Gasoline Range Research Articles

Fuel Property of Pyrolytic-Oil from Para Rubber De-Oiled Seed Residue

In this report, bio-oil was produced from the pyrolysis of Para Rubber de-oiled seed residue mixing with clay catalyst of 5-20%wt. under 400 to 600°C. Pyrolytic oil was determined for the thermal weight loss characteristic, heating value, structural and physical properties. Results showed the yield of pyrolytic oil increased with the increasing catalyst percentage, maximum yield of 24.59%wt. was revealed from the pyrolysis at 550°C. Using clay catalyst of 5%wt. at 400°C gave bio-oil with the highest heating value up to 49.17 MJ/kg. While pyrolytic oil which obtained from the mixture of de-oiled seed residue and 10%wt. clay at 400°C showed the thermal degradation behavior in the range of diesel and gasoline. All pyrolytic oils produced in this study have the major hydrocarbon structure of C-H stretching as investigated by FTIR. However, this product should be upgraded to get better properties closed to the commercial fuel.

ChemInform Abstract: Hydroisomerization of Sustainable Feedstock in Biomass‐to‐Fuel Conversion: A Critical Review

AbstractReview: 199 refs.

Production of gasoline fraction from bio-oil under atmospheric conditions by an integrated catalytic transformation process

This work aimed to develop an integrated process for production of gasoline fraction bio-fuels from bio-oil under atmospheric conditions. This novel transformation process included the catalytic cracking of bio-oil to light olefins and the subsequent synthesis of liquid hydrocarbon bio-fuels from light olefins with two reactors in series. The yield of bio-fuel was up to 193.8 g/(kg bio-oil) along with a very low oxygen content, high RONs (research octane numbers), high LHVs (lower heating values) and low benzene content under the optimizing reaction conditions. Coke deposition seems to be the main cause of catalyst deactivation in view of the fact that the deactivated catalysts was almost recovered by on-line treating the used catalyst with oxygen. The integrated transformation potentially provides a useful way for the development of gasoline range hydrocarbon fuels using renewable lignocellulose biomass.

Bio-based hydrocarbons and oxygenates from catalytic bio-ethanol dehydration: comparison between gallium and germanium oxides as promoters on HBeta zeolites with various silica to alumina ratios

Hydrocarbons and oxygenates can be produced from methanol or ethanol via dehydration and other reactions as green alternative routes. One of the most important factors, which govern the activity and product distribution, is the silica/alumina ratio (related to acid strength and acid density) of a zeolite support used as a catalyst in ethanol dehydration. H-ZSM-5 zeolite was often used as a catalyst for methanol or ethanol dehydration because of its shape selectivity, but its pore size limits the production of large hydrocarbons. In this work, the effects of acid density and acid strength in the product distribution were investigated using various silica/alumina ratios of H-Beta zeolites with a larger pore size, aiming to produce larger hydrocarbons than gasoline range. Gallium and germanium oxides were also doped on the H-Beta zeolites, and their effects on the product distribution were examined and compared. As a result, it was found that increasing silica/alumina ratio resulted in the reduction of acid density and acid strength of H-Beta zeolites, and the highest oil yield was obtained from using a moderate silica/alumina ratio of H-Beta (silica/alumina ratio = 37), which highly consisted of large hydrocarbons (aromatics with carbon numbers higher than 9). The support with the lowest acid density and strength tended to produce oxygenates, non-aromatics, and benzene rather than large hydrocarbons. When loaded on the zeolites with the lowest and highest acidity, gallium and germanium oxides suppressed the oil yield, promoted the production of oxygenates and distillate-range hydrocarbons, and did not change the selectivity of p-xylene in mixed xylenes. However, the differences made by the two promoters were observed to be enhanced by the use of the support with moderate acidity, especially on the increases in non-aromatic formation and p-xylene selectivity.

