Production Of High-octane Gasoline Research Articles

Hydroprocessing of Gasoline on Modified Alumina Catalysts

The hydroprocessing of gasoline on modified alumina catalysts makes it possible to obtain high-octane products. The implementation and development of the process have largely become possible due to the development of modified alumina catalysts that do not contain noble metals and exhibit special catalytic properties. This article discusses topical issues of petrochemistry, namely the creation of catalysts with improved characteristics for the production of high-octane gasoline with low sulfur content. New catalytic systems based on alumina and other carriers modified with transition metals, lanthanum and phosphorus were synthesized. Вy physico-chemical methods of analysis TPD of ammonia, TEM and XRD, we studied the acid–base and structural characteristics of the developed catalysts. The activity of the developed catalysts in the studied process of hydrotreating gasoline fractions depends on the structure and condition of the active centers. The process of hydrotreating straight-run gasoline in the presence of synthesized catalysts was carried out on a laboratory flow unit. It was shown that, during the hydrotreating of straight-run gasoline on the NiO-MoO3-La-P-HZSM-HY-Al2O3 catalyst, the octane number in the final product increased to 88.6, and the sulfur content decreased from 0.0088 to 0.001%. It was found that the minimum sulfur content in the gasoline hydrotreating product of 0.0005% was achieved on the catalyst CoO-WO3-La-P-HZSM-HY-Al2O3, which is significantly lower than for other studied catalytic systems. The obtained results of the sulfur content in the hydrotreating products fully comply with the Euro-5 standard. Thus, the efficiency of hydrotreating the gasoline fractions studied in this work was mainly determined by the nature of the carriers and modifiers used for the synthesis of catalysts and the technological parameters of the process. The synthesized catalysts showed high activity and selectivity, resulting in high-octane gasoline with a low sulfur content that meets international quality standards.

Engineering pore limiting diameter of metal–organic frameworks for benchmark separation of mono- and di-branched hexane isomers

The separation of mono- and di-branched hexane isomers remains an important and challenging industrial process for the production of high-octane gasoline. Suitable adsorbents with high adsorption selectivity and capacity are urgently required. Herein, we demonstrate a strategy to realize highly efficient kinetically controlled hexane isomers adsorption separation that utilizes the tunability of the pore limiting diameter in M2TTFTB (M=Zn, Mn, Cd) by metal substitution. The appropriate refinement of the partially contracted pore not only improved the kinetic selectivities, but also enhanced the host–guest interaction and increased the adsorption capacity of 3MP and nHEX. The resulting Mn2TTFTB brought about both the record capacity of 3MP and the record kinetic selectivities of 3MP/22DMB and nHEX/22DMB, exhibiting the largest productivity of high-purity 22DMB in the breakthrough experiments, which sets a new benchmark for the hexane isomers separation via a rarely reported kinetically controlled mechanism.

TECHNO-ECONOMICAL STUDY ON THE PRODUCTION OF HIGH OCTANE GASOLINE IN LIGHT NAPHTHA PLANT

The Indonesian government is optimizing the production of high-octane gasoline by utilizing existing ingredients that are plentiful and rarely used in Indonesia to keep up with the rising demand for it. Although light naphtha, a by product of the oil refinery process, has the potential to be transformed into fuel with a high Research Octane Number, its application has not yet been fully realized. The objective of this study is to carry out a study of the economic and technical feasibility of high-octane gasoline plants. A 10,000 barrel/day production potential has been built into the plant. In order to reach the RON objective of 98 for high-octane fuel, light naphtha, which has a Research Octane Number of 73, will need to be increased. The production process includes isomerization, depentanizing, and adsorption. From a technical perspective, this plant can produce high-octane gasoline from light naphtha with RON98. From an economic perspective, the Net Present Value is $ 138,247,252; Internal Rate of Return of 29.38 % per year; Pay Out Time is 3 years 5 months; and Break Even Point is 49 %. Overall, based on technical and economic perspectives, this power plant is feasible.

