis and treatment planning to maximize the likelihood of successful treatment. Magnetic resonance imaging (MRI) provides detailed information about brain tumor anatomy, making it an important tool for effective diagnosis which is requisite to replace the existing manual detection system where patients rely on the skills and expertise of a human. In order to solve this problem, a brain tumor segmentation & detection system is proposed where experiments are tested on the collected BraTS 2018 dataset. This dataset contains four different MRI modalities for each patient as T1, T2, T1Gd, and FLAIR, and as an outcome, a segmented image and ground truth of tumor segmentation, i.e., class label, is provided. A fully automatic methodology to handle the task of segmentation of gliomas in pre-operative MRI scans is developed using a U-Net-based deep learning model. The first step is to transform input image data, which is further processed through various techniques—subset division, narrow object region, category brain slicing, watershed algorithm, and feature scaling was done. All these steps are implied before entering data into the U-Net Deep learning model. The U-Net Deep learning model is used to perform pixel label segmentation on the segment tumor region. The algorithm reached high-performance accuracy on the BraTS 2018 training, validation, as well as testing dataset. The proposed model achieved a dice coefficient of 0.9815, 0.9844, 0.9804, and 0.9954 on the testing dataset for sets HGG-1, HGG-2, HGG-3, and LGG-1, respectively

Customized catalytic hydropyrolysis of biomass to high-quality bio-oil suitable for co-processing in FCC refining unit

Please click Additional Files below to see the full abstract

Stabilization of bio-oil from simulated pyrolysis oil using sulfided NiMo/Al2O3 catalyst

Pyrolysis oil comprises compounds with a broad range of functional groups making its thermal/catalytic upgrading challenging due to the formation of undesired char. In this context, the current contribution addresses the thermal and catalytic hydrotreatment of a simulated pyrolysis oil containing all the representative groups of compounds under bio-oil stabilization conditions (180–300 \ub0C, 60 bar, 4 h) using sulfided NiMo/Al2O3. The effect of reaction conditions and different oxygenated organic compounds on the yields and properties of products was compared thoroughly. Interestingly, a correlation between the presence/absence of oxygenated furan and sugar compounds was found to significantly affect the yield of liquid product containing stabilized compounds. The presence of such compound groups significantly enhances the solid formation via oligomerization and polymerization reactions. To gain further insight, the solid products were analyzed/characterized in detail to elucidate their characteristics by extracting them into a dimethyl sulfoxide (DMSO) soluble and insoluble solid fraction. It was found that in the presence of NiMo/Al2O3, increasing temperature from 180 to 300 \ub0C enhances the formation of liquid product due to transformation of some of the soluble solids, while for experiments without the catalyst, the formation of solids was significantly higher. Oppositely, during heating up to 180 \ub0C, no solids were found in the case without the catalyst, however the presence of the catalyst during heating resulted in solid formation due to various catalytic reactions that promoted char formation. Analysis of solids revealed that the structure of soluble solids at lower temperatures (180 \ub0C) using the catalyst was closely related to sugar derivatives, whereas the corresponding insoluble solids with higher molecular weight were not fully char-like developed. However, at higher temperatures, the soluble and insoluble solid compositions were found to contain aliphatic compounds and fully developed char, respectively. Therefore, the stabilization of furan particularly with attached carbonyl groups and sugars derivatives in pyrolysis oil is of great importance to improve upgrading efficiency

Upgrading of triglycerides, pyrolysis oil, and lignin over metal sulfide catalysts: A review on the reaction mechanism, kinetics, and catalyst deactivation

Human activities such as burning fossil fuels for energy production have contributed to the rising global atmospheric CO2 concentration. The search for alternative renewable and sustainable energy sources to replace fossil fuels is crucial to meet the global energy demand. Bio-feedstocks are abundant, carbon-rich, and renewable bioresources that can be transformed into value-added chemicals, biofuels, and biomaterials. The conversion of solid biomass into liquid fuel and their further hydroprocessing over solid catalysts has gained vast interest in industry and academic research in the last few decades. Metal sulfide catalysts, a common type of catalyst being used in the hydroprocessing of fossil feedstocks, have gained great interest due to their low cost, industrial relevance, and easy implementation into the current refining infrastructures. In this review, we aim to provide a comprehensive overview that covers the hydrotreating of various bio-feedstocks like fatty acids, phenolic compounds, pyrolysis oil, and lignin feed using sulfided catalysts. The main objectives are to highlight the reaction mechanism/networks, types of sulfided catalysts, catalyst deactivation, and reaction kinetics involved in the hydrotreating of various viable renewable feedstocks to biofuels. The computational approaches to understand the application of metal sulfides in deoxygenation are also presented. The challenges and needs for future research related to the valorization of different bio-feedstocks into liquid fuels, employing sulfided catalysts, are also discussed in the current work

Slurry co-hydroprocessing of Kraft lignin and pyrolysis oil over unsupported NiMoS catalyst: A strategy for char suppression

