Simulated Distillation Gas Chromatography Research Articles

Oleaginous yeast, Rhodotorula paludigena CM33, platform for bio-oil and biochar productions via fast pyrolysis

An oleaginous yeast Rhodotorula paludigena CM33 was pyrolyzed for the first time to produce bio-oil and biochar applying a bench-scale reactor. The strain possessed a high lipid content with the main fatty acids similar to vegetable oils. Prior to pyrolysis, the yeast was dehydrated using a spray dryer. Pyrolysis temperatures in the range of 400–600 °C were explored in order to obtain the optimal condition for bio-oil and biochar production. The result showed that a maximum bio-oil yield of 60% was achieved at 550 °C. Simulated distillation gas chromatography showed that the bio-oil contained 2.6% heavy naphtha, 20.7% kerosene, 24.3% biodiesel, and 52.4% fuel oil. Moreover, a short path distillation technique was attempted in order to further purify the bio-oil. The biochar was also characterized for its properties. The consequence of this work could pave a way for the sustainable production of solid and liquid biofuel products from the oleaginous yeast.

Production of Bio-hydrocarbon from Refined-Bleach-Deodorized Palm Oil using Micro Activity Test Reactor

Catalytic cracking of vegetable oil for the production of bio-hydrocarbons had been developed. In this study, the catalytic cracking of Refined-Bleach-Deodorized Palm Oil (RBDPO) had carried out over Fluid Catalytic Cracking Unit (FCCU) equilibrium catalyst in a micro activity test reactor at 510°C under various catalyst to oil (CTO) ratio of 1.20 - 2.01 g/g. The catalytic cracking of RBDPO had produced the organic liquid product (OLP) containing bio-hydrocarbon, water, gas, and coke on the catalyst converted to CO2 during the catalyst regeneration process. The increase in CTO ratio from 1.20 to 2.01, OLP yield decreased from 80.48% to 70.12%. The OLP was separated into gasoline, light cycle oil (LCO), and heavy cycle oil (HCO) based on boiling point difference by a simulated distillation gas chromatography (SimDis GC). High gasoline fraction as 31.56% was produced at CTO of 2.01 g/g. The gasoline fraction contained olefins, aromatics, paraffin, iso-paraffins, and a small amount of naphthenes and oxygenates. The presence of chemicals in the gasoline fraction influenced the research octane number (RON) of the fuel.Keyword: bio-hydrocarbon; catalytic cracking; micro activity test reactor; RBDPO

Biofuel preparation from waste chicken fat using coal fly ash as a catalyst: Optimization and kinetics study in a batch reactor

In this work, the thermal catalytic cracking of waste chicken fat on a coal fly ash catalyst was investigated. The objectives were to find the optimizing condition to produce the maximum biofuel using a 2k factorial level experimental design and to study the kinetics of the reaction. The experiment was performed in a laboratory scale 70-mL micro-reactor, and the obtained biofuel from the cracking process was analyzed by simulated distillation gas chromatography and gas chromatography-mass spectrometry. Furthermore, the fuel properties and elemental analysis of the biofuel were characterized. The effects of the temperature (420–460 °C), reaction time (45–75 min), catalyst loading (1–5% by weight; wt%) and an initial hydrogen (H2) pressure (100–500 kPa) on biofuel and gasoline yield were analyzed by analysis of variance. The main parameters were the reaction temperature and time. The optimum conditions, derived from using the design-expert software, was a reaction temperature and time of 444.4 °C and 45.50 min, respectively, with 1 wt% catalyst and an initial H2 pressure of 100 kPa to obtain a maximum yield of 76.2 wt% biofuel with 24.0 wt% gasoline. The acid value was decreased 3.9-fold to 13.5 mgKOH g−1, whereas the heating value was increased 1.10-fold to 42.92 MJ kg−1, which is slightly lower than that for commercial diesel. The kinetics were determined based on experimental data for temperatures from 410 to 470 °C and best fitted to a second order rate with an apparent activation energy and pre-exponential factor of 86.0 kJ mol-1 and 181.3 s−1, respectively. The possible reaction pathway commenced from the hydrolysis of triglyceride to heavy oxygenated compounds followed by carboxylation, carbonylation and hydrogenation to become heavy linear hydrocarbons (HCs), then the heavy linear HC might be thermally and catalytically cracked into middle or small paraffins and olefins.

