Tandem hydroalkylation and deoxygenation of lignin-derived phenolics to synthesize high-density fuels

Lignin is the most abundant naturally phenolic biomass,and the synthesis of high-performance renewable fuel from lignin has attracted significant attention.We propose the efficient synthesis of high-density fuels using simulated lignin cracked oil in tandem with hydroalkylation and deoxygenation reactions.First,we investigated the reaction pathway for the hydroalkylation of phenol,which competes with the hydrodeoxygenation form cyclohexane.And then,we investigated the effects of metal catalyst types,the loading amount of metallic,acid dosage,and reactant ratio on the reaction results.The phenol hydroalkylation and hydrodeoxygenation were balanced when 180℃ and 5 MPa H_(2)with the alkanes yield of 95%.By extending the substrate to other lignin-derived phenolics and simulated lignin cracked oil,we obtained the polycyclic alkane fuel with high density of 0.918 g·ml^(-1)and calorific value of41.2 MJ·L^(-1).Besides,the fuel has good low-temperature properties(viscosity of 9.3 mm^(2)·s^(-1)at 20℃ and freezing point below-55℃),which is expected to be used as jet fuel.This work provides a promising way for the easy and green production of high-density fuel directly from real lignin oil.

Conversion of lignin oil and hemicellulose derivative into high-density jet fuel

Synthesizing high-density fuel from lignocellulose can not only achieve green and low-carbon development,but also expand the feedstock source of hydrocarbon fuel.Here,we reported a route of producing high-density fuel from lignin oil and hemicellulose derivative cyclopentanol through alkylation and hydrodeoxygenation,HY with SiO_(2)/Al_(2)O_(3) molar ratio of 5.3 was screened as the alkylation catalyst in the reaction of model phenolic compounds and mixtures,and the reaction conditions were optimized to achieve conversion of phenolic compounds higher than 87%and selectivity of bicyclic and tricyclic products higher than 99%.Then two phenolic pools simulating the composition of two typic lignin oils were studied to validate the alkylation and analyze the competition mechanism of phenolic compounds in mixture system.Finally,real lignin oil from depolymerized of beech powder was tested,and notably80%of phenolic monomers in the oil were converted into fuel precursor.After hydrodeoxygenation,the alkylated product was converted to fuel blend with a density of 0.91 g/mL at 20℃and a freezing point lower than-60℃,very promising as high density fuel.This work provides a facile and energyefficient way of synthesizing high-performance jet fuel directly from lignocellulosic derivatives,which decreases processing energy consumption and improve the utilization rate of feedstock.

Sustainable synthesis of high-density fuel via catalytic cascade cycloaddition reaction

The access to high-density hydrocarbon fuels from biomass for the reduction of dependence on fossil resources has been a research highlight in recent years. It is well known that cycloalkanes are the components of fuels with higher energy density than straight or branched alkanes. Herein, we developed a new catalytic pattern to synthesize dimethyltetradecahydroanthracenes(DMTHA), a kind of tricyclic alkane, from biomass-derived isoprene and p-benzoquinone via a cascade Diels-Alder reaction followed by a hydrodeoxygenation reaction. Vanadium supported on titanium dioxide(V-TiO_(2)) was applied to catalyze the cascade Diels-Alder reaction and it was disclosed that V with appropriate V^(4+)/V^(5+) ratio on the surface of TiO_(2) could activate quinones. Experimental tests showed that the heating value of final products was up to 45.7 MJ/kg. The development of new high-density fuel molecules is a long-term trend for the future renewable and sustainable fuel energy application.

