Pyrolysis Fuel Oil Research Articles

Compositional Characterization of Pyrolysis Fuel Oil from Naphtha and Vacuum Gas Oil

Steam cracking of crude oil fractions gives rise to substantial amounts of a heavy liquid product referred to as pyrolysis fuel oil (PFO). To evaluate the potential use of PFO for production of value-added chemicals, a better understanding of the composition is needed. Therefore, two PFO’s derived from naphtha (N-PFO) and vacuum gas oil (V-PFO) were characterized using elemental analysis, SARA fractionation, nuclear magnetic resonance (NMR) spectroscopy, and comprehensive two-dimensional gas chromatography (GC × GC) coupled to a flame ionization detector (FID) and time-of-flight mass spectrometer (TOF-MS). Both samples are highly aromatic, with molar hydrogen-to-carbon (H/C) ratios lower than 1 and with significant content of compounds with solubility characteristics typical for asphaltenes and coke (i.e. n-hexane insolubles). The molar H/C ratio of V-PFO is lower than the one measured for N-PFO, as expected from the lower molar H/C ratio of the VGO. On the other hand, the content of n-hexane insolubles i...

The Processing of Pyrolysis Fuel Oil by Dielectric Barrier Discharge Plasma Torch

In present paper, an atmospheric-pressure low-temperature plasma treatment of pyrolysis fuel oil (PFO) was investigated in dielectric barrier discharge plasma torch reactor. The effect of the applied voltage and the volume of feedstock, as the main parameters, on the cracking of PFO were studied. By increasing the applied voltage from 10 to 16 kV, the production rate of hydrocarbons containing methane, ethylene, acetylene, propane, propylene, and C4 rise 18 times. In this case, the production rate of hydrogen increases by approximately 14 times and reaches 7.27 × 10−3 mol/min for 16 kV. In the feedstock volume investigation, based on limitation of reactor volume, the production rate of hydrocarbons decreased from 0.44 × 10−3 to 0.15 × 10−3 mol/min by increasing volume of feedstock from 1 to 5 cc.

Synthesization and Characterization of Pitch-based Activated Carbon Fiber for Indoor Radon Removal

In this study, pitch-based activated carbon fibers (ACFs) were modified with pyrolysis fuel oil (PFO). Carbonized ACF samples were activated at 850℃, 880℃ and 900℃. A scanning electron microscope (SEM) and a BET surface area apparatus were employed to evaluate the indoor radon removal of each sample. Among three samples, the BET surface area and micropore area of ACF880 recorded the highest value with 1,420 m2∙g-1 and 1,270 m2∙g-1. Moreover, ACF880 had the lowest external surface area and BJH adsorption cumulative surface area of pores with 151 m2∙g-1 and 35.5 m2∙g-1. This indicates that satisfactory surface area depends on the appropriate temperature. With the above scope, ACF880 also achieved the highest radon absorption rate and speed in comparison to other samples. Therefore, we suggest that the optimum activation temperature for PFO containing ACFs is 880℃ for effective indoor radon adsorption.

A Sustainable Nanocomposite Au(Salen)@CC for Catalytic Degradation of Eosin Y and Chromotrope 2R Dyes

Up to now, a very few catalysts have been developed approaching the heterogeneous catalytic degradation of Eosin Y and Chromotrope 2R dyes (Acid Red 29). The present study provides a complete perspective of recyclable nanocomposite Au(Salen)@CC for catalytic degradation of hazardous water pollutant dyes viz., Eosin Y & Chromotrope 2R using mild reaction conditions. New gold Salen complex doped carbon nanocomposite Au(Salen)@CC was developed by easy methodology using nano carbon cage (CC) prepared from low-priced Pyrolysis fuel oil (PFO) residue based Pitch. The UV-Vis adsorption spectroscopy results of Eosin Y and Chromotrope 2R dyes indicated complete degradation into acidic compounds which can be further mineralized to CO2 and H2O under mild reaction conditions. The heterogeneous catalyst recycled and reused successfully for four repeated experiments without loss in its adequate performance. This new sustainable and eco-friendly catalyst delivered significant degradation activity compared to existing reports and it can be further utilized for new multifunctional applications such as, radiopharmaceutical activities, heterogeneous catalysis and chiral resolution.