A Thermodynamic Analysis of Naphtha Catalytic Reforming Reactions to Produce High-Octane Gasoline

The catalytic naphtha reforming process is key to producing high-octane gasoline. Dozens of components are involved in this process in hundreds of individual catalytic reactions. Calculations of concentrations at equilibrium, using equilibrium constants, are commonly performed for a small number of simultaneous reactions. However, the Gibbs free energy minimization method is recommended for the solution of complex reaction systems. This work aims to analyze, from the point of view of thermodynamic equilibrium, the effect of temperature, pressure, and the H2/HC ratio on the reactions of the catalytic reformation process and evaluate their impact on the production of high-octane gasoline. Gibbs’s free energy minimization method was used to evaluate the molar concentrations at equilibrium. The results were compared with those obtained in the simulation of a catalytic reforming process to evaluate the optimal conditions under which the process should operate.

(Invited) Accelerating the Catalyst and Process Development Cycle for Bioenergy Applications

It is imperative that we as a global society move rapidly to dramatically reduce our greenhouse gas emissions. One component of a broader strategy to decarbonize our economy is the production of fuels and chemicals from carbon-rich renewable and waste feedstocks, such as biomass, municipal solid waste, food waste, and bio-gas. However, these heterogeneous feedstocks introduce unique challenges for conversion processes due to the presence of impurities, high water content, and diverse chemical functionalities. In order for the production of renewable fuels and chemicals to be realized on the time and volume scales needed to mitigate climate change, these applications must be developed in less time and at less cost than ever before. To meet this urgent need, the mission of the Chemical Catalysis for Bioenergy (ChemCatBio) Consortium, a member of the Department of Energy’s Energy Materials Network, is to accelerate the catalyst and process development cycle for bioenergy applications.In this contribution, our acceleration approach will be discussed with specific emphasis on two major elements: (1) our core catalyst-process development approach linking foundational science and applied engineering and (2) development of tools that improve research efficiency. Our catalyst-process development approach will be illustrated through examples, including selectivity improvement for high-octane gasoline production from dimethyl ether and mitigation of catalyst deactivation during catalytic fast pyrolysis of biomass. Two publicly available tools developed by ChemCatBio will be highlighted: CatCostTM and the Catalyst Property Database. CatCost is a state-of-the-art, spreadsheet- and web-based application that enables cost estimation of manufacturing pre-commercial catalytic materials at bulk scale. The Catalyst Property Database contains DFT-computed adsorption energies for surface species in catalytic reactions. It is designed to (1) reduce the time required to perform literature searches on previously computed catalytic pathways and intermediates by providing data in a central, searchable location and (2) enable accelerated discovery of catalyst descriptor and property correlations. These two tools form the initial foundation of an integrated catalyst design engine concept.

Non-thermal plasma assisted catalytic reforming of naphtha and its model compounds with methane at near ambient conditions

Naphtha reforming processes are widely used for high-octane gasoline production. These processes require high reaction temperature and high pressure of expensive hydrogen. Also, olefins and aromatics are produced for achieving high octane number, which could cause severe environmental issues. Here, we report a novel method of non-thermal plasma assisted catalytic reforming of naphtha at near ambient conditions. Conventionally used hydrogen has been replaced by cheaper methane in this study. Non-thermal plasma could effectively convert methane and naphtha to high-quality fuel at near room temperature and atmospheric pressure. A high-quality fuel with high content of iso-paraffin and low content of olefin and aromatic is produced over optimized Ga/mix-ZSM-5 with non-thermal plasma applied. The produced liquid product has a notably higher iso-paraffin content (increased from 21.5%–40.5%) than raw naphtha while the coke deposition (17.4 %) and the content of olefins (decreased from 13.5%–7.8%) and aromatics (dropped from 18.1%–5.9%) are well controlled. The partial desulfurization of fed coker naphtha by close to 60 % is also successfully achieved. A systematic model compounds study is conducted to investigate the involved mechanism of non-thermal plasma assisted catalytic naphtha reforming and coke deposition. Based on the studies of C6-C16 model compounds (including paraffins, olefins, dienes, cyclo-paraffins, cyclo-olefins and aromatics), a hypothetic reaction mechanism is proposed. A series of control experiments is also carried out to reveal the synergistic effect between non-thermal plasma, catalyst, and methane participation. This research thus pioneers a cost-effective and environmental-friendly route for naphtha reforming at mild conditions.