Development of Hybrid Fischer-Tropsch Synthesis Catalysts for Direct Production of Synthetic Gasoline from Coal-Based Syngas: An Indonesian Perspective

The Fischer-Tropsch Synthesis (FTS) represents an environmentally friendly method for producing liquid fuelfrom coal-based syngas via the hydrogenation of carbon monoxide. In order for such a process to be feasible,better catalysts that are capable of enhancing the reaction performance are required. In response to these needs,new catalysts were investigated and introduced in this work. The incorporation of zeolite into the iron based FTScatalyst was expected to help refine the hydrocarbon products and shift the product distribution from the typicalFTS product range to the middle iso-paraffins, which is a gasoline range, and eventually increase the yield of theliquid fuel. This study aims to develop catalyst for producing liquid fuel, particularly gasoline, from carbonmonoxide and hydrogen. The pH of the catalysts was found to have significant effect on the catalytic activity dueto its ability to control the amount of promoter to be precipitated in the catalyst, which results in a lowerreduction temperature. Physically mixing the iron based FTS catalyst with zeolite was found to have little effecton the catalytic activity and the product distribution, apart from slightly increasing the selectivity of iso-paraffins,which is the indication of isomerization activity. Coating of zeolite onto the iron based FTS catalyst to form acore-shell structure was intended to enhance the ease of migration of the reactant and thus increasing thecatalytic activity and shifting the product distribution towards the gasoline range. While zeolite shell has beensuccessfully coated uniformly on the iron based core using hydrothermal synthesis technique, the formation ofthick zeolite shell might have blocked the active FTS sites on the iron based catalyst to some extent and isbelieved to have contributed to the low activity of the core-shell catalyst.

ChemInform Abstract: Synthesis of Green Fuels from Biogenic Waste Through Thermochemical Route — The Role of Heterogeneous Catalyst: A Review

AbstractReview: 159 refs.

Production of gasoline range hydrocarbons from methanol on hierarchical ZSM-5 and Zn/ZSM-5 catalyst prepared with soft second template

Nano hierarchical mesoporous ZSM-5 catalysts were prepared with cationic dimethyldiallyl ammonium chloride acrylamide copolymer (PDDA) as a soft second template. Using ZSM-5 catalyst as a matrix, Zn/ZSM-5 catalysts were also obtained by the wet impregnation method. The effect of the PDDA amount and Zn loadings on the properties of the catalysts, including crystallinity, morphology, textural properties, acid nature and catalytic activity in MTG reaction, was investigated by XRD, FESEM, TEM, Nitrogen adsorption–desorption isotherms and NH3-TPD method, respectively. The MTG reaction was performed in a fixed bed reactor, and the result revealed that the nano hierarchical ZSM-5 catalyst prepared with a PDDA/Si molar ratio of 0.070 possesses longer stable phase of 70 h with a liquid hydrocarbon selectivity of 29.8%. Zn/ZSM-5 catalyst with a Zn/ZSM-5 ratio of 0.07 wt.% shows the highest liquid hydrocarbon selectivity, reaching 62.5%.

Design of Carbon‐Encapsulated Fe3O4 Nanocatalyst with Enhanced Performance for Fischer–Tropsch Synthesis

AbstractFischer–Tropsch synthesis (FTS), an important process for the production of liquid fuels and chemicals from syngas derived from coal and biomass, is receiving renewed interest for both industrial and academic applications. Adjusting the product distribution of hydrocarbons is the focus of research in this field. Herein, a novel carbon‐encapsulated Fe3O4 nanocatalyst was synthesized by a simple one‐step solvothermal method without calcination. The catalyst exhibited excellent catalytic activity and higher selectivity for C5–12 hydrocarbons (gasoline range products) than the traditional Fe2O3 catalyst. A 45.25 % C5–12 selectivity was obtained for Fe3O4@C, which is close to the maximum value from the Anderson–Schulz–Flory distribution.

