Gasoline Range Research Articles

Mapping the Methanol-to-Gasoline Process Over Zeolite Beta.

Decarbonizing the transportation sector is among the biggest challenges in the fight against climate change. CO2 -neutral fuels, such as those obtained from renewable methanol, have the potential to account for a large share of the solution, since these could be directly compatible with existing power trains. Although discovered in 1977, the zeolite-catalyzed methanol-to-gasoline (MTG) process has hardly reached industrial maturity, among other reasons, because maximizing the production of gasoline range hydrocarbons from methanol has proved complicated. In this work, we apply multimodal operando UV/Vis diffuse reflectance spectroscopy coupled with an online mass spectrometer and "mobility-dependent" solid-state NMR spectroscopy to better understand the reaction mechanism over zeolites H-Beta and Zn-Beta. Significantly, the influential co-catalytic role of oxymethylene species is linked to gasoline formation, which impacts the MTG process more than carbonylated species.

Experimental investigation of waste polyolefin composition on thermal conversion into petroleum-derived products

Thermal pyrolysis of polyolefins has been proposed as one of the possible ways to obtain petroleum-derived products (fuels and chemicals) from waste plastics however, there is a lack of deep understanding of the correlation between the structure and composition of polyolefin feedstock with pyrolysis oil. Pyrolysis oil has been obtained from polyethylene (PE) and polypropylene (PP) in a tubular reactor at 500 °C. TGA-DTG, 13C CP-MAS NMR, FTIR, and XRD were used to analyze the polyolefin (PE and PP) feedstock, while pyrolysis oil was characterized by GC–MS, FTIR, and 1H NMR techniques. The pyrolysis oil from virgin and waste PP yielded branched alphaolefins and cycloparaffins, while virgin and waste PE produce linear alpha olefins and linear paraffins. Mixed waste plastic (MWP) produces major amount of linear paraffins and linear alpha olefins, indicating the overall trend of branching in polyolefins (PE and PP) from feedstock to product oil is retained after pyrolysis. The alpha olefins can be used as chemical intermediates, while 2,4 dimethyl 1-heptene from PP can be used as a fine chemical precursor better feedstock for gasoline. Segregation of waste plastics is challenging task in real life but source segregation and selective collection of waste plastics from various sources can produce useful products like high octane gasoline range hydrocarbons and high-value chemicals.

Mapping the Methanol‐to‐Gasoline Process Over Zeolite Beta

AbstractDecarbonizing the transportation sector is among the biggest challenges in the fight against climate change. CO2‐neutral fuels, such as those obtained from renewable methanol, have the potential to account for a large share of the solution, since these could be directly compatible with existing power trains. Although discovered in 1977, the zeolite‐catalyzed methanol‐to‐gasoline (MTG) process has hardly reached industrial maturity, among other reasons, because maximizing the production of gasoline range hydrocarbons from methanol has proved complicated. In this work, we apply multimodal operando UV/Vis diffuse reflectance spectroscopy coupled with an online mass spectrometer and “mobility‐dependent” solid‐state NMR spectroscopy to better understand the reaction mechanism over zeolites H‐Beta and Zn‐Beta. Significantly, the influential co‐catalytic role of oxymethylene species is linked to gasoline formation, which impacts the MTG process more than carbonylated species.

Effect of time on alternative hydrocarbon production from waste PS with biodiesel of candlenut oil using catalytic cracking and Si/Al-Ceramic as catalyst

In the present study, the catalytic cracking process of polystyrene (PS) plastic waste and biodiesel of candlenut oil was carried out using Si/Al-ceramic catalyst with a mass ratio of 7:3 at 300 °C. This study aimed to investigate the effect of reaction time on the distribution of hydrocarbon fuel fractions produced. They are characterized by XRD, SEM-EDX, FTIR, and N2 gas adsorption-desorption. The products components of PS catalytic cracking were analyzed by gas chromatography-mass spectroscopy (GC-MS). The liquid fuel obtained was mixed with commercial fuel, Premium RON 88, and methyl tertiary butyl ether (MTBE) additive to determine its physicochemical properties and performance in a generator engine with gasoline-based fuel. The result showed that an increase in reaction time from 60 minutes to 120 minutes of PS cracking over Si/Al-Ceramic catalyst leads to the enrichment of long-chain hydrocarbon fraction (> C12) by 25.61% which is attributed to the formation of styrene dimer. The fuel has thermal efficiency of 26.49% with density of 0.7405 g/cm3, flashpoint of < -50 °C, calorific value of 9642.42 kcal/kg, and octane number of 92.2. These characteristics are in accordance with SNI 06-3506-1994 standard. Therefore, liquid fuel from catalytic cracking of polystyrene plastic wastes can be used as a potential alternative fuel in the gasoline range.