Hydrocarbon pneumonitis following fuel siphonage: A case report and literature review

BACKGROUND: People sometimes siphon fuel to fill their tanks. However, this is a potentially dangerous procedure and may cause hydrocarbon pneumonitis. We present the case of a patient with severe hydrocarbon pneumonitis after siphoning fuel. The patient underwent artifi cial ventilation and was admitted to hospital for 97 days. METHODS: We review the relevant literature for a better understanding of clinical features and management strategies for hydrocarbon pneumonitis following fuel siphonage.RESULTS: We reviewed 15 articles, which included 3 original articles and 12 case reports that reported the clinical features of fuel siphonage. In addition, we added our presented case for data analysis. A total of 40 cases were included in this review. The literature review found that hydrocarbon pneumonitis caused by fuel siphonage occurs worldwide and that most patients(80%) became symptomatic within 1 day of aspiration. Cough(70%), chest pain(62.5%), dyspnoea(55%), and fever(52.5%) presented in more than half of all patients. The right middle lobe(80%) was the predominantly involved lung fi eld; more than one-third of patients(36.7%) showed the involvement of two lobes.CONCLUSION: Patient history, computed tomographic scans of the chest, and bronchoalveolar lavage are the commonly used diagnostic tools. Supportive care remains the foundation of treatment, whereas antibiotics, steroids, and bronchoalveolar lavage are practical therapies. Patients' clinical improvement precedes the resolution of lesions on chest X-ray. Most complications arise from pulmonary lesions. The prognosis of patients suffering from hydrocarbon pneumonitis following fuel siphonage might be improved by accurate diagnosis and appropriate care.

Research Progress of Catalysts and Initiators for Promoting the Cracking of Endothermic Hydrocarbon Fuels

Catalytic/initiated cracking of endothermic hydrocarbon fuels is an eff ective technology for cooling a hypersonic aircraft with a high Mach number(over 5).Catalysts and initiators can promote fuel cracking at low temperatures,increase fuel conversion and the heat sink capacity,and suppress coke deposition,thereby reducing waste heat.Catalysts mainly include metal oxide catalysts,noble metal catalysts and metal nanoparticles,zeolite catalysts,nanozeolite catalysts,and coating catalysts.Moreover,initiators roughly include nitrogenous compounds,oxygenated compounds,and hyperbranched polymer initiators.In this review,we aim to summarize the catalysts and initiators for cracking endothermic hydrocarbon fuels and their mechanisms for promoting cracking.This review will facilitate the development of the synthesis and exploration of catalysts and initiators.

Investigation of heat sink of endothermic hydrocarbon fuels

Endothermic hydrocarbon fuels are advanced coolants for high-temperature structures of spacecraft. No data of tested-cooling-ability of endothermic fuels have been broadly discussed in literature. In this work a high-temperature flow calorimeter was designed, and the cooling capacity of six different hydrocarbon fuels were measured. Experimental results showed that these hydrocarbon fuels have capacity for cooling high-temperature structures, and that the cooling capacity of fuel N-1 can reach 3.15 M J/kg, which can nearly satisfy the requirement of thermal management for a Mach 3 cruise aircraft, whose heat sink requirement is about 3.5 M J/kg. The endothermic velocity of hydrocarbon fuels was also measured by the calorimeter.

Evaluation of Cellulose as a Substrate for Hydrocarbon Fuel Production by <i>Ascocoryne sarcoides</i>(NRRL 50072)

The fungal endophyte, Ascocoryne sarcoides, produced aviation, gasoline and diesel-relevant hydrocarbons when grown on multiple substrates including cellulose as the sole carbon source. Substrate, growth stage, culturing pH, temperature and medium composition were statistically significant factors for the type and quantity of hydrocarbons produced. Gasoline range (C5-C12), aviation range (C8-C16) and diesel range (C9-C36) organics were detected in all cultured media. Numerous non-oxygenated hydrocarbons were produced such as isopentane, 3,3-dimethyl hexane and d-limonene during exponential growth phase. Growth on cellulose at 23°C and pH 5.8 produced the highest overall yield of fuel range organics (105 mg * g·biomass-1). A change in metabolism was seen in late stationary phase from catabolism of cellulose to potential oxidation of hydrocarbons resulting in the production of more oxygenated compounds with longer carbon chain length and fewer fuel-related compounds. The results outline rational strategies for controlling the composition of the fuel-like compounds by changing culturing parameters.