The effect of carbon black on reforming of pyrolysis fuel oil for a binder pitch

Pyrolysis fuel oil (PFO) has been reformed to increase the quinoline-insoluble (QI) content by adding carbon black for use as a binder pitch because petroleum-based pitch generally has a low QI content. The prepared pitch was analyzed for its aromaticity (fa), QI content, molecular weight distribution, coking value (CV), softening point (SP), and carbonization yield. The QI content of the reformed pitches increased from 0.4% to 14.1%, whereas the average molecular weight of only quinoline-soluble content decreased by increasing the carbon black content. These results indicate that carbon black adsorbs low-molecular-weight compounds and serves as nuclei for the growth of QI particles. For these reasons, the SP and carbonization yield showed a decreasing tendency, but increased when QI sharply increased.

Selective hydrocracking of pyrolysis fuel oil into benzene, toluene and xylene over CoMo/beta zeolite catalyst

Cobalt promoted Mo/β (Beta zeolite) catalysts were prepared with different metallic loadings (0.5–1.5) by a co-impregnation method. The catalytic activities of the synthesized catalysts were investigated for the selective hydrocracking of tetralin and pyrolysis fuel oil (PFO) into mono-aromatic hydrocarbons (MAH) such as benzene, toluene and xylene (BTX) in a fixed-bed reactor system. Prior to using the CoMo/β catalyst for crude PFO hydrocracking, different reaction parameters (including metallic loading, temperature, H2 pressure, and LHSV) were investigated for the hydrocracking of a model feed, tetralin, to determine the best conditions for maximum BTX yield. The CoMo(0.5)/β catalyst with a Co/Mo ratio of 0.5 produced the highest MAH yield of 62.6% at 99.5% conversion of tetralin, continuously for 140 h of reaction time without any deactivation. Furthermore, the CoMo(0.5)/β catalyst was found to be superior among the tested CoMo/β catalysts for hydrocracking real feed PFO, and it produced a maximum MAH yield of 54.8% at 99.1% conversion of PFO. The synthesized catalysts were characterized using different characterization techniques, including BET, NH3-TPD, SEM-EDS and ICP, to evaluate their physiochemical properties and determine the active sites present in the catalysts.

열분해잔사유로부터 불균일계 불소화공정에 의해 제조된 메조페이스 피치의 특성

In this study, we have prepared mesophase pitch from pyrolysis fuel oil (PFO) by heterogeneous reforming process. This process was conducted by direct fluorination at various temperature and followed by the heat treatment at 390 ℃. The re- formed pitch was then investigated by softening point analysis, elemental analysis, fourier-transform infrared spectroscopy, high resolution X-ray diffraction and polarization microscope analysis. Carbon contents of reformed pitch increased according to increasing the reaction temperature of fluorination, while oxygen, nitrogen and sulfur contents were completely eliminated. As the fluorination temperature increased, the creation, growth, coalescence and alignment process of mesophase spheres were observed. Also the interlayer spacing of carbon hexagonal planar structure decreased, while its crystalline size increased. In addition, aromatic ring compound contents increased by the condensation polymerization of aliphatic compound. These results can be attributed to the radical reactivity of the fluorine increased as the reaction temperature increased. It was considered that the fluorination reaction could help PFO to generate aromatic compounds, via promoting polymerization by radical reaction.