Production of high octane gasoline by catalytic cracking of petroleum gasoil with palm’s triglyceride and oleic acid

The use of gasoline with appropriate octane number will affect directly to meet superfine engine performance and avoiding from knocking effect. Improvement of gasoline quality in fluid catalytic cracking process usually is achieved by replacement of new catalyst which needs higher production cost. This research work aimed to describe the alternative method for improving gasoline octane in catalytic cracking by means of feedstock modification using mixture of vacuum gasoil and few of palm’s triglyceride and oleic acid. The experimental work of cracking reaction was performed in a fluid-bed reactor of ACE unit using REY zeolite catalysts at temperature of 530 °C and catalyst-oil ratio of 5.5 g/g. The liquid product was analyzed by a gas chromatograph of simulated distillation to determine yields of gasoline, light cycle oil and bottom product continued by a gas chromatograph of detailed hydrocarbon analysis to obtain hydrocarbon composition and calculated research octane number of gasoline. Analysis of gaseous product was performed using a gas chromatograph of refinery gas analyzer to detect yields of dry gas and LPG, whereas coke deposited on spent catalyst was analyzed using the infra-red method. From the research work, it was found that feedstock prepared from vacuum gasoil added with 5 % refined bleached deodorized palm oil and oleic acid (9:1) had increased gasoline RON from 91.8 to 98.2. The improvement of gasoline octane was contributed by the presence of double-bond fatty acid that triggered promoting effect to aromatisation and hydrogen transfer reactions in the formation of more iso-paraffins, olefins and aromatics in gasoline.

A pore-engineered metal-organic framework with mixed ligands enabling highly efficient separation of hexane isomers for gasoline upgrading

The separation of hexane isomers into their individual components, especially the mono- and di-branched isomers, is one of the most important while challenging industrial processes for the production of high-octane gasoline. In this work, a pore-engineered metal-organic framework with mixed ligands, CAU-10-H/Br, is designed based on the parent structures of CAU-10-H and CAU-10-Br through multivariate metal-organic frameworks strategy, whose channels partially decorated with -Br group possess suitable pore size (5.4 Å), enabling access to n-hexane (4.3 Å) and 3-methylpentane (5.0 Å), but excluding 2,2-dimethylbutane (6.2 Å). The adsorption isotherms indicate that this material has adequate adsorption capacity of n-hexane and 3-methylpentane, about 1.5 and 0.7 mmol⋅g−1 at 303 K and the pressure of 50 Torr, respectively. CAU-10-H/Br shows extraordinary separation performance exceeding most of the reported MOFs in the breakthrough experiments, manifested as almost complete exclusion of 2,2-dimethylbutane and sufficient separation time between 3-methylpentane and 2,2-dimethylbutane. The configurational-bias Monte Carlo and density functional theory calculations reveal the orientations of the guest molecules in the channels and the adsorption sites for host-guest interaction. Moreover, the high stability of CAU-10-H/Br suggests it has a huge potential in the industrial separation of hexane isomers.

Blending Characteristics of Isooctene, MTBE, and TAME as Gasoline Components

Currently, one of the most important problems in Russian refineries is the lack of production of high-octane gasoline that meets current and future environmental requirements. One solution for this...

The Mysteries of Science in Solving Applied Problems

The solution of various applied problems usually leads to the need to find answers to purely scientific fundamental questions and discover new phenomena. The article gives examples of such discoveries. It was discovered that flammability of polymeric materials can be decreased by dispersion of a material containing microencapsulated low-boiling flame retardants on exposure to an external fire source. The composition of the Earth’s atmosphere is analyzed in terms of dynamic equilibrium of the processes of oxygen production from forests and the consumption for their combustion during fires. The study of the amazing kinetics of the preparation of polyformaldehyde from formaldehyde and its cyclic trimer, trioxane, was explained, firstly, in the creation of the theory of reversible heterogeneous polymerization of trioxane and led to a fundamentally new, thermodynamic, method of regulating the molecular and supramolecular structure of the polymer. Secondly, on the example of polymerization of formaldehyde, a possible advantage of “diffusion” over “kinetic” modes was discovered. A similar effect was confirmed for the process of sulfuric acid alkylation of high-octane gasoline production.