Guayule (Parthenium argentatum) pyrolysis biorefining: Production of hydrocarbon compatible bio-oils from guayule bagasse via tail-gas reactive pyrolysis

Abstract Guayule (Parthenium argentatum) is a woody desert shrub cultivated in the southwestern United States as a source of natural rubber, organic resins, and high energy biofuel feedstock from crop residues. We used guayule bagasse, the residual biomass after latex extraction as feedstock in a pyrolysis process that employs a reactive gas environment to formulate a special intermediate bio-oil product that allows use of conventional hydrotreating with conventional noble metal catalysts and a simple distillation process to synthesize hydrocarbon (drop-in) fuels. The said guayule-bagasse tail gas reactive pyrolysis (TGRP) process comprises pyrolyzing the guayule bagasse in a fluidized-bed reactor in the presence of a reactive and flammable tail gas (comprising CO ∼ 30%, CH4 ∼ 16%, CO2 ∼ 40%, H2 ∼ 10%, C2H4 ∼ traces) generated in the pyrolysis process and without the use of catalyst to produce bio-oil with C/O molar ratio of 14/1 in organic yields of 34–40 wt% having an energy content of 31–37.5 MJ/kg. When we further processed the said bio-oil by centrifugation, we obtained 85 wt% yield and further 50–65 wt% yields following a continuous hydrotreatment over common noble metals (Pt, Ru or Pd) on a carbon support. Distillation of this mixture yielded >95 wt% hydrocarbon liquid fuel mixture comprising 30.4% gasoline (C5–C7), 37% jet (C8–C12) and 24% diesel (C13–C22). Analysis of a composite mixture of the hydrotreated product from the bagasse showed the majority of the sample (66%) was C12 and below, which falls within the gasoline (naphtha) range with the greatest fraction of naphtha falling within the C8–C10 range. Beyond C12, the molecular weights increased through the diesel range (34%), with C37 being the highest observable molecular weight. The product met several ASTM standards for drop-in fuels, but the sulfur content (primarily due to latex extraction additives) was relatively high at around 300 ppm, indicating that hydrodesulfurization may be required to be infrastructure ready.

Fischer-Tropsch synthesis on Co-Al2O3-(promoter)/ZSM5 hybrid catalysts for the production of gasoline range hydrocarbons

The Fischer-Tropsch synthesis (FTS) reaction was investigated for the direct production of gasoline range hydrocarbons (C5-C9) from syngas on Ru-, Pt- and La-promoted Co-Al2O3/ZSM-5 (Si/Al=25) hybrid catalysts prepared by co-precipitation method in a slurry. The hybrid catalysts were characterized by BET surface area, XRD, H2-TPR and NH3-TPD analyses. Their physicochemical properties were correlated with the activity and selectivity of the catalysts. The promoted Co-Al2O3-(promoter)/ZSM-5 hybrid catalysts were superior to the unpromoted Co-Al2O3/ ZSM-5 catalyst in terms of better C5-C9 yield. In particular, the Co-Al2O3-Pt/ ZSM-5 hybrid catalyst exhibited the highest catalytic activity with a low C1 and olefin selectivity and a high C5-C9 selectivity. It could be due to not only a higher value for the reduction degree by H2-TPR, but also assigned to weak acidic sites of a low temperature desorption peak by NH3-TPD.

Increasing Octane Value in Catalytic Cracking of n-Hexadecane with Addition of *BEA Type Zeolite

In this study, multifunctional catalysts were developed by adding *BEA or MFI zeolite with high Si/Al ratio to a residual fluidized catalytic cracking (RFCC) catalyst and tested in the catalytic cracking of n-hexadecane, which is a heavy crude oil model compound, for the purpose of increasing the octane value of produced gasoline under the strong hydrogen transfer activity of the RFCC catalyst. Reaction products analysis revealed that the addition of *BEA zeolite to the RFCC catalyst increased the yields of olefins and multi-branched paraffins, which resulted in improvement of the octane value without sacrificing gasoline yield. On the contrary, the addition of MFI zeolite decreased the gasoline yield because it cracks the gasoline range olefins into LPG range olefins. In general, it is difficult to increase the yield of multi-branched molecules because the multi-branched molecule is more easily cracked than linear molecules. Our results suggest the possibility for the selective acceleration of isomerization reaction by the addition of less acidic *BEA zeolite to the RFCC catalyst.

