Co-Hydroprocessing of Fossil Middle Distillate and Bio-Derived Durene-Rich Heavy Ends under Hydrotreating Conditions

Methanol-to-gasoline (MTG) and dimethyl ether-to-gasoline (DTG), as industrially approved processes for producing greenhouse gas-neutral gasoline, yield byproducts rich in heavy mono-ring aromatics such as 1,2,4,5-tetramethylbenzene (durene). Due to its tendency to crystallize and the overall poor fuel performance, the heavy fuel fraction is usually further processed using aftertreatment units designed for this purpose. This research article discusses the co-hydroprocessing (HP) of bio-derived heavy gasoline (HG) with fossil middle distillate (MD), drawing on available refinery hydrotreaters. Co-HP experiments were conducted in a laboratory-scale fixed bed reactor using an industrial CoMo/g-Al2O3 catalyst, varying the space-time between 0.7 and 4.0 cm3 Cat h cm3 Feed and the reaction temperature between 340 and 390 °C. In addition to the durene conversion, special attention was paid to the octane and cetane numbers (CN) of gasoline and MD, respectively. A six-lump model with ten parameters was developed to predict relevant fuel yields dependent on the process conditions. Under stable catalyst conditions, C10 aromatic conversions of more than 60% were obtained, while the CN remained close to that of pure MD. Harsh process conditions increased the gasoline yield up to 20% at the cost of MD, while the kerosene yield remained almost constant. With an optimized lumping model, fuel yields could be predicted with an R2 of 0.998. In this study, co-HP heavy aromatic-rich MTG/DTG fuels with fossil MD were proven to be a promising process strategy compared to a stand-alone after-treatment

Standard-Compliant Gasoline by Upgrading a DTG-Based Fuel through Hydroprocessing the Heavy-Ends and Blending of Oxygenates

Methanol-to-gasoline (MTG) and dimethyl ether-to-gasoline (DTG) fuels are rich in heavy aromatics such as 1,2,4,5-tetramethylbenzene, resulting in low volatilities due to a lack of light ends, increased emission tendencies and drivability problems due to crystallization. Approaches addressing these issues mainly focus on single aspects or are optimized for petroleum-based feedstocks. This research article introduces an upgrading strategy for MTG and DTG fuels through hydroprocessing (HP) heavy-ends and applying a sophisticated blending concept. Different product qualities were prepared by HP heavy gasoline (HG) and Fischer-Tropsch wax using commercially available Pt/HZSM-5 and Pt/SAPO-11 catalysts in a fixed-bed reactor. The products were used for blending experiments, focusing on gasoline volatility characteristics. Accordingly, methanol, ethanol, methyl tert-butyl ether (MTBE), and ethyl tert-butyl ether (ETBE) were evaluated in a second blending experiment. The results were finally considered for preparing blends meeting EN 228. HP of HG was found to improve the amount of light-ends and the vapor pressure of the DTG fuel with increasing reaction temperature without, however, satisfying EN 228. The front-end volatility was further improved by blending methanol due to the formation of near-azeotropic mixtures, while ethyl tert-butyl ether (ETBE) considerably supported the mid-range volatility. A final blend with an alcohol content of less than 3 vol.%, mostly meeting EN 228, could be provided, making it suitable even for older vehicles

Performance Characteristics of an 8 MW(th) Combined Heat and Power Plant Based on Dual Fluidized Bed Steam Gasification of Solid Biomass

The work focuses on a dual fluidized bed gasification technology for which a model has been developed and validated accompanying the operation of the 8 MWth biomass combined heat and power plant in Guessing/Austria. The reactor concept is a circulating fluidized bed system with a large steam-fluidized bubbling bed integrated into the solids return loop. The solids circulation rate is shown versus the riser exit velocity. Further, plant performance maps are presented for both electric and heat power output. The water content of the fuel is a major parameter with respect to plant performance. High fuel water content at high gas engine load means high gas velocities in the riser (erosion limit) and higher heat share in the produced energy

Concepts for the Integration of Renewable Synthetic Fuels into an Existing Refinery Structure [Konzepte zur Integration erneuerbarer synthetischer Kraftstoffe in einen bestehenden Raffinerieverbund]

Die Bewältigung der globalen Klimakrise fordert neben neuen Ansätzen auch Strategien zur Transformation fossiler Technologien im Sinne der Nachhaltigkeit. Im Verkehrssektor ist der zukünftige nicht-fossile Energiemix weiterhin nur schwer absehbar. Neben der sicheren Elektrifizierung des Nahverkehrs ist es unumgänglich für die Übergangsphase sowie auch für den Transportsektor Alternativen aufzuzeigen. In der vorliegenden Studie wird die Integration erneuerbarer Benzin- und Dieselkraftstoffe nach der Biomass-to-Liquid- und Power-to-Liquid-Route in eine Raffinerie diskutiert und basierend auf Bilanzen bewertet

Experimental Demonstration and Validation of Hydrogen Production Based on Gasification of Lignocellulosic Feedstock