Low-temperature destructive hydrodechlorination of long-chain chlorinated paraffins to diesel and gasoline range hydrocarbons over a novel low-cost reusable ZSM-5@Al-MCM nanocatalyst: a new approach toward reuse instead of common mineralization

Low-temperature destructive hydrodechlorination of long-chain chlorinated paraffins to diesel and gasoline range hydrocarbons over a novel low-cost reusable ZSM-5@Al-MCM nanocatalyst: a new approach toward reuse instead of common mineralization

Prospective electric heavy oil upgrading at ambient pressure by high energy electron beam

To alleviate increasing problems of greenhouse gas emissions, two approaches should be deployed: the development of sustainable energy technologies such as wind and solar to reduce the share of fossil fuels, and greener refining and upgrading technologies of fossil/bio-fuels. Here, we introduce an electric method that uses high energy electron beam to achieve heavy oil upgrading in a methane environment at ambient pressure with nearly zero GHG emissions. Two extra-heavy crude oil samples were treated by the electron beam at different conditions. Conversion and yields to gasoline and diesel range fuels were quantified. Detailed economic analysis shown that using low specific energy input (SEI or dose), 500 kJ/kg, <$1.5/barrel, this upgrading process converts heavy fractions (>C40, ∼20 $/barrel) to stable intermediate products (C10–C24, ∼75 $/barrel) in diesel range. No coke was found in treated oil. Product yields (C10–C24) were ∼9 molecules/100 eV, comparable with thermal methods. Sufficient product separation is crucial to the success of this method. This method is electrically driven, easily adaptable to renewable intermittent electricity. It has potentially zero GHG emissions, and is attractive for on-site upgrading of heavy/bio fuels and integration with distributed renewable energy.

Technical analysis of the modified Fischer-Tropsch synthesis process for direct CO2 conversion into gasoline fuel: Performance improvement via ex-situ water removal

The modified Fischer-Tropsch synthesis (FTS) process is a promising technology for direct CO2 conversion into liquid fuels. However, the low yield of liquid fuels (below 29%) observed during CO2-FTS process is still of great concern for commercial deployment. Therefore, new strategies are needed to improve both CO2 conversion and liquid fuel yield during CO2-FTS process. A steady-state model based on first principles and a modified Anderson-Schulz-Flory (ASF) distribution was developed for the CO2-FTS process to predict gasoline range hydrocarbons (C5-C11). The model was implemented in Aspen Plus® using Fortran® routines and model validation was performed for different H2/CO2 feed ratios. Two process configurations (including a three-stage reactor in series and a single reactor with recycle) were considered for CO2-FTS performance analysis and improvement through ex-situ water removal. Both CO2-FTS process configurations showed significant improvements in CO2 conversion (from 34 to above 70%) with up to 61.0% gasoline yield. Though the single reactor with recycle achieved a higher CO2 conversion and gasoline production rate than the 3-stage reactor in series, the comparative analysis at the same CO2 conversion of 71.5% revealed that both process configurations have a similar process efficiency of roughly 66.4%.