Effect of Liquid-phase Oxidation Impurities on Solubility of Water in Hydrocarbon Fuels

The effect of liquid-phase oxidation impurities on the solubility of water in hydrocarbon fuels was studied.The results show that the concentration of polar surfactant molecules in the first region increases(true solution)during fuel oxidation,and since the oxidation groups(-COOH,-O=O,-OH,etc.)have similar dipole momentμ,the dielectric loss tangent tanδincreases linearly in this region with surfactant concentration.Upon further oxidation,micelle structures begin to form at a certain point.Micelle formation leads to a sharp decrease in the dipole moment attributable to the monomer unitμ/n,where nis the number of molecules in a micelle.A several-fold decrease in the dipole moment leads to a sharp drop in tanδ.Upon further increase in the number and size of micelles,the dipole moment remains practically unchanged,and the dielectric loss tangent begins to increase linearly again with surfactant concentration.If the critical concentration for micelle formation is achieved upon further oxidation of hydrocarbon liquids,micelle formation processes occur spontaneously in the solution,and the true solution becomes a colloidal system(sol).The resulting micelles are structured with hydrocarbon radicals of molecules toward the outside and hydrophilic(polar)groups toward the inside.Water molecules are located inside micelles and held so securely that water molecules do not aggregate as temperature decreases.The reason for significant differences in the equilibrium solubility of water in hydrocarbon fuels is the different oxidation factors of product samples,resulting from the accumulation of various concentrations of oxidation products,which are natural surfactants,in hydrocarbon fuels.

Conversion of Municipal Waste Plastic into Liquid Hydrocarbon Fuel Using a Stainless Steel Reactor

Plastic wastes from milk containers, soft drink bottles, plastic wraps, plastic flatware, etc. have been successfully converted into fuel. Two approaches for the conversion of waste post consumer plastic into fuel have been investigated： （1） muffle furnace to reactor liquefaction system; （2） direct liquefaction system. Majority of used plastics are derived from ethylene, propylene, butadiene and benzene. Waste plastics are plastics that are used by the people in their daily life. It is collected from outside and city municipalities. Some of them are coded and rests are non-coded. A developed process discussed in this paper works with most of the waste plastic, both coded and non-coded. The plastics are heated up at 120-380 ℃ temperature to melt. The gaseous vapor is then condensed into liquid fuel.

De-polymerization of Waste Polymers to Produce Hydrocarbon Fuel Utilizing Thermal Degradation

Waste plastics are one of the biggest environmental concerns the world faces today. Waste plastics exposure to the environment is very hazardous. Over time waste plastics photo-degrade and become very tiny dust particles. These dust particles contain very harmful compounds including benzene, sulfur, carbon and many others. According to studies, waste plastic pollutions are one of the biggest reasons for the depletion of the ozone layer and contributor of global warming. Many scientists have been trying to figure out how to utilize these waste plastics and convert them into useful energy sources. It is possible to convert waste plastics into energy because they are made from petroleum. Scientists have succeeded in developing many methods including pyrolysis, catalytic cracking, thermal degrading and others. The purpose of this experiment is to convert these environmentally harmful waste materials into useful energy source using simple and viable methods. A particular thermal degradation process was successful in extracting fuel from waste plastics at 370-420 ~C. In this paper we will discuss our performed experiment and provide detailed analysis of the produced fuel. Thorough instrumental analysis of the produced fuel showed very considerable results including high energy contents, low levels of harmful emissions and compatibility with various types of existing appliances.