Volatiles reaction during pyrolysis of corn stalk – Its influence on bio-oil composition and coking behavior of volatiles

Reaction of nascent volatiles is unavoidable during biomass pyrolysis and significantly influences the product yield, bio-oil quality and coking on the reactor wall. However, experimental studies in this aspect are still very limited. This work aims to advance the knowledge in this aspect using a two-stage reactor. Volatiles were generated in-situ from pyrolysis of corn stalk at 540 °C and swept off to the second-stage reactor preheated at 440–650 °C with a residence time of 1.5–4.7 s. The bio-oil quality was evaluated using simulated distillation gaschromatography. Results show that with increasing the volatiles temperature, the bio-oil yield decreases but the quality is improved: the contents of phenols, aldehydes and monocyclic aromatics increase significantly, those of esters and alcohols increase slightly and the contents of ketones, acids and furans decreases. Effect of volatiles residence time on the bio-oil quality depends on the volatiles temperature: becoming worse at 440 °C and better at 600 °C with increasing the residence time. The volatiles reaction also generates a few tetrahydrofuran-insoluble compounds, depositing on the downstream wall of the second-stage reactor (termed coke-wall) or suspending in bio-oil (termed soot-oil). The coke-wall yield increases with increasing volatiles temperature and residence time and is generally higher than the soot-oil yield.

Synergistic effect of bifunctional mesoporous ZSM-5 supported Fe-Co catalyst for selective conversion of syngas with low Ribblet ratio into synthetic fuel

Abstract The present study focuses on the catalytic conversion of H2 deficient and CO2 containing syngas over bifunctional Fe-Co bimetallic catalysts supported on mesoporous HZSM-5 (mesoHZSM-5). Mesoporosity was introduced on commercial ZSM-5 with silica to alumina mole ratio (SAR) 50 using post-synthetic modification technique by organic base treated selective desilication process with preserved MFI crystal integrity. Fe-Co bimetallic active metals were loaded on mesoHZSM-5 varying Fe-Co ratio with a constant total metal loading of 30% using the sonication process to increase active metal dispersion. The catalytic activity of synthesized catalysts was tested on a laboratory scale fixed-bed reactor using a feed mixture comprising of H2/CO/CO2/N2 (44/34/16/6 mol%). With 0.5Fe-Co/mesoHZSM-5 catalyst, high CO and CO2 conversion along with 50.6% selectivity towards a nC13-C23 range of synthetic fuel were achieved. 65% (w/w) of mainly linear saturated C13-C23 diesel range hydrocarbons are observed in quantitative liquid products distribution by Simulated Distillation Gas Chromatography (SimDis-GC). Synergistic effect of milder Bronsted acidity and hierarchial porous structure of Fe-Co bimetallic catalyst supported over mesoporous ZSM-5 resulted in enhanced syngas conversion towards high-quality C13-C23 range liquid synthetic fuel with stable catalytic activity for a longer time. The outcome of this study has a potential cost advantage for Coal to liquids (CTL) and Biomass to liquid (BTL) process by eliminating cost enhancing pretreatment (CO2 removal and H2 enrichment) units of syngas for production of liquid synthetic fuel.

Cleaner alternative liquid fuels derived from the hydrodesulfurization of waste tire pyrolysis oil

Waste tires are attractive sources for alternative energy due to their long hydrocarbon chains with a high heating value. However, the condensed (volatile portion) pyrolysis oil derived from waste tires contains a relatively large level of sulfur compounds (1.15wt%), which is not appropriate for use in combustion engines. Therefore, this research aimed to improve the waste tire pyrolysis oil (WTPO) via hydrodesulfurization (HDS) catalyzed by molybdenum (Mo), nickel–Mo (NiMo) or cobalt–Mo supported on alumina (γ-Al2O3). The maximum % sulfur removal (87.8%) was achieved when the reaction was performed at 250°C for 30min using a 2wt% NiMo/γ-Al2O3 catalyst loading based on the WTPO content and 20bar initial hydrogen pressure. The amount of sulfurous compounds in the waste tire pyrolysis oil was determined using gas chromatography spectroscopy equipped with a flame photometric detector (GC–FPD). The HDS of the WTPO was effective to reduce the sulfurous compounds, especially thiophene and its derivatives. The results from the simulated distillation gas chromatography (GC–SIMDIS) showed that the hydrodesulfurized WTPO (HDS-WTPO) was mainly composed of a light naphtha fraction (ca. 69%). The heating value of the HDS-WTPO (44MJ/kg) was similar to those for commercial diesel (45MJ/kg) and gasoline (gasohol) fuels (47MJ/kg).