Selective Production of Gasoline Fuel Blendstock from Methanol using a Metal-doped HZSM-5 Zeolite Catalyst

The increasing demand for substitutes for petroleum has become a global concern due to the looming petroleum crisis and the need to reduce carbon dioxide emissions. This study seeks a viable approach for converting methanol into petrochemicals and fuel-range hydrocarbons. A ZSM-5 zeolite catalyst was synthesised and modified with 0.5 wt% transition metals (Co and Ni) to improve selectivity towards the desired liquid product (gasoline) in the methanol-to-hydrocarbon (MTH) conversion. The synthesised catalyst was characterised using various techniques. The catalysts were further evaluated for methanol conversion into fuels and petrochemicals (BTX) under varying weight hourly space velocity (WHSV) (7 and 12 h-1) at 350 oC. Results showed that the synthesised catalyst exhibited characteristic features of a typical MFI framework of a zeolite catalyst. The catalyst evaluation results revealed that changes in operating conditions affected product distribution. A WHSV of 12 h-¹ favoured the production of gasoline range hydrocarbons (C5-C12) with a yield of over 80 % for all catalysts. In addition, C12+ hydrocarbons were produced with a selectivity of 12.6 %, 0.7 % and 7.5 % for Ni-doped, Co-doped and HZSM-5 catalysts, respectively. In particular, the Co-doped catalyst showed a 7.1 % higher BTX yield under these specific operating conditions (12 h-1 and 350 oC). Compared to 7 h-1, increasing the WHSV to 12 h-1 favoured the production of liquid hydrocarbons. Incorporating a small amount of transition metal into the parent catalyst improved the selectivity of the target products and overall liquid hydrocarbon yield. The results concluded that the synthesised catalyst is promising for the MTH process, and catalytic performance can be enhanced by metal modification and optimising reaction conditions to improve biofuel production.

Techno-Economic Analysis of the Production of Liquid Biofuels from Sewage Sludge via Hydrothermal Liquefaction.

This work addresses the process and economic performance of the production of gasoline and diesel range fuels from urban sewage sludge. The overall production route involves direct conversion of the sewage sludge to an intermediate oil phase, so-called biocrude, via hydrothermal liquefaction at near-critical water conditions and further upgrading of the biocrude based on conventional refinery processes. The overall mass and energy yields of combined naphtha and middle distillate from sewage sludge on dry basis are approximately 19 and 60%, where the naphtha fraction represents about 45% of the total, with a minimum fuel selling price ranging between 2.4 and 0.8 €/liter assuming full investment in both the biocrude production and upgrading plant with sewage sludge feed capacities in the range of 3 to 30 dry-ton/day. If existing equipment at refinery can be used for upgrading of the biocrude, the minimum fuel selling price can be reduced by approximately 7%.

Agricultural and Forestry Biomass for Meeting the Renewable Fuel Standard: Implications for Land Use and GHG Emissions

Agricultural land and forestland are considered as two largest potential biomass sources for meeting the Renewable Fuel Standard (RFS) mandate for cellulosic biofuels. However, the land use change and greenhouse gas (GHG) savings with both agricultural and forest biomass production are yet to be examined systematically. This paper examines the effects of implementing a 16-billion gallon (60 billion liters) cellulosic biofuel mandate by 2035 on the mix of agricultural and forest biomass, land use change and GHG emissions by using a dynamic partial equilibrium model of the agricultural, forestry and transportation sectors in the US. Our results show that crop residues play a significant role in supplying cellulosic ethanol before 2030, while energy crops are the major feedstocks used for meeting the RFS cellulosic mandate after 2030. Milling and logging residues are economically viable supplements to agricultural biomass for cellulosic ethanol production, though their role in total biomass is small. Across different scenarios of cellulosic ethanol mandate that can be met with either agricultural biomass only or with both agricultural and forest biomass, we find GHG savings from displacing the gasoline range from 0.61 to 0.82 B MgCO2e over the 2015–2035 period. Induced land use change effects associated with expanded feedstock production are modest between and within the agricultural and forestry sectors. We conclude that a mixed feedstock base maximizes the economic and environmental benefits of cellulosic biofuel production. The mitigation potential of cellulosic biofuels is severalfold larger than natural-based solutions such as grassland restoration.