Waste Plastic Conversion into Hydrocarbon Fuel Materials

The increased demand and high price for energy sources are driving efforts to convert organic compounds into useful hydrocarbon fuels. Although much of this work has focused on biomass, there are strong benefits to deriving fuels from waste plastic material. Natural State Research Inc. （NSR） has invented a simple and economically viable process to decompose the hydrocarbon polymers of waste plastic into the shorter chain hydrocarbon of liquid fuel （patent pending）. The method and principle of the production/process will be discussed. Initial tests with several widely used polymers indicate a high potential for commercialization.

机器学习辅助的烃类分子性质预测与燃料的高通量筛选

通过数据收集、结构优化和量化计算,建立了碳数从1到50的2899个烃类分子“结构-多种性质”数据集,性质包含熔点(T_(m))、沸点(T_(b))、密度(ρ)、0 K下的内能(U_(0))、298.15 K下的内能(U)、298.15 K下的焓(H)、298.15 K下的吉布斯自由能(G)。以表示分子结构的库伦矩阵作为模型输入,建立了决策树回归模型、交叉验证的最小绝对收缩和选择算子回归模型、交叉验证的岭回归模型、极限梯度提升回归模型4种不同的机器学习模型。通过比较不同模型预测性质的精度得出,极限梯度提升回归模型更适用于预测烃类分子的熔点、沸点、密度等通过实验测得的性质,交叉验证的岭回归模型更适用于预测烃类分子的内能、焓、吉布斯自由能等能量的通过理论计算得到的性质。同时,最优的机器学习组合模型可以准确预测相同碳数、不同种类和同分异构体烃类分子的性质。使用最优的机器学习模型计算了34种已通过实验合成的高密度碳氢燃料的密度,计算值与实验值的平均绝对误差为0.0290 g·cm^(-3)。进而,预测了开源数据库GDB-13C中的319,893个烃类分子的燃料性质,并高通量筛选出了37种低凝固点、高密度的新型碳氢燃料候选分子。采用基团贡献法和DFT方法进一步计算了筛选出的碳氢分子的关键燃料性质,这些新型分子与典型燃料JP-10和QC的质量热值和比冲相当。

Ni doped La_(0.6)Sr_(0.4)FeO_(3-δ) symmetrical electrode for solid oxide fuel cells

The conventional Ni cermet anode suffers from severe carbon deposition and sulfur poisoning when fossil fuels are used. Alternative anode materials are desired for high performance hydrocarbon fuel solid oxide fuel cells （SOFCs）. We report the rational design of a very active Ni doped La0.6Sr0.4FeO3‐δ（LSFN） electrode for hydrocarbon fuel SOFCs. Homogeneously dispersed Ni‐Fe alloy nanoparticles were in situ extruded onto the surface of the LSFN particles during the operation of the cell. Sym‐metric SOFC single cells were prepared by impregnating a LSFN precursor solution onto a YSZ （yt‐tria stabilized zirconia） monolithic cell with a subsequent heat treatment. The open circuit voltage of the LSFN symmetric cell reached 1.18 and 1.0 V in humidified C3H8 and CH4 at 750？？, respective‐ly. The peak power densities of the cells were 400 and 230 mW/cm2 in humidified C3H8 and CH4, respectively. The electrode showed good stability in long term testing, which revealed LSFN has good catalytic activity for hydrocarbon fuel oxidation.

A unified model for the formation and distribution of both conventional and unconventional hydrocarbon reservoirs