Methanol to high-octane gasoline within a market-responsive biorefinery concept enabled by catalysis

Biofuels production from lignocellulosic biomass is hindered by high conversion costs in the generation of high-quality fuels, driving research towards the development of new pathways with less severe conditions, higher yields and higher-quality products. Here, we present a market-responsive biorefinery concept based on methanol as the key intermediate, which generates high-octane gasoline (HOG) and jet fuel blendstocks from biomass. Process models and techno-economic analysis are linked with both fundamental and applied catalyst development research to quantify the impact of catalyst advancements on process economics. By facilitating reincorporation of C4 by-products during dimethyl ether homologation, a Cu-modified beta zeolite catalyst enabled a 38% increase in yield of the HOG product and a 35% reduction in conversion cost compared to the benchmark beta zeolite catalyst. Alternatively, C4 by-products were directed to a synthetic kerosene that met five specifications for a typical jet fuel, with a minor increase in the fuel synthesis cost versus the HOG-only case. The production of high-value fuels from bio-derived methanol requires improvement to become economically viable. Here, process advancements for the production of high-octane gasoline are reported, and the effects that these have on making the process competitive with market rates of fossil fuels are analysed.

Исследование активности каталитической системы Pr/NH4(ЦВМ) в превращении н-гексана

Due to the rapid growth of consumption of high-quality, environmentally friendly motor fuels and the exhaustion of oil reserves, the modernization of existing technologies and processes for the production of high-octane gasoline remains relevant. One of these processes, which allows to obtain fuels that meet environmental standards, is the process of catalytic reforming. This work is devoted to the study of the activity of the pure carrier – NH4(ZSM) and the catalytic system Pr/NH4(ZSM) (the amount of praseodymium is 0.7% wt.) prepared by the impregnation method based on pure zeolite NH4(ZSM) (n-hexane transformation). The analysis of the obtained conversion products was performed by gas-liquid chromatography. The activity of the catalyst was evaluated according to parameters such as the degree of conversion of raw materials, the selectivity of the formation of products. On the basis of experimental data, it was shown that when n-hexane is converted on a catalyst in an air flow, high-octane components of the fuel can be obtained. As a result of systematic studies of pure NH4(ZSM), it was shown that with an increase in temperature, the conversion of n-hexane to 99.6% at a temperature of 500 ºС increases. The introduction of praseodymium into the catalyst leads to a redistribution of the number of acid and metal reaction centers, which is accompanied by a maximum conversion rate of 99.5% at a temperature of 350 ºС, an increase in the proportion of aromatic and gaseous compounds in the conversion products. As a result of the conversion of n-hexane on the two systems, valuable gaseous and liquid products were obtained. All liquid products obtained at different temperatures have large octane number values, which is explained by the high content of isomer products at low temperatures of the experiment and aromatic products at high temperatures of the experiment.

Production of high-octane gasoline via hydrodeoxygenation of sorbitol over palladium-based bimetallic catalysts

A methodology for the synthesis of gasoline-range fuels from carbon neutral resources is introduced. Sorbitol, a sugar-based compound, was employed as a raw material because the compound is readily obtained from cellulose. Gasoline-range hydrocarbons were produced via hydrodeoxygenation (HDO) on zirconium phosphate-supported Pd-bimetallic (Pt−Pd, Ru−Pd, Ni−Pd, Fe−Pd, Co−Pd, W−Pd) catalysts. Among the tested catalysts, the bimetallic W−Pd/ZrP catalyst exhibited the highest yield of gasoline products, peaking at ∼70%. However, with the bimetallic Fe−Pd and Co−Pd catalysts, high-octane gasoline products were made (research octane number (RON) of the products was higher than 100). The Fe−Pd catalyst also showed the highest initial activity for the HDO of sorbitol. This study demonstrates that HDO in the Pd-system is a promising option to produce high-quality gasoline-range hydrocarbons from lignocellulosic biomass.