Experimental Study of Thermal and Catalytic Decomposition of PVC Wastes

The excessive use of plastics in the last years is the challenge that has arisen in managing plastic wastes to avoid dangerous effects. Polyvinyl chloride is part of these wastes. It can be utilized to produce fuel-like petroleum fractions depending on pyrolysis, which is the thermal decomposition of plastics in the absence of oxygen. This work aims to reduce environmental pollution and reuse plastic waste as an alternative fuel source. A comparison of the thermal and catalytic processes under the optimum temperature 450 oC, pressure 20 bar, and residence time 1hour in a semi-batch reactor with and without adding Pt/Al2O3 and NiMo/Al2O3 catalysts. Thermo-gravimetric analysis (TGA) analysis was made for PVC. Catalysts were characterized by X-RAY diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The liquid and gas products were analyzed by (GC/MS) to evaluate the quality of products. In the hydro-cracking reaction, most gas products were produced using NiMo/Al2O3 catalyst, about 62.29 wt%. The aromatic and saturated-aliphatic in the liquid using NiMo/Al2O3 catalysts were 21.07 and 72.81 wt%. The aromatics and saturated aliphatic in the liquid product using thermal non-catalytic and Pt/Al2O3 catalysts were 23.83 wt% & 63.52 wt% and 21.88 wt% & 64.01, respectively. The ratio of gasoline range components is the highest in the hydrocracking process on NiMo/Al2O3 catalysts. Using catalytic-hydrocracking on Pt/Al2O3 gives the highest diesel range component. It was confirmed that the generated undesirable product seems was very few in the hydrocracking reactions compared to the thermal cracking reactions.

Critical role of sodium migration in iron-based FT- zeolite tandem catalyst system for syngas hydrogenation to gasoline

Exploration the role of promotor in the Fischer-Tropsch zeolite (FTO-ZEO) tandem catalyst systems is of paramount importance in improving the selectivity of target products. Herein, by varying the contents of Na promotor in xNa-FeOx, the evolution of Na in FTO-ZEO system during reaction and the resultant catalytic performance for FT synthesis have been investigated. When the content of Na falls in the range of 0.5–5 %, the syngas conversion performance on bare FeOx catalysts reaches a performance-platform period, while that on tandem catalysts show a volcano-like trend. With a set of control experiments, it is speculated that there is a migration process of Na from xNa-FeOx to the H-ZSM-5 moiety. The changed acidity of H-ZSM-5 causes the transformation of products toward higher carbon alkanes and aromatics in the gasoline range with a selectivity of 71.5 %. This work makes an important progress by showing the phenomenon of Na migration during reaction, which puts forward the influence of promoters on FTO-ZEO system and gives a new insight of zeolites modification.

Copper catalyzed co‐pyrolysis of polyethylene terephthalate with low and high density polyethylene for liquid fuel production

AbstractBACKGROUNDMunicipal waste contains low density polyethylene (LDPE), high density polyethylene (HDPE), and polyethylene terephthalate (PET) in enormous amount. As these plastics are non‐biodegradable and pose serious threats to the environment, efforts have been made towards their safe disposal with energy recovery and value added chemicals by subjecting them to heat under oxygen deficient conditions. This study deals with the co‐pyrolysis of the three types of waste polymers, with special focus on the conversion of PET into liquid fuel by its interaction with the other two polymers.ResultsThe individual pyrolysis of LDPE and HDPE produced pyrolysis oil, whereas PET produced only wax. The co‐pyrolysis of the three polymers with different mixing ratios showed that PET hindered oil formation and increasing its amount more than 20 wt% in the polymer mixture resulted in wax formation. The thermal process produced 8 wt% pyrolysis oil, 32.3 wt% wax, 39.7 wt% pyro‐gases and 20 wt% coke while the catalytic process with copper catalyst produced 32.5 wt% pyrolysis oil, 3 wt% wax, 46.5 wt% pyro‐gases, and 18 wt% coke under optimum conditions.ConclusionThe thermal pyrolysis oil contained long chain paraffins as major components, while short chain isoparaffin and naphthenes were predominant in the catalytic pyrolysis oil owing to which marked differences were observed in the physicochemical properties of both oils. The fractionally distilled fractions of catalytic pyrolysis oil in gasoline, kerosene, and diesel range showed profound similarities with standard fuels in terms of fuel properties particularly the gasoline range fraction. © 2022 Society of Chemical Industry (SCI).

Chemistry of Ketene Transformation to Gasoline Catalyzed by H-SAPO-11.