The discovery and large-scale exploration of unconventional oil/gas resources since 1980s have been considered as the most important advancement in the history of petroleum geology;that has not only changed the balance of supply and demand in the global energy market,but also improved our understanding of the formation mechanisms and distribution characteristics of oil/gas reservoirs.However,what is the difference of conventional and unconventional resources and why they always related to each other in petroliferous basins is not clear.As the differences and correlations between unconventional and conventional resources are complex challenging issues and very critical for resources assessment and hydrocarbon exploration,this paper focused on studying the relationship of formations and distributions among different oil/gas reservoirs.Drilling results of 12,237 exploratory wells in 6 representative petroliferous basins of China and distribution characteristics for 52,926 oil/gas accumulations over the world were applied to clarify the formation conditions and genetic relations of different oil/gas reservoirs in a petroliferous basin,and then to establish a unified model to address the differences and correlations of conventional and unconventional reservoirs.In this model,conventional reservoirs formed in free hydrocarbon dynamic field with high porosity and permeability located above the boundary of hydrocarbon buoyancy-driven accumulation depth limit.Unconventional tight reservoirs formed in confined hydrocarbon dynamic field with low porosity and permeability located between hydrocarbon buoyancy-driven accumulation depth limit and hydrocarbon accumulation depth limit.Shale oil/gas reservoirs formed in the bound hydrocarbon dynamic field with low porosity and ultra-low permeability within the source rock layers.More than 75%of proved reserves around the world are discovered in the free hydrocarbon dynamic field,which is estimated to contain only 10%of originally generated hydrocarbons.Most of undiscovered resources distributed in the confined hydrocarbon dynamic field and the bound hydrocarbon dynamic field,which contains 90%of original generated hydrocarbons,implying a reasonable and promising area for future hydrocarbon explorations.The buried depths of hydrocarbon dynamic fields become shallow with the increase of heat flow,and the remaining oil/gas resources mainly exist in the deep area of“cold basin”with low geothermal gradient.Lithology changing in the hydrocarbon dynamic field causes local anomalies in the oil/gas dynamic mechanism,leading to the local formation of unconventional hydrocarbon reservoirs in the free hydrocarbon dynamic field or the occurrence of oil/gas enrichment sweet points with high porosity and permeability in the confined hydrocarbon dynamic field.The tectonic movements destroy the medium conditions and oil/gas components,which leads to the transformation of conventional oil/gas reservoirs formed in free hydrocarbon dynamic field to unconventional ones or unconventional ones formed in confined and bound hydrocarbon dynamic fields to conventional ones.

Review on the Relationship Between Liquid Aerospace Fuel Composition and Their Physicochemical Properties

The development of advanced air transportation has raised new demands for high-performance liquid hydrocarbon fuels.However,the measurement of fuel properties is time-consuming,cost-intensive,and limited to the operating conditions.The physicochemical properties of aerospace fuels are directly infl uenced by chemical composition.Thus,a thorough investigation should be conducted on the inherent relationship between fuel properties and composition for the design and synthesis of high-grade fuels and the prediction of fuel properties in the future.This work summarized the eff ects of fuel composition and hydrocarbon molecular structure on the fuel physicochemical properties,including density,net heat of combustion(NHOC),low-temperature fl uidity(viscosity and freezing point),fl ash point,and thermal-oxidative stability.Several correlations and predictions of fuel properties from chemical composition were reviewed.Additionally,we correlated the fuel properties with hydrogen/carbon molar ratios(n H/C)and molecular weight(M).The results from the least-square method implicate that the coupling of H/C molar ratio and M is suitable for the estimation of density,NHOC,viscosity and eff ectiveness for the design,manufacture,and evaluation of aviation hydrocarbon fuels.

Comparison of toxicity effects of fuel oil treated by different dispersants on marine medaka(Oryzias melastigma) embryo

This study aims to evaluate the subacute toxic effects of oil under different treatments on marine organism by simulating natural contaminative processes. In this study, 120# （RMD15） fuel oil was selected as the pollutant and marine medaka （Oryzias melastigma） embryos as the experimental organism. The developmental toxicity of different volume concentrations （0.05%, 0.2%, 1% and 5%） of water-accommodated fractions, biologically-enhanced water-accommodated fractions, and chemically-enhanced water-accommodated fractions on the embryos in different exposure time （8, 15 and 22 d） were compared and the content of relevant polycyclic aromatic hydrocarbons （PAHs） was studied （in dispersion and in vivo）. The subacute toxic effects were assessed in terms of antioxidant activities of enzymes （superoxide dismutase, catalase and glutathione S-transferase） and the blue sac disease （BSD） indexes.The results showed that the BSD indexes of the treatment groups were significantly higher than the respective control groups and showed positive correlations with both concentration and exposure time. The experiments with three antioxidant enzymes indicated that enzymatic activities of the embryos changed dramatically under the oxidation stress of petroleum hydrocarbons, especially after adding the dispersants. With the increase of petroleum hydrocarbon concentration and exposure time, the three enzymes showed different degrees of induction and inhibition effects.