Discovery and Evolution of Polyoxopalladates.

Noble metal catalysts, in particular palladium-containing materials, are of prime commercial interest, because of their role as oxidation catalysts in automobile emission-control systems and reforming catalysts for the production of high-octane gasoline. However, despite almost two centuries of research, the precise structure of such materials is still ill-defined on the sub-nanometer scale, which severely limits the understanding of the underlying catalytic mechanisms. As a burgeoning class of structurally well-defined noble metal oxide nanoclusters, polyoxopalladates (POPs) have been highly rated as ideal models to fully decipher the molecular mechanism of noble metal-based catalysis. Being at the frontier of polyoxometalates (POMs), the chemistry of POPs, which are based exclusively on PdII centers as addenda is currently progressing rapidly, owing to their structural and compositional novelty, high solution stability, combined with promising applications especially as noble metal-based catalysts. Controlled hydrolysis-condensation processes of square-planar PdIIO4 units in the presence of external oxyacid heterogroups (e.g., AsO43-, PO43-, and SeO32-) drive the self-assembly of such discrete, polynuclear PdII-oxo nanoclusters in facile one-pot reactions using aqueous solvents. By now, more than 70 POPs have been discovered, encompassing a large structural variety, including cube, star, bowl, dumbbell, wheel, and open-shell archetypes. Moreover, the POP cages can serve as adaptable molecular containers for encapsulation/interaction with a range of metallic elements across the s, p, d, and f blocks of the periodic table, resulting in a library of host-guest assemblies of varying shapes and sizes. Besides a delicate balance of experimental variables, the fine-tuning of POP structure, composition, and properties is possible by systematic replacement of the metal ion guest and/or the capping heterogroups. Besides, nearly all POPs obtained so far could be perfectly rationalized by theoretical calculations, and even prediction of the design and synthesis of new POP structures is possible. The excellent stability of POPs in the solid state and in solution (both aqueous and organic media) and gas phase allows for applications mainly in homo- and heterogeneous catalysis or as molecular precursors for monodisperse nanoparticles via an ingenious bottom-up route for functional nanotechnology. Apart from catalysis, owing to the unique structural features of POPs, other areas of interest exist, for example, in magnetism as molecular spin qubits and in biology as aqueous-phase macromolecular models. Overall, as a distinct subclass of POMs, POPs not only integrate the advantages of tunable shape, size, composition, solution stability, redox activity, and facile synthetic procedures, but drive immense potential for achieving an atom-to-atom fabrication and modulation of nanostructures as well, thereby providing models for unveiling mechanistic insight of noble metal-based catalysis at the molecular level, which will, in turn, guide the programmed assembly of nanomaterials with improved performance in a controllable manner. This Account is directed to cover the main structural types of POPs and to discuss the structure-directing template effects induced by the guest ions on the resultant host-guest assemblies.

The catalytic naphtha reforming process: hydrodesulfurization, catalysts and zeoforming

High-octane gasoline production by catalytic naphtha reforming is a major process in the petroleum industry. Sulfur components involved in the reforming process are causing pollutions and catalyst poisoning. Hydrodesulfurization has been developed to remove sulfur species from naphtha. Bimetallic and trimetallic catalysts are used to improve the naphtha reforming. Another solution to produce gasoline is the zeoforming process, which involves zeolites. This article reviews the naphta reforming reaction.

Hydride Transfer versus Deprotonation Kinetics in the Isobutane-Propene Alkylation Reaction: A Computational Study.

The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C–C bond formation between a tert-butyl fragment and an additional olefin, or via deprotonation of the tert-butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle.

Solid acids: potential catalysts for alkene–isoalkane alkylation

Production of high-octane gasoline is important to improve upon the performance and hence economics of oil companies worldwide.