Pitch-based carbon fibers from coal tar or petroleum residue under the same processing condition

Spinnable pitches and carbon fibers were successfully prepared from petroleum or coal pyrolysis residues. After pyrolysis fuel oil (PFO), slurry oil, and coal tar were simply filtered to eliminate the solid impurities, the characteristics of the raw materials were evaluated by elemental analysis, 13C nuclear magnetic resonance spectrometer, matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOF-MS), and so on. Spinnable pitches were prepared for melt-spinning carbon fiber through a simple distillation under strong nitrogen flow, and further vacuum distillation to obtain a high softening point. Carbon fibers were produced from the above pitches by single-hole melt spinning and additional heat treatment, for oxidization and carbonization. Even though spinnable pitches and carbon fibers were processed under the same conditions, the melt-spinning and properties of the carbon fiber were different depending on the raw materials. A fine carbon fiber could not be prepared from slurry oil, and the different diameter carbon fibers were produced from the PFO and coal tar pitch. These results seem to be closely correlated with the initial characteristics of the raw materials, under this simple processing condition.

Petrochemical-waste-derived high-performance anode material for Li-ion batteries

To end the unsustainable disposal of pyrolysis fuel oil (PFO), which is a type of petrochemical waste, we investigate the use of PFO as a carbon source for soft carbon and evaluate it as an anode material for lithium-ion batteries. This material exhibites a much higher reversible capacity (366.5mAhg−1) than that of commercial soft carbon (236.4mAhg−1) and an extremly stable cyclability. The PFO-derived soft carbon retained 99.0% of its initial capacity after 100 cycles, and a rate capability test indicated that it retained a higher capacity at all investigated current densities compared with that of a commercial product. To further improve its lithium storage capacity, the PFO-derived soft carbon was composited with nano silicon. Notably, even after the composite was formed, the high rate capability was maintained. It was demonstrated that petrochemical waste can be converted into high-performance anode material, and this sustainable approach is readily applicable to the commercial production of anode material.

Cobalt promoted Mo/beta zeolite for selective hydrocracking of tetralin and pyrolysis fuel oil into monocyclic aromatic hydrocarbons

The Mo/β (beta zeolite) catalyst was prepared by wet-impregnation and modified with cobalt promoter. The catalytic activity of monometallic Mo/β catalyst in selective hydrocracking of tetralin into monocyclic aromatic hydrocarbons (MAH) such as benzene, toluene and xylene (BTX) was investigated in fixed bed reactor and compared its activity with bimetallic CoMo/β catalyst. The catalytic results indicates that, incorporation of promoter (Co) not only improved their catalytic activity in hydrocracking reactions but also showed long term stability as compared with Mo/β. Effect of different SiO2/Al2O3 ratio (25, 75, 150) in beta zeolite was investigated on catalytic activity of CoMo/β. CoMo/β with SiO2/Al2O3 of 25, gave highest 62.6% of desired MAH yield at 99.5% conversion of tetralin for more than 140h of reaction time. Likely, CoMo/β catalyst was also found to be effective for the conversion of pyrolysis fuel oil (PFO) into MAH. Crude PFO was distilled out at 170°C and total amount of 55wt.% PFO was received after distillation. In the PFO hydrocracking, it produced 43.3% of MAH product yield at 70% conversion of PFO, which is significantly higher than the conversion (48%) and MAH yield (34.2%) obtained from monometallic Mo/β catalysts. CoMo/β catalyst was found to be more stable as well as active for longer reaction time (140h).

Dielectric barrier discharge plasma torch treatment of pyrolysis fuel oil in presence of methane and ethane

For the first time, atmospheric-pressure low-temperature plasma treatment of pyrolysis fuel oil (PFO) was investigated in dielectric barrier discharge (DBD) plasma torch reactor. Main parameters including working gas flow rate and Ar/CH4 ratio along with the effects of separate Ar/C2H6 on the cracking of PFO were studied. By increasing the flow of argon and methane, the production rate of hydrocarbons containing ethane, ethylene, acetylene, propane, propylene, C4, and C5 increased from 1.72 to 10.48 ml/min for 4000 ml/min argon plus 400 ml/min methane as the working gas. In this case, the production rate of hydrogen increases from 10.58 to 56.86. The production rate of hydrocarbons increased from 3.53 to 13.5 ml/min by decreasing Ar/CH4 ratio from 40 to 5.6. By changing the type of working gas from methane to ethane, the production of hydrocarbons considerably increased from 6.47 to 17.75 ml/min.