Pyrolysis oil (PO) assisted Kraft lignin (KL) liquefaction over an unsupported NiMoS catalyst in a paraffin solvent was explored in this work. A paraffin solvent was used to represent hydrogenated vegetable oil (HVO) which is a biofuel. We have for the first time showed that when co-processing Kraft lignin with pyrolysis oil in a paraffin solvent the char formation could be completely suppressed. The complex composition of PO, containing various compounds with different functional groups, was able to aid the depolymerization pathways of lignin by obstructing the condensation path of reactive lignin derivatives. To further understand the role of different functional groups present in pyrolysis oil during lignin liquefaction, we investigate the co-hydroprocessing of Kraft lignin with various oxygenate monomers using unsupported NiMoS. 4-propylguaiacol (PG) was found to be the most efficient monomer for stabilizing the reactive lignin intermediates, resulting in a low char yield (3.7%), which was 4 times lower than the char production from Kraft lignin hydrotreatment alone. The suppressed rate of lignin fragment repolymerization can be attributed to the synergistic effect of functional groups like hydroxyl (-OH), methoxy (-OCH3), and propyl (-C3H7) groups present in PG. These groups were found to be able to stabilize the lignin depolymerized fragments and blocked the repolymerization routes enabling efficient lignin depolymerization. It was found that the presence of a co-reactant like PG during the heating period of the reactor acted as a blocking agent facilitating further depolymerization routes. Finally, a reaction network is proposed describing multiple routes of lignin hydroconversion to solid char, lignin-derived monomers, dimers, and oligomers, explaining why the co-processing of pyrolysis oil and Kraft lignin completely suppressed the solid char formation

Elucidating the role of NiMoS-USY during the hydrotreatment of Kraft lignin

Major hurdles in Kraft lignin valorization require selective cleavage of etheric and C–C linkages and subsequent stabilization of the fragments to suppress repolymerization reactions to yield higher monomeric fractions. In this regard, we report the development of efficient NiMo sulfides and ultra-stable Y zeolites for the reductive liquefaction and hydrodeoxygenation of Kraft lignin in a Parr autoclave reactor at 400 \ub0C and 35 bar of H2 (@25 \ub0C). Comparing the activity test without/with catalyst, it is revealed that NiMo sulfides over ultra-stable Y zeolites (silica/alumina = 30) achieved a significant reduction (∼50 %) of the re-polymerized solid residue fraction leading to a detectable liquid product yield of 30.5 wt% with a notable monocyclic and alkylbenzenes selectivity (∼61 wt%). A physical mixture counterpart, consisting of hydrothermally synthesized unsupported NiMoS and Y30, on the other hand, shows lower selectivity for such fractions but higher stabilization of the lignin fragments due to enhanced access to the active sites. Moreover, an extended reaction time with higher catalyst loading of the impregnated NiMoY30 facilitated a remarkable alkylbenzene (72 wt%) selectivity with an increased liquid yield of 38.9 wt% and a reduced solid residue of 16.4 wt%. The reason for the high yield and selectivity over NiMoY30, according to the catalyst characterization (H2-TPR, XPS, TEM) can be ascribed to enhanced stabilization of depolymerized fragments via H2-activation at a lower temperature and high hydrodeoxygenation ability. In addition, the better proximity of the acidic and deoxygenation sites in NiMoY30 was beneficial for suppressing the formation of polycyclic aromatics

Influence of bio-oil phospholipid on the hydrodeoxygenation activity of NiMoS/Al2O3 catalyst

Hydrodeoxygenation (HDO) activity of a typical hydrotreating catalyst, sulfided NiMo/γ-Al2O3for deoxygenation of a fatty acid has been explored in a batch reactor at 54 bar and 320\ub0C in the presence of contaminants, like phospholipids, which are known to be present in renewable feeds. Oleic acid was used for the investigation. Freshly sulfided catalyst showed a high degree of deoxygenation activity; products were predominantly composed of alkanes (C17 and C18). Experiments with a major phospholipid showed that activity for C17 was greatly reduced while activity to C18 was not altered significantly in the studied conditions. Characterization of the spent catalyst revealed the formation of aluminum phosphate (AlPO4), which affects the active phase dispersion, blocks the active sites, and causes pore blockage. In addition, choline, formed from the decomposition of phospholipid, partially contributes to the observed deactivation. Furthermore, a direct correlation was observed in the accumulation of coke on the catalyst and the amount of phospholipid introduced in the feed. We therefore propose that the reason for the increased deactivation is due to the dual effects of an irreversible change in phase to aluminum phosphate and the formation of choline

Kinetic study of hydrodeoxygenation of stearic acid as model compound for renewable oils

The kinetics during hydrodeoxygenation (HDO) of stearic acid (SA) was investigated to explore the fundamental chemistry and the reaction scheme involved for the reaction with a sulfide NiMo/Al2O3catalyst. Intermediates like octadecanal (C18 O) and octadecanol (C18 OH) were used to resolve the reaction scheme and explain the selectivity for the three major reaction routes (decarboxylation, decarbonylation and direct-HDO). Several reaction parameters, like temperature, pressure, feed concentration and batch-reactor stirring rate, were explored for their effect on changes in rate of conversion and selectivity. A weaker dependence on pressure (40–70 bar) and strong dependence on temperature (275–325 \ub0C) was found for the product distribution during HDO of SA. A model based on Langmuir–Hinshelwood type kinetics was developed to correlate the experimental data. The model well predicted trends in variation of selectivities with the reaction conditions, in part by including intermediates like octadecanol and octadecanal and it predicted phenomenon like inhibiting effects of the fatty acid. The proposed kinetic model is expected to be applicable to liquid phase HDO of different renewable feeds containing long chain fatty acids, methyl esters and triglycerides etc