Methanol to clean gasoline over nanostructured CuO–ZnO/HZSM-5 catalyst: Influence of conventional and ultrasound assisted co-impregnation synthesis on catalytic properties and performance

In current paper, the catalytic conversion of methanol to gasoline range hydrocarbons has been studied over CuO(7%)–ZnO(5%)/HZSM-5(Si/Al = 65) catalysts prepared via conventional co-impregnation and ultrasonic methods. The samples were characterized by XRD, FESEM, BET, EDX, TEM and FTIR techniques. Characterizations proved smaller crystal size, more specific surface area and more uniform dispersion for the ultrasonic-assisted synthesized sample. Also, the performance test was done and ultrasonic-assisted synthesized catalyst showed 25% more selectivity to aromatics and 14% more selectivity to octanes and it has more potential to produce desirable products for gasoline cut.

Catalytic Cracking of Heavy Aromatics and Polycyclic Aromatic Hydrocarbons over Fluidized Catalytic Cracking Catalysts

The distribution of products in the range of gasoline and middle distillate cuts obtained in the catalytic cracking of heavy aromatics and polycyclic aromatic hydrocarbons over a fluidized catalytic cracking (FCC) catalyst was studied. 1-Phenyloctane, biphenyl, fluorene, 9,10-dihydrophenanthrene, naphthalene, phenanthrene, pyrene, and benz[a]anthracene were used as model compounds of alkylaromatic, naphthenic-aromatic, and polyaromatic hydrocarbons, which are present in vacuum gas oil and residual feedstocks in the FCC process. The catalyst was used in its fresh and equilibrium forms at 450 °C in a Chemical Reactor Engineering Centre Riser Simulator reactor with reaction times from 2 to 6 s. Thermal cracking reactions overwhelm the catalytic conversion of naphthenic-aromatic compounds, such as fluorene and 9,10-dihydrophenanthrene. Under the same conditions, the fresh catalyst was more active than the equilibrium catalyst. The alkylaromatic, naphthenic-aromatic, and polyaromatic hydrocarbons, showed catalytic conversions that increased, were relatively stable, and decreased, respectively, as a function of the reaction time. The distribution of products suggested that the most important reactions were thermal dehydrogenation, hydrogen transfer, ring opening, cracking, and condensation. It was shown that all of the model compounds are cracked, yielding particularly benzene in the gasoline range and coke.

Application of headspace single-drop microextraction (HS-SDME) technique in geochemical exploration for petroleum

Abstract All surface geochemical exploration methods for oil and gas are based on the theory that hydrocarbons generated and trapped at depth seep in varying but detectable quantities to the surface, and the main components detected are usually C1 -C5 hydrocarbons. The C1 -C4 hydrocarbons could come from degradation of organic matter by microbial organisms, while the gasoline range hydrocarbons are totally sourced from thermogenic processes. Therefore, the detection of gasoline range hydrocarbons in soils or sediments could be the most direct evidence for hydrocarbon seepage and the method used to detect the C6 -C12 range hydrocarbons could be a useful technique for surface geochemical exploration method for petroleum. However, because the concentration of gasoline range hydrocarbons in the soils or sediments are usually very low, and the present techniques for detecting those hydrocarbons are not adequate, the gasoline range hydrocarbons have seldom been used in surface geochemical exploration for oil and gas. In this study, the headspace single-drop microextraction (HS-SDME) technique coupled with gas chromatography-flame ionization detection (GC-FID) was employed to determine C6 -C12 gasoline range hydrocarbons in well drilling mud sample. The results show that the C6 -C12 hydrocarbons in the samples could be detected by HS-SDME, and the reservoir depth determined by the concentration of C6 -C12 hydrocarbons was the same with the actual petroleum reservoir depth, which indicated further that the HS-SDME method could be used in geochemical exploration for petroleum.