Comparative Effect of Gasoline Formulations on Fuel Economy and Emissions of Modern GDI Engine

In this paper the effect of gasoline formulations on fuel economy and emissions were studied,aiming at exploring the optimized fuel formulation that can alleviate energy crisis and greenhouse effect to some extent.Five gasoline blends with same research octane number(RON)were designed and tested on a calibrated gasoline direct injection(GDI)engine under the mapped characteristic conditions.Test results illustrate that the optimized fuel formulation shows good superiority in fuel economy,and reduces carbon dioxide(CO2)emissions at low engine speeds with medium loads.The brake-specific fuel consumption(BSFC)decreased by a maximum value of 3.26%mainly because of the improvement of combustion velocity and the optimization of low heating value.The optimized fuel formulation simultaneously increases total hydrocarbon(THC)emissions.Nevertheless,it also markedly reduces CO2 emissions,reaching the maximum value of 2.34%.The research results can be applied practically by refineries to reduce the CO2 emissions and to alleviate the greenhouse effect.

Using KELEA (Kinetic Energy Limiting Electrostatic Attraction) to Improve the Efficiency of Fuel Combustion

There are many reports of devices and fuel additives being able to enhance the performance of automobiles and other forms of transportation that rely upon the combustion of gasoline or diesel fuels. The claims extend from increased mileage and power to significant reductions in toxic exhaust emissions of carbon monoxide and unburnt hydrocarbons. Progress towards more widespread applications of means of improving fuel efficiency has been impeded by the lack of a coherent explanation of the mechanism of action. Fuel combustion allows for the conversion of much of the available chemical energy in volatile hydrocarbons to mechanical energy, which moves the pistons within an engine. It is proposed that the amount of chemical energy in hydrocarbons can be increased by the absorption of an environmental force termed KELEA (kinetic energy limiting electrostatic attraction). In addition to providing greater mechanical energy with relatively less heat output, the combustion of KELEA activated fuels proceeds further with less toxic emissions of carbon monoxide and unburnt hydrocarbons from incomplete combustion. KELEA activation of fuels should become standard practice in the transportation industry, with potential additional benefits in slowing the rate of global warming.

Influence of Combustion Initial Conditions on Emissions Production Rates and Released Heat for Methane Fuel Mixtures

An estimation of combustion products (pollutants) which include CO, CO2 and NO mole fraction are reported in this paper for premixed methane/air flames. Different mixtures were used in this study, including lean, stoichiometric and rich subjected to varying degrees of pressures and temperatures ranging from 5 - 40 bars and 350 - 600 K, respectively. In this work, computer software was used to calculate the produced emissions species as well as the final (adiabatic) temperatures for each mixture. Results show that rich mixture of methane fuel produces the highest rate for carbon monoxide (CO) with slight increase as pressure and temperature increase. Where the stoichiometric mixture produces the highest rate of carbon dioxide (CO2). Results showed that this type of emission decreases with the increase of pressure and temperature. On the other hand, nitric acid (NO) was found to be the highest for the lean mixture with sharp increase as pressure and temperature increase. Finally, the combustion heat (Q) for each mixture where plotted against pressure and it was found that the rich mixture of methane produced the highest rates. Results also showed that combustion heat increases sharply with increased pressures and temperatures.