Although ketene has been proposed to be an active intermediate in a number of reactions including OXZEO (metal oxide-zeolite)-catalyzed syngas conversion, dimethyl ether carbonylation, methanol to hydrocarbons, and CO2 hydrogenation, its chemistry and reaction pathway over zeolites are not well understood. Herein, we study the pathway of ketene transformation to gasoline range hydrocarbons over the molecular sieve H-SAPO-11 by kinetic analysis, in situ infrared spectroscopy, and solid-state nuclear magnetic resonance spectroscopy. It is demonstrated that butene is the reaction intermediate on the paths toward gasoline products. Ketene transforms to butene on the acid sites via either acetyl species following an acetic acid ketonization pathway or acetoacetyl species with keto-enol tautomerism following an acetoacetic acid decarboxylation pathway when in the presence of water. This study reveals experimentally for the first time insights into ketene chemistry in zeolite catalysis.

Catalytic hydrogenolysis of plastic to liquid hydrocarbons over a nickel-based catalyst

The catalytic hydrogenolysis of a typical model compound of mulching film waste, polyethylene, was investigated as a potential way to improve economic efficiency of mulching film recycling. Nickel-based heterogeneous catalysts are proposed for polyethylene hydrogenolysis to produce liquid hydrocarbons. Among catalysts supported on various carriers, Ni/SiO2 catalyst shows the highest activity which may due to the interactions between nickel and silica with the formation of nickel phyllosilicate. As high as 81.18% total gasoline and diesel range hydrocarbon was obtained from the polyethylene hydrogenolysis at relatively mild condition of 280 °C, and 3 MPa cold hydrogen pressure. The result is comparable to what have been reported in previous studies using noble metal catalysts. The gasoline and diesel range hydrocarbon are n-alkanes with a distribution at a range of C4–C22. The gas products are primarily CH4 along with a small amount of C2H6 and C3H8. High yield of CH4 as much as 9.68% was observed for the cleavage of molecule occurs along the alkane chain.

Fuel property impacts on gaseous and PM emissions from a multi-mode single-cylinder engine

The U.S. Department of Energy’s Co-Optima initiative has focused on improving fuel economy and vehicle performance while reducing emissions through the simultaneous development of emerging sustainable fuels with beneficial properties and advanced combustion strategies. A major thrust has been the development of advanced compression ignition (ACI) combustion strategies of gasoline range fuels in combination with spark-ignited (SI) combustion in a single engine capable of multi-mode operation to achieve high power density with enhanced part load efficiency. The aim of this study was to further the understanding of how emissions from both ACI and SI strategies operating on the same fuels in the same engine are impacted by different fuel properties. This investigation focused on particulate matter (PM) and gaseous hydrocarbon emissions from 6 different fuels across 3 different combustion modes on the same single-cylinder engine designed for multi-mode operation: SI combustion, partial fuel stratification (PFS), and spark-assisted compression ignition (SACI). In each of these modes, 3 different CA50 phasings were studied such that all 6 fuels could be studied at the same phasings. Three of the six different fuels used were specially formulated in a previous investigation to study the impact of fuel distillation and aromatic content while maintaining the research octane number (RON) and octane sensitivity. Additionally, neat isooctane and two ethanol containing fuels (RD5-87 and Co-Optima E30) were studied. Different fuel and phasing impacts on emissions were observed across the three combustion modes. Fuel properties were found to impact soot PM and particle number more than the CA50 phasing, while the phasing had more impact on NOx emissions. The NOx emissions were reduced in the PFS mode for all fuels compared to SI combustion, but the SACI combustion mode did not reduce NOx emissions. Although PFS produced low soot PM emissions like SI, total PM mass emissions were significantly higher due to large organic carbon (OC) PM mass contribution. Both PFS and SACI had greater particle number emission than SI operation with small nuclei mode particles dominating in PFS compared to large agglomeration particles in SACI.

Hydrocarbon Biodegradation in Utah’s Great Salt Lake

The Great Salt Lake comprises two high salinity arms, the North at 34% salinity, and the larger South at 16%. The biodegradation of gasoline range alkanes, cycloalkanes, aromatics, alkenes and cycloalkenes was extensive in samples from both arms, although slower than in fresh- and sea-water. Less volatile hydrocarbons in weathered crude oil were degraded less extensively, and again more slowly than in sea or fresh-water. The substrates subject to degradation are substantially more diverse than has previously been reported, and indicate that biodegradation will likely be the eventual fate of any petroleum hydrocarbons that enter the lake and do not evaporate. The biodegradation is, however, much slower than in other environments, and we discuss whether it might be increased to meet anthropogenic pollution, perhaps by nutrient supplementation with organic nitrogen.