HPLC Method for Monitoring the Conjugated Dienes and Olefins in FCC, Coker Gasolines, and their Hydrogenated Products

The conjugated dienes if present in gasoline have the tendency to polymerize and cause fouling during various refinery processes. Therefore the conjugated dienes need to be reduced. While the conjugated dienes in gasoline are undesirable, the olefins are desirable and act as octane booster. The selective hydrogenation unit selectively reduces conjugated dienes keeping the content of olefins more or less intact. A method based on HPLC-UV-RI has been reported to simultaneously monitor the conjugated dienes and olefins content in the gasoline range samples. The reported method has the detection level of 0.02 (w/W)% for the total conjugated dienes with respect to 2,4-dimethyl 1,3-pentadiene (DMP). The calibration curve for DMP is drawn in the range 0.2–2.5% (w/W) and the R2 is found to be 0.9972. The method is also applicable for the estimation of olefins content above 10% (w/W) level with respect to 1-octene. The calibration curve is drawn in the range 10–50% (w/W) of 1-octene and the R2 is found to be 0.9995.

Catalytic pyrolysis of waste plastic from electrical and electronic equipment

Plastic waste collected from waste electrical and electronic equipment (WEEE) was pyrolysed in the presence of zeolite catalysts to produce a gasoline range aromatic oil. The plastic was from equipment containing cathode ray tubes (CRTs) and also plastic waste from refrigeration equipment. In addition, for comparison the main plastics contained in the WEEE, in the form of high impact polystyrene (HIPS) and acrylonitrile-butadiene-styrene (ABS) were also pyrolysed in the presence of the zeolite catalysts. Two zeolite catalysts; Y zeolite and ZSM-5 were used. Catalytic pyrolysis took place in a two stage fixed bed, batch reactor with the plastic pyrolysed in the first stage and the evolved pyrolysis gases catalysed in the second stage reactor. The quantity of oil produced from uncatalysed pyrolysis of plastics from CRTs and refrigerators was more than 80wt%. The gases consisted of hydrogen, methane and C2–C4 hydrocarbons. When the zeolite catalysts were introduced there was a decrease of between 5 and 10wt% in oil yield and a corresponding increase in gas yield. The composition of the oils derived from the uncatalysed pyrolysis of WEEE plastics were mainly aromatic with high concentrations of styrene, derived from the HIPS and ABS present in the plastic waste. Addition of the zeolite ZSM-5 and Y zeolite to the pyrolysis process resulted in significant concentrations of benzene, toluene and ethylbenzene in the product oil but reduced concentrations of styrene. The oils from both thermal and catalysed pyrolysis also contained significant concentrations of polycyclic aromatic hydrocarbons for example, naphthalene, phenanthrene and pyrene.

Production of Hydrocarbons via Hydrodeoxygenation of Lignin-Derived Phenolic Compounds

Lignin is the component with the highest carbon content in biomass. The transformation of lignin to high-grade liquid fuels can be achieved via hydrodeoxygenation(HDO) of phenolic intermediates derived from the products of lignin depolymerization. The octane numbers of the hydrodeoxygenation products of phenolic intermediates are quite high. They have vapor pressures and carbon atom number (C6 similar to C10) within the range of gasoline. Thus, these hydrodeoxygenation products would be the most desirable components for a fungible liquid transportation fuel. This is very meaningful to application of lignin. Recently, researches about the hydrodeoxygenation of phenolic compounds develop rapidly. In this paper, the HDO reactions of phenolic compounds using sulfided Mo-based catalyst, noble metal catalyst and inexpensive non-sulfided catalyst are reviewed in detail. It is found that most of the investigated catalysts are bifunctional catalysts, combining the hydrogenation function of active metal with hydrolysis and dehydration of support. The catalytic mechanism for the HDO of phenolic compounds is sketched, and the effects of catalyst supporter on the catalytic activity are also discussed. Furthermore, the current technique challenges are summarized, and future technologic explorations for the efficient hydrodeoxygenation of lignin-derived phenolic compounds are proposed.