Direct production of high octane gasoline and ULSD blend stocks by LCO hydrocracking

Hydrocracking of light cycle oil (LCO) is of great scientific and industrial importance to obtain high quality of gasoline and diesel. In this work, a novel LCO hydrocracking technology (FD2G) was proposed, and three kinds of hydroprocessing catalysts (i.e., FC-14, FC-24 and FC-26) were tested under different pilot-scale operational conditions and/or types. All the three catalysts are found to be active for direct production of high octane gasoline and ultra low sulfur diesel (ULSD) blend stocks, and the FC-24 catalyst is the most active and selective toward production of high octane gasoline. The quality of gasoline and diesel products is highly sensitive to pressure and operation type. Furthermore, the FC-24 catalyst was also tested in a large-scale industrial plant. It is found that the yield of gasoline blend stock reaches 30–50wt%, the octane number of gasoline is 91–94 and the sulfur content is less than 10μg/g; the cetane number of diesel blend stock increases 10–14 units in comparison to the feed stock, and the sulfur content is less than 10μg/g.

Effect of Super Acid and Heteropolyacid on Residue Hydroprocessing

Production of highly branched aromatics and saturates from conversion of vacuum residue is of interest for production of high octane gasoline, gasoil, jet fuels and lubricants. In this study vacuum residue is hydroprocessed with superacid and hetropolyacid based catalysts at severe reaction conditions: 400-440pC reaction temperature, 100bar of hydrogen pressure, 4-8hours of reaction run time. A moderate conversion level, over 85% achieved with Mo-superacid at given reaction conditions. Upto 90% residue conversion and hydrotreating activities like HDM, HDS and HDAsp observed with Mo based heteropolyacid. Mo based acid catalysts have superiority over W based catalysts. Product distribution indicated that most part of liquid yield contain gasoil than gasoline.

High-temperature catalytic reforming of n-hexane over supported and core-shell Pt nanoparticle catalysts: role of oxide-metal interface and thermal stability.

Designing catalysts with high thermal stability and resistance to deactivation while simultaneously maintaining their catalytic activity and selectivity is of key importance in high-temperature reforming reactions. We prepared Pt nanoparticle catalysts supported on either mesoporous SiO2 or TiO2. Sandwich-type Pt core@shell catalysts (SiO2@Pt@SiO2 and SiO2@Pt@TiO2) were also synthesized from Pt nanoparticles deposited on SiO2 spheres, which were encapsulated by either mesoporous SiO2 or TiO2 shells. n-Hexane reforming was carried out over these four catalysts at 240-500 °C with a hexane/H2 ratio of 1:5 to investigate thermal stability and the role of the support. For the production of high-octane gasoline, branched C6 isomers are more highly desired than other cyclic, aromatic, and cracking products. Over Pt/TiO2 catalyst, production of 2-methylpentane and 3-methylpentane via isomerization was increased selectively up to 420 °C by charge transfer at Pt-TiO2 interfaces, as compared to Pt/SiO2. When thermal stability was compared between supported catalysts and sandwich-type core@shell catalysts, the Pt/SiO2 catalyst suffered sintering above 400 °C, whereas the SiO2@Pt@SiO2 catalyst preserved the Pt nanoparticle size and shape up to 500 °C. The SiO2@Pt@TiO2 catalyst led to Pt nanoparticle sintering due to incomplete protection of the TiO2 shells during the reaction at 500 °C. Interestingly, over the Pt/TiO2 catalyst, the average size of Pt nanoparticles was maintained even after 500 °C without sintering. In situ ambient pressure X-ray photoelectron spectroscopy demonstrated that the Pt/TiO2 catalyst did not exhibit TiO2 overgrowth on the Pt surface or deactivation by Pt sintering up to 600 °C. The extraordinarily high stability of the Pt/TiO2 catalyst promoted high reaction rates (2.0 μmol · g(-1) · s(-1)), which was 8 times greater than other catalysts and high isomer selectivity (53.0% of C6 isomers at 440 °C). By the strong metal-support interaction, the Pt/TiO2 was turned out as the best catalyst with great thermal stability as well as high reaction rate and product selectivity in high-temperature reforming reaction.