Palladium, Gold, and Gold–Palladium Nanoparticle-Supported Carbon Materials for Cyclohexane Oxidation

Transition metal supported porous carbon materials have become a promising aspirant in energy storage, solid catalysis, and material chemistry. Palladium, gold, and gold–palladium anchored carbon composites (CPC-25/170, CGC-25/170, and CGPC-25/170) with two different sized carbon cages (∼25 and 170 nm) were constructed using nano-silica ball (NSB) as the template and a pyrolysis fuel oil (PFO) based pitch residue as the carbon source. The Pd, Au, and Au–Pd doped carbon nanoreactors were characterized by various physicochemical analysis methods. The developed materials were used as heterogeneous catalysts for the oxidation of cyclohexane to cyclohexanol and cyclohexanone using H2O2 at room temperature (25°C) and atmospheric pressure. The most active catalyst CGC-170 showed combined cyclohexanol and cyclohexanone yield of 7.7% after 4 h reaction time. The conversion of 2.4%, 0.05%, and 0.32% was achieved using CGC-25, CGPC-25, and CGPC-170 catalysts, respectively. Recyclability of the catalysts maintains no observable loss of performance during catalytic oxidation reaction.

Effect of microwave plasma torch on the pyrolysis fuel oil in the presence of methane and ethane to increase hydrogen production

Pyrolysis fuel oil (PFO) processing by microwave plasma torch was developed for the production of hydrogen. The PFO cracking process was performed at atmospheric pressure in the absence of catalyst and effect of plasma gas on the production rate of hydrogen and light hydrocarbons (C2–C4) was evaluated. In the first step, effect of the applied power and the working gas flow rate was investigated. In the second step, the applied power and working gas rate were set to 650 W and 4000 sccm, respectively, which were provided by combining methane or ethane as 0%, 2.5%, 7.5%, and 20% with argon. By increasing the percentage of the existing methane in argon, production rate of the sum of the light hydrocarbons was increased and that of hydrogen was reduced, but it was more than the case when argon was applied alone. By increasing ethane percentage, hydrogen production and light hydrocarbon rate were increased. The best conditions of the plasma gas for producing hydrogen at the power of 650 W were obtained as 5CC PFO feed, 2500 sccm (80%) argon, and 500 sccm (20%). The hydrogen production rate in optimized conditions was 2343.16SCCM with selectivity of 84.41%. Sum of the obtained hydrocarbons in this test was 434.25 sccm. Another parameter in the present study was the feed volume processed by plasma. In this case, 5 cc, 3 cc, and 1 cc of the feed were tested when the plasma gas was 3000 sccm argon with the power of 650 W. The results showed that, by increasing the feed, the products were increased. In the processing of 5 cc feed with plasma, 896.41 sccm hydrogen and 61 sccm light hydrocarbon were produced.

A new pitch reforming from pyrolysis fuel oil by UV irradiation

In this study, pyrolysis fuel oil (PFO) was reformed using heat-treatment and UV irradiation, along with a cross-linker at various concentrations. Oxygen elements of the reformed pitches were increased as the amount of the cross-linker was increased. UV-treated reformed pitches were also composed of more aromatic carbon compounds than pitches reformed by heat-treatment. The softening points of the reformed pitches were measured in the range of 113.6–181.1°C according to the quantity of cross-linker used. The UV irradiation reforming is practical and helpful for the production of more aromatic pitch.