Quality improvement of oil palm shell-derived pyrolysis oil via catalytic deoxygenation over NiMoS/γ-Al2O3

Crude bio-oil derived from biomass pyrolysis is inappropriate for applying in any combustion engines due to its large amount of oxygenated compounds inducing bio-oil with instability, high corrosiveness and low heating value. Thus, the aim of this research was to improve the quality of oil palm shell (OPS)-derived pyrolysis oil containing high amount of oxygenated compounds (molar oxygen/carbon (O/C) ratio=1.09) and total acid number (TAN) (151mg potassium hydroxide (KOH)/g) via catalytic deoxygenation using nickel–molybdenum sulfide supported on gamma-alumina (NiMoS/γ-Al2O3) in a fixed-bed reactor. At a constant packed bed height of 5cm, the desired catalyst fraction in the reactor was adjusted by adding γ-Al2O3 beads. After hydrogen-mediated reduction of the catalyst at 550°C, the catalytic deoxygenation using 0.50–1.00 (by wt) of catalyst fraction at 300–450°C under N2 atmosphere yielded deoxygenated bio-oil with lower molar O/C ratio and TAN value of 0.11–0.29 and 43–77mgKOH/g, respectively. Gas chromatography–mass spectrometry (GC–MS) analysis revealed that the oxygenated compounds in the crude bio-oil were mainly converted as phenol and its derivatives. The results from the simulated distillation gas chromatography (GC-SIMDIS) also showed that the major component in the deoxygenated bio-oil was in the range of naphtha fraction (ca. 40wt%).

Kinetics of the In-Situ Upgrading of Heavy Oil by Nickel Nanoparticle Catalysts and Its Effect on Cyclic-Steam-Stimulation Recovery Factor

Summary The effect of nickel nanoparticles on in-situ upgrading of heavy oil (HO) during aquathermolysis and the effect of this process on the recovery through cyclic steam injection were studied. High-temperature experiments were conducted with a benchtop reactor to study the kinetics of the reactions among oil, water, and sandstones in the presence and absence of the nickel nanoparticles. Eighteen experiments were conducted at three different temperatures and at three different lengths of time, and the evolved hydrogen sulfide during the reaction was analyzed. The kinetic analysis showed that nickel nanoparticles reduce the activation energy of the reactions corresponding to the generation of hydrogen sulfide by approximately 50%. This reaction was the breakage of C-S bonds in the organosulfur compounds of the HO. The maximal catalysis effect was observed to be at a temperature of approximately 270°C. Also, the simulated-distillation gas-chromatography (GC) analysis of the oil sample, after the aquathermolysis reactions, confirmed the catalysis effect of nickel nanoparticles. According to this analysis, by catalytic process, the concentration of the components lighter than C30 increased whereas the concentration of heavier components decreased. Next, the effect of the catalytic aquathermolysis on the recovery factor of the steam-stimulation technique was studied. The stimulation experiments consisted of three injection/soaking/production phases. The results showed that the nickel nanoparticles increased the recovery factor by approximately 22% when the nanoparticles were injected with a cationic surfactant and xanthan-gum polymer. This increase of recovery was approximately 7% more than that of the experiment conducted with the surfactant and polymer only.

Catalytic Pyrolysis of LDPE Plastic Wastes over Mortar Cement Catalyst

A CaO based catalyst synthesized from mortar previously used in construction was chosen for pyrolysis of LDPE plastic waste. The samples were calcined at temperatures of 500 and 800 °C for comparison purpose. After calcination, two mixed oxides were obtained, denoted as catalyst A and B. The chemical composition of the metal oxide catalysts and the liquid products of the pyrolysis were characterized by X-ray Fluorescence (XRF) and Simulated Distillation - Gas Chromatography (SD-GC), respectively. The XRF analysis indicated that the catalyst, reformed from the mortar cement, consisted of CaO, silica (silicon dioxide, SiO2) and alumina (aluminium (III) oxide, Al2O3) as the main constituents, though, the composition of each compound differed because of the influence of calcination temperature. Catalyst A had 41.96% of CaO, 4.27% of Al2O3 and 30.82% of SiO2 when the catalyst B had 37.04% of CaO, 2.38% of Al2O3 and 37.31% of SiO2. The amount of CaO in the catalyst B was found to be less in catalyst A. The catalyst A gave higher percentage yield of naphtha oil (48±1.14%v/v), compared to catalyst B (21±1.26%v/v). The performance of this catalyst (A) towards the pyrolysis of plastic wastes was compared to commercial grade ZSM-5 and FCC catalysts. It was found that the catalyst A, CaO based catalyst, reformed from the mortar cement, gave the highest yield of naphtha oil (48±1.14%v/v) compared to ZSM-5 (26±1.52%v/v) and FCC (16±1.09%v/v). The optimum operating temperature for the pyrolysis was found at 410 °C (in the temperature range 370 °C to 450 °C) and the optimum catalyst (A) composition was 0.3 %w/w of mortar cement catalyst in LDPE. This optimum condition gave 86.67± 0 %w/w of liquid, 12.49± 0.24 %w/w of gas and 0.84± 0.24 %w/w of solid. The catalyst A showed the best performance amongst all the catalysts towards the pyrolysis process of plastic wastes.