Beyond ethanol: a techno‐economic analysis of an integrated corn biorefinery for the production of hydrocarbon fuels and chemicals

AbstractDried distillers grains with solubles (DDGS) are potential feedstocks for the production of hydrocarbon fuels and chemicals from catalytic pyrolysis. This study evaluates the economic feasibility of a 2000‐metric‐ton‐corn‐per‐day integrated biorefinery with an add‐on facility processing corn DDGS to hydrocarbons. In addition to ethanol, the integrated facility would produce a wide range of hydrocarbons, including aromatics, olefins, and synthetic gasoline and diesel. The hydrocarbon products command a substantially higher market value than that of the pre‐processed DDGS: $109 million per year vs. $78 million per year. The add‐on DDGS conversion facility contributes an extra $152 million of capital investment compared with the stand‐alone corn ethanol production scenario. The operating costs for the integrated scenario are also higher than for the stand‐alone scenario, mainly due to increases in utilities, labor costs, and capital depreciation. The minimum fuel selling price (MFSP) for the integrated scenario is $2.27/gallon, which is comparable to the MFSP of $2.18/gallon for the stand‐alone scenario. Sensitivity analysis shows that the feedstock cost, hydrocarbon yield, and fixed capital investment have the greatest impacts on the MFSP. With the benefit of products diversity, the proposed integrated corn biorefinery may be competitive with conventional stand‐alone ethanol production. © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd

Direct Synthesis of Hierarchical ZSM-5 Zeolite and Its Performance in Catalyzing Methanol to Gasoline Conversion

A simple method was developed and tested to synthesize hierarchical ZSM-5 zeolites using tetrapropylammonium hydroxide as a sole structure directing agent to generate intercrystalline mesopores. XRD analysis confirmed the formation of ZSM-5 zeolites. SEM and TEM imaging analyses revealed the presence of hierarchical structure, formed by self-assembly of highly crystalline, nanosized primary particles. Solid-state MAS NMR analysis showed the vast majority of Al atoms were tetrahedrally incorporated with Si atoms in the zeolite framework. N2 physisorption studies indicated that the mesopores of an average pore size of 30 nm were created in the hierarchical ZSM-5 zeolites with an abundance of micropores. The performance of these zeolites in catalyzing methanol to gasoline conversion was evaluated using a fixed-bed reactor operating at 350 °C with ca. 16.5% methanol in nitrogen at a total pressure of 1.1 MPa and WHSV of 1.2 h–1. The hierarchical ZSM-5 zeolites exhibited almost 100% methanol conversion and 59% selectivity toward the gasoline range hydrocarbons. The coke formation on the used catalyst was studied using a N2 physisorption technique and a thermogravimetric analyzer. The hierarchical ZSM-5 zeolite showed less than 2% coke formation and deposition over 24 h on stream, much less compared to the conventional ZSM-5 zeolite with nearly 8% carbon deposition under the same reaction conditions.

Techno-economic performance analysis of biofuel production and miniature electric power generation from biomass fast pyrolysis and bio-oil upgrading

The techno-economic performance analysis of biofuel production and electric power generation from biomass fast pyrolysis and bio-oil hydroprocessing is explored through process simulation. In this work, a process model of 72 MT/day pine wood fast pyrolysis and bio-oil hydroprocessing plant was developed with rate based chemical reactions using Aspen Plus® process simulator. It was observed from simulation results that 1kgs−1 pine wooddb generate 0.64kgs−1 bio-oil, 0.22kgs−1 gas and 0.14kgs−1 char. Simulation results also show that the energy required for drying and fast pyrolysis operations can be provided from the combustion of pyrolysis by-products, mainly, char and non-condensable gas with sufficient residual energy for miniature electric power generation. The intermediate bio-oil product from the fast pyrolysis process is upgraded into gasoline and diesel via a two-stage hydrotreating process, which was implemented by a pseudo-first order reaction of lumped bio-oil species followed by the hydrocracking process in this work. Simulation results indicate that about 0.24kgs−1 of gasoline and diesel range products and 96W of electric power can be produced from 1kgs−1 pine wooddb. The effect of initial biomass moisture content on the amount of electric power generated and the effect of biomass feed composition on product yields were also reported in this study. Aspen Process Economic Analyser® was used for equipment sizing and cost estimation for an nth plant and the product value was estimated from discounted cash flow analysis assuming the plant operates for 20years at a 10% annual discount rate. Economic analysis indicates that the plant will require £16.6 million of capital investment and product value is estimated at £6.25/GGE. Furthermore, the effect of key process and economic parameters on product value and the impact of electric power generation equipment on capital cost and energy efficiency were also discussed in this study.