The worldwide production of hydrogen in 2010 was estimated to be approximately 50 Mt/a, mostly based on fossil fuels. By using lignocellulosic feedstock, an environmentally friendly hydrogen production route can be established. A flow sheet simulation for a biomass based hydrogen production plant was published in a previous work. The plant layout consisted of a dual fluidized bed gasifier including a gas cooler and a dust filter. Subsequently, a water gas shift plant was installed to enhance the hydrogen yield and a biodiesel scrubber was used to remove tars and water from the syngas. CO$_{2}$ was removed and the gas was compressed to separate hydrogen in a pressure swing adsorption. A steam reformer was used to reform the hydrocarbon-rich tail gas of the pressure swing adsorption and increase the hydrogen yield. Based on this work, a research facility was erected and the results were validated. These results were used to upscale the research plant to a 10 MW fuel feed scale. A validation of the system showed a chemical efficiency of the system of 60% and an overall efficiency of 55%, which indicates the high potential of this technology

Influence of Gasification Operating Parameters on Performance of the Nong Bua Dual Fluidized Bed Gasification System in Thailand

Gasification system performance generally depends on feed moisture content, activity of bed material, gasifier and combustor temperatures, and scrubber media. The tar concentration and gas composition of product gas are two indicators of the gasification system performance. In this research, the effects of gasifier temperature and the activity of bed material on the tar concentration and gas composition of the product gas produced from a dual fluidized bed (DFB) gasification system power plant were investigated. The DFB gasification system power plant is located in Nong Bua district, Nakhon Sawan province, Thailand. Two periods of gasification operation were examined. These two periods were when the olivine was freshy activated and then after a period of operation. The gasifier temperature had several peaks during the operation, which caused the product gas composition to fluctuate. When the olivine had been used for a period, the percentage of hydrogen was approximately 3% higher than when the olivine had been freshly activated, and a lower heating value was observed, which was probably due to lower heating value of hydrogen. The tar concentration was substantially lower when compared with the freshly activated olivine. When the olivine was used for a period, the average tar concentration was 5622 mg/Nm3 (this is after 95 h continuous operating time) while the average tar concentration of the freshly activate olivine was 872125 mg/Nm3 (which was after 34.5 h continuous operating time). It was concluded that the average tar concentration and gas composition were influenced by the activity of the bed material and the gasification temperatur

Power to Fuels: Dynamic Modeling of a Slurry Bubble Column Reactor in Lab-Scale for Fischer Tropsch Synthesis under Variable Load of Synthesis Gas

This research developed a comprehensive computer model for a lab-scale Slurry Bubble Column Reactor (SBCR) (0.1 m Dt and 2.5 m height) for Fischer–Tropsch (FT) synthesis under flexible operation of synthesis gas load flow rates. The variable loads of synthesis gas are set at 3.5, 5, 7.5 m3/h based on laboratory adjustments at three different operating temperatures (483, 493 and 503 K). A set of Partial Differential Equations (PDEs) in the form of mass transfer and chemical reaction are successfully coupled to predict the behavior of all the FT components in two phases (gas and liquid) over the reactor bed. In the gas phase, a single-bubble-class-diameter (SBCD) is adopted and the reduction of superficial gas velocity through the reactor length is incorporated into the model by the overall mass balance. Anderson Schulz Flory distribution is employed for reaction kinetics. The modeling results are in good agreement with experimental data. The results of dynamic modeling show that the steady state condition is attained within 10 min from start-up. Furthermore, they show that step-wise syngas flow rate does not have a detrimental influence on FT product selectivity and the dynamic modeling of the slurry reactor responds quite well to the load change conditions

Solubility of Tar Model Compounds in Various Solvents for Tar Removal in a Dual Fluidized Bed Biomass Gasification Process

Production of high quality product gas via biomass steam gasification is a promising technology. However, impurities in the product gas, namely tars, cause problems in the downstream gas processing operations and thus they need to be removed efficiently. Oil scrubbing is an effective solution for tar removal due to its non-polar characteristic which is similar to tar nature. In this research, solubility values of five simulated tar compounds were experimentally investigated for selecting the new scrubbing solvent. The simulated tar compounds investigated represent those found in the dual fluidized bed steam gasification of wood biomass, which are: naphthalene, biphenyl, anthracene, fluoranthene, and pyrene. The scrubbing solvents tested in this research are classified into biodiesels, vegetable oils, and diesel. Biodiesel used are rapeseed methyl ester (RME) and 2 different palm methyl esters (denoted as PME1 and PME2). Vegetable oils are sunflower oil, refined palm oil, Thai rice bran oil, and crude palm oil. All of the solubility tests were performed in the laboratory-scale test-rig at 30, 50, 70, and 80°C. Biodiesels are found to be the effective solvent in dissolving the tar compounds. PME1 shows the similar tar removal performance to RME but is more readily available; therefore, PME1 is chosen to be used as a scrubbing solvent at the Thailand 1 MWel prototype DFB gasifier at Nong Bua district in Nakhon Sawan province, Thailand