CRACKING OF USED VEGETABLE OIL MIXED WITH POLYPROPYLENE WASTE IN THE PRESENCE OF ACTIVATED CARBON

With respect to high energy demand and increasing price of fossil fuels, alternative energy is a concerned issue worldwide. Waste cooking oils and plastic wastes are attractive as starting materials for value creation due to their high existing volumes and cost saving from waste treatment. Therefore, in this work, liquid fuel was synthesized by cracking of used vegetable oil (UVO) mixed with polypropylene waste (PP) in the presence of activated carbon from coconut shell. The reactions were studied at a constant hydrogen pressure of 0.1 MPa in a batch reactor. The weight ratios of used vegetable oil and polypropylene waste were varied at 30 : 70, 50 : 50 and 70 : 30 with activated carbon to raw materials ratios of 2.5 and 5 wt% at the reaction temperature of 390 and 430°C, and reaction time of 30 and 60 mins. The amounts of gas, liquid and solid fractions were analyzed. The highest yield of total liquid hydrocarbon product was attained at a ratio of used vegetable oil to polypropylene waste of 30 : 70 wt% with activated carbon to raw materials ratios of 2.5 wt%, reaction temperature of 430°C and reaction time of 30 mins. Under these conditions, gas, liquid and solid fractions of 19.56, 79.69 and 0.75 wt% were observed. The distribution of oil fractions in liquid product was analyzed by the simulated distillation gas chromatography based on ASTM D2887, which is the standard test method for the boiling-range distribution of petroleum fractions. It was comprised of naphtha, kerosene, light gas oils, heavy gas oils and long residue of 33.20, 14.62, 19.72, 2.49 and 9.66 wt%, respectively.

Co-liquefaction of Coal and Used Tire in Supercritical Water

The co-liquefaction of lignite coal and used tire was performed in a 250-ml batch reactor, in supercritical water under a nitrogen atmosphere to investigate the effects of temperature (380-440℃), water/feedstock ratio (4/1-10/1 (wt./wt.)) and the % used tire content in the feedstock (0-100 wt.%) on the conversion efficiency, liquid yield and oil composition attained. The maximum conversion and oil yield were 67 and 50%, respectively, obtained at 400℃ at 1 min, with water/feedstock ratio of 10/1 and 80% used tire content. The distillation characteristics of the oil products, analyzed by simulated distillation gas chromatography, revealed that the oil composition depended significantly on the reaction temperature. The co-liquefaction of coal and used tire yielded a synergistically increased level of oil production. Moreover, the total conversion level obtained with co-liquefaction alone was almost equal to those obtained in the presence of either Fe2O3 or NiMo as catalysts, under the same conditions. Therefore, supercritical water is a good medium for the dissolution of the volatile matter from a coal and used tire matrix.

Characterization of Liquids Derived From Laboratory Coking of Decant Oil and Co-Coking of Pittsburgh Seam Bituminous Coal with Decant Oil

In this study, decant oil and a blend of Pittsburgh seam bituminous coal with decant oil were subjected to coking and co-coking in a laboratory-scale delayed coker. Higher yields of coke and gas were obtained from co-coking than from coking. Coal addition into the feedstock resulted in lighter overhead liquid. GC/MS analyses of gasoline, jet fuel, and diesel show that co-coking of coal/decant oil gave higher quantity aromatic components than that of coking of decant oil alone. Simulated distillation gas chromatography analyses of overhead liquids and GC/MS analyses of vacuum fractions show that when coal was reacted with a decant oil, the coal constituents contributed to the distillable liquids. To address the reproducibility of the liquid products, overhead liquid samples collected at the first, third, and fifth hours of experiments of 6 h duration were evaluated using simulated distillation gas chromatography and 1H and 13C NMR. NMR analyses of the liquid products showed that, even though there were sli...

Solvent Extraction of Aromatic Components from Lube-Oil Cut byN-methylpyrrolidone (NMP)

A method has been developed for the modeling of complex hydrocarbon mixtures which is based on the accurately simulated distillation gas chromatography analysis as well as the extended method of Ruzicka et al for making the model molecules. The method has been used for modeling of the complex mixture of the lube-oil cut SAE 10 in the aromatics extraction process with the solvent N-methylpyrrolidone (NMP) from the Tehran Refinery. To carry out the liquid-liquid equilibria calculations, the van der Waals surface and volume size parameters of the model molecules and NMP as well as their interaction parameters are required which they are calculated by the Bondi's group contribution method with the NMP molecule taken as a functional group according to the approach of Rahman et al. Solvent extraction process at two temperatures of 50 and 42 °C both at 1 atm have been carried out in a batch mixer-settler and the properties of resultant phases (extract and raffinate) have been determined by the precise measuring systems using the standard methods of ASTM and the well-known Riazi's equations. Finally, the results of the equilibrium calculations have been compared with the experimental data and good agreement was found.