CO2 utilization for the production of liquid hydrocarbons by coupled steam and dry reforming of bioethanol

ABSTRACT Ethanol is an interesting fuel that can be produced by both renewable and nonrenewable resources and can be used as fuel or additive to fuels. But bioethanol is not equivalent one by one by fossil fuels in vehicles. In this study, the production of liquid hydrocarbons as synthetic fuels using bioethanol reforming has been simulated by Aspen HYSYS. For this purpose, two processes for syngas production have been proposed: 1: bioethanol steam reforming (ESR) and 2: bioethanol steam reforming coupled with dry reforming (ESR+EDR). Effective parameters including temperature, steam-to-carbon ratio, residence time, and feed split ratio have been evaluated. It is shown that the value of H2/CO using the syngas produced from ESR is in the range of 5. This ratio was modified using ESR+EDR without and with CO2 injection by 2.5 and 2, respectively. These values are suitable for the production of liquid hydrocarbons in the gasoline range. The C5 + selectivity using synthesis gas produced in the Fischer-Tropsch reactor in the ESR and the ESR+EDR without and with CO2 injection has been obtained by is 17.21%, 40.43%, and 42.96%, while CO2 selectivity has been emitted by 0.11, 0.53, and 0.71.

Heterogeneous Catalysis for CO2 Conversion into Chemicals and Fuels

Catalytic conversion of CO2 into chemicals and fuels is a viable method to reduce carbon emissions and achieve carbon neutrality. Through thermal catalysis, electrocatalysis, and photo(electro)catalysis, CO2 can be converted into a wide range of valuable products, including CO, formic acid, methanol, methane, ethanol, acetic acid, propanol, light olefins, aromatics, and gasoline, as well as fine chemicals. In this mini-review, we summarize the recent progress in heterogeneous catalysis for CO2 conversion into chemicals and fuels and highlight some representative studies of different conversion routes. The structure–performance correlations of typical catalytic materials used for the CO2 conversion reactions have been revealed by combining advanced in situ/operando spectroscopy and microscopy characterizations and density functional theory calculations. Catalytic selectivity toward a single CO2 reduction product/fraction should be further improved at an industrially relevant CO2 conversion rate with considerable stability in the future.Graphical

Hydrocarbons recovery through catalytic pyrolysis of compostable and recyclable waste plastics using a novel desk-top staged reactor

The overall objective of this study is to develop a novel two-staged fixed-bed reactor to evaluate the catalytic pyrolysis of recyclable (HDPE) and compostable waste plastics and to enhance the selectivity of gasoline range hydrocarbons in pyrolysis liquid. In this research, both used and unused compostable bioplastics, recyclable high-density polyethylene (HDPE) grocery bags, and unused HDPE were used as a feedstock Additionally, a mixture of recyclable plastic and compostable bioplastic with 1:1 ratio was pyrolyzed at 500 °C, and the pyrolysis oil products were compared with commercial gasoline. Zeolite Socony Mobil-5 (ZSM-5) was used as a catalyst in all the catalytic pyrolysis experiments, which produced wax-free shorter chain hydrocarbons similar to commercial gasoline. The addition of recyclable HDPE in compostable plastics improved the selectivity of gasoline range hydrocarbon ( C 6 − C 12 ) by 10% and increased the calorific value of pyrolysis liquids by 7.5% (43 MJ/kg), which is equivalent to commercial gasoline. Moreover, both compostable and recyclable plastics produced aromatic and aliphatic hydrocarbons that have potential applications in lubricants, additives, and petrochemical industries. • An addition of recyclable HDPE to compostable plastics improved the selectivity of gasoline range hydrocarbons by 10%. • Recyclable and compostable mixed plastics produced 7.5% higher calorific value pyrolysis liquid than compostable plastics. • The selectivity of gasoline range hydrocarbons (C 6 -C 12 ) was over 90% in pyrolysis liquid. • Compostable bioplastics produced chemicals that have applications in lubricant, additives and petrochemical industries.