Boron-doped carbon prepared from PFO as a lithium-ion battery anode

A petroleum-based Li-ion battery anode was prepared by thermal condensation of pyrolysis fuel oil (PFO) and a subsequent carbonization process. H3BO3 was used as a catalyst for efficient thermal condensation, carbonization and battery performance. The influence of the carbonization temperature on the carbon structure and battery performance was also investigated. Notably, H3BO3 promoted thermal condensation and formation of a graphitic carbon structure and acted as a boron doping agent. Boron-doping attenuated the highly active sites in carbon and effectively controlled formation of the SEI layer, which resulted in an increase in the initial efficiency of the anode. For the sample carbonized at 900 °C, a reversible capacity of 301 mAh/g and an initial efficiency of 78.6% were obtained. In addition, the samples obtained at different carbonization temperatures were all highly stable over 50 cycles, with capacity retentions greater than 90%.

Development of Palladium, Gold and Gold-Palladium Containing Metal-Carbon Nanoreactors: Hydrogen Adsorption

Metal-carbon nanoreactors (MCNRs) were prepared from a pristine carbon cage (CC) using a simple and efficient template method with nano silica ball (NSB), pyrolysis fuel oil (PFO) and transition metals, such as palladium and gold. Metal nanoparticles were embedded in approximately 25 and 170 nm sized, highly ordered carbon cages. The newly developed Pd, Au and Au-Pd doped carbon nanoreactors were characterized by microanalysis, <TEX>$N_2$</TEX> adsorption-desorption isotherm, powder X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), transmission electron microscopy and inductively coupled plasma (ICP) analysis. The ordered MCNRs have exhibited dynamic hydrogen adsorption capability compared to the carbon cage.

The effects of microwave plasma torch on the cracking of Pyrolysis Fuel Oil feedstock

Cracking of Pyrolysis Fuel Oil (PFO) using a microwave plasma torch in liquid has developed a new process for production of valuable petrochemical hydrocarbons. Main parameters, including the power and flow rate of the carrier gases on the cracking operation were studied. The major products obtained were hydrogen and light C1, C2, C3, and C4 hydrocarbon compounds. Increasing of the power and gas flow improved the cracking of PFO, but, they were unable to change the selectivity of products. Optimal conditions were 850W for power and 5000sccm (ml/min) for flow rate and the production rate of C4 and H2 were 27.37sccm and 446.31sccm, respectively.

Preparation of multi metal–carbon nanoreactors for adsorption and catalysis

Metal–incorporated composite carbon materials have engendered great progress in the fields of catalysis, energy storage and material science because of their size and chemical and physical properties. In this study, a modern technique was applied for the development of multi metal–carbon nanoreactors (MCNRs) from a pristine carbon cage (CC) using template method with nano silica ball (NSB), pyrolysis fuel oil (PFO) and metal nanocrystals such as gold, copper, nickel, potassium and manganese. The newly prepared Au, Cu, Ni, K and Mn deposited carbon nanoreactors were fully characterized by various analytical techniques. Due to their easy fabrication protocols and broad potential applications, the MCNRs were used successfully for the chemisorptions of hydrogen and ethylene gases alongside the solvent–free heterogeneous catalytic oxidation of a secondary alcohol. The MCNRs have exhibited dynamic adsorption performance and excellent catalytic activity.

A non-chromatographic method for the separation of highly pure naphthalene crystals from pyrolysis fuel oil

An innovative approach towards the extraction of highly pure naphthalene crystals was developed using efficient and inexpensive non-chromatographic solvent extraction method from pyrolysis fuel oil (PFO). Self-crystallization of naphthalene was established during the cooling process of extracted liquor. Naphthalene crystals were recrystallized with ethanol and fully characterized by various analytical techniques such as 1H and 13C NMR, FT-IR, TGA, GCMS etc. In general, the solvent extraction and self-crystallization techniques were capable of producing accurate data for native naphthalene from PFO.

Properties of Modified Bitumen Obtained from Natural Bitumen by Adding Pyrolysis Fuel Oil

Properties of Modified Bitumen Obtained from Natural Bitumen by Adding Pyrolysis Fuel Oil